Process to purify fluorinated dihydroolefins

Abstract

A process to reduce the concentration of at leat one impurity in a product mixture comprising a fluorinated dihydroolefin and the impurity is provided wherein the fluorinated dihydroolefin has the formula RF1CH=CHRF2, wherein RF1 and RF2 are C1 to C6 fluoroalkyl groups, and the impurity is a fluorinated olefin, a fluorinated diene, a fluorinated alkyne or a mixture of two or more thereof. In one embodiment, the at least one impurity comprises a fluorinated olefin having the formula RF1CH=CFRF2.

Description

TITLE OF THE INVENTIONPROCESS TO PURIFY FLUORINATED DIHYDROOLEFINSFIELD

[0001] The present disclosure is directed to the purification of fluorinated alkene compounds. More particularly, the present disclosure is directed to the purification of the fluorinated dihydroolefins (HFO) E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (E-153-10mczz; E-CF3CF2CH=CHCF2CF3) and E-1,1,1,4,4,5,5,5-octafluoropent-2-ene (E-1438mzz; E- CF3CH=CHCF2CF3).BACKGROUND

[0002] Fluorinated dihydroolefins defined by the formula (I) E- or Z-RF1CH=CHRF2, wherein RF1and RF2are, independently, Ci to Ce perfluoroalkyl groups and having boiling points greater than 30°C are considered candidates for use as solvents, blowing agents, and heat transfer fluids for various applications, including immersion cooling and phase change cooling (e.g., of electronics, including data center cooling). Product streams containing E- or Z-RF1CH=CHRF2compounds may be produced by multiple processes, such as those disclosed in US8552227, US 2022 / 0185749, US 2022 / 0388929, WO 2021 / 119078, WO 2023 / 164093, WO 2025 / 160043, WO 2025 / 160052, WO 2025 / 160054, and WO 2025 / 160058.

[0003] Processes to manufacture the fluorinated dihydroolefins may introduce one or more hydrofluoroolefin impurities (i.e., RF1CH=CFRF2) as byproducts. For examples, processes to prepare E-153-10mczz, provide product streams containing impurities such as isomers of HFO-152-11 (“152-11”, undecafluorohexene), including Z-HFO-152-11mcyz (Z-1 ,1 ,1 ,2,2,3,5,5,6,6,6-undecafluoro-3-hexene). The presence of such byproducts can negatively impact performance and / or environmental or health concerns. Hydrofluoroolefins such as HFO-152-11 isomers have a normal boiling point that is close to (E-153-10mczz) and are not easily separated by distillation.

[0004] Accordingly, there is a need for techniques and processes to effectively and efficiently remove impurities from the fluorinated dihydroolefin product streams to enhance performance or .SUMMARY

[0005] The present invention provides a process to reduce the concentration of at least one impurity from a product mixture comprising a fluorinated dihydroolefin and the at least one impurity, wherein the fluorinated dihydroolefin has a formula RF1CH=CHRF2, wherein RF1and RF2are Ci to Ce fluoroalkyl groups, and the at least one impurity is selected from the group consisting of a hydrofluoroolefin, a perfluorinated olefin, a fluorinated diene, a fluorinated alkyne and a mixture of two or more thereof, wherein the process comprises contacting the product mixture with an aqueous basic solution to produce a treated product mixture. The aqueous basic solution may comprise sodium hydroxide or potassium hydroxide.

[0006] The inventors have unexpectedly found that in the preparation of certain fluorinated dihydroolefins, distillation is insufficient to remove certain impurities, thus preventing high purity in the desired fluorinated dihydroolefin products. Moreover, certain impurities have been identified as having detrimental properties, such as adverse effects on health or the environment and / or negative impact on use. For these reasons, it is desirable to remove the impurities or at least reduce the concentration of any such impurity to provide a high purity product.

[0007] In certain embodiments, a process produces a product stream comprising a fluorinated dihydroolefin and one or more impurities, wherein the one or more impurities, wherein the one or more impurities can be a mixture of two or more of a fluorinated olefin, a fluorinated diene, and a fluorinated alkyne.

[0008] The product stream may optionally undergo one or more purification steps, such as distillation to produce a purified product stream. The product stream or purified product stream can be the product mixture used in the process described herein.

[0009] The product mixture contains 10% or less, or 5% or less, or 2% or less, or 1 % or less of at least one impurity to be reduced in concentration or removed from the product mixture. The treated product mixture may contain less than 1000 ppm, or less than 750 ppm, or less than 500 ppm, or less than 100 ppm, or less than 50 ppm, or less than 10 ppm.

[0010] In certain embodiments, the process for the contacting step is performed in the presence of a phase transfer agent or a polar organic solvent. In one embodiment, the contacting step is performed in the presence of a polar organic solvent, such as methanol.

[0011] The fluorinated dihydroolefin can be, for example E-1, 1,1, 2, 2, 5, 5, 6,6,6-decafluoro-3-ene (E-153-1 Omczz). When the fluorinated dihydroolefin is E-153-10mczz, the hydrofluoroolefin impurity is or comprises undecafluorohexene (HFO- 152-11 or simply “152-11”). In certain embodiments, when the fluorinated dihydroolefin is E-153-10mczz, the 152-11 impurity is or comprises Z-HFO-152-11mcyz (Z-1 ,1 ,1 ,2,2,3,5,5,6,6,6-undecafluoro-3-hexene). In certain embodiments, when the fluorinated dihydroolefin is E-153-1 Omczz, the impurity is or comprises Z-HFO-152-11myz (Z-1 ,1 ,1 ,2,4,4,5,5,6,6,6-undecafluorohex-2-ene). In certain embodiments, when the fluorinated dihydroolefin is E-153-1 Omczz, the hydrofluoroolefin impurity is or comprises 1,1 ,1,4,4,5,5,6,6,6-decafluoro-2-hexene. In certain embodiments, when the fluorinated dihydroolefin is E-153-1 Omczz, the hydrofluoroolefin impurity is or comprises 1,1 ,1,4,4,5,5,6,6,6-decafluoro-2-methoxyhex-2-ene. In certain embodiments, when the fluorinated dihydroolefin is E- 153-1 Omczz, the hydrofluoroolefin impurity is or comprises 1 ,1 ,1 ,4,4,4-hexafluoro-2-methoxy-2-butene. In certain embodiments, when the fluorinated dihydroolefin is E-153-1 Omczz, the hydrofluoroolefin impurity is or comprises 1 ,1 ,1 , 2, 2, 5, 5, 6,6,6-decafluoro-3-methoxyhex-3-ene.

