Process for producing hydrochloro(fluoro)carbon compounds

Abstract

Provided herein is a process involving contacting a haloalkane reactant with an olefin in the presence of a catalyst system to produce a product stream including a haloalkane insertion product, wherein the product stream contains less than about 10 wt.% of byproduct telomers, oligomers, dimers and / or other polymeric products, as well as compositions produced by this process.

Description

TITLE OF THE INVENTIONPROCESS FOR PRODUCING HYDROCHLORO(FLUORO)CARBON COMPOUNDSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Patent Application No. 63 / 662,866, filed June 21, 2024, the disclosure of which is incorporated herein by reference in its entirety.FIELD OF THE INVENTION

[0002] The present invention is directed to processes for producing hydrochloro(fluoro)carbon compounds with reduced or no formation of byproduct telomers.BACKGROUND OF THE INVENTION

[0003] The fluorocarbon industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for many applications has been the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, foam blowing agents and propellants. In addition to ozone depleting concerns, global warming is another environmental concern in many of these applications. Thus, there is a need for compositions that meet both low ozone depletion standards as well as having low global warming potentials. Certain hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) are believed to meet both goals.

[0004] Catalyzed reactions of haloalkanes to form hydrochloro(fluoro)carbon compounds are known in the art. Such hydrochloro(fluoro)carbons are often useful materials for the production of fluoroalkanes, particularly hydrofluoroalkanes and more particularly HFCs, and fluoroolefins, particularly HCFOs and HFOs. These compounds are useful as refrigerants, fire extinguishants, heat transfer media, propellants, foaming agents, gaseous dielectrics, sterilant carriers, polymerizationmedia, particulate removal fluids, carrier fluids, buffing abrasive agents, displacement drying agents and power cycle working fluids.

[0005] Although the preparation of such hydrochloro(fluoro)carbon starting materials has been in commercial practice for several decades, the industry continues to seek improvement in these processes to achieve efficiency and waste reduction. For example, the products of the conventional reactions to produce these starting materials also include varying amounts of telomers as byproducts, which must then be separated from the product stream and disposed of as waste. It would be desirable to provide an improved process for producing such starting materials that minimizes the formation of telomer byproducts.SUMMARY OF THE INVENTION

[0006] In one aspect, the present invention relates to a process comprising contacting a haloalkane reactant with an olefin in the presence of a catalyst system to produce a product stream comprising a haloalkane insertion product, wherein the product stream contains less than about 10 wt.% of byproduct telomers, oligomers, dimers and / or other polymeric products.

[0007] In one aspect, the present invention relates to a process comprising contacting a haloalkane reactant with an olefin in the presence of a catalyst system to produce a product stream comprising a haloalkane insertion product, wherein selectivity of the haloalkane insertion product is between about 90% to about 99.5% and wherein selectivity of byproduct telomers, oligomers, dimers and / or other polymeric products is less than 10%.

[0008] In one embodiment, the process is carried out at a reduced pressure, for example, in the range of about 15 psig to about 50 psig, or about 25 psig to about 50 psig, or about 20 psig, or about 25 psig, or about 30 psig, or about 35 psig, or about 40 psig, or about 45 psig, or about 50 psig.

[0009] In one embodiment, the process is carried out in the presence of a moisture content of less than about 1000 ppm, or less than about 750 ppm, or less than about 500 ppm.

[0010] In one aspect, the present invention relates to a composition comprising (i) HCC-240fa, (ii) one or more additional compounds selected from the group consisting of 1 -chlorobutane; 1 ,2,3-trichloropropene (CHCI=CCI-CH2CI, HCO- 1240xd); HCO-1230xd (CHCI=CCI-CHCI2, 1 ,2,3,3-tetrachloropropene); 1 ,1 , 1 ,3- tetrachloropropane (CCI3-CH2-CH3, HCC-250fb); 1 ,4 dichlorobutane; 1 ,2-dichloro- cyclobutane, 1 ,1 ,4,4-tetrachlorobutadiene; 1 ,1 , 3, 4 tetrachlorobutadiene; 1 , 1 ,1 , 2,3- pentachloropropane (HCC-240db); 1 ,1 ,3,3-tetrachloro-1-propene (CCI2=CH-CHCI2); C5H7CI3 isomer(s); C4H7CI3 isomer(s), and (iii) byproduct (higher molecular weight) telomers, oligomers, dimers and other polymers of the formula CC (CH2CHCI)nCI, where n > 2, wherein the composition contains less than about 10 wt% of the CCl3(CH2CHCI)nCI byproducts.

