Integrated process to make 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene

Abstract

An integrated process for producing E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene starting with ethylene and perfluoroethyl iodide.

Description

TITLE OF THE INVENTION INTEGRATED PROCESS TO MAKE 1,1,1,2,2,5,5,6,6,6-DECAFLUORO-3-HEXENE FIELD

[0001] The present application relates to processes of preparing1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene. BACKGROUND

[0002] A growing public awareness of the environmental impacts from theextraction, transportation and use of fossil fuels are motivating a new environmental sustainability driver in the form of regulations and reduction in output of CO2 equivalence in the atmosphere. In particular, new environmental regulations on refrigerants have forced the refrigeration and air-conditioning industry to look for new refrigerants with low global warming potential (GWP). Replacement refrigerants with low global warming potentials (GWP) and ozone depletion potential (ODP) for both existing and new applications in thermal management segments will need to adhere to these new regulations.

[0003] Certain hydrofluoroolefins, such as 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene(E-C2F5CH=CHC2F5, HFO-153-10mczz), are believed to meet both goals. Inparticular, E-isomer of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene may be useful in heattransfer 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 1,1,1,2,2,5,5,6,6,6-decafluoro-3- hexene. SUMMARY

[0004] Disclosed is an integrated process for the preparation of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, C2F5CH=CHC2F5 (also referred to herein as 153-10mczz) in a series of interrelated steps beginning with perfluoroethyl iodide (PFEI) and ethylene as the starting material.

[0005] The present invention involves 4 steps as illustrated in Fig.1. All four stepsinvolve liquid phase reactions.

[0006] Step 1 comprises reacting PFEI with ethylene in the presence of a radicalinitiator. The initiator can be chosen from an azo initiator or a peroxide. Step 1 is generally performed at a reaction temperature of from about 50°C to about 80°C. The product of Step 1 is CF3CF2CH2CH2I (1,1,1,2,2-pentafluoro-4-iodobutane, which may be referred to herein as “PFEEI”).

[0007] Step 2 comprises reacting PFEEI with an alkali metal hydroxide in thepresence of a phase transfer catalyst. The phase transfer catalyst can be chosen from ammonium and phosphonium salts. For example, tetraalkyl ammonium bromide and tetraalkyl phosphonium bromide. The product of Step 2 is 3,3,4,4,4- pentafluoro-1-butene (CF3CF2CH=CH2, 1345zf). Alternatively, the phase transfer catalyst may comprise a glycol or a crown ether.

[0008] Step 3 comprises reacting 1345zf with PFEI in the presence of a radicalinitiator. The initiator can be chosen from an azo initiator or a peroxide. Step 3 is generally performed at a reaction temperature of from about 100°C to about 150°C. Preferred temperatures depend on the selection of radical initiator. Step 3 can be also performed at a reaction temperature of from about 180°C to about 220°C without using an initiator. The product of Step 3 is CF3CF2CH2CHICF2CF3 (1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane).

[0009] Step 4 comprises reacting CF3CF2CH2CHICF2CF3 with an alkali metalhydroxide in the presence of an oxygen-containing phase transfer catalyst. In certain embodiments, Step 4 is performed at temperatures between 20-90°C. The product of Step 4 is 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (C2F5CH=CHC2F5, HFO-153-10mczz, more briefly, 153-10mczz).

[0010] The oxygen-containing catalyst may be chosen from a glycol having theformula, H(OCH2CH2)nOH where n is ≥ 1, e.g., 2, 3, 4 or greater; propylene glycol, a mono ether of polyethylene glycol or a mono ether of propylene glycol. Alternative, the oxygen-containing catalyst may be a crown ether.

[0011] In one embodiment for Step 4, the oxygen-containing catalyst is a glycolcatalyst.

[0012] In one embodiment for Step 4, when the oxygen-containing catalyst is aglycol catalyst, n = 1, and the glycol catalyst comprises HOCH2CH2OH (ethyleneglycol, EG). In one embodiment, n = 2, and the glycol catalyst comprises (HOCH2CH2)2O (diethylene glycol, DEG). In one embodiment, n = 3, and the glycol catalyst comprises H(OCH2CH2)3OH (triethylene glycol, TrEG). In one embodiment, n = 4, and the glycol catalyst comprises H(OCH2CH2)4OH (tetraethylene glycol, TeEG). In one embodiment, n ≥ 5, and the glycol catalyst comprises H(OCH2CH2)nOH [H(OCH2CH2)nOH is referred to herein as polyethylene glycol, PEG].

[0013] In one embodiment for Step 4, when the oxygen-containing catalyst is aglycol catalyst, the glycol catalyst comprises PEG having the formula HO(CH2CH2O)nCH2CH2OH and the value of n provides a PEG having molecular weight of about 100 to about 10000.

[0014] In one embodiment for Step 4, when the oxygen-containing catalyst is aglycol catalyst, the glycol catalyst comprises polypropylene glycol having the formula HO(C3H6O)nC3H6OH where the value of n provides a molecular weight in the range of about 100 to about 10000.

[0015] In one embodiment for Step 4, when the oxygen-containing catalyst is aglycol catalyst, the glycol catalyst comprises a mono ether of polyethylene glycol having the formula R(OCH2CH2)nCH2CH2OH, wherein R is a C1 to C5 group and the value of n provides a molecular weight up to about 10000.

[0016] In one embodiment for Step 4, when the oxygen-containing catalyst is aglycol catalyst, the glycol catalyst comprises a mono ether of polypropylene glycol having the formula R(OC3H6)nC3H6OH, wherein R is a C1 to C5 group and the value of n provides a molecular weight up to about 10000.

[0017] In one embodiment for Step 4, the oxygen-containing catalyst comprises acrown ether.

[0018] The product of Step 4 is suitable for use in high temperature, and / orelectrical and / or heat exchange environments.

[0019] In one embodiment of the invention disclosed herein the process is anintegrated process and uses excess initiator for Step 1 and / or Step 3 to produce the product iodo-fluoroalkane that is dehydroiodinated with a base in the presence of aphase transfer catalyst (PTC) in Step 2 and Step 4, respectively, to form the corresponding fluoroalkene.

[0020] In one embodiment of the invention described herein the initiator is selectedsuch that it can be thermally decomposed from a crude product to eliminate purification steps prior to a subsequent dehydroiodination, without thermally decomposing the carbon-containing iodide.

[0021] In another embodiment of the invention described herein the processfurther comprises thermally treating the Step 1 product to eliminate the initiator and using the treated Step 1 product as a starting material for Step 2 without purification. In another embodiment of the invention described herein the process further comprises thermally treating the Step 3 product to eliminate the initiator and using the treated Step 3 product as a starting material for Step 4 without purification.

[0022] In another embodiment of the invention described herein the processfurther comprises thermally treating the Step 1 product to eliminate the initiator and using the treated Step 1 product as a starting material for Step 2 without purification and thermally treating the Step 3 product to eliminate the initiator and using the treated Step 3 product as a starting material for Step 4 without purification.

[0023] In other embodiments of the present invention described herein integratedprocesses facilitate reactions between PFEI and alkenes using an excess of (CH3)2C(CN)N=NC(CH3)2CN (azodiisobutyronitrile, 2,2′-azobis(2-methylpropionitrile) or AIBN) as a polymerization / isomerization to initiator produce perfluoroalkyl iodides which are converted to fluoroalkenes.

[0024] The present invention provides a process to produce a product comprisingC2F5CH=CHC2F5 having a ratio of E-C2F5CH=CHC2F5 to Z-C2F5CH=CHC2F5 of atleast 80:20 or at least 85:15, or at least 90:10, or at least 95:5, or at least 98:2, or at least 99:1. The product of Step 4 disclosed herein can be concentrated and / orpurified to provide E-C2F5CH=CHC2F5 at a purity of at least 99%, 99.5%, 99.9%,99.99% or 99.999%, using one or more distillation, azeotrope separation or absorbents, or aqueous wash.

[0025] In another embodiment disclosed herein comprising a process of firstproducing CF3CF2CH2CH2I, second producing CF3CF2CH=CH2; third producingCF3CF2CH2CHICF2CF3 and then a fourth producing C2F5CH=CHC2F5, wherein thesecond and fourth producing steps involve dehydroiodination.

[0026] Unless otherwise defined, all technical and scientific terms used hereinhave 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Fig.1 illustrates an integrated reaction process as disclosed herein.

[0028] Figs.2A and 2B respectively, show the 19F and 1H NMR spectra taken ofisolated 153-10mczz (E / Z ratio 89:11) from Example 6.

[0029] Figs.3A and 3B respectively, show the 19F and 1H NMR spectra taken ofcrude reaction mixture (organic layer) after 18h at ambient temperature from Example 7.

[0030] Fig. 4 shows the 1H NMR taken of isolated product from Example 8.

[0031] Fig. 5 shows the 19F NMR spectra taken of starting material (bottomspectrum), product (middle spectrum) and organic residue from the reaction vessel (top spectrum) from Example 8.

[0032] Figs.5A, 5B, and 5C show the 1H NMR spectra taken of the crude reactionmixture at different conversions of C2F5CH2CHIC2F5 to 153-10mczz (E- C2F5CH=CHC2F5) from Example 10, with conversions of C2F5CH2CHIC2F5 at 100%,20%and 10%, respectively. Figs. 5D and 5E show the 19F NMR spectra taken ofthe crude reaction mixture at different conversions of C2F5CH2CHIC2F5 to 153-10mczz (E-C2F5CH=CHC2F5) from Example 10. Fig.5F shows the 1H NMR spectrataken of isolated 153-10mczz (E-C2F5CH=CHC2F5) from Example 9A-D.

[0033] Fig. 6 shows the NMR spectra taken of crude 153-10mczz fromExample 11.DETAILED DESCRIPTION

[0034] In one embodiment disclosed herein the process involves a first radicalinitiated reaction to produce a reaction mixture containing a first crude alkyl halide product which is thermally treated to remove the initiator and provide an initiator-free mixture which is the dehydroiodinated to form a first crude fluoroalkene. The first crude fluoroalkene is reacted with one of a catalyst or radical initiator to produce a second crude alkyl halide, and then the second crude alkyl halide is dehydroiodinated with an oxygen-containing catalyst to produce the desired fluoroalkene.

