METHODS AND COMPOSITIONS FOR REMOVAL OF 1243zf FROM 1252zc USING SOLUTIONS OF METAL HYDRIDE CATALYSTS IN LIQUID HYDROSILANES

Abstract

Disclosed herein are a method of preparing a solution of a metal hydride catalyst and a composition for a solution of a metal hydride catalyst, the solution comprising gt; and 50% of a liquid hydrosilane that is both a solvent component of the metal hydride catalyst and a reactant in a process for converting HFO-1243zf in the composition or product stream to HFO-1252zc.

Description

Cross-references to related applications

[0001] This application claims priority to U.S. Provisional Application No. 63 / 527,217, filed July 17, 2023, and U.S. Provisional Application No. 63 / 565,036, filed March 14, 2024, the disclosure of each of which is incorporated herein by reference in its entirety. Technical Field

[0002] The present invention relates to methods and compositions for removing 3,3,3-trifluoropropylene (HFO-1243zf, CF3CH=CH2) from a 1,1-difluoropropylene (HFO-1252zc, CF2=CHCH3) product stream. background

[0003] This invention relates to methods, intermediates, compositions, and uses for the production of difluoroolefins, particularly difluoropropylene. Background Technology

[0004] For decades, the fluorocarbon industry has been striving to find alternative refrigerants to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that are being phased out under the Montreal Protocol. Solutions for many applications involve the commercialization of HFC compounds used as refrigerants, solvents, fire extinguishing agents, foaming agents, and propellants. These currently most widely used new compounds, such as HFC refrigerants, HFC-134a, and HFC-125, have zero ozone depletion potential (ODP) and are therefore unaffected by the current Montreal Protocol phase-out provisions. In addition to ozone depletion, global warming is another environmental concern for many of these applications. According to the UN IPCC Fifth Assessment Report (AR5), HFC refrigerants such as HFC-134a and HFC-125 have global warming potentials (GWPs) of 1,300 and 3,170, respectively.

[0005] This regulatory environment is constantly evolving, and the characteristics taken into consideration are no longer limited to ODP and GWP. More specifically, there is a need for refrigerant compositions that not only meet low ODP standards and have low global warming potential, but also exhibit low or no flammability, provide excellent performance in a variety of applications, and meet the standards of evolving regulations.

[0006] There is a need in the field for novel refrigerants that meet evolving regulations and provide heat transfer and refrigerant properties that meet or exceed those of conventional refrigerants.

[0007] Some fluoropropylenes, such as HFO-1252zc, are potential novel refrigerants. Effective and efficient methods for preparing and purifying HFO-1252zc and its compositions are still needed. Summary of the Invention

[0008] HFO-1252zc is a fluoroolefin compound and a candidate for use as a next-generation refrigerant molecule with the desired low GWP and ODP properties. One route for producing HFO-1252zc involves dehydrofluorinating 1,1,1-trifluoropropane (HFC-263fb, CF3CH2CH3), which yields a product mixture comprising HFO-1252zc and at least HFO-1243zf. In some embodiments, HFO-1243zf is a byproduct present in an amount of 1 mol% to 10 mol% relative to HFO-1252zc. The boiling point of HFO-1243zf is relatively close to that of HFO-1252zc, and therefore makes it difficult, if not impractical, to remove HFO-1243zf from HFO-1252zc using conventional separation techniques such as distillation. Furthermore, various chemical methods for producing HFO-1252zc (including the hydrodefluorination of HFO-1243zf) can produce 1-fluoropropylene (HFO-1261ze) as a minor byproduct with a similar boiling point. Completely separating HFO-1261ze from HFO-1252zc using conventional techniques including distillation may be impractical or impossible.

[0009] One aspect of the invention disclosed herein relates to a method for increasing the HFO-1252zc content of a composition or product stream by contacting a composition or product stream comprising HFO-1252zc and at least HFO-1243zf present at a first level with a solution of a metal hydride catalyst. In some embodiments, the metal hydride catalyst is selected from copper hydride, silver hydride, or gold hydride. In some embodiments, the solution of the metal hydride catalyst comprises a stable ligand and a liquid hydrosilane as a solvent component in the solvent system at >50% w / w relative to the co-solvent. The liquid hydrosilane is also a reactant in the catalytic reaction cycle with the metal hydride catalyst.

[0010] In some embodiments, the liquid hydrosilane is a tetravalent silicon compound containing one or more Si-H bonds, and can be produced by formula R 1 R 2 R 3 SiH is defined, where R 1 R 2 R 3Each is independently H, Alk (C1 to C6 alkyl group), Ar (aryl), SiR3 (silyl), OSiR3 (silyloxy), OR (alkoxy), NR2 (amino), or halogen. Specific examples of liquid hydrosilanes may include triethylsilane, dimethylphenylsilane, and 1,1,3,3-tetramethyldisiloxane. A metal hydride catalyst in the presence of a liquid hydrosilane can selectively and catalytically convert HFO-1243zf to HFO-1252zc as outlined in Scheme 1, thereby reducing the amount of HFO-1243zf in the composition or product stream to a second level relative to HFO-1252zc, which is lower than the first level, such as to less than or equal to about 0.1 mol%, while simultaneously increasing the amount of HFO-1252zc in the product stream.

[0011] (1)

[0012] The second aspect relates to solutions of metal hydride catalysts, wherein a liquid hydrosilane is a solvent component in a solvent system for the metal hydride catalyst, and the solvent system comprises, is substantially composed of, or is composed of any co-solvent in the solvent system at an amount of >50% w / w, >55% w / w, >60% w / w, >70% w / w, >80% w / w, >90% w / w, >95% w / w, or 100%. Solutions of metal hydride catalysts containing more than 50% w / w of liquid hydrosilane can catalytically convert HFO-1243zf to HFO-1252zc with at least 98% or at least 99% selectivity, and are more efficient, while requiring a relatively small amount of metal hydride catalyst solution.