[0011] In one aspect, the present invention relates to a composition comprising (i) HCC-230fa, (ii) one or more additional compounds selected from the group consisting of from CCI3CCI2CH2CI, CCI3CCIHCH2CI and CCI3CH2CH2CI, and (iii) byproduct (higher molecular weight) telomers, oligomers, dimers and other polymers of the formula CCl3(CH2CCl2)nCI, where n > 2, wherein the composition contains less than about 10 wt% of the CCl3(CH2CCl2)nCI byproducts.DETAILED DESCRIPTION OF THE INVENTION

[0012] The invention provides a process for preparing a haloalkane, and more particularly a hydrochloro(fluoro)carbon.

[0013] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0014] 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.

[0015] The transitional phrase "consisting essentially of" is used to define a composition, method or apparatus 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. The term 'consisting essentially of occupies a middle ground between “comprising” and 'consisting of'.

[0016] 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 describe such an invention using the terms “consisting essentially of’ or “consisting of.”

[0017] 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.

[0018] Unless otherwise defined, as used herein, the term “about” is understood as within a range of normal tolerance in the art, for example within 2 standard deviations of the mean. “About” can be understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value, preferably as within 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value. Unless otherwise clear from the context, all numerical values provided herein are modified by the term “about.”

[0019] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the disclosed compositions, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a particularpassage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

[0020] In one embodiment, the present invention relates to a process, and more particularly an olefin insertion process, comprising contacting a haloalkane reactant with an olefin in the presence of a catalyst system to produce a haloalkane product, wherein the process is carried out under reaction conditions which suppress or minimize formation of byproduct telomers, oligomers, dimers and other polymeric products. More particularly, the olefin insertion process comprises contacting a haloalkane reactant with an olefin in the presence of a catalyst system to produce a haloalkane product, wherein the process is carried out under reaction conditions which suppress or minimize multiple adducts of the olefin to halogenated carbons. In some embodiments, the product stream produced by the reaction comprises the haloalkane product and less than about 10 wt.% of byproduct telomers, oligomers, dimers and / or other polymeric products, preferably at least byproduct telomers, oligomers and dimers, and more preferably at least byproduct telomers and / or oligomers. In some embodiments, the product stream produced by the reaction comprises the haloalkane product and less than about 10 wt.% of byproduct telomers, oligomers, dimers and / or other polymeric products, more preferably less than about 8 wt.%, more preferably less than about 6 wt.%, or less than about 5 wt.%, or less than about 4 wt.%, or less than about 3 wt.%, or less than about 2 wt.% or less than about 1 wt.%, or less than about 0.5 wt.%, based on a total weight of the product stream (also referred to herein as reaction mixture or composition).

[0021] In some embodiments, the process is carried out under reaction conditions which enhance the yield of the target haloalkane product relative to the undesired (higher molecular weight) telomers. In particular, a reduced reaction pressure, preferably in the range of about 15 psig to about 50 psig, or about 20 psig, or about 25 psig, or about 30 psig, or about 35 psig, or about 40 psig, or about 45 psig, or about 50 psig, and all values and ranges therebetween, can reduce the formation of telomers, oligomers, dimers and / or other polymeric products, as described in further detail herein.

[0022] Metal salts, especially metal halides, and organic phosphate esters or nitrile complexes produces free chloride ions, trace HCI formation and / or iron halides which, in the presence of moisture, lead to free chloride in an acidic environment and corrosive media. Accordingly, in some embodiments, the total moisture present in the reactor is controlled or maintained to be below 500 ppm, preferably below 200 ppm, more preferably below 100 ppm, to minimize corrosion in the reaction.

[0023] In some embodiments, the process further comprises separating the haloalkane product from the product stream as a useful starting material for the production of various types of fluorochemicals, such as HFCs and HFOs.

[0024] In some embodiments, the process further comprises recovery and recycling of unreacted haloalkane reactant to the feed stream.

[0025] In some embodiments, haloalkanes useful in the process of the invention are of the formula CnHmXp wherein n is an integer from 1 to 200, preferably from 1 to 20, most preferably from 1 to 5, X is a halogen such as fluorine, chlorine, bromine, iodine, or mixtures thereof, and m and p are each independently 0 to 2n+2 provided that m+p=2n+2. In one embodiment, the haloalkane reactant is a C1 to C5 compound. In another embodiment, the haloalkane reactant is a C1 , C2 or C3 compound.