[0035] In one embodiment described herein the process is integrated and involvesa first radical initiated reaction to produce a reaction mixture containing a first crude fluoroiodoalkane which mixture may be thermally treated to remove the initiator and provide an initiator-free product mixture which is directly dehydroiodinated to form a first crude fluoroalkene. The first crude fluoroalkene is reacted with one of a catalyst or radical initiator to produce a second crude fluoroiodoalkane, and then dehydroiodinated with an oxygen-containing phase transfer catalyst (PTC) to produce the desired fluoroalkene.

[0036] For purposes of clarity, certain terms used herein are defined. Thus, asused herein the terms “alkane” and “alkyl” shall be understood to include both branched and straight-chain saturated aliphatic hydrocarbon groups having the specified number of carbon atoms. For example, C1-C8, as in “C1-C8 alkyl” is defined to include groups having 1, 2, 3, 4, 5, 6, 7, or 8 carbons in a linear or branched arrangement. For example, “C1-C8alkyl” specifically includes methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, pentyl, hexyl, heptyl, octyl, and so on. In an embodiment, if the number of carbon atoms is not specified, “alkyl” refers to C1-C8 alkyl and in a further embodiment, “alkyl” refers to C1-C6 alkyl.

[0037] As used herein the term “olefin” shall be understood to mean a C3-C8 orhigher alkene.

[0038] As used herein the term “fluoroolefin” shall be understood to mean a C3-C8or higher olefin that incorporates at least one CF3 group.

[0039] As used herein the term “aqueous and / or alcoholic base” shall beunderstood to mean an alkali metal base. Non-limiting examples include KOH and NaOH.

[0040] As used herein the term “phase transfer catalyst” shall be understood tomean a catalyst that facilitates the migration of a reactant from one phase into another phase where reaction occurs. Ammonium and phosphonium salts, glycol catalysts described herein, and crown ethers can be phase transfer catalysts.

[0041] The hydrofluoroalkene product of Step 4 can be used as a heat transfermedium, working fluid, along or combined with other components suitable for use as the heat transfer medium or working fluid to carry heat to and from a source. Such heat transfer compositions may also be useful as a refrigerant in a cycle wherein the fluid undergoes a phase change; that is, from a liquid to a gas and back, or vice versa. Examples of heat transfer systems include but are not limited to air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, high temperature heat pumps, mobile refrigerators, mobile air conditioning units, electric storage cooling systems, battery cooling, immersion cooling systems, data-center cooling systems, and combinations thereof.

[0042] In some embodiments the hydrofluoroalkene product of Step 4 can be usedfor immersion cooling is used to cool electronic devices, such as datacenter servers, insulated-gate bipolar transistor (IGBT) devices, telecommunication infrastructure, military electronics, televisions (TVs), cell phones, monitors, drones, automotive batteries, powertrains for electric vehicles (EVs), avionics devices, power devices and displays. Immersion cooling systems are heat transfer devices wherein there is no compressor, and the heat transfer medium possesses suitable dielectric properties. Generally, the object to be cooled is at least partially immersed in (in direct contact with) the heat transfer fluid contained in a vessel. In some embodiments, the heat transfer fluid may evaporate and condense in the vessel. In other embodiments, there may be no phase transition involved.

[0043] As use herein, a refrigerant is a compound or mixture of compounds(blend) that function as a heat transfer fluid in a cycle wherein the fluid undergoes a phase change from a liquid to a gas and back.

[0044] 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).

[0045] The transitional phrase “consisting of” excludes any element, step, oringredient 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.

[0046] The transitional phrase “consisting essentially of” is used to define acomposition, 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.’

[0047] Where applicants have defined an invention or a portion thereof with anopen-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.”

[0048] Also, use of “a” or “an” are employed to describe elements and componentsdescribed 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 atleast one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0049] Further, when an amount, concentration, or other value or parameter isgiven as either a range, preferred range, or a list of upper preferable values and 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. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.

[0050] The process described herein includes one or more of the followingreaction steps, including an integrated process including Steps 1-4: Step 1: CF3CF2I + CH2=CH2 → CF3CF2CH2CH2I Step 2: CF3CF2CH2CH2I + KOH → CF3CF2CH=CH2 + KI + H2O Step 3: CF3CF2CH=CH2 + C2F5I → CF3CF2CH2CHICF2CF3 Step 4: CF3CF2CH2CHICF2CF3 + KOH → C2F5CH=CHC2F5 + KI + H2O Step 1

[0051] In certain embodiments of the invention described herein, Step 1 comprisesreacting pentafluoroiodoethane (pentafluoroethyliodide, iodopentafluoroethane, PFEI) and ethylene in the presence of a radical initiator to produce 1,1,1,2,2- pentafluoro-4-iodobutane (PFEEI).

[0052] The radical initiator may be any initiator suitable for use. Preferablysuitable for use at a temperature above 30°C, preferably suitable for use at a temperature within the range of 30-90°C. For example, the radical initiator may be an azo initiator, such as azobisisobutyronitrile (CH3)2C(CN)N=NC(CH3)2CN (AIBN) or a peroxide, such as benzoyl peroxide or di-tert-butyl peroxide. In one embodiment, the radical initiator is AIBN. In one embodiment, the radical initiator is benzoyl peroxide. In one embodiment, the radical initiator is di-tert-butyl peroxide. An advantage of using an initiator is operating at a lower temperature. In addition, surprisingly higher yields of C2F5CH2CH2I may be produced.

[0053] In certain embodiments, Step 1 comprises using a starting materialcomprising PFEI and one or more of I2 and IF5.

[0054] In certain embodiments of the invention disclosed herein, prior to Step 1, astarting material comprising CF3CF2I is washed with a base or sulfite salt, e.g., KOHand / or Na2SO3 or Na2S2O5.

[0055] In one embodiment, an excess amount of a radical initiator is used inStep 1. In one particular embodiment, excess initiator is used when certain additional the starting material for Step 1 comprises PFEI and one or both of I2 and IF5.

[0056] In one embodiment a starting material comprising PFEI and one or more ofI2 and IF5 is washed with a base or sulfite salt, e.g., KOH and / or Na2SO3 and / or Na2S2O3 and / or Na2S2O5. In one embodiment, a starting material comprising PFEI and one or more of I2 and IF5 is washed with KOH. In one embodiment, a starting material comprising PFEI and one or more of I2 and IF5 is washed with Na2SO3. In one embodiment, a starting material comprising PFEI and one or more of I2 and IF5 is washed with KOH and Na2SO3. Using the washed starting material may improve reactivity of PFEI in Step 1. It is believed the washing of the starting material comprising CF3CF2I removes impurities such as I2 and IF5 which are the common impurities in PFEI.

[0057] Step 1 is an exothermic reaction. Temperature excursions due to anexotherm occurring may be addressed by internal or external means. For example, an external cooling system may be used to remove heat generated in the exothermic reaction. When an exotherm occurs, reactor pressure decreases due to consumption of ethylene. Allowing the reactor pressure to decrease as ethylene is added or feeding ethylene more slowly will also mitigate the potential for these excursions.

[0058] The initiator may be thermally removed by decomposition. For example,AIBN can be thermally removed by decomposition at moderate temperatures, such as at temperature above 30°C or above 50°C or above 80°C. As a result, the need for additional separation / purification steps typically used for removal of catalyst and / or initiators may be avoided. Thus, the thermally treated CF3CF2CH2CH2I crudeproduct of Step 1 can be directly used for Step 2 without purification operations to remove the catalyst.

[0059] In a batch process, Step 1 may comprise the following steps:Step 1a. Charge initiator such as solid AIBN to a reactor. Step 1b. Inert the reactor by N2 pressurization / venting, then evacuate. (This step provides low oxygen in the reactor. Step 1c. Charge the reactor with PFEI. Step 1d. Begin agitation in the reactor and pressurize the reactor with ethylene (2% of total charge). Step 1e. Heat the reactor to 30-80°C, preferably 50-80°C, such as 60-70°C. Step 1f. Add ethylene to maintain reactor pressure less than < 120 psig. Step 1g. Allow the reactor pressure to reduce over time to limit the ethylene partial pressure. Step 1h. When a target mass of ethylene has been added, maintain temperature at 30-80°C, preferably 50-80°C, such as 60-70°C for a period of time of 30 minutes to 5 hours, such as for 2 hours. Step 1i. Decompose the initiator, by heating the reactor. For example, if the initiator is AIBN, heat the reactor to a temperature of about 80°C or greater for a minimum of about 30 minute such as for 1 hour, then increase heat such as to 85-100°C and hold for a minimum of about 30 minute such as for 1 hour. Step 1j. Cool the reactor to ambient temperature. Step 1k. Vent the residual pressure from the head space and purge with N2 to remove residual ethylene. Step 1l. Cease agitation. The product of Step 1 is used as the starting material for Step 2. No further purification is needed.

[0060] Step 1 reactor material of construction is capable of tolerating theenvironment created by the reactants and products, for example, alloys comprising nickel.

[0061] In certain embodiments of the invention disclosed herein, prior to Step 1, astarting material comprising CF3CF2I is washed with a base or sulfite salt, e.g., KOH and / or Na2SO3 and / or Na2S2O3 and / or Na2S2O5. Using the washed starting material improves reactivity of PFEI in Step 1. It is believed the washing of the starting material comprising CF3CF2I removes impurities such as I2 and IF5 which are the common impurities in PFEI.

[0062] In certain embodiments disclosed herein the reaction temperature forStep 1 is greater than 50°C, 60°C, 70°C, or 80°C, less than 60°C, 70°C, or 80°C.

[0063] In a certain embodiment, the reaction temperature for Step 1 is in the rangeof 50-80°C. In a certain embodiment, the reaction temperature for Step 1 is in the range of 60-75°C and the initiator is AIBN.

[0064] In one embodiment, thermal decomposition of AIBN as the radical initiatorfollowing the reaction of PFEI and ethylene in the presence of a radical initiator may be performed at a temperature of about 80°C or greater for a minimum of about 30 minute such as for 1 hour, then increase heat such as to 85-100°C and hold for a minimum of about 30 minute such as for 1 hour.

[0065] In one embodiment, thermal decomposition of a peroxide radical initiatorfollowing the reaction of PFEI and ethylene in the presence of a radical initiator may be performed at a temperature of 160 to 250°C, preferably 180-230°C, more preferably 190-210°C. Step 2

[0066] In the invention described herein, Step 2 comprises reacting a startingmaterial comprising PFEEI produced in accordance with Step 1 with an alkali metal hydroxide in the presence of a phase transfer catalyst.