[0013] The second aspect of the implementation includes a solution of a copper hydride catalyst, wherein a liquid hydrosilane is a solvent component in a solvent system for the copper hydride catalyst, and the solvent system comprises, is substantially composed of, or is composed of any cosolvent in the solvent system in an amount of >50% w / w, >55% w / w, >60% w / w, >70% w / w, >80% w / w, >90% w / w, >95% w / w, or 100%.

[0014] In some implementations, the co-solvent can be excluded, and the liquid hydrosilane can be 100% of the solvent system.

[0015] A solution of copper hydride catalyst with more than 50% w / w liquid hydrosilane can catalytically convert HFO-1243zf to HFO-1252zc with at least 98% or at least 99% selectivity and is more efficient, while requiring a relatively small amount of copper hydride catalyst solution.

[0016] The third aspect relates to a method for manufacturing a metal hydride solution, and comprises, substantially comprises, or comprises the following steps: (1) providing a liquid hydrosilane as a solvent component in an amount of >50% w / w, >55% w / w, >60% w / w, >70% w / w, >80% w / w, >90% w / w, >95% w / w, or 100% relative to any co-solvent in the solvent system; (2) contacting the metal hydride or a metal hydride catalyst precursor with a stable ligand and the liquid hydrosilane; (3a) dissolving the metal hydride in the solvent system or (3b) reacting the metal hydride catalyst precursor with the liquid hydrosilane and dissolving it in the solvent to form a solution of general formula Q. x MH y A solution of a metal hydride catalyst, where Q is a stable ligand, MH y It is a metal hydride, where x and y are independent integers from 1 to 3, and M is selected from copper (Cu), silver (Ag), or gold (Au).

[0017] The third aspect of the implementation includes: (1) contacting a Stryker reagent (copper hydride) or a metal acetate (a precursor of a metal hydride catalyst) selected from copper acetate, silver acetate or gold acetate with a stable ligand (Q) and a liquid hydrosilane as a solvent component in an amount of >50% w / w, >55% w / w, >60% w / w, >70% w / w, >80% w / w, >95% w / w or 100% relative to any co-solvent in the solvent system; (2) contacting the Stryker reagent or the metal acetate with the stable ligand and the liquid hydrosilane; (3a) dissolving the Stryker reagent in the solvent system or (3b) reacting the metal acetate with the liquid hydrosilane and dissolving it in the solvent system to form a solution of the metal hydride catalyst at a temperature of about 25°C to 80°C, preferably greater than 25°C to 60°C. An example of a method for manufacturing / producing a solution of a metal hydride catalyst using copper acetate (II) as a precursor of the metal hydride catalyst, triethyl phosphite ((EtO)3P) as a stable ligand (Q) and excess triethylsilane (Et3SiH) as a liquid hydrosilane (both as reactants and solvent components with the metal acetate) can be represented by the reaction shown in scheme (2).

[0018] (2)

[0019] In some embodiments disclosed herein, the metal hydride catalyst has the general formula Q. x MH yThe ligand is essentially composed of or consists of, wherein Q is a stable ligand having one or more binding sites, which may contain phosphorus, nitrogen, oxygen, sulfur, a stable carbide, or a combination thereof. The stable ligand may be selected from the group consisting of PR3, R3PO, NR3, SR2, OR2, or CR2, wherein each R is independently: H, C1-C8 alkyl, aryl, silyl, C1-C8 alkoxy, amino, or a halogen selected from F, Cl, Br, or I, and the metal M is selected from Cu, Au, or Ag, and x and y are independently integers from about 1 to 3. Specific examples of stable ligands may include trialkyl phosphites, including triethyl phosphite.

[0020] In some embodiments, the solution of the metal hydride catalyst contains a cosolvent of less than 50% by weight, less than 25% by weight, or less than 5% by weight relative to the liquid hydrosilane in the solvent system, and may contain 0% by weight of the cosolvent. The cosolvent may include aromatic compounds such as benzene, toluene, xylene, silanes such as hexamethyldisiloxane, or excess stabilizing ligands (Q). The cosolvent may contribute to forming a homogeneous solution of the metal hydride catalyst.

[0021] The fourth aspect disclosed in this article involves HFO-1252zc, HFC-263fb, HFO-1243zf, and metal hydride catalysts (Q). x MH y A composition of a liquid hydrosilane or hydrosiloxane. Some embodiments include a composition in which the metal M may be copper, the stabilizing ligand may be triethyl phosphite, the hydrosiloxane may be tetramethyldisiloxane, and HFO-1243zf may be present in an amount of less than 0.1 mol% or from 0.1 mol% to 10 mol% relative to HFO-1252zc.

[0022] Other aspects disclosed herein relate to mixtures / compositions containing HFO-1252zc and about 0.26% (GC-FID area%) of HFO-1261ze (cis isomer and trans isomer), wherein the composition is not acutely toxic upon inhalation.

[0023] Other aspects disclosed herein relate to compositions comprising or consisting substantially of HFO-1252zc and HFO-1261ze, preferably less than about 50% by weight of HFO-1261ze, more preferably less than about 1% by weight of HFO-1261ze.

[0024] Other aspects disclosed herein relate to a refrigerant composition comprising or consisting substantially of HFO-1252zc and HFO-1261ze in amounts of <about 5% by weight, preferably <about 3% by weight, more preferably less than about 1% by weight.

[0025] Other aspects disclosed herein relate to refrigerant blends comprising or consisting of C3 or C4 fluoroolefins, HFO-1252zc, and <5% by weight, preferably <3% by weight, more preferably <1% by weight of HFO-1261ze, substantially thereof.

[0026] Other aspects disclosed herein relate to compositions of HFO-1252zc and HFO-1261ze (cis and trans isomers).