[0026] In some embodiments, the haloalkane reactant is selected from chlorocarbons, chlorofluorocarbons, hydrochlorocarbons and hydrochlorofluorocarbons.

[0027] In one embodiment, chlorocarbons are compounds having only carbon and chlorine, including but not limited to carbon tetrachloride (CCU), perchloroethane (CCI3CCI3), and the like. In one embodiment, the haloalkane reactant is carbon tetrachloride.

[0028] In one embodiment, chlorofluorocarbons are compounds having carbon, hydrogen, fluorine, and chlorine, including but not limited to dichlorodifluoromethane (CCI2F2), trichlorofluoroethane (CCI3F), 1 ,1 ,1-trichloro-2,2,2-trifluoroethane (CFC- 113a, CF3CCI3), 1 ,1 ,2-trichloro-1 ,2,2- trifluoroethane (CFC-113, CF2CICFCI2), and the like. In one embodiment, the haloalkane reactant is CFC-113a.

[0029] In some embodiments, the moisture content of the haloalkane feed is preferably less than about 100 ppm, or less than about 50 ppm, or less than about 30 ppm, inclusive of all values and ranges therebetween.

[0030] In some embodiments, olefins useful in the process of the present invention are of the formula CnHyXz wherein n is an integer from 2 to 200, preferably from 2 to 20 and most preferably from 2 to 4, X is a halogen such as fluorine, chlorine, bromine, iodine, or mixtures thereof, and y and z are each independently 0 to 2n provided that y+z=2n.

[0031] In one embodiment, the olefin is an unsaturated hydrocarbon, with at least one double bond, optionally substituted with Cl, F or combinations thereof. In another embodiment, the olefin is selected from vinyl chloride (CH2=CHCI), 3,3,3- trifluoropropene (CF3CH=CH2), vinyl fluoride (CH2=CHF), vinylidene chloride (CH2=CCl2), vinylidene fluoride (CH2=CF2), allyl chloride (CH2=CHCH2CI), and the like. In some embodiments, the olefin is vinyl chloride, vinylidene chloride or 3,3,3- trifluoropropene.

[0032] In some embodiments, the olefin is not ethylene. More particularly, in some embodiments, the listing of potential compounds which may be utilized as the olefin reactant in the process of the present invention excludes ethylene.

[0033] In some embodiments, the moisture content of the olefin feed is preferably less than about 100 ppm, or less than about 50 ppm, or less than about 30 ppm, inclusive of all values and ranges therebetween.

[0034] The catalyst system preferably comprises, consists essentially of or consists of a catalyst and a co-catalyst.

[0035] In some embodiments, the catalysts useful in the present invention include metal ions and neutral metallic species. Suitable catalysts include, for example, but are not limited to, cuprous salts, organometallic cuprous compounds, metallic iron components, metallic nickel components and iron chlorides. Exemplary cuprous salts and organometallic cuprous compounds include, without limitation, cuprous chloride (CuCI), cuprous bromide, cuprous cyanide, cuprous sulfate, and cuprous phenyl.The iron powder useful in this invention is preferably a fine powder of pure metalliciron, preferably with a particle size smaller than 325 mesh. Preferably, cuprous chloride or iron powder is used as the catalyst.

[0036] In certain embodiments, the metallic iron component of the catalyst may be from any source (including a combination of sources) of an iron component, may be any iron containing species such as FeCh and FeCh, and may be iron powder, iron shavings, iron wire, iron screen or iron turnings. In other embodiments, copper or copper halides may be used in combination with an organic nitrile compound, such as but not limited to acetonitrile or propionitrile.

[0037] In certain embodiments, the metallic iron component of the catalyst may be from any source (including a combination of sources) of a nickel component, may be any nickel containing species, and may be nickel powder, nickel shavings, nickel wire, nickel screen, nickel shots or nickel turnings.

[0038] Co-catalysts useful in the present invention include, but are not limited to, organic ligands capable of forming a complex with the catalyst used and capable of bringing the catalyst into solution.

[0039] In some embodiments, suitable ligands include organic amines, such as, without limitation, tert-butylamine, n-butylamine, sec-butylamine, 2-propylamine, benzylamine, tri-n-butylamine, pyridine and combinations thereof. In one embodiment, the preferred organic amine is tert-butylamine. Alternatively, the cocatalyst may be a nitrile including, without limitation, acetonitrile, propionitrile, n- butyronitrile, benzonitrile, phenylacetonitrile and combinations thereof. In one embodiment, the preferred nitrile is acetonitrile particularly where the catalyst is a copper containing material.