[0012] The fluorinated dihydroolefin can be, for example E-1, 1,1, 4, 4, 5,5,5-octafluoropent-2-ene (i.e. , E-1438mzz). In certain embodiments, when the fluorinated dihydroolefin is E-1438mzz, the hydrofluoroolefin impurity is nonafluoropentene (HFO-1429). In certain embodiments, when the fluorinated dihydroolefin is E-1438mzz and the hydrofluoroolefin impurity is HFO-1429, the HFO-1429 impurity is Z-1 ,1 ,1 ,2,4,4, 5,5, 5-nonafluoropent-2-ene (Z-HFO-1429myz).

[0013] Surprisingly the concentration of the impurity is significantly reduced when the product mixture is contacted with an aqueous basic solution. In certain embodiments, the concentration of the hydrofluoroolefin impurity is significantly reduced and in certain embodiments is reduced to a concentration of less than 1000ppm, or less than 750 ppm, or less than 500 ppm, or less than 100 ppm, or less than 50 ppm, or less than 10 ppm.BRIEF DESCRIPTION OF THE FIGURES

[0014] Figure 1 illustrates possible reactions of an impurity and reaction products of the formula RF1CH=CFRF2and a ketone reaction product according to the process disclosed herein.

[0015] Figure 2 provides a graph of pseudo first order kinetics based on reaction modeling of Z-HFO-152-11 mcyz with KOH (aq.) and methanol taken from Example 6.DETAILED DESCRIPTION

[0016] The present invention relates broadly to purification of compositions comprising fluorinated dihydroolefins.GENERAL TERMS

[0017] Compounds may be referred to herein by the compound name (e.g., E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene) orASHRAE designation (e.g., E-HFO-153-10mczz, or more simply, E-153-10mczz) or chemical formula (e.g., CF3CF2CH=CHCF2CF3) and optionally prefaced by “CFC”, “HCFC”, “HFC”, “CFO”, “HCFO”, or“HFO”, meaning “chlorofluorocarbon”, “hydrochlorofluorocarbon”, “hydrofluorocarbon”, “chlorofluoroolefin”, “hydrochlorofluoroolefins”, or “hydrofluoroolefin”. The absence of the preface does not change the meaning of the compound.

[0018] The term “isomers” is used to represent one or more compounds having the recited chemical formula that are identified using standard analytical techniques (GC and GC-mass spectrometry). The isomers may include one or more compounds having the recited chemical formula, such as linear, branched and cyclic compounds). Alternatively, isomers may include unsaturated compounds (having a double bond) or cyclic compounds having the same chemical formula or multiple unsaturations (two or more double bonds) or combinations with cyclic structures.

[0019] More specifically, when a compound is recited as a chemical formula, one or more isomers having the recited formula are included. For example, the chemical formula “CeHFn” includes compounds having the recited chemical formula (e.g., CeHFn) are included (such as linear, branched and cyclic compounds).

[0020] In addition, with respect to compounds having unsaturation (double bond), the compound may have “E-“ and “Z-“ isomers. If neither “E-“ nor “Z-“ are identified, the compound disclosed may contain one or both isomers. Specific isomers are identified as “E-“ or “Z-“. For example, HFO-152-11 mcyz may include one or both of E-HFO-152-11 mcyz and Z-HFO-152-11 mcyz, whereas specific isomers are identified as “E-HFO-152-11 mcyz” and “Z-HFO-152-11 mcyz.

[0021] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” contains” or any other variation thereof, are intended to cover a nonexclusive 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).

[0022] 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.

[0023] 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”.

[0024] 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.”

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.PROCESS

[0030] The present invention provides a process to reduce the concentration of at least one impurity from a product mixture comprising a fluorinated dihydroolefin and the at least one impurity, wherein the fluorinated dihydroolefin has a formula RF1CH=CHRF2, wherein RF1and RF2are Ci to Ce fluoroalkyl groups, and the at least one impurity is selected from the group consisting of a fluorinated olefin, a fluorinated diene, a fluorinated alkyne and a mixture of two or more thereof. The process comprises contacting a product mixture comprising a fluorinated dihydroolefin and at least one impurity to be removed with an aqueous basic solution to produce a treated product mixture, wherein the fluorinated dihydroolefin has the formula RF1CH=CHRF2, wherein RF1and RF2are Ci to Ce fluoroalkyl groups.

[0031] In the process of this invention, the contacting step creates an interaction between the product mixture and the aqueous caustic solution. This interaction may be through mixing (including static mixing), agitation (a specific form of mixing), shaking or other mechanism.

[0032] In one embodiment, the at least one impurity comprises a fluorinated olefin. In one embodiment, the fluorinated olefin has the formula RF1CH=CFRF2, wherein RF1and RF2are Ci to Ce fluoroalkyl groups.