[0027] Other aspects disclosed herein relate to compositions comprising or substantially comprising HFO-1252zc and HFO-1261ze, based on a total weight of less than 50% by weight of the composition.

[0028] Other aspects disclosed herein relate to compositions comprising or substantially comprising HFO-1252zc and HFO-1261ze based on a total weight of less than about 1% by weight of the composition.

[0029] Other aspects disclosed herein relate to compositions comprising or substantially comprising HFO-1252zc and HFO-1261ze in amounts greater than 0 and less than about 5% by weight.

[0030] Other aspects disclosed herein relate to compositions comprising or substantially comprising at least one C3 or C4 fluoroolefin, HFO-1252zc and less than about 1% by weight of HFO-1261ze.

[0031] Other aspects disclosed herein relate to compositions comprising, consisting of, or substantially consisting of, HFO-1252zc and at least one additional compound selected from E-1-fluoropropene (trans-HFO-1261ze), Z-1-fluoropropene (cis-HFO-1261ze), 1,1,1-trifluoropropane (HFC-263fb), 3,3,3-trifluoropropene (HFO-1243zf) and propylene, wherein the amount of E / Z-HFO-1261ze is less than about 1 wt%.

[0032] Other aspects disclosed herein relate to compositions wherein the amount of E / Z-HFO-1261ze is selected from the group consisting of > about 0 and < about 0.5% by weight, > about 0 and < about 0.25% by weight, and > about 0 and < about 0.1% by weight.

[0033] This summary has described various aspects and embodiments of the invention and is not intended to be limiting. As used herein, one aspect is a defining characteristic of the invention, as may be recited in the independent claims and further disclosed in the detailed description. Embodiments may be considered variations or specific implementations of aspects that may be recited in the dependent claims and further disclosed in the detailed description. Certain exemplary embodiments have been described herein and are for illustrative purposes only and should not be construed as limiting the scope of the invention. Alternative embodiments, including modifications, combinations, and improvements of the exemplary embodiments, will occur to those skilled in the art, and all such alternative embodiments are within the scope of the invention. Detailed Implementation

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In case of any conflict, this specification and its included definitions shall prevail. Although methods and materials similar to or equivalent to those described herein may be used in the practice or testing of embodiments of the invention, suitable methods and materials are described below. Furthermore, materials, methods, and examples are illustrative only and are not intended to be limiting.

[0035] As disclosed in this article, in the pursuit of improving the manufacturing yield of HFO-1252zc, the applicant unexpectedly discovered that metal hydride catalysts (Q x MH y A solution of [a specific compound] can selectively convert HFO-1243zf to HFO-1252zc, regardless of whether HFO-1243zf exists as a pure compound or as a component of a composition or mixture of reaction products containing a large amount of HFO-1252zc, wherein Q is a ligand having one or more binding sites, wherein x and y are independently integers from 1 to 3, and wherein the solution of the metal hydride catalyst substantially comprises a liquid hydrosilane as a solvent component and has a reduced amount of co-solvent. The method of the present invention simultaneously reduces the amount of HFO-1243zf to approximately 0.1 mol% and increases the amount of HFO-1252zc in the composition or product stream.

[0036] Before addressing the details of the implementation schemes described herein, certain terms are defined or clarified as follows.

[0037] As used herein, the term "hydrogen (halo)alkane" means a molecule containing hydrogen, carbon, and optionally fluorine and / or chlorine and / or bromine and / or iodine, and without a carbon-carbon double bond (halogen-fluorine, chlorine, bromine, iodine). Examples are described throughout this specification. The term hydrogen (halo)alkane encompasses both alkanes and halogen-substituted alkanes.

[0038] As used herein, the term “dehydrohalogenation” means the loss of HX from a hydrohalogenated alkane, where X = F, Cl, Br, I, and H and X are located on adjacent carbons in the hydrohalogenated alkane. For example, as used herein, the term “dehydrofluorination” means the process in which hydrogen and fluorine are removed from adjacent carbons in the molecule during this period; and as used herein, the term “dechlorination” means the process in which hydrogen and chlorine are removed from adjacent carbons in the molecule during this period.

[0039] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article of manufacture, or apparatus. Furthermore, unless expressly stated otherwise, “or” refers to an inclusive or non-exclusive or. For example, conditions A or B satisfy any of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0040] The transitional phrase "consistently composed of..." is used to define compositions or methods that include materials, steps, features, components, or elements in addition to those disclosed in the literature, provided that these additionally included materials, steps, features, components, or elements do not significantly affect the essential and novel features of the invention protected by the claims, particularly the mode of action of any process in carrying out the invention to achieve the desired result. The term "consistently composed of..." occupies an intermediate position between "comprising" and "composed of...".

[0041] The transitional phrase "composed of..." does not include any unspecified elements, steps, or components. If included in the claims, protection will not be provided for materials other than those described, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements described in that clause; other elements as a whole are not excluded from the claims.

[0042] Where the applicant has defined the invention or a part thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise stated) that the description should be interpreted as also including inventions using terms such as “substantially composed of” or “composed of”.

[0043] Furthermore, the terms "an" or "a" are used to describe the elements and components described herein. This is for convenience only and to give a general meaning to the scope of the invention. This description should be understood to include one or at least one, and the singular includes the plural, unless it is obvious that it means otherwise.

[0044] When quantities, concentrations, or other values ​​or parameters are given as a list of ranges, preferred ranges, or preferred upper and / or preferred lower limits, it should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred range value and any lower or preferred range value, regardless of whether the range is disclosed individually. Wherever a numerical range is given herein, the range is intended to include its endpoints, as well as all integers and fractions within that range, unless otherwise indicated.