[0067] The phase transfer catalyst (“PTC”) may be chosen from ammonium andphosphonium salts. For example, tetraalkyl ammonium halide and tetraalkyl phosphonium halide. The halide may be Cl or Br. When the PTC is or comprises an ammonium or phosphonium halide salt, examples include tetra-n-butylammonium bromide (TBAB), and trioctylmethylammonium chloride (Aliquat®336). In one embodiment, the PTC is tetrabutylammonium bromide.

[0068] In one embodiment, the PTC is a glycol catalyst, having the formula,H(OCH2CH2)nOH where n is ≥ 1, e.g., 2, 3, 4 or greater; polypropylene glycol (PrG), a mono ether of polyethylene glycol or a mono ether of polypropylene glycol.

[0069] In one embodiment, n=1, and the glycol catalyst comprises HOCH2CH2OH(ethylene glycol, EG). In one embodiment, n = 2, and the glycol catalyst, comprises (HOCH2CH2)2O (diethylene glycol, DEG). In one embodiment, n = 3, and the glycol catalyst, comprises H(OCH2CH2)3OH (triethylene glycol, TrEG). In one embodiment, n = 4, and the glycol catalyst, comprises H(OCH2CH2)4OH (tetraethylene glycol, TeEG). In one embodiment, n ≥ 5, and the glycol catalyst, comprises H(OCH2CH2)nOH [H(OCH2CH2)nOH is referred to herein as polyethylene glycol, PEG].

[0070] In one embodiment, the amount of PTC added in Step 2 is about 0.05 kg / kgof the PFEEI in the starting material for Step 2 comprising the product produced in Step 1.

[0071] In one embodiment, the starting material for Step 2 comprises PFEEIproduced in accordance with Step 1 wherein the starting material for Step 1 is washed with a base or sodium salt prior to Step 1.

[0072] In one embodiment, the product from Step 1 comprising PFEEI alsocomprises excess radical initiator and the excess radical initiator is removed by thermal decomposition prior to use of the product from Step 1 as the starting material for Step 2.

[0073] In one embodiment, alkali metal hydroxide (MOH) solution used in Step 2 isan aqueous solution of KOH. Alternatively, the alkali metal hydroxide solutions of LiOH and NaOH may be used. The concentration of alkali metal hydroxide can be in the range of 20-60% or 20-45%.

[0074] The amount of PTC used is from about 0.1% to about 10%, preferably fromabout 0.5% to about 5%, more preferably from about 0.5% to about 1.5%.

[0075] In one embodiment of this invention, in a particular batch operation, Step 2comprises charging an aqueous solution of KOH and solid phase transfer catalyst to a reactor, heating the reactor to 80°C while agitating, slowly feeding the product of Step 1 comprising PFEEI to the reactor, producing Step 2 product, forming a vaporcomprising 1345zf. Further steps comprise passing the vapor comprising 1345zf through a reflux condenser (held at a temperature, for example, of 35°C, from which Step 1 product comprising PFEEI and water are condensed. During the process of Step 2, following condensing of Step 1 product and water, the vapor comprising 1345zf is vented from the reactor to maintain the reactor pressure at 17 psig. The vapor comprising 1345zf is passed through a molecular sieve dryer, a second condenser at -15°C, and collected as Step 2 product in a receiver held at a pressure of 2 psig. The Step 2 product comprising 1345zf is used in Step 3.

[0076] In a batch process, Step 2 may comprise the following general operatingsteps: Step 2a. Set up a reactor fitted with agitation mechanism, a reflux condenser, and a drying and collection system. Step 2b. Charge KOH to the reactor followed by deionized water to make 30 wt% KOH. Step 2c. Charge solid tetrabutylammonium bromide phase transfer catalyst to the reactor. Step 2d. Inert the reactor by N2 pressurization / venting then partially evacuate. Step 2e. Set the drying and collection system tracing to 43°C for collection Step 2 product comprising 1345zf. Step 2f. Start the reactor agitation and heat the reactor to 80°C. Step 2g. Feed Step 1 product to the reactor. Step 2h. Apply coolant to the reactor reflux condenser to maintain the outlet temperature of the reflux condenser at 35°C. Step 2i. Vent the vapor comprising 1345zf from the reactor as needed to maintain a reactor pressure of 17 psig. Step 2j. Pass the vapor comprising 1345zf through the dryer, a second condenser, and collect the condensed liquid comprising 1345zf in a receiver. Step 2k. When the feed is complete, hold the reactor at temperature to complete the reaction.Step 2l. Remove residual Step 2 product comprising 1345zf from the reactor to the collection system using N2 and add to receiver containing 1345zf (from Step 2j).

[0077] The product of Step 2, 3,3,4,4,4-pentafluoro-1-butene (CF3CF2CH=CH2,1345zf), is used as the starting material for Step 3. No further purification is needed.

[0078] In certain embodiments disclosed herein the reaction for Step 2 and thedehydroiodination reaction is conducted at a temperature greater than 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, less than 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, and ranges between from 30°C to one of 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, ranges between from 40°C to one of and 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, ranges between from 50°C to one of 60°C, 70°C, 80°C, 90°C, or 100°C, ranges between from 70°C to one of 80°C, 90°C, 100°C, ranges between from 80°C to one of 90°C or 100°C and all values and ranges therebetween.

[0079] The amount of PTC used can be from about 0.1% to about 10%, preferablyfrom about 0.5% to about 5%, more preferably from about 0.5% to about 1.5%. For example, the amount of PTC added may be about 0.0075 kg / kg of product produced in Step 1.

[0080] Step 2 reactor material of construction is capable of tolerating theenvironment created by the reactants and products, including alloys where needed. For certain upstream and downstream operations of the reactor, stainless steel may be used. Step 3

[0081] In the invention described herein, Step 3 comprises a process of reacting astarting material comprising 1345zf produced in accordance with Step 2 with PFEI to produce CF3CF2CH2CHICF2CF3 (1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane).

[0082] In one embodiment of Step 3, the process is performed in the absence of aradical initiator. When the process of Step 3 is performed in the absence of a radical initiator, the temperature of the reaction is greater than 150°C or greater than 175°C or greater than 200°C, such as 200-250°C.

[0083] In one embodiment of Step 3, the process comprises reacting a startingmaterial comprising 1345zf produced in accordance with Step 2 with PFEI in the presence of a radical initiator to produce CF3CF2CH2CHICF2CF3 (1,1,1,2,2,5,5,6,6,6- decafluoro-3-iodohexane). Advantageously, lower temperatures can be used when Step 3 is performed in the presence of a radical initiator.

[0084] In one embodiment a starting material comprising PFEI may contain I2 andIF5. The I2 and IF5 can be removed from PFEI by washing with a base or sulfite salt, e.g., KOH and / or Na2SO3. In one embodiment, a starting material comprising PFEI and one or more of I2 and IF5 is washed with KOH. In one embodiment, a starting material comprising PFEI and one or more of I2 and IF5 is washed with Na2SO3. In one embodiment, a starting material comprising PFEI and one or more of I2 and IF5 is washed with KOH and Na2SO3. Using the washed starting material may improve reactivity of PFEI in Step 3. It is believed the washing of the starting material comprising CF3CF2I removes impurities such as I2 and IF5 which are the common impurities in PFEI.

[0085] The radical initiator may be any initiator suitable for use. Preferablysuitable for use at a temperature of 100°C or more, preferably suitable for use at a temperature within the range of 110-150°C. For example, the radical initiator may be an azo initiator capable of operating at a temperature of 100°C or more or a peroxide, such as benzoyl peroxide or di-tert-butyl peroxide. Peroxides are preferred.

[0086] In one embodiment, the radical initiator is benzoyl peroxide, and thetemperature is in the range of 100-150°C, preferably 110-130°C.

[0087] In one embodiment, the radical initiator is t-butyl peroxide, and thetemperature is in the range of 100-150°C, preferably 110-145°C or 120-140°C or 130-145°C.

[0088] In a certain embodiment, the process of Step 3 comprises reacting PFEIwith a starting material comprising 1345zf in the presence or absence of a radical initiator.

[0089] The process of Step 3 may be performed as a batch process. In oneembodiment of a batch process for Step 3, the process comprises charging a reactorwith PFEI, liquid di-tert-butyl peroxide (“DTBP”) initiator, heating the reactor to 130°C, adding liquefied starting material comprising 1345zf, monitoring pressure, which increases (which increase may rise to 300 psig) and then decreases as starting material comprising 1345zf is added.

[0090] The starting material comprising 1345zf is produced according to theprocess of Step 2 as disclosed herein.

[0091] In a batch process, Step 3 may comprise the following steps:Step 3a. Inert the reactor by N2 pressurization / venting, then evacuate. (This step provides low oxygen in the reactor.) Step 3b. Charge PFEI to the reactor. Step 3a. Charge liquid DTBP initiator to the reactor. Step 3c. Heat the reactor to 130°C. Step 3d. Feed liquid starting material comprising 1345zf to the reactor with a metering pump. Step 3e. After the feed is complete, maintain reactor conditions to complete the reaction. Step 3f. Hold the reactor at 145°C for sufficient time to decompose the DTBP. Step 3g. Cool the reactor to ambient temperature. Step 3h. The product of Step 3 comprises CF3CF2CH2CHICF2CF3 (1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane). The product of Step 3 is used as the starting material for Step 4. No further purification is needed.

[0092] In one embodiment, thermal decomposition of radical initiator following thereaction of PFEI and 1345zf in the presence of a radical initiator may be performed at a temperature 130-250°C, such as 140-180°C or 140-160°C or 180-230°C or 190-210°C. Lower temperatures may require longer times for thermal decomposition. Step 4

[0093] In the invention described herein, Step 4 comprises reacting a startingmaterial comprising CF3CF2CH2CHICF2CF3 (1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane) produced in accordance with Step 3 with an alkali metal hydroxide in the presence of a phase transfer catalyst.

[0094] The phase transfer catalyst for Step 4 is an oxygen-containing catalyst.

[0095] The oxygen-containing catalyst may be chosen from a glycol catalysthaving the formula, H(OCH2CH2)nOH where n is ≥ 1, e.g., 2, 3, 4 or greater; propylene glycol, a mono ether of polyethylene glycol or a mono ether of propylene glycol.