[0033] In one embodiment, the fluorinated dihydroolefin is E-153-10mczz. In one embodiment, when the fluorinated dihydroolefin is E-153-10mczz, the impurity comprises undecafluorohexene (CeHFn isomers, including HFO-152-11 isomers). In one embodiment, the undecafluorohexene is or comprises Z-1, 1,1, 2, 2, 3, 5, 5, 6,6,6-undecafluoro-3-hexene (HFO-152-11mcyz). In one embodiment, the undecafluorohexene is or comprises HFO-152-11myz (Z-1, 1,1 , 2, 4, 4, 5, 5, 6,6,6-undecafluorohex-2-ene).

[0034] The aqueous basic solution may comprise sodium hydroxide or potassium hydroxide. The process may further comprise one or more additions to the contacting step such as a polar organic solvent or a quaternary ammonium phasetransfer agent. The additions may be added in combination with or independently from the aqueous basic solution.

[0035] In one embodiment, the aqueous basic solution comprises sodium hydroxide. In one embodiment, the aqueous basic solution comprises potassium hydroxide.

[0036] The process may be performed in the presence of a polar organic solvent or a phase transfer agent.

[0037] In one embodiment, the process is performed in the presence of a polar organic solvent. The polar organic solvent may be chosen from nitrile, ether, alcohol, amide, ketone, sulfoxide, ester, or mixtures thereof. The polar organic solvent may be sulfolane.

[0038] The alcohol may be, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, or tertiary butanol. The nitrile may be acetonitrile, propionitrile, butyronitrile, methyl glutaronitrile, adiponitrile, or benzonitrile. The sulfoxide may be dimethyl sulfoxide. The amide may be N,N-dimethyl formamide, N,N-dimethyl acetamide, N-methyl pyrrolidinone. The ester may be ethylene carbonate or propylene carbonate. The ketone may be methyl ethyl ketone, methyl isoamyl ketone, diisobutyl ketone. The ether may be anisole, 2-methyltetrahydrofuran, tetrahydrofuran, dioxane, diglyme, triglyme, tetraglyme.

[0039] The choice of polar organic solvent may depend on the boiling point product and the ease of separation of traces of the polar organic solvent from the product during purification. Preferred polar organic solvents include alcohol, nitrile, ether.

[0040] In one embodiment, a preferred polar organic solvent for the reaction is methanol.

[0041] In one embodiment, the process is performed in the presence of a phase transfer agent. The phase transfer agent can be ionic or neutral. In one embodiment, the phase transfer agent is selected from the group consisting of crown ethers, onium salts, cryptands and polyalkylene glycols and mixtures and derivatives thereof.

[0042] In some embodiments, the phase transfer agent is a crown ether. In some embodiments, the crown ether is 18-crown-6. Preferably 18-crown-6 is used in combination with potassium hydroxide aqueous solution. In some embodiments, the crown ether is 15-crown-5. Preferably 15-crown-5 is used in combination with sodium hydroxide aqueous solution. Derivatives of the above crown ethers are also useful, e.g., dibenzo-18-crown-6, dicyclohexano-18-crown-6.

[0043] In some embodiments, onium salts include quaternary phosphonium salts and quaternary ammonium salts that may be used as the phase transfer agent 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.

[0044] In other embodiments, cryptands are another class of compounds useful in the reaction as phase transfer agents. For example, 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) is a useful cryptand phase transfer agent.

[0045] In some embodiments, polyalkylene glycol ethers are useful as phase transfer agents. 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.

[0046] Combinations and mixtures of the above-described phase transfer agents from within one of the groups may also be useful as well as combinations or mixtures of two or more phase transfer agents selected from more than one group.

[0047] In one embodiment, the amount of phase transfer agent 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 agent 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 agent 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.

[0048] In one embodiment, the process comprises contacting a product mixture with an aqueous basic solution to produce a treated product mixture, wherein the product mixture comprises a fluorinated dihydroolefin and at least one impurity, the fluorinated dihydroolefin having a formula RF1CH=CHRF2, wherein RF1and RF2areCi to Ce fluoroalkyl groups. The impurity is selected from the group consisting of a fluorinated olefin, a fluorinated diene, a fluorinated alkyne and a mixture of two or more thereof.

[0049] In one embodiment, the process comprises contacting a product mixture comprising a fluorinated dihydroolefin, having the formula RF1CH=CHRF2, and a hydrofluoroolefin impurity, having the formula RF1CH=CFRF2, wherein RF1and RF2are Ci to Ce fluoroalkyl groups, with an aqueous basic solution and a phase transfer agent.

[0050] In one embodiment, the process comprises contacting a product mixture comprising a fluorinated dihydroolefin, having the formula RF1CH=CHRF2, and a hydrofluoroolefin impurity, having the formula RF1CH=CFRF2, wherein RF1and RF2are Ci to Ce fluoroalkyl groups, with an aqueous basic solution and a polar organic solvent.

[0051] The fluorinated dihydroolefin can be, for example E-1, 1,1, 2, 2, 5, 5, 6,6,6-decafluoro-3-ene (E-153-1 Omczz). The hydrofluoroolefin impurity can be undecafluorohexene (CeHFn). In certain embodiments, the undecafluorohexene is Z-HFO-152-11mcyz (Z-1 ,1 ,1 ,2,2,3,5,5,6,6,6-undecafluoro-3-hexene). In one embodiment, the undecafluorohexene is or comprises HFO-152-11 myz (Z- 1.1.1.2.4.4.5.5.6.6.6-undecafluorohex-2-ene).

[0052] In one embodiment, E-153-1 Omczz is produced from a vapor phase fluorination process such as fluorination of HCFC-548mafd (3,5,5-trichloro- 1.1.1.2.2.6.6.6-octafluorohexane). In such a process, undecafluorohexene isomers (including HFO-152-11 isomers) may be produced as impurities (equation I, where cat. means catalyst).>""" " " " "

[0053] In particular, it has been found that the presence 152-11 isomers in a dielectric fluid comprising E-153-1 Omczz can reduce stability of the dielectric fluid. In addition, certain 152-11 isomers have adverse health effects (that is, are toxic).