[0040] As another alternative, the co-catalyst may be an amide including, without limitation, hexamethylphosphoramide (HMPA), dimethylformamide and combinations thereof. In one embodiment, hexamethylphosphoramide is the most preferred amide. Also suitable are combinations of amines, nitriles, amides, phosphines and phosphates.

[0041] The co-catalysts are chelating agents and may also serve as solvents. In some embodiments, a solvent may help dissolve the solid catalyst. When a solvent is used, it preferably serves as the co-catalyst. Useful solvents non-exclusivelyinclude nitrile compounds. The catalysts, co-catalysts and solvents useful in the present invention are commercially available.

[0042] In some embodiments, the co-catalyst is a phosphorous containing compound, such as a phosphine ligand, such as an alkylphosphine or arylphosphine, including but not limited to triphenyl phosphine, tributyl phosphine and the like. In one embodiment, the phosphine ligand comprises triphenylphosphine. In another embodiment, the phosphine ligand consists essentially of triphenylphosphine. In another embodiment, the phosphine ligand consists of triphenylphosphine.

[0043] In other embodiments, the catalyst may comprise a phosphorous containing compound, such as a phosphate ligand, such as but not limited to, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, diethyl phosphate, dibutyl phosphate, monophenyl phosphate, monobutyl phosphate, dimethylphenyl phosphate, diethylphenyl phosphate, dimethyethyl phosphate, phenyl ethyl methyl phosphate, and a C5 to C20 long chain phosphate.

[0044] The catalysts and co-catalysts useful in the present invention form a catalyst system. In one embodiment, the catalyst is selected from cuprous salts, organometallic cuprous compounds, iron wire, iron shavings, iron powder, iron chlorides, nickel powder, nickel shavings, nickel wire, nickel screen, nickel shots or nickel turnings. In one embodiment, the co-catalyst is selected from organic amines, nitriles, amides, phosphates, phosphines and combinations thereof.

[0045] In one embodiment of the catalyst system, the catalyst is CuCI and the co- catalyst is acetonitrile (CH3CN), tert-butylamine (t-Bu-NH2), n-butylamine (n-Bu-NH2), sec-butylamine (sec-Bu-NH2), benzyl-amine (benzyl-NH2), ethanol-amine, pyridine or tri-n-butylamine (n-BusN). In another embodiment of the catalyst system, the catalyst is iron powder, or iron wire, and / or ferric chloride and the co-catalyst is HMPA, tributylphosphite((BuO)3P), trichloroethylphosphite((CICH2CH2O)3P), triphenylphosphite((PhO)3P), tributylphosphate, or triphenylphosphate. In another embodiment of the catalyst system, the catalyst system is cuprous chloride / tert- butylamine, cuprous chloride / acetonitrile, iron powder / hexamethylphosphoramide or iron powder / tributylphosphate. Most preferably, cuprous chloride / tert-butylamine or iron powder / tributylphosphate is used.

[0046] In some embodiments, the iron catalyst comprises iron metal, iron oxide, iron hydrate, and / or iron hydroxide during the reaction start-up or when a new iron catalyst is introduced to replace an old or spent catalyst. However, over the course of the reaction, the iron halides concentration increases and thus iron halide become the dominant catalyst of the catalyst system.

[0047] In some embodiments, the moisture content of the catalyst system is preferably less than about 1000 ppm, or less than about 750 ppm, or less than about 500 ppm, inclusive of all values and ranges therebetween.

[0048] In one embodiment, the haloalkane insertion product preferably comprises at least one hydrochloro(fluro)carbon, and more particularly a hydrochlorocarbon or hydrochlorofluorocarbon. More particularly, in some embodiments, the haloalkane insertion product is represented by the formula R1CH2R2, where R1is a halogenated or partially halogenated C1 to C4 compound, optionally branched, and where R2is one of (i) CHxC -x, where x is an integer from 0 to 1 ; (ii) CHxFyC , where x is an integer from 0 to 1 and y is an integer from 0 to 1 ; or (iii) CHCICF3.

[0049] In one embodiment, hydrochlorocarbons produced by the process of the present invention are compounds having carbon, hydrogen, and chlorine, including but not limited to chloromethane (CH3CI), methylene chloride (CH2CI2), trichloromethane (CHCI3), chloroethane (CH3CH2CI), dichloroethane (CH3CHCI2 or CH2CICH2CI), 1 ,1 ,1 ,3,3-pentachloropropane (HCC-240fa, CCI3CH2CHCI2), 1 ,1 ,1 ,3,3,3-hexachloropropane (HCC-230fa, CCI3CH2CCI3) and the like.