[0096] In one embodiment, the oxygen-containing catalyst is a crown ether.

[0097] In one embodiment for Step 4, n = 1, and the glycol catalyst comprisesHOCH2CH2OH (ethylene glycol, EG). In one embodiment, n = 2, and the glycol catalyst comprises (HOCH2CH2)2O (diethylene glycol, DEG). In one embodiment, n = 3, and the glycol catalyst comprises H(OCH2CH2)3OH (triethylene glycol, TrEG). In one embodiment, n = 4, and the glycol catalyst comprises H(OCH2CH2)4OH (tetraethylene glycol, TeEG). In one embodiment, n ≥ 5, and the glycol catalyst comprises H(OCH2CH2)nOH [H(OCH2CH2)nOH is referred to herein as polyethylene glycol, PEG].

[0098] In one embodiment for Step 4, the glycol catalyst comprises PEG havingthe formula HO(CH2CH2O)nCH2CH2OH and the value of n provides a PEG having molecular weight of about 100 to about 10000.

[0099] In one embodiment for Step 4, the glycol catalyst comprises polypropyleneglycol having the formula HO(C3H6O)nC3H6OH where the value of n provides a molecular weight in the range of about 100 to about 10000.

[0100] In one embodiment for Step 4, the glycol catalyst comprises a mono etherof polyethylene glycol having the formula R(OCH2CH2)nCH2CH2OH, wherein R is a C1 to C5 group and the value of n provides a molecular weight up to about 10000.

[0101] In one embodiment for Step 4, the glycol catalyst comprises a mono etherof polypropylene glycol having the formula R(OC3H6)nC3H6OH, wherein R is a C1 to C5 group and the value of n provides a molecular weight up to about 10000.

[0102] The amount of alkali metal hydroxide (MOH) used is from about 0.1% toabout 10%, preferably from about 0.5% to about 5%, more preferably from about 0.5% to about 1.5%. M is Li, Na or K.

[0103] In one embodiment, the amount of oxygen-containing catalyst added inStep 4 is about 0.05 kg / kg of the CF3CF2CH2CHICF2CF3 in the starting material for Step 4 comprising the product produced in Step 3.

[0104] In certain embodiments disclosed herein the reaction for Step 4 thedehydroiodination reaction is conducted at a temperature of ambient or greater, such as 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, less than 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, and ranges between from 30°C to one of 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, ranges between from 40°C to one of and 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, ranges between from 50°C to one of 60°C, 70°C, 80°C, 90°C, or 100°C, ranges between from 70°C to one of 80°C, 90°C, 100°C, ranges between from 80°C to one of 90°C or 100°C and all values and ranges therebetween.

[0105] In the dehydroiodination embodiments disclosed herein, e.g., Steps 2 and4, the base is defined by the formula MOH as an aqueous solution including but are not limited to greater than one of 30% MOH, 35% MOH, 40% MOH, 50% MOH or 60 % MOH, where M is selected from one of Na, Li, or K and all values and ranges therebetween. In certain embodiments, the alkali metal hydroxide is KOH or NaOH and the KOH or NaOH is used as an aqueous solution. The aqueous solution includes, but is not limited, to greater than one of 30% KOH or NaOH, 35% KOH or NaOH, 40% KOH or NaOH, 50% KOH or NaOH or 60 % KOH or NaOH.

[0106] In certain embodiments of the present invention the process disclosedherein for Step 2 producing a product comprising 1345zf and the process disclosed herein for Step 4 producing a product comprising C2F5CH=CHC2F5 are performed in the absence of an organic solvent.

[0107] In certain embodiments of the invention disclosed herein, the crude productfrom Step 3 can be charged directly into Step 4 without purification.

[0108] In certain embodiments disclosed herein the product of Step 4 comprisingC2F5CH=CHC2F5 can be purified by contacting the crude product with an adsorbent or using azeotropes to remove impurities.

[0109] In certain embodiments the absorbent for removing impurities from adesired fluoroalkene comprises a zeolite.

[0110] In certain embodiments an azeotrope of C2F5CH=CHC2F5 and acetone canbe used to remove impurities from the product of Step 4.

[0111] In one embodiment of this invention, in a particular batch operation, Step 4is a process which comprises charging an aqueous solution of KOH and then adding oxygen-containing catalyst to a reactor. Preferably a concentrated KOH solution having a KOH concentration of 45% is used. In addition, an excess of KOH is preferred, based on the amount of CF3CF2CH2CHICF2CF3 to be fed. Having an excess of KOH improves yield. The process of Step 4 further comprises feeding the starting material comprising the product of Step 3 comprising CF3CF2CH2CHICF2CF3 and PFEI to the reactor, producing a reaction mixture comprising the Step 4 product, C2F5CH=CHC2F5. As C2F5CH=CHC2F5 forms, the C2F5CH=CHC2F5 and PFEI from the Step 3 product vaporize in the reactor. The vapor comprising C2F5CH=CHC2F5 and PFEI passes through a reflux condenser to remove water and unreacted CF3CF2CH2CHICF2CF3. The vapor comprising C2F5CH=CHC2F5 and PFEI passes through a molecular sieve dryer and is condensed in a -15°C second condenser, and collected in a receiver.

[0112] Crude product from Step 4 is a mixture of mainly PFEI, E-C2F5CH=CHC2F5,Z- C2F5CH=CHC2F5, C4F10, acetone and t-butanol. Purified product is suitable for use in heat transfer applications.

[0113] In a batch process, Step 4 may comprise the following general operatingsteps: Step 4a. Charge 45 wt% KOH to a reactor equipped with a vapor drying and product collection system. Step 4b. Charge liquid triethylene glycol (TrEG) to the reactor. Step 4c. Inert the reactor by N2 pressurization / venting.Step 4d. Set the vapor drying and product collection system tracing to 55°C to collect Step 4 product comprising E-C2F5CH=CHC2F5.Step 4e. Start the reactor agitation and heat the reactor to 60°C. Step 4f. Feed Step 3 product to the reactor. Step 4g. Apply coolant to the reactor reflux condenser to maintain the vapor outlet temperature at 42°C. Step 4h. Vent the PFEI / C2F5CH=CHC2F5 vapor from the reactor as required to maintain the reactor pressure at 5 psig. Step 4i. Pass the vapor comprising PFEI / C2F5CH=CHC2F5 through a dryer, a second condenser, and collect the liquid in a receiver. Step 4j. Control the receiver pressure at 2.5 psig. Step 4k. When the feed is complete, adjust the reactor pressure to 0 psig and the receiver pressure. to -2.5 psig. Step 4l. Continue to heat the reactor at 75°C for a time sufficient complete the reaction. Step 4m. Remove by purge residual C2F5CH=CHC2F5 from the reactor through the collection system using N2. And add to receiver containing C2F5CH=CHC2F5.

[0114] Distillation. The crude Step 4 product comprises PFEI andC2F5CH=CHC2F5 (mainly E-isomer). In one embodiment, the Step 4 productcomprises about 70 wt% PFEI and 26 wt% E-C2F5CH=CHC2F5 with othercompounds, such as, for example, acetone and t-butanol.

[0115] Acetone cannot be separated from E-C2F5CH=CHC2F5 by distillation;however, can be removed by washing and carbon treatment.

[0116] A multi-distillation column system (that is, a system comprising 2 or moredistillation columns) may be used for purification of E-C2F5CH=CHC2F5. In oneembodiment, a first column is used to remove primarily C4F10 and PFEI overhead asa distillate for subsequent reuse. In a second column E-C2F5CH=CHC2F5 may beseparated from Z-C2F5CH=CHC2F5 , in which E-C2F5CH=CHC2F5 may be removedoverhead as a distillate. A single column batch distillation system may also be usedfor the purification of E-C2F5CH=CHC2F5 through the collection of multiple distillatefractions.

[0117] It is important to remove iodine-containing compounds (PFEI orCF3CF2CH2CHICF2CF3) during the Step 4 distillation to prevent discoloration in thepurified product comprising E-C2F5CH=CHC2F5 , for example, upon exposure tolight.

[0118] Figure 1 illustrates an integrated reaction process as disclosed herein forproducing 153-10mczz, C2F5CH=CHC2F5. Steps 1-4 provide a process to prepare 153-10mczz from PFEI and ethylene. Step 1 is a radical-initiated process which produces C2F5CH2CH2I (PFEEI). Step 2 is a liquid-phase dehydroiodination using a base and a phase transfer catalyst to produce C2F5CH=CH2 (1345zf). A base- derived salt is a byproduct. Step 3 is a second radical-initiated process to produce C2F5CH2CHIC2F5 (1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane) from the Step 2 product and PFEI. Step 4 is similar to Step 2 and is a liquid-phase dehydroiodination using a base and a phase transfer catalyst, which is an oxygen-containing catalyst, to produce C2F5CH=CHC2F5. In certain embodiments disclosed herein thedehydroiodinated compound is 153-10mczz with an E / Z ratio provides wherein E-153-10mczz of at least 80%, or at least 85%, or at least 90%, or at least 95%, or at least 98%, or at least 99%.

[0119] The present invention provides composition comprising C2F5CH=CHC2F5having a ratio of E / Z of at least 80:20 and at least one compound chosen from C2F5CH2CH(C2F5)CH2CHIC2F5 (isomeric di-adducts), C2F5[CH2 CH(C2F5)]2CH2CHIC2F5 (isomeric tri-adducts) and perfluorobutane (C4F10). In one embodiment, the composition comprises C2F5CH=CHC2F5 and C2F5CH2CH(C2F5)CH2CHIC2F5 (isomeric di-adducts). In one embodiment, the composition comprises C2F5CH2CH(C2F5)CH2CHIC2F5 (isomeric di-adducts) and C2F5[CH2 CH(C2F5)]2CH2CHIC2F5 (isomeric tri-adducts). In one embodiment, thecomposition comprises C2F5CH=CHC2F5 having a ratio of E / Z of at least 85:15 andfurther comprising C2F5CH2CH(C2F5)CH2CHIC2F5 (isomeric di-adducts). In oneembodiment, the composition comprises C2F5CH=CHC2F5 having a ratio of E / Z of atleast 90% and further comprising C2F5CH2CH(C2F5)CH2CHIC2F5 (isomeric di- adducts). In one embodiment, the composition comprises C2F5CH=CHC2F5 having aratio of E / Z of at least 95:5 and further comprising C2F5CH2CH(C2F5)CH2CHIC2F5(isomeric di-adducts). In one embodiment, the composition comprisesC2F5CH=CHC2F5 having a ratio of E / Z of at least 90:10 and further comprisingC2F5CH2CH(C2F5)CH2CHIC2F5 (isomeric di-adducts) and C2F5[CH2 CH(C2F5)]2CH2CHIC2F5 (isomeric tri-adducts).