[0054] The fluorinated dihydroolefin can be, for example E-1, 1,1, 4, 4, 5, 5, 5-octafluoropent-2-ene (i.e. , E-HFO-1438mzz). The hydrofluoroolefin impurity can be nonafluoropentene (HFO-1429). In certain embodiments, the HFO-1429 impurity is Z-1 , 1 , 1 ,2,4,4,5,5,5-nonafluoropent-2-ene (Z-HFO-1429myz).

[0055] The processes disclosed herein provide compositions of fluorinated dihydroolefins with low levels of the at least one impurity. Thus, there is provided a composition comprising a fluorinated dihydroolefin having the formula RF1CH=CHRF2, wherein RF1and RF2are Ci to Ce fluoroalkyl groups and less than 1000 ppm, or less than 750 ppm, or less than 500 ppm, or less than 100 ppm, or less than 50 ppm, or less than 10 ppm of an impurity, wherein the at least one impurity is selected from the group consisting of a fluorinated olefin, a fluorinated diene, a fluorinated alkyne and a mixture of two or more thereof.

[0056] In certain embodiments, the composition comprising fluorinated dihydroolefins with low levels of an impurity are produced by the process disclosed herein. When the process is performed in the presence of a polar organic solvent, the composition may further comprise the polar organic solvent. Thus, in certain embodiments there is provided a composition comprising a fluorinated dihydroolefin with low levels of the at least one impurity and further comprising a polar organic solvent. The preferred polar organic solvent is methanol. In one particular embodiment, there is provided a composition comprising a fluorinated dihydroolefin with low levels of the at least one impurity and further comprising methanol.

[0057] The compositions disclosed herein can be used as a refrigerant, heat transfer fluid, foam expansion agent, power cycle working fluid, among other uses.

[0058] In one embodiment there is a composition comprising a fluorinated dihydroolefin, wherein the fluorinated dihydroolefin is E-153-1 Omczz, and the composition comprises less than 1000 ppm, or less than 750 ppm, or less than 500 ppm, or less than 100 ppm, or less than 50 ppm, or less than 10 ppm of an impurity.

[0059] In one embodiment, there is provided a composition comprising E-153-10mczz and an impurity wherein the impurity is selected from the group consisting of Z-HFO-152-11 mcyz (Z-1 , 1 ,1 ,2,2,3,5,5,6,6,6-undecafluoro-3-hexene), Z-HFO-152-11 myz (Z-1 ,1 , 1 ,2,4,4,5,5,6,6,6-undecafluorohex-2-ene), 1,1,1 , 4, 4, 5, 5, 6,6,6-decafluoro-2-hexene, 1,1,1 ,4,4,4-hexafluoro-2-methoxy-2-butene,1.1.1.2.2.5.5.6.6.6-decafluoro-3-methoxyhex-3-ene, and combinations of two or more thereof.

[0060] In one embodiment, the impurity is selected from the group consisting of Z-HFO-152-11 mcyz (Z-1 ,1,1 ,2,2,3,5,5,6,6,6-undecafluoro-3-hexene), Z-HFO-152-11 myz (Z-1 ,1 ,1 ,2,4,4,5,5,6,6,6-undecafluorohex-2-ene), .

[0061] In one embodiment, the impurity is Z-HFO-152-11 mcyz (Z- 1.1.1.2.2.3.5.5.6.6.6-undecafluoro-3-hexene) or Z-HFO-152-11 myz (Z- 1.1.1.2.4.4.5.5.6.6.6-undecafluorohex-2-ene).

[0062] In one embodiment, a composition of this invention can be used as a working fluid in an immersion cooling unit. An immersion cooling unit includes 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 a fluorinated dihydroolefin, wherein the fluorinated dihydroolefin is E-153-10mczz, and the composition comprises less than 1000 ppm, or less than 750 ppm, or less than 500 ppm, or less than 100 ppm, or less than 50 ppm, or less than 10 ppm of an impurity, wherein the impurity is Z-HFO-152-11 mcyz (Z-1 ,1 ,1 ,2,2,3,5,5,6,6,6-undecafluoro-3-hexene) or Z-HFO-152-11 myz (Z-1 , 1 , 1 ,2,4,4,5,5,6,6,6-undecafluorohex-2-ene).

[0063] In one embodiment, a composition of this invention can be used as a working fluid in cooling of electronic devices. Examples of electronic devices of the present invention include, but are not limited to microprocessors, wafers used to manufacture semiconductor devices, power control semiconductors, electrical distribution switch gear, power transformers, rectifiers, power converters, circuit boards, multi-chip modules, packaged and unpackaged semiconductor devices, lasers, chemical reactors, fuel cells, and electrochemical cells. In some embodiments, the device can include a chiller, a heater, ora combination thereof.

[0064] The term transformer as used herein will be understood to be a piece of static apparatus which by electromagnetic induction transforms alternating voltage and current between two or more windings at the same frequency and usually atdifferent values of voltage and current; liquid-filled transformers are well-known and the liquid in the transformer normally constitutes a coolant.

[0065]

[0066] In one embodiment, the present invention provides a composition comprising a fluorinated dihydroolefin with low levels of an impurity, wherein the fluorinated dihydroolefin is E-1 ,1 ,1 ,4,4,5,5,5-octafluoropent-2-ene, and the composition comprises less than 1000 ppm, or less than 750 ppm, or less than 500 ppm, or less than 100 ppm, or less than 50 ppm, or less than 10 ppm of an impurity, wherein the impurity is Z-1 ,1 ,1 ,2,4,4,5,5,5-nonafluoropent-2-ene. The composition comprising E-1,1,1,4,4,5,5,5-octafluoropent-2-ene, can be used as a refrigerant, heat transfer fluid, foam expansion agent, power cycle working fluid, among uses.DESCRIPTION OF THE FIGURES

[0067] Figure 1 illustrates potential mechanisms for the reactions of impurities when the fluorinated dihydroolefin in E-153-10mczz and an impurity is Z-HFO-152-11mcyz.