[0050] In one embodiment, hydrochlorofluorocarbons produced by the process of the present invention are compounds having carbon, hydrogen, fluorine, and chlorine, including but not limited to chlorodifluoromethane (CHF2CI), dichlorofluoromethane (CHFCI2), chlorofluoromethane (CH2FCI), 2,2-dichloro-1 , 1 , 1 - trifluoroethane (CHCI2CF3), 1 ,2-dichloro-1 ,1 ,2-trifluoroethane (CHFCICCIF2), 2,2- dichloro-1 , 1 ,2-trifluoroethane (CHF2CFCI2), 2-chloro-1 ,1 , 1 ,2-tetrafluoroethane (CHFCICF3), 2,2,4,4-tetrachloro-1 ,1 ,1-trifluorobutane (CF3CCI2CH2CHCI2, HCFC- 343mfn), and the like.

[0051] The process may be conducted with or without a solvent, wherein a catalyst and co-catalyst are dissolved in a haloalkane reactant to form a homogenous mixture, followed by feeding the mixture to a reaction zone along with a haloalkenereactant. The reaction is most preferably a solid-free reaction. This may be accomplished simply due to the nature of the reactants and / or catalysts or by removal of solids such as by filtration or by decantation. After reaction, the reactor effluent is distilled, preferably flash-distilled, to separate a haloalkane reaction product (e.g., HCC-240fa, HCC-230fa or HCFC-343mfn), any unreacted haloalkane starting material (e.g., CCU) and any unreacted haloalkene or alkene starting material (e.g., vinyl chloride monomer) from a catalyst / co-catalyst mixture. The catalyst / co-catalyst mixture is then preferably recycled back to a catalyst preparation tank as a mixture. The process may be carried out in either a batch or a continuous system. The production system may also be closed to provide substantially complete recycling of any unreacted haloalkane starting material and haloalkene (olefin) starting material. In some embodiments, the haloalkane and olefin reactants and the catalyst and co-catalyst are commercially available.

[0052] The specific haloalkane reactant and olefin used, as well as the catalyst, co-catalyst, and reaction conditions used will depend on the desired hydrochloro(fluoro)carbon product and will be selected to optimize suppression or minimization of the formation of byproduct telomers, oligomers, dimers and / or other polymeric products.

[0053] Formation of the byproduct (waste) telomers, oligomers, dimers and / or other polymeric products can be somewhat controlled by manipulating reaction variables, particularly the reaction pressure. Corrosivity can be controlled by manipulating reaction variables, such as moisture. In one embodiment, the insertion reaction may be carried out at a reduced pressure and reduced moisture content.

[0054] In one embodiment, the insertion reaction is carried out at a reduced pressure in the range of about 15 psig to about 50 psig, or about 25 psig to about 50 psig, or about 20 psig, or about 25 psig, or about 30 psig, or about 35 psig, or about 40 psig, or about 45 psig, or about 50 psig.

[0055] In one embodiment, the insertion reaction is carried out in the presence of a reduced amount of moisture. In one embodiment, the moisture content in the reactor is maintained or controlled to be about 500 ppm or less, or about 200 ppm or less, or about 100 ppm or less. The reduced moisture content minimizes the presence offree halides such as chloride in an acidic environment, therefore, leading to less corrosion.

[0056] In one embodiment, the insertion reaction may be carried out at an elevated temperature. In another embodiment, the insertion reaction may be carried out at a temperature between about 70°C and about 150°C, preferably between about 80°C and about 130°C, or between about 90°C and about 120°C, more preferably between about 100°C and about 120°C.

[0057] In some embodiments, a ratio of the number of moles of haloalkane reactant to moles of olefin is from about 5:1 to about 1 :0.8. In another embodiment, the molar ratio of haloalkane reactant to moles of olefin is from about 1:1 to about 3: 1. In another embodiment, the molar ratio of halocarbon reactant to moles of olefin is from about 1 : 1 to about 2: 1.

[0058] In one aspect of the disclosure, a number of moles of co-catalyst may be measured in relation to a number of moles of olefin present in the reaction system. For example, in one embodiment, a molar ratio of phosphate ligand or phosphine ligand to olefin may be from about 0.01 :1 to about 0.1 :1, preferably from about 0.02:1 to about 0.08:1 , more preferably from about 0.03:1 to about 0.07:1.