[0120] Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a particular passage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting. EXAMPLES Example 1 – Reaction of perfluoroethyl iodide (PFEI) and ethylene to make 1,1,1,2,2-pentafluoro-4-iodobutane CF3CF2I + CH2=CH2 → CF3CF2CH2CH2I (Step 1)

[0121] Into a 400ml Hastelloy C shaker tube, was loaded 0.5gazobisisobutyronitrile (AIBN), and then the shaker tube was sealed and vacuumed. 300g PFEI was charged into the shaker tube and the shaker tube was pressured with ethylene to 80 psig. The mixture was heated to 65°C with agitation where the pressure increased to 156 psig and then dropped to 108 psig during the reaction time. Then the temperature was maintained at around 65°C and ethylene was continuously charged to maintain the shaker tube pressure around 150 psig until a total 20g of ethylene was charged. After all the ethylene was charged, the shaker tube was heated to 70°C and agitated at 70°C for about 30 min, then cooled to room temperature. GC analysis of the product showed 97% of CF3CF2CH2CH2I (1,1,1,2,2- pentafluoro-4-iodobutane).Example 2 – Reaction of 1,1,1,2,2-pentafluoro-4-iodobutane with KOH to make 3,3,4,4,4-pentafluoro-1-butene (1345zf) CF3CF2CH2CH2I + KOH → CF3CF2CH=CH2 + KI + H2O (Step 2)

[0122] 1.6g tetrabutylammonium bromide (TBAB), 160g of 35 wt. % KOH and210g 1,1,1,2,2-pentafluoro-4-iodobutane were loaded into a 400ml Hastelloy C shaker tube, sealed, chilled to 0°C and vacuumed. Then the mixture was heated to 80°C with agitation and agitated at 80°C for 4 hours. The GC analysis of organic reaction product shows 99.3% of CF3CF2CH=CH2 in the product. Example 3 – Reaction of 3,3,4,4,4-pentafluoro-1-butene (1345zf) with PFEI to produce CF3CF2CH2CHICF2CF3 (1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodobutane) CF3CF2CH=CH2 + C2F5I → CF3CF2CH2CHICF2CF3 (Step 3)

[0123] 1.8g Di-tert-butyl peroxide was charged into a 400ml Hastelloy C shakertube reactor, then shaker tube was sealed and vacuumed. The 160g PFEI was transferred into shaker tube and heated to 125°C with agitation, 1345zf was pumped into shaker tube at 0.2ml / min until 86g of HFO-1345zf was added. After all 1345zf was added, the reactor was agitated at 125°C for another 5 hrs. The GC analysis of organic reaction product showed 38.6% of C2F5CHICH2C2F5 in the product. The main by-products are the 2ndand 3rdmoles of HFO-1345zf inserted into C2F5CH2CHIC2F5 which were labeled as 1345-di-adduct and 1345-tri-adduct in the GC (FID) analysis given in Table 1.. TABLE 1 Compounds GC area%1345zf 4.90%PFEI 7.97%C2F5CH2CHIC2F5 38.61% CF3CF2CH2CH2I 2.76%Di-tert-butyl peroxide 0.62%1345-di-adduct 17.67%1345-di-adduct 19.42%1345-di-adduct 0.18%1345-tri-adduct 1.53%1345-tri-adduct 0.93%Compounds GC area%1345-tri-adduct 0.65%1345-tri-adduct 0.25%1345-tri-adduct 0.01%Other compounds 4.50%Example 4 – Reaction of 3,3,4,4,4-pentafluoro-1-butene (1345zf) with PFEI thermally to produce CF3CF2CH2CHICF2CF3 (1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane) CF3CF2CH=CH2 + C2F5I → CF3CF2CH2CHICF2CF3 (Step 3)

[0124] A 400ml Hastelloy C shaker tube was sealed and vacuumed.140g PFEIand 20g 1345zf were transferred into shaker tube and heated to 220°C with agitation. The mixture was heated and agitated at 220°C for 2hr, and then 20g 1345zf was pumped into the shaker tube every hour until 80g total of 1345zf was added. After all 1345zf was added, tube contents were agitated at 220°C for another 2hrs. The GC analysis of organic reaction product shows 57.71% of C2F5CHICH2C2F5 in the product. The main by products are the 2ndand 3rd1345zf inserted into C2F5CH2CHIC2F5 which are labeled as 1345-di-adduct and 1345-tri- adduct in the GC (FID) analysis below. TABLE 2 Compounds GC area%C2F5I 7.39%1345zf 9.95%C2F5CHICH2C2F5 57.71% 1345-di-adduct 5.10%1345-di-adduct 5.30%1345-di-adduct 9.60%1345-tri-adduct 0.26%1345-tri-adduct 0.17%1345-tri-adduct 0.14%1345-tri-adduct 0.05%Other compounds 4.32%Example 5 – Reaction of 3,3,4,4,4-pentafluoro-1-butene (1345zf) with PFEI to produce CF3CF2CH2CHICF2CF3 (1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane) with di-tert-butyl peroxide (DTBP) as initiator CF3CF2CH=CH2 + C2F5I → CF3CF2CH2CHICF2CF3 (Step 3)

[0125] 3.4g Di-tert-butyl peroxide was charged into a 400ml Hastelloy C shakertube, sealed, and vacuumed. The 287g PFEI was transferred into the shaker tube and heated to 125°C with agitation, 1345zf was pumped into shaker tube at 0.11ml / min until 57g of 1345zf was added. After all 1345zf was added, the reactor was agitated at 125°C for another 4 hrs; a sample was taken out for GC analysis, then it was heated at 125°C for another 4 hrs and another sample was taken for GC analysis. Then the reactor was heated to 135°C for 4 hrs and a sample was taken for GC analysis. After another 4 hrs at 135°C, a final sample was taken for GC analysis. The GC (FID, are %) analyses are list in Table 3 below. The excess initiator DTBP was completely decomposed after 4 hours of treatment at 135°C. TABLE 3 GC area% 7hr feed + 8hr 7hr feed + 7hr feed + 4hr 7hr feed + 8hr at 125C + 4hr 8hr at 125C + at 125°C at 125°C at 135°C 8hr at 135°C 1345zf 4.50% 0.19% 0.01% 0.00%acetone 2.31% 2.97% 2.99% 2.56%t-butanol 0.48% 0.57% 0.58% 0.17%C2F5CH2CHIC2F5 49.41% 51.00% 49.43% 49.66%DTBP 1.16% 0.70% ND NDExample 6 – Preparation of C2F5CH=CHC2F5 (153-10mczz) Using Peg 400 Catalyst C2F5CH2CHIC2F5 + KOH → C2F5CH=CHC2F5 + KI (Step 4)

[0126] A 20 ml glass sample vial equipped with magnetic stir bar and 3.1 gC2F5CH2CHIC2F5 (purity 95%, containing 5 % of C2F5CH2CH(C2F5)CH2CHIC2F5,) was added to a mixture of 10 ml of 45% aqueous KOH, 1 g of PEG 400 at ambient temperature. Polyethylene Glycol 400 (PEG-400, Aldrich) is defined by the generalformula H(OCH2CH2)nOH, where n= is a value to provide a molecular weight with a viscosity of ~120 mPa.sv (20°C). The reaction mixture was vigorously agitated. Theformation of white precipitate was seen after 5-10 min. According to 19 F NMRconversion of C2F5CH2CHIC2F5 after 30min was 100%, while C2F5CH2CH(C2F5)CH2CHIC2F5 was not affected, per NMR. Reaction also produced yellow semisolid blob material which was not soluble in water, acetone or o-xylene. Vacuum transfer of the product into cold trap (-78°C, at 200 to 10 mm Hg resulted in isolation of 1.5 g of 153-10mczz with a E / Z ratio of 89:11and purity >95%. The reaction was repeated three times using the same scale, typical yield of the productwas 1.5-1.7 g. The 19F and 1H spectra taken of isolated C2F5CH=CHC2F5 (153-10mczz) (E / Z ratio 89:11) produced in this Example 6 are provided in Fig.2A andFig.2B. Product removal was done under vacuum at 200 to 10 mm Hg. Typical yield is 1.5-1.7 g of pure product. A small second layer in sample vial after transfer was usually observed, identified by NMR as C2F5CH2CH(C2F5)CH2CHIC2F5. Example 7 – Preparation of C2F5CH=CHC2F5 – Effect of KOH Concentration (Step 4)

[0127] Example 6 was repeated using a solution of 3g KOH in 10 ml H2O (23 wt %solution); 0.3 g PEG 400, 3.1 g C2F5CH2CHIC2F5. Only 50% conversion was achieved after 16h at ambient (room) temperature. Heating for another 12 hrs at 40°C did not increase yield; catalyst became yellow-orange solid floating on the surface; 3ml of 45 % KOH solution in water was added and agitation was continued at ambient temperature, the conversion went up to 76% after one hour and to 97%;after 2.5 hrs. At this point the ratio E-, Z- isomers of 153-10mczz and startingmaterial was 86.2:10.5:3.3, respectively, NMR). The 19F and 1H spectra taken ofcrude reaction mixture (organic layer) after 18h at ambient temperature produced inthis Example 7 are provided in Fig. 3A and Fig.3B. respectively.Example 8 – Preparation of C2F5CH=CHC2F5 - Effect of Catalyst (Various Polyethylene Glycols (PEGs) – PEG 200, PEG 600, PEG 1000) (Step 4)

[0128] Example 1 was repeated by adding 3.1 g C2F5CH2CHIC2F5 to a mixture of10 ml of 45 wt.% KOH solution and 0.2 g of PEG 400, (mildly exothermic reaction). The NMR scan indicated full conversion into 153-10mczz that after 30min. Vacuumtransfer was initiated and 1.5 g of 153-10mczz was isolated, yield was calculated: 1.5g / 2.08g x100% = 72% (80% calculated based on converted iodide), ratio E / Z isomers 90:10.