[0068] Figure 2 shows a fit of the GC data to pseudo first order reaction rate plots for the 152-11mcyz disappearance and the MFAE formation taken from Example 6. Using toluene as an internal standard, the E-153-10mczz did not significantly change with respect to a relative mean E-153-10mczz concentration during the reaction at 30°C.

[0069] Figure 2 shows a pseudo-first-order reaction kinetic plot for a 152-11 mcyz disappearance [Ln(AR / Ao)] vs. time at a specified temperature, and for MFAE formation [-Ln(1-Ap / Aoc)] vs. time at a specified temperature, wherein AR and Ao are the 152-11 mcyz concentrations at any time and time = 0, respectively, and Ap and A / are the MFAE concentrations at any time and at an estimate for time = infinity, respectively. The slope of a line corresponds to a pseudo-first-order rate constant at the specified reaction stoichiometry and temperature. The E-153-10mczz relative concentration (stability) versus a toluene internal standard under the 152-11 mcyz reaction conditions at 30°C is also shown.

[0070] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the artto 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.

[0071] The following Examples are provided to illustrate certain aspects of the invention and shall not limit the scope of the appended claims.EXAMPLESComparative Example 1. Distillation of crude 153-10mczz

[0072] A still pot contained a crude product mixture containing E-153-1 Omczz from a vapor phase fluorination of HCFC-548mafd performed in accordance with U.S Provisional Patent Application No. 63 / 623,383 filed January 22, 2024, and 63 / 680,351 , filed August 7, 2024. The crude product mixture was distilled at atmospheric pressure using a 5’ x 1” ID 40-plate Oldershaw column fitted with a high reflux ratio still head and magnetic take-off valve. Fractions were slowly collected at high distillation reflux ratios between 20:1 and 40:1 and analyzed by gas chromatography (GC) with both mass spectral (MS) identification and thermal conductivity (TCD) detection. The results are provided in Table 1.TABLE 1

[0073] As can be seen from the data in Table 1 , a major 152-11 isomer, Z-HFO-152-11mcyz, was not appreciably separated from the E-153-10mczz product by distillation.Example 2. HFO-152-11 mcyz reaction with aqueous KOH in methanol

[0074] A 10-g sample of fraction 3 from Example 1 was combined with 1 g of aqueous 45% KOH and 4 g of methanol in a 25-mL PFA sample bottle with cap. The mixture was magnetically and vigorously stirred overnight. The organic layer was analyzed by GC and no 152-11 mcyz was detected. A peak matching a product from reaction of the 152-11 mcyz with methanol, 1,1,1,4,4,5,5,6,6,6-decafluoro-2-methoxyhex-2-ene, was observed at a longer retention time.Example 3. HFO-152-11 mcyz reaction with aqueous KOH in the presence of a phase transfer catalyst

[0075] A 10-g sample of fraction 3 from Example 1 was combined with 1 g of aqueous 45% KOH, 4 g of water, and 0.25 g of tetrabutylammonium bromide in a 25-mL PFA sample bottle with cap. The mixture was magnetically and vigorously stirred overnight. The organic layer was analyzed by GC and the 152-11 mcyz was reduced from 5.88% to 1.64%.Example 4. HFO-152-11 mcyz reaction with aqueous KOH in the presence of ethylene glycol

[0076] A 10-g sample of fraction 3 from Example 1 was combined with 2 g of aqueous 45% KOH and 4 g of ethylene glycol in 250-mL round bottom (RB) flask that was fitted with a reflux condenser. The mixture was magnetically and vigorously stirred at reflux overnight. The organic layer was analyzed by GC and the 152-11 mcyz was reduced from 5.88% to 4.12%.Example 5. HFO-152-11 mcyz reaction with aqueous KOH in methanol

[0077] A 745-g sample of E-153-10mczz containing approximately 5.8% of 152-11 mcyz was combined with 77 g of 45% KOH and 76 g of methanol in a 2L HDPEcarboy. The mixture was magnetically stirred at ambient room temperature over a weekend. The product mixture separated into a phase rich in E-153-10mczz and a methanol-rich phase. GC analysis with both mass spectral (MS) identification and thermal conductivity (TCD) detection of a phase containing E-153-10mczz showed no remaining 152-11 mcyz or other 152-11 isomers.

[0078] The product mixture was transferred to a 2L separatory funnel and a volume of water approximately equivalent to an aqueous methanol phase was added to further separate E-153-10mczz dissolved in the aqueous methanol phase and extract methanol in the E-153-10mczz phase. The phases were separated and the E-153-10mczz phase was washed with an equivalent mass of water.

[0079] Distillation purification: The separated E-153-10mczz phase was dried over anhydrous magnesium sulfate and filtered into a 1 L still pot of an Oldershaw distillation apparatus (5’ x 1” ID, 40 plates) comprising a high reflux-ratio still head and magnetic take-off valve. The E-153-10mczz phase (709.5g) was distilled at reflux ratios between 10:1 and 20:1 and Table 2 summarizes the results.