[0045] As used herein, the term “about” is intended to account for variations due to experimental error (e.g., adding or subtracting approximately 10% from the indicated value; ±1%, ±2%, ±3%, … ±10%). Unless otherwise expressly stated, all measurements reported herein should be understood to be modified by the term “about”, whether or not the term is explicitly used.

[0046] Some compounds present in the compositions of this invention may exist as different configurational isomers or stereoisomers. This invention is intended to include all monoconfigurative isomers, monostereomers, or any combination or mixture thereof. Monomeric or multiple isomers of the same compound may be used in any proportion.

[0047] In one respect, the applicant has unexpectedly discovered that a solution of a metal hydride catalyst selected from copper hydride, silver hydride, or gold hydride and a liquid hydrosilane as a solvent at >50% w / w relative to the co-solvent catalytically converts HFO-1243zf to HFO-1252zc with at least 98%, preferably at least 99%, selectivity. The liquid hydrosilane is a reactant in the catalytic reaction cycle with the metal hydride catalyst and is a tetravalent silicon compound containing one or more Si-H bonds, and can be produced by formula R... 1 R 2 R 3 SiH is defined, where R 1 R 2 R 3 Each of these components is independently H, Alk (C1 to C6 alkyl group), Ar (aryl), SiR3 (silyl), OSiR3 (silyloxy), OR (alkoxy), NR2 (amino), or a halogen. Specific examples of liquid hydrosilanes may include triethylsilane, dimethylphenylsilane, and tetramethyldisiloxane. A metal hydride catalyst in the presence of a liquid hydrosilane can selectively and catalytically convert HFO-1243zf to HFO-1252zc as outlined in Scheme 1, thereby reducing the amount of HFO-1243zf in the composition or product stream to less than or equal to about 0.1 mol%, while simultaneously increasing the amount of HFO-1252zc in the composition or product stream.

[0048] (1)

[0049] The second aspect relates to solutions of metal hydride catalysts, wherein a liquid hydrosilane is the solvent component for the metal hydride catalyst, and the solvent comprises, is substantially composed of, or is composed of, a liquid hydrosilane present relative to a cosolvent in amounts of >50% w / w, >55% w / w, >60% w / w, >70% w / w, >80% w / w, >90% w / w, or >95% w / w and 100% w / w, or >90% w / w up to and including 100% w / w. Solutions of metal hydride catalysts having >50% w / w of liquid hydrosilane can catalytically convert HFO-1243zf to HFO-1252zc with at least 98% or at least 99% selectivity, and are more efficient, requiring a relatively small amount of metal hydride catalyst solution.

[0050] The second aspect of the implementation includes a solution of a copper hydride catalyst, wherein a liquid hydrosilane is the solvent component for the copper hydride catalyst, and the solvent comprises, is substantially composed of, or is composed of, a liquid hydrosilane present relative to the co-solvent in amounts of >50% w / w, >55% w / w, >60% w / w, >70% w / w, >80% w / w, >90% w / w, or >95% w / w and 100% w / w, or >90% w / w up to and including 100% w / w. A solution of a copper hydride catalyst having >50% w / w of liquid hydrosilane can catalytically convert HFO-1243zf to HFO-1252zc with at least 98% or at least 99% selectivity and is more efficient, requiring a relatively small amount of copper hydride catalyst solution.

[0051] The third aspect relates to a method for manufacturing a solution of a metal hydride catalyst, and comprises, substantially comprises, or comprises the following steps: (1) providing an excess of liquid hydrosilane as a solvent component in an amount of >50% w / w, >55% w / w, >60% w / w, >70% w / w, >80% w / w, >90% w / w, or >95% w / w, or >90% w / w up to and including 100% w / w; (2) contacting the metal hydride or metal hydride catalyst precursor with a stable ligand and the liquid hydrosilane; and (3a) dissolving the metal hydride in the solvent or (3b) reacting the metal hydride catalyst precursor with the liquid hydrosilane and dissolving it in the solvent to form general formula Q. x MH y A solution of a metal hydride catalyst, where Q is a stable ligand, MH yIt is a metal hydride, where x and y are independent integers from 1 to 3, and M is selected from copper (Cu), silver (Ag), or gold (Au).

[0052] The third aspect of the implementation includes: (1) contacting a Stryker reagent (copper hydride) or a metal acetate selected from copper acetate, silver acetate or gold acetate (a precursor of the metal hydride catalyst) with a stable ligand (Q) and an excess of liquid hydrosilane as a solvent component in an amount of >50% w / w, >55% w / w, >60% w / w, >70% w / w, >80% w / w, >90% w / w or >95% w / w, or >90% w / w up to and including 100% w / w relative to the co-solvent; (2) contacting the Stryker reagent or the metal acetate with the stable ligand and the liquid hydrosilane; and (3a) dissolving the Stryker reagent in a solvent, or (3b) reacting the metal acetate with the liquid hydrosilane and dissolving it in a solvent to form a solution of the metal hydride catalyst at a temperature of about 25°C to 80°C, preferably greater than 25°C to 60°C.

[0053] An example of a method for preparing / producing a solution of a metal hydride catalyst using copper acetate (II) as a precursor of the metal hydride catalyst, triethyl phosphite ((EtO)3P) as a stable ligand (Q) and excess triethylsilane (Et3SiH) as a liquid hydrosilane (both as a reactant and a solvent with the metal acetate) can be represented by the reaction shown in scheme (2).

[0054] (2)

[0055] In some embodiments disclosed herein, the metal hydride catalyst comprises the general formula Q. x MH y The ligand is essentially composed of or consists of, wherein Q is a stable ligand having one or more binding sites, which may comprise phosphorus, nitrogen, oxygen, sulfur, a stable carbide, or a combination thereof. The stable ligand may be selected from the group consisting of PR3, R3PO, NR3, SR2, OR2, or CR2, wherein each R is independently: H, C1-C8 alkyl, aryl, silyl, C1-C8 alkoxy, amino, or a halogen selected from F, Cl, Br, or I, and the metal M is selected from Cu, Au, or Ag, and x and y are independently integers from about 1 to 3. Specific examples of stable ligands may include trialkyl phosphites, including but not limited to triethyl phosphite.