[0129] The 1H NMR spectrum of the isolated product produced in Example 8 isshown in Fig. 4.

[0130] Fig.5 shows the 19F NMR spectra taken of starting material, product andorganic residue form the reaction vessel in this Example 8. The bottom spectrum isthe 19F NMR spectrum taken of the starting material, the middle spectrum is the 19FNMR spectrum of the isolated 153-10mczz, the top spectrum is the 19F NMRspectrum taken of the organic residue in sample vial after removal of 153-10mczz by vacuum transfer. The top spectrum shows a trace of 153-10mczz, and is mostly C2F5CH2CH(C2F5)CH2CHIC2F5 (isomeric di-adducts) with some C2F5[CH2 CH(C2F5)]2CH2CHIC2F5 (isomeric tri-adducts).

[0131] Various PEGs (PEG 200, PEG 600, PEG 1000) were evaluated as acatalyst for the preparing 153-10mczz using 45% aqueous KOH (at 10 mol% catalyst loading) and all of them were found to have activity similar to PEG 400, producing 153-10mczz in 75-85% yield. Example 9A-D – Synthesis of 153-10mczz – Comparison of Activity of Different Glycol Catalysts (Step 4)

[0132] The following experiments were conducted to illustrate the conversion toC2F5CH=CHC2F5 for experiments A, B, C and D according to the following reaction scheme: C2F5CH2CHIC2F5 + KOH → C2F5CH=CHC2F5 (Step 4)

[0133] Reactions were conducted using ethylene glycol, HOCH2CH2OH (EG),diethylene glycol, (HOCH2CH2)2O (DEG), triethylene glycol, H(OCH2CH2)3OH (TrEG) and tetraethylene glycol, H(OCH2CH2)4OH (TeEG).

[0134] Run 9A: 2 g C2F5CH2CHIC2F5, 0.15 g ethylene glycol (EG) and 5 ml of 45% aqueous KOH were reacted at 40°C for 3 hrs. with a 53% conversion. The reaction continued for another 15 hrs. and conversion increased to 75%.

[0135] Run 9B: 2 g C2F5CH2CHIC2F5, 0.2 g of diethylene glycol (DEG) and 5 ml of45% aqueous KOH were reacted at 40°C and had a 20% conversion after 0.5 hrs.

[0136] Run 9C: 2 g C2F5CH2CHIC2F5, 0.2 g of triethylene glycol (TrEG) and 5 ml of 45% aqueous KOH were reacted for 45 min to give 100% conversion of starting material. The reaction product was vacuum transferred in cold trap to give 2.1 g of C2F5CH=CHC2F5 (88% purity). The yield of isolated C2F5CH=CHC2F5 was 87%.

[0137] Run 9D: 4 g of C2F5CH2CHIC2F5, 0.2 g of tetraethylene glycol (TeEG), and 10 ml of 45% aqueous KOH were reacted at 40°C. The reaction was exothermic leading to 98% conversion of starting material after 1 hour at 40°C. The yield of isolated C2F5CH=CHC2F5 (purity 92%), was 91%.

[0138] Figs.6A, 6B, and 6C show the 1H NMR spectra taken of the crude reactionmixture at different conversions of C2F5CH2CHIC2F5 to 153-10mczz; (E-C2F5CH=CHC2F5) produced in this Example 9. Fig.6A presents conversion at 10%;Fig. 6B presents conversion at 20%; Fig.6C presents conversion at 100%.

[0139] Figs. 6D and 6E show the 19F NMR spectra taken of the crude reactionmixture at different conversions of C2F5CH2CHIC2F5 to 153-10mczz; (E- C2F5CH=CHC2F5) produced in this Example 9.

[0140] Fig. 6F shows the 1H NMR spectra taken of isolated 153-10mczz (E-C2F5CH=CHC2F5) produced in this Example 9. Example 10 – 153-10mczz Synthesis Using 18 – Crown-6 Ether as Catalyst (Step 4)

[0141] 10 ml 45% KOH solution in water and 0.2 g of 18-crown-6 ether wereplaced in a 20 ml glass sample vial equipped with a magnetic stir bar. 3.1 g of C2F5CH2CHIC2F5 was added with vigorous agitation to provide a reaction mixture. The reaction was mildly exothermic. As determined by NMR analysis, 100% conversion of C2F5CH2CHIC2F5 to 153-10mczz was achieved after 1 hour. The reaction mixture was removed from sample vial under vacuum and product was collected in cold trap. Product was isolated as 1.5 g (72%) of 153-10mczz, (purity 97%, ratio E / Z isomers 95:5).Example 11 – Preparation of C2F5CH=CHC2F5 Using Purified Starting Material and Triethylene glycol (TrEG) as a Catalyst C2F5CH2CHIC2F5 + KOH -------->C2F5CH=CHC2F5 + KI (Step 4)

[0142] A 500 ml three neck flask equipped with a thermocouple, heavy magneticstir bar, an addition funnel and distillation head equipped with 40 cm with Vigreux column, was loaded with 120 ml of 45 wt. % KOH solution in water, 1g (0.0067 mol) of TrEG (triethylene glycol) and 80 g C2F5CH2CHIC2F5 (97% purity, 0.197 mol). The KOH / TrEG reaction mixture was first preheated to 65°C and C2F5CH2CHIC2F5 was added slowly, over a 1h period and the product (153-10mczz) was distilled simultaneously and collected as a liquid in a receiver cooled using ice bath. The flask temperature was brought up to 65°C and 153-10mczz started to distill over about 2.5 h, with the flask temperature of 65°C to 105°C. The product with a b.p. of 47- 50°C was collected into cold (wet ice) receiver and 43.8g of crude 153-10mczz (expected 52.3g) was isolated. The yield of 153-10mczz was 84% with a purity of 99% (1% C2F5CH2CHIC2F5 + di-adduct). The E / Z isomers of 153-10mczz- ratio was ~ 95:5.

[0143] The reaction was scaled up, using 567 g of crude C2F5CH2CHIC2F5 (purity79 wt %) starting material. Fig.7 shows the 1H NMR spectra taken of the isolated153-10mczz produced in this Example 11. Example 12 – Preparation of C2F5CH=CHC2F5 Using Starting Material of 75% purity C2F5CH2CHIC2F5 + KOH → C2F5CH=CHC2F5 + KI (Step 4)

[0144] 650 mL of 45 wt % KOH solution in water was combined with 19 g oftriethylene glycol in a 2000 ml three neck round bottom flask equipped with a thermocouple, heavy magnetic stir bar, an addition funnel and distillation head containing 40 cm with Vigreux column. The flask was preheated to 62°C and then 455 g of C2F5CH2CHIC2F5 (purity of 75% ) was added dropwise. The flask was kept above 65°C during the addition so the column was under reflux (started at a pot / flask temperature of 68°C and head temperature of 42°C, respectively) while C2F5CH2CHIC2F5 was still being added. Product was collected as a liquid in a pre- chilled (wet ice) receiver. Collection of the product happened mostly when the pottemperature was 63°C and the head temperature was 43°C. When addition of the C2F5CH2CHIC2F5 was complete the pot temperature was 66°C and the head temperature was 44°C. The product was washed with ice cold water and stored overmagnesium sulfate. The product (207g, 90% yield) was identified by 1H, 19F NMRand GC / MS as C2F5CH=CHC2F5 (mixture E- and Z- isomers, ratio 97:3). E-C2F5CH=CHC2F5,19F NMR (CDCl3): -85.02 (3F, t, 1.4 Hz), -117.84 (2F, dq, 7.4, 1.4Hz) ppm; 1H NMR (CDCl3): 6.26(t, 7.4 Hz) ppm. Z-C2F5CH=CHC2F5, 19F NMR(CDCl3): -85.22 (3F, t, 1.2 Hz), -112.36(2F, dd, 5.7, 7.4 Hz) ppm; 1H NMR (CDCl3):5.99 (m) ppm. Example 13 – Synthesis of C2F5CH=CHC2F5 Using Starting Material Containing C2F5I (Step 4)

[0145] Crude product (C2F5CH2CHIC2F5) contained residual perfluoroethyl iodide(PFEI) (up to 45 wt%) and in order to avoid additional steps involving distillation to remove PFEI and other impurities (including acetone, and others), a number of experiments using C2F5CH2CHIC2F5 product containing 35-45 wt% of PFEI and other by-products were performed. Example 13 provides a typical procedure used for these experiments.

[0146] A 500 ml flask equipped with thermocouple, gas inlet tube, distillation headcontaining 40 cm with Vigreux column and connected to -78°C cold trap and N2 blanket was charged with 180 ml 45 wt. % aqueous KOH solution, 2.35 g of TrEG catalyst. The KOH / TrEG reaction mixture was vigorously agitated using heavy magnetic stir bar and preheated to 45°C. Crude C2F5CH2CHIC2F5 (270 g, purity 36 wt. %; contained 46 wt.% of C2F5I) was slowly fed into the flask from an inverted cylinder using an inlet tube. The reaction temperature increased to 50°C and temperature was maintained through addition. The temperature of the reflux condenser was set to 14°C, resulting in C2F5I being flash distilled and collected in the cold trap. The addition of 270 g of crude C2F5CH2CHIC2F5 took about 3h. The reaction mixture turned light brown in color and the head temperature during addition (mild reflux) stayed at 20-22°C.