[0080] In Table 2, MFAE is C2F5CH=C(OCH3)C2F5. MFAE is illustrated in Figure.2.TABLE 2

[0081] The heart cut comprising Fractions 2 and 3 in Table 2 showed an E-153-10mczz purity that was greater than 99.8%. The majority of the MFAE product(s) from reaction of methanol with 152-11 were retained in the heel.Example 6. HFO-152-11 mcyz reaction rate with methanol and E-153-10mczz stability

[0082] A 75-g sample of E-153-1 Omczz containing 5.43% 152-11 mcyz and 0.75 g of toluene was placed in a 250-mL jacketed round bottom flask fitted with an air condenser connected to a nitrogen pad, a thermocouple, a 1 .5” x 5 / 8” footballshaped magnetic stir bar, and a sampling port having a Teflon® stopcock.Water / glycol was recirculated from a chiller / heater bath through the jacket to maintain and control the temperature in the flask for two reactions at 20°C and 30°C.

[0083] With maximum magnetic stirring (900 - 1000 rpm), a premade mixture of 7.5-g of 45% aqueous KOH (4 eq) and 7.5 g of methanol was quickly added to the flask and a timer was started. Approximately 1-mL samples were periodically removed through the sampling port using a syringe and needle, and quickly quenched by addition to an equivalent volume of water resulting in an aqueous phase and an E-153-1 Omczz phase. The E-153-1 Omczz phase was analyzed by GC with both mass spectral (MS) identification and thermal conductivity (TCD) detection.Example 7. HFO-1429myz reaction with aqueous KOH in methanol

[0084] A 10-g sample of a chilled mixture of E-1,1,1,4,4,5,5,5-octafluoropent-2-ene (i.e., E-HFO-1438mzz) containing 5% of Z-HFO-1429myz (i.e., Z-1 ,1 ,1 , 2, 4, 4, 5,5,5-nonafluoropent-2-ene) is combined with 1 g of aqueous 45% KOH and 4 g of methanol in a 25-mL PFA sample bottle and tightly capped. The mixture is magnetically and vigorously stirred overnight at ambient room temperature. Thesample bottle is chilled in an ice bath and the organic layer is analyzed by GC. No HFO-1429myz is detected.Example 8. Purification of E-153-10mczz by reaction with KOH / methanol

[0085] E-153-10mczz was prepared according to the 4-step process disclosed in WO 2025 / 160058. The product recovered from step 4 containing up to 10% by weight of 152-11 isomers was treated with a premade mixture of aqueous methanolic solution of KOH, wherein ratio of MeOH / KOH to 152-11 isomers was 15:4:1. The concentration of 152-11 isomers in the E-153-10mczz product was monitored overtime.

[0086] The reaction mixture was purified by Oldershaw distillation at lab scale and final analysis of the purified product was performed using gas chromatography flame ionization detection (GC-FID) and mass spectrometry (MS). The final product contained 99.96 wt% of E-153-10mczz. The final product also contained less than 200 ppm by weight of each of the following impurities : 1 ,1 ,1 ,4,4,5, 5, 6,6,6-decafluoro-2-hexene, 1,1,1 ,4,4,4-hexafluoro-2-methoxy-2-butene, and1.1.1.2.2.5.5.6.6.6-decafluoro-3-methoxyhex-3-ene. Methanol is present in the final product at less than 50 ppm.

[0087] The concentration of each of the HFO-152-11 isomers was below the detection limit by GC / FID, with the main isomer of 152-11 being Z- 1.1.1.2.2.3.5.5.6.6.6-undecafluorohex-3-ene (limit of detection of the main HFO-152-11 isomer is about 20 ppm).

[0088] As can be seen from the Examples, the process of this invention provides a composition comprising a fluorinated dihydroolefin having a concentration of an impurity selected from the group consisting of a fluorinated olefin, a fluorinated diene, a fluorinated alkyne and a mixture of two or more thereof of less than 1000 ppm, or less than 750 ppm, or less than 500 ppm, or less than 100 ppm, or less than 50 ppm, or less than 10 ppm of the impurity.

[0089] In particular, a composition comprising E-153-10mczz comprises less than 1000 ppm, or less than 750 ppm, or less than 500 ppm, or less than 100 ppm, or less than 50 ppm, or less than 20 ppm of HFO-152-11 isomers. A composition isprovided comprising E-153-10mczz and less than 20 ppm of Z-1, 1,1, 2, 2, 3, 5, 5, 6, 6, 6-undecafluorohex-3-ene.

Claims

CLAIMSWhat is claimed is:

1. A process to reduce the concentration of an impurity from a product mixture comprising a fluorinated dihydroolefin and the impurity, wherein the fluorinated dihydroolefin has a formula RF1CH=CHRF2, wherein RF1and RF2are Ci to Ce fluoroalkyl groups, and the impurity is selected from the group consisting of a fluorinated olefin, a fluorinated diene, a fluorinated alkyne and a mixture of two or more thereof, comprising contacting the product mixture with an aqueous basic solution to produce a treated product mixture.

2. The process of claim 1 , wherein the impurity is a mixture of two or more of a fluorinated olefin, a fluorinated diene, and a fluorinated alkyne.

3. The process of claim 1 , wherein the contacting is performed in the presence of a phase transfer agent or a polar organic solvent.

4. The process of claim 3, wherein the contacting is performed in the presence of a phase transfer agent.

5. The process of claim 3, wherein the contacting is performed in the presence of a polar organic solvent.

6. The process of any of claims 1-5, wherein the treated product mixture contains an aqueous phase and a phase rich in the fluorinated dihydroolefin.

7. The process of claim 6, further comprising separating the aqueous phase from the phase rich in the fluorinated dihydroolefin.

8. The process of claim 7, further comprising drying the phase rich in the fluorinated dihydroolefin to provide a dried fluorinated dihydroolefin-rich phase.

9. The process of claim 7, further comprising distilling the phase rich in the fluorinated dihydroolefin to provide a composition comprising the fluorinated dihydroolefin.

10. The process of claim 8, further comprising distilling the dried fluorinated dihydroolefin-rich phase to provide a composition comprising the fluorinated dihydroolefin.