[0056] In some embodiments, the solution of the metal hydride catalyst contains a co-solvent as a solvent in less than about 50% by weight, less than about 25% by weight, or less than about 5% by weight relative to the liquid hydrosilane, and may contain 0% by weight of the co-solvent. The co-solvent may include an aromatic compound, such as benzene, toluene, xylene, a silane such as hexamethyldisiloxane, or an excess of less than about 50% by weight of a stable ligand (Q). The co-solvent may contribute to the formation of a homogeneous solution.

[0057] The fourth aspect disclosed in this article involves HFO-1252zc, HFC-263fb, HFO-1243zf, and metal hydride catalysts (Q). x MH y A composition of a liquid hydrosilane or hydrosiloxane. Some embodiments include a composition in which the metal M may be copper, the stabilizing ligand may be triethyl phosphite, the hydrosiloxane may be tetramethyldisiloxane, and HFO-1243zf may be present in an amount of less than about 0.1 mol% or about 0.1 mol% to about 10 mol% relative to HFO-1252zc.

[0058] In some embodiments of the invention, HFC-263fb can be converted to HFO-1252zc in the liquid and / or gas phases, and the converted HFO-1243zf byproduct can be selectively converted to additional HFO-1252zc in a liquid-phase reactor using a metal hydride catalyst solution. Reactors used for HFC-263fb conversion or for selective HFO-1243zf removal can operate in batch, semi-batch, and continuous modes, and are integrated for continuous operation. The reactors disclosed herein may include preheaters, coolers, evaporators, heat exchangers, feed and effluent lines, units associated with mass transfer, contact vessels (premixers), distillation columns, and valves associated with the reactors, heat exchangers, vessels, columns, and units used in the methods of the various embodiments disclosed herein should also be constructed of corrosion-resistant materials.

[0059] Aspects of the invention will now be described with reference to the following embodiments. Example Example 1 - Preparation of a solution of a metal hydride catalyst in liquid hydrosilane

[0060] A 0.20 M copper hydride catalyst solution in 4.9 M 1,1,3,3-tetramethyldisiloxane (TMDS) was prepared in a dry 500 mL 3-necked RB flask equipped with a heating manifold, magnetic stirrer, condenser connected to a nitrogen manifold, and thermocouple. 10 g of copper(II) acetate monohydrate (50.1 mmol) was added to the flask along with 24.9 g of triethyl phosphite (150 mmol) and 150 g of TMDS. The mixture was heated to approximately 50 °C to approximately 70 °C with magnetic stirring, and the blue-green copper(II) acetate solid slowly dissolved over a period of approximately 12 hours to form a reddish copper hydride catalyst solution. The copper hydride catalyst solution was cooled to ambient temperature and then transferred to 250 mL volumetric flasks. The RB flasks were rinsed twice with an additional approximately 14 g of TMDS and added to the volumetric flasks to adjust the volume to the mark. Example 2 - NMR-scale reaction of HFO-1243zf with a metal hydride catalyst in a solution of liquid hydrosilane

[0061] 0.4 mL of the metal hydride catalyst solution from TMDS in Example 1 was added to a 5 mm NMR tube and then refrigerated in liquid nitrogen. The NMR tube was evacuated and then backfilled with approximately 0.15 mmol of 3,3,3-trifluoropropylene (HFO-1243zf). The NMR tube was then flame-sealed and heated to ambient temperature (approximately 25 °C), and then placed in a 600 MHz NMR spectrometer at the same ambient temperature. Data were collected periodically. 19 F NMR spectra showed that the conversion of HFO-1243zf at 10 hours was at least 99.9%, with a selectivity of 98.4% for HFO-1252zc and a selectivity of 1.4% for HFC-263fb. Example 3 - Preparation of copper(I) hydride catalyst solution

[0062] A solution of copper hydride (I) catalyst in 1,1,3,3-tetramethyldisiloxane (TMDS) was prepared by the reduction reaction of copper acetate (II) with TMDS in the presence of a stable ligand. 20.0 g (0.100 mol) of copper acetate (II) monohydrate was placed in a 1 L 3-necked RB flask under nitrogen atmosphere, equipped with a condenser (15 °C), thermocouple sheath, and heating film. 500 mL (approximately 2.83 mol) of TMDS and 50 mL of triethyl phosphite (approximately 0.29 mol) were added to the flask. The reaction mixture was heated to approximately 50 °C to approximately 70 °C with magnetic stirring, and the solid and blue-green copper acetate (II) slowly dissolved over approximately 3 hours, releasing hydrogen gas to form a reddish-brown solution of the copper hydride (I) catalyst. Example 4 - Hydrodefluorination of HFO-1243zf to produce HFO-1252zc and HFO-1261ze as byproducts

[0063] 250 mL of the catalyst solution from Example 3 was loaded into a evacuated 600 mL Hastelloy Parr reactor. The reactor contents were heated to approximately 60 °C with stirring, and then 206 g (approximately 2.15 mol) of HFO-1243zf was added over 1 to 2 hours to maintain the reaction temperature at 60 °C in the reactor cooling loop. The reaction mixture was stirred at 60 °C for 21 hours. At this point, the gas sample from the headspace of the Parr reactor was analyzed by gas chromatography-mass spectrometry (MS) and flame ionization (FID), showing that the remaining HFO-1243zf was less than 500 ppm. The crude HFO-1252zc product vapor (177 g) at 60 °C was then transferred to a evacuated 300 mL Hoke cylinder chilled in dry ice. The liquid sample from the Hoke cylinder was analyzed by gas chromatography after warming to ambient room temperature. Table 1 below shows that the composition of the reactor headspace and the liquid sample in the Hoke cylinder both contain HFO-1252zc and HFO-1261ze.