[0147] After addition of the 270g was finished, the reaction mixture was kept at 55-62°C, while low boiling material was collected using a -78°C cold trap. A total of 138g material was collected, which was determined by NMR to be a mixture of 13 wt%(16.6g), 153-10mczz and 86 wt. % PFEI and small amount of perfluorobutane (C4F10). At a pot temperature of 62°C, the collection of liquid fraction was started. The head temperature slowly went up to 47-50°C while the pot temperature as was increased from 62°C to 114°C over a 1.5-hour period, collecting 44.5 g of liquid, wet product, which was dried over MgSO4. NMR and GC analysis of crude productindicated the presence of E- and Z- 153-10mczz isomers of C2F5CH=CHC2F578.8and 3.4 wt. %, C2F5I = 9.7 wt %, and [C2F5CH2]2 = 8.1%. The ratio ~ E / Z isomers ofC2F5CH=CHC2F5 was 96:4. Combined yield of C2F5CH=CHC2F5 was 83.4%. Example 14 – Preparation of C2F5CH=CHC2F5 Using Dipropylene Glycol as Catalyst (Step 4) C2F5CH2CHIC2F5 + KOH → C2F5CH=CHC2F5 + KI

[0148] 162 ml of 45 wt % KOH solution in water and 4.7 g of dipropylene glycol(DPG) were placed in a three neck 500 mL round bottom flask equipped with a thermocouple, addition funnel, heavy magnetic stir bar and a distillation head similar to described in previous Examples. 115 grams of C2F5CH2CHIC2F5 (purity 95%) was slowly added to the flask at 40-45°C over 30 minutes period. Product 50.6g (93% yield) was collected, which according to NMR and GC / MS was C2F5CH=CHC2F5,purity 97%, with a ratio of E / Z isomers of 96:4.Example 15 – Preparation of C2F5CH=CHC2F5 Using Tripropylene Glycol as Catalyst (Step 4) C2F5CH2CHIC2F5 + KOH → C2F5CH=CHC2F5 + KI (Step 4)

[0149] In a 500 ml flask equipped with a thermocouple, addition funnel, heavymagnetic stir bar and a distillation head similar to described in previous Examples, 162 ml of 45 wt % KOH solution in water and 6.7 grams of tripropylene glycol (TrPG) were combined and 115 g of C2F5CH2CHIC2F5 were added. The temperature of condenser on the distillation head was maintained at 0°C and the product was collected as liquid in a cold receiver. Product 50.1 g (92% yield) was isolated of a fraction having b.p.45-50°C, which was shown by NMR to be C2F5CH=CHC2F5153-10mczz (purity 98%, containing 2 % starting material, ratio E / Z isomers 96:4).Example 16 – Distillation (Step 4 Product)

[0150] PFEI was removed from the Step 4 reaction product by distillation. Theproduct mixture from the Step 4 reaction contains primarily E-153-10mczz and PFEI and was sent to a two-column continuous distillation train. The crude Step 4 product was fed to approximately the center of the first column which has 55 theoretical plates and operates at 25 psig head pressure. PFEI and low boiling compounds were taken off overhead as required to control the column temperature profile, while E-153-10mczz and high boiling compounds were taken off from the reboiler to maintain reboiler level. The stream from the reboiler is sent to the approximate center of a second distillation column that has 94 theoretical plates and was operateed at 5 psig head pressure. E-153-10mczz was taken as a liquid distillate off the top of the column as required to control reboiler level, while high boiling compounds were purged from the reboiler to control the reboiler temperature. PFEI can be removed to below the GC (FID) detection level by this method while the E- 153-10mczz purity in the distillate by this method is typically >98.5%. TABLE 4 Pre-distillation Post-distillation Compound GC area% GC area%E-153-10mczz 63.90% 99.10%PFEI 18.90% 0.00%Other Compounds 17.20% 0.90%

[0151] In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification is to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of invention.

[0152] It is to be appreciated that certain features are, for clarity, described hereinin the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination.OTHER EMBODIMENTS

[0153] Embodiment 1. A process comprising conducting a first reaction byreacting ethylene with perfluoroethyl iodide in the presence of a radical initiator to produce a first alkyl iodide product mixture comprising 1,1,1,2,2-pentafluoro-4- iodobutane; dehydroiodinating 1,1,1,2,2-pentafluoro-4-iodobutane in the presence of an alkali metal hydroxide and phase transfer catalyst to form a first fluoroalkene product mixture comprising 3,3,4,4,4-pentafluoro-1-butene; reacting 3,3,4,4,4- pentafluoro-1-butene with perfluoroethyl iodide, optionally in the presence of a radical initiator, to produce a second alkyl iodide product mixture comprising 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane; and dehydroiodinating 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane with an oxygen-containing catalyst to produce a second fluoroalkene product mixture comprising 1,1,1,2,2,5,5,6,6,6- decafluoro-3-hexene.

[0154] Embodiment 1a. A process of embodiment 1 further comprising thermallytreating the first alkyl iodide product mixture comprising 1,1,1,2,2-pentafluoro-4- iodobutane to remove the initiator and provide an initiator-free product mixture.

[0155] Embodiment 2. A process embodiment comprising: contacting CF3CF2Iand CH2=CH2 to produce a first product mixture comprising CF3CF2CH2CH2I in the presence of a first radical initiator; contacting CF3CF2CH2CH2I with an alkali metal hydroxide and phase transfer catalyst to form a second product mixture comprising CF3CF2CH=CH2; contacting CF3CF2CH=CH2 with C2F5I, optionally in the presence of a radical initiator to form a third product mixture comprising CF3CF2CH2CHICF2CF3; contacting CF3CF2CH2CHICF2CF3 with an alkali metal hydroxide in the presence of an oxygen-containing catalyst to form a fourth product mixture comprising C2F5CH=CHC2F5, and optionally recovering and purifying at least one of the first, second, third or fourth product mixtures to form a purified product mixtures and the desired fluoroalkene.

[0156] Embodiment 2a. A process of embodiment 2 wherein the first radicalinitiator is an azo initiator or a peroxide.

[0157] Embodiment 2b. A process embodiment 2 further comprising recoveringand purifying at least one of the first, second, third or fourth product mixtures of process embodiment 2 to form a purified product mixture of the desired fluoroalkene.

[0158] Embodiment 2b. A process embodiment 2 further comprising recoveringand purifying the fourth product mixture comprising C2F5CH=CHC2F5 to a purity of at least 99%, 99.9% or 99.99%.

[0159] Embodiment 3. A composition produced according to Embodiment 1 orEmbodiment 2 wherein the composition comprises E-C2F5CH=CHC2F5 and Z-C2F5CH=CHC2F5 in a ratio of at least 80:20, or at least 85:15, or at least 90:10, or at least 95:5, or at least 98:2 or at least 99:1.

[0160] Embodiment 3a. A composition according to Embodiment 3 wherein thecomposition comprises at least 99%, 99.5%, 99.9%, 99.99% or 99.999% of E-C2F5CH=CHC2F5.

[0161] Embodiment 4. A composition comprising C2F5CH=CHC2F5 having a ratioof E / Z of at least 80% and at least one compound chosen from C2F5CH2CH(C2F5)CH2CHIC2F5 (isomeric di-adducts), C2F5[CH2 CH(C2F5)]2CH2CHIC2F5 (isomeric tri-adducts) and perfluorobutane (C4F10). Embodiment 4a. A composition comprising C2F5CH=CHC2F5 and C2F5CH2CH(C2F5)CH2CHIC2F5 (isomeric di-adducts). Embodiment 4b. A composition comprising C2F5CH2CH(C2F5)CH2CHIC2F5 (isomeric di-adducts) and C2F5[CH2 CH(C2F5)]2CH2CHIC2F5 (isomeric tri-adducts). Embodiment 4c. Acomposition comprising C2F5CH=CHC2F5 having a ratio of E / Z of at least 85% andfurther comprising C2F5CH2CH(C2F5)CH2CHIC2F5 (isomeric di-adducts).Embodiment 4d. A composition comprising C2F5CH=CHC2F5 having a ratio of E / Z ofat least 90% and further comprising C2F5CH2CH(C2F5)CH2CHIC2F5 (isomeric di- adducts). Embodiment 4e. A composition comprising C2F5CH=CHC2F5 having aratio of E / Z of at least 95% and further comprising C2F5CH2CH(C2F5)CH2CHIC2F5(isomeric di-adducts). Embodiment 4f. A composition comprising C2F5CH=CHC2F5having a ratio of E / Z of at least 90:10 and further comprisingC2F5CH2CH(C2F5)CH2CHIC2F5 (isomeric di-adducts) and C2F5[CH2 CH(C2F5)]2CH2CHIC2F5 (isomeric tri-adducts).

[0162] Embodiment 5. A cooling process and system embodiment using thecomposition of Embodiment 3 or Embodiment 4.

[0163] Embodiment 5. A process of Embodiment 1 or 2 wherein the desiredfluoroalkene C2F5CH=CHC2F5 is purified to provide to provide E-C2F5CH=CHC2F5having a purity of at least 99%.

[0164] Embodiment 6. A process of Embodiment 1 or 2 wherein the desiredfluoroalkene C2F5CH=CHC2F5 is purified to provide to provide E-C2F5CH=CHC2F5having a purity of at least 99.5%.

[0165] Embodiment 7. A process of Embodiment 1 or 2 wherein the desiredfluoroalkene C2F5CH=CHC2F5 is purified to provide to provide E-C2F5CH=CHC2F5having a purity of at least 99.9%.

[0166] Embodiment 8. A process of Embodiment 1 or 2 wherein Step 1 isconducted at a temperature from 50 to 100°C.

[0167] Embodiment 9. A process of Embodiment 1 or 2 wherein Step 2 isconducted at a temperature from 50 to 120°C.

[0168] Embodiment 10. A process of Embodiment 1 or 2 wherein Step 3 isconducted at a temperature from 80 to 250°C.

[0169] Embodiment 11. A process of Embodiment 1 or 2 wherein Step 4 isconducted at a temperature between from 20 to 100°C.

[0170] Embodiment 12. A composition embodiment comprising the first alkyliodide product mixture comprising 1,1,1,2,2-pentafluoro-4-iodobutane of process Embodiment 1 or 2.

[0171] Embodiment 13. A composition embodiment comprising the firstfluoroalkene product mixture comprising 3,3,4,4,4-pentafluoro-1-butene of process Embodiment 1 or 2.

[0172] Embodiment 14. A composition embodiment comprising the second alkyliodide product mixture comprising 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane of process Embodiment 1 or 2.

[0173] Embodiment 15. A composition embodiment comprising the secondfluoroalkene product mixture comprising 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene of process Embodiment 1 or 2.

[0174] Embodiment 16. An immersion cooling system comprising a compositioncomprising at least 99%, 99.5%, 99.9%, 99.99% or 99.999% of E-C2F5CH=CHC2F5prepared according to the process of Embodiment 1 or Embodiment 2. Embodiment 16a. An immersion cooling system according to Embodiment 16 wherein thecomposition comprises at least 99% of E-C2F5CH=CHC2F5. Embodiment 16b. Animmersion cooling system according to Embodiment 16 wherein the compositioncomprises at least 99.5% of E-C2F5CH=CHC2F5. Embodiment 16c. An immersioncooling system according to Embodiment 16 wherein the composition comprises atleast 99.9% of E-C2F5CH=CHC2F5. Embodiment 16d. An immersion cooling systemaccording to Embodiment 16 wherein the composition comprises at least 99.99% of E-C2F5CH=CHC2F5. Embodiment 16e. An immersion cooling system according toEmbodiment 16 wherein the composition comprises at least 99.999% of E-C2F5CH=CHC2F5.