11. The process of claim 1 , wherein the fluorinated dihydroolefin is E- 1.1.1.2.2.5.5.6.6.6-decafluoro-3-ene.

12. The process of claim 11 , wherein the impurity comprises undecafluorohexene.

13. The process of claim 12, wherein the undecafluorohexene is Z- 1.1.1.2.2.3.5.5.6.6.6-undecafluoro-3-hexene.

14. The process of claim 12, wherein the undecafluorohexene is comprises HFO- 152-11 myz (Z-1 , 1 , 1 ,2,4,4,5,5,6,6,6-undecafluorohex-2-ene).

15. The process of claim 1 , wherein the fluorinated dihydroolefin is E- 1,1,1 ,4,4,5,5,5-octafluoropent-2-ene.

16. The process of claim 5 wherein the hydrofluoroolefin impurity is nonafluoropentene.

17. The process of claim 16, wherein the nonafluoropentene is Z-1 , 1 , 1 , 2, 4, 4, 5,5,5- nonafluoropent-2-ene.

18. The process of any of claims 1 -17, wherein the aqueous basic solution comprises sodium hydroxide or potassium hydroxide.

19. The process of claim 18, wherein the aqueous basic solution comprises sodium hydroxide.

20. The process of claim 18, wherein the aqueous basic solution comprises potassium hydroxide.

21. The process of claim 4, wherein the phase transfer agent is selected from the group consisting of crown ethers, onium salts, cryptands and polyalkylene glycols and mixtures and derivatives thereof.

22. The process of claim 21 , wherein the phase transfer agent is a crown ether.

23. The process of claim 21 , wherein the phase transfer agent is an onium salt.

24. The process of claim 23, wherein the onium salt is a quaternary ammonium salt or a quaternary phosphonium salt.

25. The process of claim 23, wherein the onium salt is tetramethylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride,methyltrioctylammonium chloride, tetra-n-butylammonium chloride, tetra-n- butylammonium bromide, tetra-n-butylammonium hydrogen sulfate, tetra-n- butylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, triphenylmethylphosphonium bromide or triphenylmethylphosphonium chloride.

26. The process of claim 25, wherein the aqueous basic solution comprises sodium hydroxide.

27. The process of claim 25, wherein the aqueous basic solution comprises potassium hydroxide.

28. The process of claim 21 , wherein the phase transfer agent is a cryptand.

29. The process of claim 21 , wherein the phase transfer agent is polyalkylene glycol.

30. The process of claim 29, wherein the polyalkylene glycol is diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, diisopropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol or tetramethylene glycol.

31. The process of claim 30, wherein the aqueous basic solution comprises sodium hydroxide.

32. The process of claim 30, wherein the aqueous basic solution comprises potassium hydroxide.

33. The process of claim 5, wherein the polar organic solvent is chosen from nitrile, ether, alcohol, amide, ketone, ether, sulfoxide, ester, or mixtures thereof.

34. The process of claim 33, wherein the polar organic solvent is a nitrile.

35. The process of claim 34, wherein the nitrile is acetonitrile, propionitrile, butyronitrile, methyl glutaronitrile, adiponitrile, or benzonitrile.

36. The process of claim 33, wherein the polar organic solvent is an ether.

37. The process of claim 36, wherein the ether is anisole, 2-methyltetrahydrofuran, tetrahydrofuran, dioxane, diglyme, triglyme, or tetraglyme.

38. The process of claim 33, wherein the polar organic solvent is an alcohol.

39. The process of claim 36, wherein the alcohol is methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, or tertiary butanol.

40. The process of claim 39, wherein the alcohol is methanol.

41. The process of claim 39, wherein the aqueous basic solution comprises sodium hydroxide.

42. The process of claim 39, wherein the aqueous basic solution comprises potassium hydroxide.

43. The process of claim 39, wherein the fluorinated dihydroolefin is E- 1.1.1.2.2.5.5.6.6.6-decafluoro-3-ene.

44. The process of claim 43, wherein the impurity comprises undecafluorohexene.

45. The process of claim 44, wherein the impurity comprises Z- 1.1.1.2.2.3.5.5.6.6.6-undecafluoro-3-hexene.

46. The process of claim 44, wherein the impurity comprises Z- 1.1.1.2.4.4.5.5.6.6.6-undecafluorohex-2-ene.

47. The process of claim 39, wherein the fluorinated dihydroolefin is E- 1,1,1 ,4,4,5,5,5-octafluoropent-2-ene.

48. The process of claim 47, wherein the impurity comprises nonafluoropentene.

49. The process of claim 48, wherein the impurity comprises Z-1 ,1 ,1 ,2,4,4, 5,5,5- nonafluoropent-2-ene (Z-HFO-1429myz).

50. The process of claim 33, wherein the polar organic solvent is an amide.

51. The process of claim 50, wherein the amide is N,N-dimethyl formamide, N,N- dimethyl acetamide, or N-methyl pyrrolidinone.

52. The process of claim 33, wherein the polar organic solvent is a ketone.

53. The process of claim 52, wherein the ketone is methyl ethyl ketone, methyl isoamyl ketone, or diisobutyl ketone.

54. The process of claim 33, wherein the polar organic solvent is a sulfoxide.

55. The process of claim 54, wherein the sulfoxide is dimethyl sulfoxide.

56. The process of claim 33, wherein the polar organic solvent is an ester.

57. The process of claim 56, wherein the ester is ethylene carbonate or propylene carbonate.

58. A process to reduce the concentration of an impurity from a product mixture comprising a fluorinated dihydroolefin and the impurity, wherein the fluorinated dihydroolefin is E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-ene, and the impurity is undecafluorohexene, comprising contacting the product mixture with an aqueous basic solution in the presence of a polar organic solvent to produce a treated product mixture.