[0064] Example 5 - Distillation purification of crude HFO-1252zc .

[0065] The crude HFO-1252zc product from Example 4 was transferred to an insulated glass distillation apparatus comprising an 18-inch jacketed distillation column containing stainless steel Pro-Pak. ® Distillation packing material and a distillation head incorporating a dry ice condenser and needle valve were used to regulate the extraction rate. The major distillate fraction, boiling at -29°C, was collected in a Hokke cylinder purged with nitrogen and cooled to dry ice. Liquid samples from the Hokke cylinders were analyzed by gas chromatography upon warming to ambient room temperature. Table 2 below shows that the purified HFO-1252zc contained 0.26% of the HFO-1261ze isomer.

[0066] Example 6 - Acute inhalation toxicity of 1252zc containing 1261ze byproduct .

[0067] A sample of the purified HFO-1252zc mixture from Example 4 was administered at 50,000 ppm in a 1-hour acute inhalation study in a rat model. No deaths following inhalation were reported at the end of the prescribed observation period. Example 7 - Processing of a product stream containing 1252zc and 1243zf byproducts

[0068] Assembly by Hastelloy ®A 600 mL pressure reactor, constructed of C276 and including a pressure vessel and a reactor head with a magnetic-mechanical stirrer, was leak-tested with 125 psig nitrogen and then evacuated. 100 mL of the copper hydride catalyst solution from the TMDS of Example 1 was transferred to the pressure reactor. The reaction vessel was refrigerated with dry ice, and approximately 44 liters (STP) of the product stream containing HFO-1252zc and 5 mol% of HFO-1243zf byproducts from the gaseous defluorination of HFC-263fb was condensed into the pressure reactor. The contents of the pressure reactor were heated and maintained at 45°C with stirring. The vapor space was sampled at 8 hours and analyzed by gas chromatography-mass spectrometry (GC-MS). The concentration of HFO-1243zf retained in the product stream was less than 0.1 mol. Example 8 - Preparation of copper(I) catalyst solution in a solvent system containing a co-solvent

[0069] A solution of copper hydride (I) catalyst in a solvent system containing 60% (v / v) 1,1,3,3-tetramethyldisiloxane (TMDS) and 40% (v / v) benzene was prepared by the reduction reaction of copper acetate (II) with TMDS in the presence of a stable ligand. 12.0 g (0.0600 mol) of copper acetate (II) monohydrate was placed in a 1 L 3-necked RB flask under nitrogen atmosphere, equipped with a condenser (15 °C), thermocouple sheath, and heating film. 228 g (approximately 1.70 mol) of TMDS, 176 g (approximately 200 mL) of benzene, and 31 mL of triethyl phosphite (approximately 0.18 mol) were added to the flask. The reaction mixture was heated to 50 °C to 70 °C with magnetic stirring, and the solid and blue-green copper acetate (II) slowly dissolved over approximately 3 hours, releasing hydrogen gas to form a reddish-brown copper hydride (I) catalyst solution. Other implementation plans

[0070] Implementation Scheme 1: A method comprising: a) contacting a composition or product stream comprising 3,3,3-trifluoropropene (HFO-1243zf, CF3CH=CH2) with a solution of a metal hydride catalyst comprising a stable ligand and a liquid hydrosilane as a solvent component in a solvent system, wherein the amount of HFO-1243zf is present at a first level, and wherein the composition or product stream optionally further comprises 1,1-difluoropropene (HFO-1252zc, CF2=CHCH3); b) selectively converting the HFO-1243zf to HFO-1252zc with the solution of the metal hydride catalyst to reduce the amount of HFO-1243zf in the composition or product stream to a second level below the first level, wherein the level of HFO-1243zf is relative to the HFO-1252zc in the product stream, and wherein the solution of the metal hydride catalyst contains more than 50% relative to any co-solvent. The liquid hydrosilane as a solvent component in the solvent system, w / w.

[0071] Implementation Scheme 2, according to the method of claim 1, wherein the stable ligand is triethyl phosphite, and wherein the liquid hydrosilane is selected from the group consisting of triethylsilane, dimethylphenylsilane, and 1,1,3,3-tetramethyldisiloxane.

[0072] Implementation scheme 3 is the method according to any one of claims 1 and 2, wherein any co-solvent is excluded, and the liquid hydrosilane is 100% of the solvent system.

[0073] Implementation scheme 4 is the method according to any one of claims 1 to 3, wherein the stable ligand has one or more binding sites.

[0074] Implementation Scheme 5, according to any one of claims 1 to 4, wherein the metal hydride in the solution of the metal hydride catalyst is selected from the group consisting of copper hydride, silver hydride and gold hydride.

[0075] Implementation Scheme 6, according to any one of claims 1 to 5, wherein the product stream further comprises 1,1,1-trifluoropropane (HFC-263fb, CF3CH2CH3).

[0076] Implementation Scheme 7 A method for producing a solution of a metal hydride catalyst, the method comprising: a) providing a liquid hydrosilane as a solvent component in a solvent system in an amount >50% w / w relative to any co-solvent; b) contacting a metal hydride or a metal hydride catalyst precursor with a stable ligand and the liquid hydrosilane; c) dissolving the metal hydride in the solvent system to form the solution of the metal hydride catalyst, or reacting the metal hydride catalyst precursor with the liquid hydrosilane and dissolving it in the solvent system to form the solution of the metal hydride catalyst.

[0077] Implementation scheme 8, according to the method of claim 7, wherein the metal hydride is a Stryker reagent, and the metal hydride catalyst precursor is selected from the group consisting of copper acetate, silver acetate, and gold acetate.