[0175] Embodiment 17. A method comprising cooling a devices selected from oneof electronic devices, datacenter servers, insulated-gate bipolar transistor (IGBT) devices, telecommunication infrastructure, military electronics, televisions (TVs), cell phones, monitors, drones, automotive batteries, powertrains for electric vehicles (EVs), avionics devices, power devices and displays by one of direct or indirect contact of a composition comprising at least 99%, 99.5%, 99.9%, 99.99% or99.999% of E-C2F5CH=CHC2F5 prepared according to the process of Embodiment 1or Embodiment 2. Embodiment 17a. A method according to Embodiment 17wherein the composition comprises at least 99% of E-C2F5CH=CHC2F5.Embodiment 17b. A method according to Embodiment 17 wherein the compositioncomprises at least 99.5% of E-C2F5CH=CHC2F5. Embodiment 17c. A methodaccording to Embodiment 17 wherein the composition comprises at least 99.9% of E-C2F5CH=CHC2F5. Embodiment 17d. A method according to Embodiment 17wherein the composition comprises at least 99.99% of E-C2F5CH=CHC2F5.Embodiment 17e. A method according to Embodiment 17 wherein the compositioncomprises at least 99.999% of E-C2F5CH=CHC2F5.

[0176] Embodiment 18. A system comprising devices in need of cooling selectedfrom one of electronic devices, datacenter servers, insulated-gate bipolar transistor (IGBT) devices, telecommunication infrastructure, military electronics, televisions (TVs), cell phones, monitors, drones, automotive batteries, powertrains for electricvehicles (EVs), avionics devices, power devices and displays capable of direct or indirect contact with a composition comprising at least 99%, 99.5%, 99.9%, 99.99%or 99.999% of E-C2F5CH=CHC2F5 prepared according to the process of Embodiment1 or Embodiment 2. Embodiment 18a. A system according to Embodiment 18wherein the composition comprises at least 99% of E-C2F5CH=CHC2F5.Embodiment 18b. A system according to Embodiment 18 wherein the compositioncomprises at least 99.5% of E-C2F5CH=CHC2F5. Embodiment 18c. A systemaccording to Embodiment 18 wherein the composition comprises at least 99.9% of E-C2F5CH=CHC2F5. Embodiment 18d. A system according to Embodiment 18wherein the composition comprises at least 99.99% of E-C2F5CH=CHC2F5.Embodiment 18e. A system according to Embodiment 18 wherein the compositioncomprises at least 99.999% of E-C2F5CH=CHC2F5.

[0177] Embodiment 19. An energy transfer system comprising a circuit andmotive force for contacting a device in need of cooling with heat transfer comprising E-C2F5CH=CHC2F5 which is at least 99.5% pure, preferably at least 99.9% pure.

[0178] In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification is to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of invention.

[0179] It is to be appreciated that certain features are, for clarity, described hereinin the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination.

Claims

CLAIMS What is claimed is:

1. A process comprising: Step 1) comprising reacting a starting material comprising perfluoroethyl iodide with ethylene in the presence of a radical initiator to produce a Step 1 product comprising 1,1,1,2,2-pentafluoro-4-iodobutane; Step 2) comprising reacting the Step 1 product with an alkali metal hydroxide in the presence of a phase transfer catalyst to produce a Step 2 product comprising 3,3,4,4,4-pentafluoro-1-butene; Step 3) comprising reacting a starting material comprising perfluoroethyl iodide with the Step 2 product to produce a Step 3 product comprising 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane; and Step 4) comprising reacting the Step 3 product with an alkali metal hydroxide in the presence of a phase transfer catalyst, which is an oxygen- containing catalyst to produce a Step 4 product comprising 1,1,1,2,2,5,5,6,6,6- decafluoro-3-hexene.

2. The process of claim 1, wherein Step 1 is performed in the presence of an excess of radical initiator and further comprises: thermally treating the Step 1 product to eliminate the initiator.

3. The process of claim 1 or claim 2 wherein the radical initiator in Step 1 is an azo initiator, such as azobisisobutyronitrile (CH3)2C(CN)N=NC(CH3)2CN (AIBN) or a peroxide.

4. The process of claim 3 wherein the radical initiator in Step 1 is azobisisobutyronitrile (CH3)2C(CN)N=NC(CH3)2CN (AIBN).

5. The process of claim 1 wherein the radical initiator in Step 3 is benzoyl peroxide.

6. The process of claim 1 wherein the radical initiator in Step 3 is di-tert-butyl peroxide.

7. The process of any of claims 1-4 wherein Step 1 is performed at a temperature within the range of 30-90°C.

8. The process of any of claims 1-4, wherein prior to Step 1, the starting material comprising CF3CF2I further comprises one or more of I2 and IF5 and is washed with a base or sulfite salt.

9. The process of claim 1 wherein the base is KOH or NaOH 10. The process of claim 1 wherein the sulfite is Na2SO3.

11. The process of claim 1 wherein the phase transfer catalyst of Step 2 is an ammonium or phosphonium salt.

12. The process of claim 11 wherein the phase transfer catalyst is a tetraalkyl ammonium halide or a tetraalkyl phosphonium halide.

13. The process of claim 12 wherein the phase transfer catalyst is tetra-n- butylammonium bromide or trioctylmethylammonium chloride.

13. The process of claim 1 wherein the phase transfer catalyst of Step 2 is a glycol catalyst.

14. The process of claim 13, wherein the glycol catalyst comprises H(OCH2CH2)nOH [H(OCH2CH2)nOH, [PEG] wherein the value of n provides a PEG having molecular weight of about 100 to about 10000.

15. The process of claim 13, wherein the glycol catalyst comprises polypropylene glycol having the formula HO(C3H6O)nC3H6OH where the value of n provides a molecular weight in the range of about 100 to about 10000.

16. The process of claim 13, wherein the glycol catalyst comprises ethylene glycol.

17. The process of claim 13, wherein the glycol catalyst comprises diethylene glycol.

18. The process of claim 13, wherein the glycol catalyst comprises triethylene glycol.

19. The process of claim 13, wherein the glycol catalyst comprises tetraethylene glycol.

20. The process of claim 13, wherein the glycol catalyst comprises a mono ether of polyethylene glycol having the formula R(OCH2CH2)nCH2CH2OH, wherein R isa C1 to C5 group and the value of n provides a molecular weight up to about 10000.

21. The process of claim 13, wherein the glycol catalyst comprises a mono ether of polypropylene glycol having the formula R(OC3H6)nC3H6OH, wherein R is a C1 to C5 group and the value of n provides a molecular weight up to about 10000.

22. The process of any of claims 1-21 wherein the alkali metal hydroxide (MOH) solution used in Step 2 is an aqueous solution of KOH.

23. The process of claim 1, wherein Step 3 is performed in the absence of a radical initiator.

24. The process of claim 1, wherein Step 3 is performed in the presence of a radical initiator.

25. The process of claim 24, wherein the radical initiator in Step 3 is a peroxide initiator capable of operating at a temperature of 100°C.

26. The process of claim 25 wherein the radical initiator in Step 3 is benzoyl peroxide.

27. The process of claim 26 wherein the temperature is in the range of 100-150°C.

28. The process of claim 25 wherein the radical initiator in Step 3 is di-tert-butyl peroxide.

29. The process of claim 28 wherein the temperature is in the range of 100-150°C.

30. The process of claim 1 wherein an oxygen-containing catalyst of Step 4 is a glycol catalyst having the formula, H(OCH2CH2)nOH where n is ≥ 1, e.g., 2, 3, 4 or greater; propylene glycol, a mono ether of polyethylene glycol or a mono ether of propylene glycol.

31. The process of claim 1 wherein an oxygen-containing catalyst of Step 4 is a crown ether.

32. The process of claim 30 wherein the oxygen-containing catalyst of Step 4 is a glycol catalyst and the glycol catalyst comprises HOCH2CH2OH (ethylene glycol, EG).

33. The process of claim 30 wherein the oxygen-containing catalyst of Step 4 is a glycol catalyst and the glycol catalyst comprises (HOCH2CH2)2O (diethylene glycol, DEG).

34. The process of claim 30 wherein the oxygen-containing catalyst of Step 4 is a glycol catalyst and the glycol catalyst comprises H(OCH2CH2)3OH (triethylene glycol, TrEG).

35. The process of claim 30 wherein the oxygen-containing catalyst of Step 4 is a glycol catalyst and the glycol catalyst comprises H(OCH2CH2)4OH (tetraethylene glycol, TeEG).

36. The process of claim 30 wherein the oxygen-containing catalyst of Step 4 is a glycol catalyst and the glycol catalyst comprises H(OCH2CH2)nOH [H(OCH2CH2)nOH, [PEG] wherein the value of n provides a PEG having molecular weight of about 100 to about 10000.

37. The process of claim 30 wherein the oxygen-containing catalyst of Step 4 is a glycol catalyst and the glycol catalyst comprises polypropylene glycol having the formula HO(C3H6O)nC3H6OH where the value of n provides a molecular weight in the range of about 100 to about 10000.

38. The process of claim 30 wherein the oxygen-containing catalyst of Step 4 is a glycol catalyst and the glycol catalyst comprises a mono ether of polyethylene glycol having the formula R(OCH2CH2)nCH2CH2OH, wherein R is a C1 to C5 group and the value of n provides a molecular weight up to about 10000.

39. The process of claim 30 wherein the oxygen-containing catalyst of Step 4 is a glycol catalyst and the glycol catalyst comprises a mono ether of polypropylene glycol having the formula R(OC3H6)nC3H6OH, wherein R is a C1 to C5 group and the value of n provides a molecular weight up to about 10000.

40. The process of claim 1 further comprising thermally treating the Step 1 product to eliminate the initiator and using the treated Step 1 product as a starting material for Step 2 without purification.

41. The process of claim 1 further comprising thermally treating the Step 3 product to eliminate the initiator and using the treated Step 3 product as a starting material for Step 4 without purification.

42. The process of claim 40 further comprising thermally treating the Step 3 product to eliminate the initiator and using the treated Step 3 product as a starting material for Step 4 without purification.

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