59. A process to reduce the concentration of an impurity from a product mixture comprising a fluorinated dihydroolefin and the impurity, wherein the fluorinated dihydroolefin is E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-ene, and the impurity is undecafluorohexene, comprising contacting the product mixture with an aqueous basic solution in the presence of a polar organic solvent to produce a treated product mixture, wherein the polar organic solvent is an alcohol.

60. A process to reduce the concentration of an impurity from a product mixture comprising a fluorinated dihydroolefin and the impurity, wherein the fluorinated dihydroolefin is E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-ene, and the impurity is undecafluorohexene, comprising contacting the product mixture with an aqueous basic solution in the presence of a polar organic solvent to produce a treated product mixture, wherein the polar organic solvent is methanol.

61. A composition comprising a fluorinated dihydroolefin having the formula RF1CH=CHRF2, wherein RF1and RF2are Ci to Ce fluoroalkyl groups and less than 1000 ppm, or less than 750 ppm, or less than 500 ppm, or less than 100 ppm, or less than 50 ppm, or less than 10 ppm of an impurity, wherein the impurity is selected from the group consisting of a fluorinated olefin, a fluorinated diene, a fluorinated alkyne and a mixture of two or more thereof.

62. The composition of claim 61 further comprising a polar organic solvent.

63. The composition of claim 62, wherein the polar organic solvent is methanol.

64. A composition comprising is E-1 , 1 , 1 ,2,2,5,5,6,6,6-decafluoro-3-ene and an impurity wherein the impurity is selected from the group consisting of Z-1.1.1.2.2.3.5.5.6.6.6-undecafluoro-3-hexene, Z-1, 1,1, 2, 4, 4, 5, 5, 6, 6, 6- undecafluorohex-2-ene, 1,1,1 ,4,4,5,5,6,6,6-decafluoro-2-hexene, 1,1,1 ,4,4,4- hexafluoro-2-methoxy-2-butene, 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-methoxyhex- 3-ene, and combinations of two or more thereof.

65. The composition of claim 64, wherein the fluorinated dihydroolefin is E- 1.1.1.2.2.5.5.6.6.6-decafluoro-3-ene, and the composition comprises less than 1000 ppm, or less than 750 ppm, or less than 500 ppm, or less than 100 ppm, or less than 50 ppm, or less than 10 ppm of an impurity, wherein the impurity is Z-1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene or Z-1 ,1 ,1 ,2,4, 4,5, 5,6, 6,6- undecafluorohex-2-ene.

66. The composition of claim 65, wherein the impurity is Z-HFO-152-11mcyz (Z- 1.1.1.2.2.3.5.5.6.6.6-undecafluoro-3-hexene).

67. The composition of claim 65, wherein the impurity is Z-HFO-152-11 myz (Z- 1.1.1.2.4.4.5.5.6.6.6-undecafluorohex-2-ene).

68. The composition of claim 65, wherein the impurity is Z-HFO-152-11mcyz (Z- 1.1.1.2.2.3.5.5.6.6.6-undecafluoro-3-hexene) and Z-HFO-152-11 myz (Z- 1.1.1.2.4.4.5.5.6.6.6-undecafluorohex-2-ene).

69. The composition of claim 61 , wherein the fluorinated dihydroolefin is E- 1,1,1,4,4,5,5,5-octafluoropent-2-ene, and the composition comprises less than 1000 ppm, or less than 750 ppm, or less than 500 ppm, or less than 100 ppm, or less than 50 ppm, or less than 10 ppm of an impurity, wherein the impurity is Z-1 ,1 ,1 ,2,4,4,5,5,5-nonafluoropent-2-ene.

70. A composition comprising £-1,1,1 ,2,2,5,5,6,6,6-decafluoro-3-ene and less than 1000 ppm, or less than 750 ppm, or less than 500 ppm, or less than 100 ppm, or less than 50 ppm, or less than 20 ppm of HFO-152-11 isomers.71 . A composition comprising £-1,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-ene and less than 20 ppm of Z-1,1,1 ,2,2,3,5,5,6,6,6-undecafluorohex-3-ene.

72. Use of the composition of any of claims 61-71 as a refrigerant.

73. Use of the composition of any of claims 61-71 as a foam expansion agent.

74. Use of the composition of any of claims 64-68 a heat transfer application.

75. Use of the composition of any of claims 64-69 as a power cycle working fluid.

76. 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-ene and less than 1000 ppm, or less than 750 ppm, or less than 500 ppm, or less than 100 ppm, or less than 50 ppm, or less than 10 ppm of an impurity, wherein the impurity is Z-HFO-152-11mcyz (Z-1 ,1 ,1 ,2,2,3,5,5,6,6,6-undecafluoro-3- hexene) or Z-HFO-152-11 myz (Z-1 , 1 , 1 ,2,4,4,5,5,6,6,6-undecafluorohex-2-ene) or a combination thereof.

77. An apparatus for heat transfer comprising: a device; and a mechanism for transferring heat to or from the device, the mechanism comprising a working fluid that comprises the composition of claim 61.

78. The apparatus for heat transfer of claim 77, wherein the device is selected from a microprocessor, a semiconductor wafer used to manufacture a semiconductor device, a power control semiconductor, an electrochemical cell, a battery pack, an electrical distribution switch gear, a power transformer, a circuit board, a multi-chip module, a packaged or unpackaged semiconductor device, a fuel cell, and a laser.

79. A method of transferring heat comprising: providing a device, wherein the device is selected from a microprocessor, a semiconductor wafer used to manufacture a semiconductor device, a power control semiconductor, an electrochemical cell, a battery pack, an electrical distribution switch gear, a power transformer, a circuit board, a multi-chip module, a packaged or unpackaged semiconductor device, a fuel cell, and a laser; and transferring heat to or from the device using a heat transfer fluid that comprises the composition of claim 61.

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