[0078] Implementation Scheme 9: The method according to any one of claims 7 to 8, wherein the liquid hydrosilane is a tetravalent silicon compound containing one or more Si-H bonds, and is derived from formula R. 1 R 2 R 3 SiH is defined, where R 1 R 2 and R 3 Each is independently selected from the group consisting of H, Alk (C1 to C6 alkyl groups), Ar (aryl), SiR3 (silyl), OSiR3 (silyloxy), OR (alkoxy), NR2 (amino), and halogens.

[0079] Implementation scheme 10 is the method according to any one of claims 7 to 9, wherein the stable ligand comprises triethyl phosphite.

[0080] Implementation scheme 11 is the method according to any one of claims 7 to 10, wherein any co-solvent is excluded, and the liquid hydrosilane as a solvent component is 100% of the solvent system.

[0081] Implementation scheme 12 is the method according to any one of claims 7 to 11, wherein any co-solvent is selected from the group consisting of benzene, toluene, xylene, silane or an excess of the stable ligand.

[0082] Implementation Scheme 13: A solution of a metal hydride catalyst, said solution comprising a stable ligand and a liquid hydrosilane as a solvent component in the solvent system at >50% relative to any co-solvent.

[0083] Implementation Scheme 14: The solution according to claim 13, wherein the metal hydride catalyst has the general formula QxM-Hy, wherein Q is the stable ligand, M-Hy is the metal hydride, x and y are independent integers from 1 to 3, and M is selected from the group consisting of copper (Cu), silver (Ag), and gold (Au).

[0084] Embodiment 15 is a solution according to any one of claims 13 to 14, wherein the stable ligand comprises phosphorus, nitrogen, oxygen, sulfur, a stable carbide, or a combination thereof, and wherein the stable ligand is selected from PR. 3 R 3 PO, NR 3 SR 2 OR 2 Or: CR 2 A group consisting of each R 2 and R 3 Each is independently selected from the group consisting of: H, C1-C8 alkyl, aryl, silyl, C1-C8 alkoxy, amino, and halogens selected from the group consisting of F, Cl, Br, and I.

[0085] Implementation Scheme 16 is a solution according to any one of claims 13 to 15, wherein the stable ligand comprises triethyl phosphite.

[0086] Embodiment 17 is a solution according to any one of claims 13 to 16, wherein the liquid hydrosilane is a tetravalent silicon compound containing one or more Si-H bonds, and is derived from formula R. 1 R 2 R 3 SiH is defined, where R 1 R 2 R3 is independently selected from the group consisting of H, Alk (C1 to C6 alkyl groups), Ar (aryl), SiR3 (silyl), OSiR3 (silyloxy), OR (alkoxy), NR2 (amino), and halogens.

[0087] Implementation Scheme 18 is a solution according to any one of claims 13 to 17, wherein the liquid hydrosilane is selected from the group consisting of triethylsilane, dimethylphenylsilane or 1,1,3,3-tetramethyldisiloxane.

[0088] Implementation scheme 19, the solution according to any one of claims 13 to 18, further comprises HFC-263fb, HFO-1252zc and HFO-1243zf.

[0089] Implementation Scheme 20: The solution according to any one of claims 13 to 19, wherein any co-solvent is excluded, and the liquid hydrosilane as a solvent component is 100% of the solvent system.

[0090] Implementation Scheme 21: A composition comprising HFO-1252zc and E / Z-1-fluoropropylene (E / Z-HFO-1261ze).

[0091] Embodiment 22: The composition of claim 21, wherein the composition comprises less than about 50% by weight of E / Z-HFO-1261ze.

[0092] Implementation scheme 23 is the composition according to any one of claims 21 to 22, wherein the composition comprises less than about 1% by weight of E / Z-HFO-1261ze.

[0093] Embodiment 24 A refrigerant composition comprising HFO-1252zc and an amount of E / Z-HFO-1261ze greater than 0% by weight and less than about 5% by weight.

[0094] Implementation Scheme 25: A refrigerant comprising at least a C3 or C4 fluoroolefin, HFO-1252zc, and less than about 1% by weight of E / Z-HFO-1261ze.

[0095] Embodiment 26 A composition comprising 1,1-difluoropropene (HFO-1252zc) and at least one additional compound selected from the group consisting of E-1-fluoropropene (trans-HFO-1261ze), Z-1-fluoropropene (cis-HFO-1261ze), 1,1,1-trifluoropropane (HFC-263fb), 3,3,3-trifluoropropene (HFO-1243zf) and propylene, wherein the amount of E / Z-1-fluoropropene is less than about 1 wt%.

[0096] Embodiment 27 is the composition according to claim 26, wherein the amount of E / Z-1-fluoropropylene is selected from one of > about 0 and < about 0.5% by weight, > about 0 and < about 0.25% by weight, and > about 0 and < about 0.1% by weight.

[0097] While certain aspects, embodiments, and principles have been described above, it should be understood that this description is exemplary only and not intended to limit the invention or the appended claims. The various aspects, embodiments, and principles described above can be used individually or in combination with each other.

Claims

1. A method comprising: a) Contacting a composition or product stream containing 3,3,3-trifluoropropylene (HFO-1243zf, CF3CH=CH2) with a solution of a metal hydride catalyst containing a stable ligand and a liquid hydrosilane as a solvent component in a solvent system, wherein the amount of HFO-1243zf is present at a first level, and wherein the composition or product stream optionally further comprises 1,1-difluoropropylene (HFO-1252zc, CF2=CHCH3); and b) Selectively converting HFO-1243zf to HFO-1252zc using the solution of the metal hydride catalyst to reduce the amount of HFO-1243zf in the composition or product stream to a second level below the first level. The level of HFO-1243zf is relative to HFO-1252zc in the product stream, and the solution of the metal hydride catalyst contains liquid hydrosilane as a solvent component in the solvent system at a concentration greater than 50% w / w relative to any co-solvent.

2. The method according to claim 1, wherein the stable ligand is triethyl phosphite, and wherein the liquid hydrosilane is selected from the group consisting of triethylsilane, dimethylphenylsilane and 1,1,3,3-tetramethyldisiloxane.

3. The method according to any one of claims 1 and 2, wherein any co-solvent is excluded, and the liquid hydrosilane is 100% of the solvent system.

4. The method according to any one of claims 1 to 3, wherein the stable ligand has one or more binding sites.

5. The method according to any one of claims 1 to 4, wherein the metal hydride in the solution of the metal hydride catalyst is selected from the group consisting of copper hydride, silver hydride and gold hydride.

6. The method according to any one of claims 1 to 5, wherein the product stream further comprises 1,1,1-trifluoropropane (HFC-263fb, CF3CH2CH3).

7. A method for producing a solution of a metal hydride catalyst, the method comprising: a) Provide liquid hydrosilane as a solvent component in an amount >50% w / w relative to any cosolvent in the solvent system; b) Contact the metal hydride or metal hydride catalyst precursor with the stable ligand and the liquid hydrosilane; c) Dissolving the metal hydride in the solvent system to form the solution of the metal hydride catalyst, or reacting the metal hydride catalyst precursor with the liquid hydrosilane and dissolving it in the solvent system to form the solution of the metal hydride catalyst.

8. The method according to claim 7, wherein the metal hydride is a Stryker reagent, and the metal hydride catalyst precursor is selected from the group consisting of copper acetate, silver acetate, and gold acetate.

9. The method according to any one of claims 7 to 8, wherein the liquid hydrosilane is a tetravalent silicon compound containing one or more Si-H bonds, and is derived from formula R. 1 R 2 R 3 SiH is defined, where R 1 R 2 and R 3 Each is independently selected from the group consisting of H, Alk (C1 to C6 alkyl groups), Ar (aryl), SiR3 (silyl), OSiR3 (silyloxy), OR (alkoxy), NR2 (amino), and halogens.

10. The method according to any one of claims 7 to 9, wherein the stable ligand comprises triethyl phosphite.

11. The method according to any one of claims 7 to 10, wherein any co-solvent is excluded, and the liquid hydrosilane as a solvent component is 100% of the solvent system.

12. The method according to any one of claims 7 to 11, wherein any co-solvent is selected from the group consisting of benzene, toluene, xylene, silane or an excess of the stable ligand.

13. A solution of a metal hydride catalyst, said solution comprising a stable ligand and a liquid hydrosilane as a solvent component in a solvent system, comprising >50% relative to any co-solvent.

14. The solution according to claim 13, wherein the metal hydride catalyst has the general formula QxM-Hy, wherein Q is the stable ligand, M-Hy is the metal hydride, x and y are independent integers from 1 to 3, and M is selected from the group consisting of copper (Cu), silver (Ag) and gold (Au).

15. The solution according to any one of claims 13 to 14, wherein the stable ligand comprises phosphorus, nitrogen, oxygen, sulfur, a stable carbide, or a combination thereof, and wherein the stable ligand is selected from PR. 3 R 3 PO, NR 3 SR 2 OR 2 Or: CR 2 A group consisting of each R 2 and R 3 Each is independently selected from the group consisting of: H, C1-C8 alkyl, aryl, silyl, C1-C8 alkoxy, amino, and halogens selected from the group consisting of F, Cl, Br, and I.

16. The solution according to any one of claims 13 to 15, wherein the stable ligand comprises triethyl phosphite.

17. The solution according to any one of claims 13 to 16, wherein the liquid hydrosilane is a tetravalent silicon compound containing one or more Si-H bonds, and is derived from formula R. 1 R 2 R 3 SiH is defined, where R 1 R 2 R3 is independently selected from the group consisting of H, Alk (C1 to C6 alkyl groups), Ar (aryl), SiR3 (silyl), OSiR3 (silyloxy), OR (alkoxy), NR2 (amino), and halogens.

18. The solution according to any one of claims 13 to 17, wherein the liquid hydrosilane is selected from the group consisting of triethylsilane, dimethylphenylsilane or 1,1,3,3-tetramethyldisiloxane.

19. The solution according to any one of claims 13 to 18 further comprises HFC-263fb, HFO-1252zc and HFO-1243zf.

20. The solution according to any one of claims 13 to 19, wherein any co-solvent is excluded, and the liquid hydrosilane as a solvent component constitutes 100% of the solvent system.

21. A composition comprising HFO-1252zc and E / Z-1-fluoropropylene (E / Z-HFO-1261ze).

22. The composition of claim 21, wherein the composition comprises less than about 50% by weight of E / Z-HFO-1261ze.

23. The composition according to any one of claims 21 to 22, wherein the composition comprises less than about 1% by weight of E / Z-HFO-1261ze.

24. A refrigerant composition comprising HFO-1252zc and an amount of E / Z-HFO-1261ze greater than 0% by weight and less than about 5% by weight.

25. A refrigerant comprising at least a C3 or C4 fluoroolefin, HFO-1252zc and less than about 1% by weight of E / Z-HFO-1261ze.

26. A composition comprising 1,1-difluoropropene (HFO-1252zc) and at least one additional compound selected from the group consisting of E-1-fluoropropene (trans-HFO-1261ze), Z-1-fluoropropene (cis-HFO-1261ze), 1,1,1-trifluoropropane (HFC-263fb), 3,3,3-trifluoropropene (HFO-1243zf) and propylene, wherein the amount of E / Z-1-fluoropropene is less than about 1 wt%.

27. The composition according to claim 26, wherein the amount of E / Z-1-fluoropropylene is selected from the group consisting of > about 0 and < about 0.5% by weight, > about 0 and < about 0.25% by weight, and > about 0 and < about 0.1% by weight.

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