[0059] The reactor or vessel, distillation columns, feed lines, effluent lines and any other associated units utilized in carrying out any of the process embodiments disclosed herein should be constructed from materials which are resistant to the corrosive effects of hydrogen fluoride, such as nickel and its alloys, including Hastelloy, Monel, and Inconel, or vessels lined with fluoropolymers.

[0060] In one embodiment, the reaction may be conducted in a reaction zone comprising any reaction vessel of appropriate size for the scale for the reaction. In one embodiment, the reaction zone is a reaction vessel comprised of materials which are resistant to corrosion. In one embodiment, these materials comprise alloys, such as nickel-based alloys such as Hastelloy®, nickel-chromium alloys commercially available from Special Metals Corp, under the trademark Inconel® (hereinafter “Inconel®”) or nickel-copper alloys commercially available from Special Metals Corp. (New Hartford, New York) under the trademark Monel®, or vessels having fluoropolymers linings. In another embodiment, the reaction vessel may bemade of other materials of construction including stainless steels, in particular of the austenitic type, and copper-clad steel.

[0061] The process thus further comprises separating the target hydrochloro(fluoro)carbon compound from the reaction product stream. More particularly, the desired hydrochloro(fluoro)carbon product may be separated from any unreacted starting material, solvent, and any byproduct telomers, oligomers, dimers and / or other polymeric products by conventional techniques such as distillation. The low boiling fraction will typically be the starting halogenated alkane and the alkene (olefin) which may be recovered and recycled to the reactor. The unreacted starting materials, particularly the starting halogenated alkane such as carbon tetrachloride, may be further refined, and the solvent recycled to the reactor. Higher boiling material will comprise the solvent and any higher boiling telomer, oligomer, dimes and / or other polymeric byproducts. The higher boiling phase may be further refined, and the solvent recycled to the reactor. The separation of the two liquid phases in the reactor may be done at temperatures between the reaction temperature and ambient temperature; cooling the reaction mixture lower than room temperature is usually not necessary. The process may further comprise optionally purifying the target hydrochloro(fluoro)carbon compound, such as by adsorption or another conventional purification method known in the art.

[0062] In some embodiments, the processes of the present invention are carried out in the same location or facility where one or more of the starting materials (i.e. , haloalkane reactant and / or olefin) are made, or proximate locations or facilities where one or more of the starting materials. In some embodiments, proximity of the reactor for processes of the present invention to sources of one or more of the starting material eliminate the need for storage, handling and / or transportation of the starting material(s). In some embodiments, the haloalkane reactant or olefin may be produced in respective reactors at the same site where the processes of the present invention are carried out, and may be stored onsite, if needed, or may be transferred directly from an upstream reactor to a downstream reactor via piping, tubing, etc. which fluidly connects the reactors. In some embodiments, the process is preferably carried out proximate a carbon tetrachloride manufacturing site, and / or proximate a vinyl chloride manufacturing site, and / or proximate a vinylidene chloride manufacturing site, and / or proximate a CFC-113a manufacturing site.Embodiment for Production of HCC-240fa

[0063] In one embodiment, the invention provides a process for producing HCC- 240fa using carbon tetrachloride as the haloalkane feed material and vinyl chloride as the olefin.

[0064] In one embodiment, for the production of HCC-240fa, the catalyst is selected from cuprous salts, organometallic cuprous compounds, iron wire, iron shavings, iron powder, iron chlorides, nickel powder, nickel shavings, nickel wire, nickel screen, nickel shots or nickel turnings. In one embodiment, the catalyst comprises iron metal, iron oxide, iron hydrate, and / or iron hydroxide.

[0065] In one embodiment, for the production of HCC-240fa, the co-catalyst is selected from organic amines, nitriles, amides, phosphates and combinations thereof.

[0066] In one embodiment, a moisture content of the catalyst system is about 1000 ppm or less, or about 750 ppm or less, or about 500 ppm or less, inclusive of all values and integers therebetween.

[0067] In one embodiment, the invention provides an olefin insertion process comprising contacting carbon tetrachloride with vinyl chloride in the presence of a catalyst system that consists of metallic iron and a phosphate to produce HCC-240fa under reaction conditions which suppress or minimize formation of byproduct telomers, oligomers, dimers and other polymeric products.

[0068] The olefin insertion process of the present invention may be conducted in a liquid-phase reactor operating in batch, semi-batch, semi-continuous, or continuous modes.

[0069] In some embodiments, unreacted carbon tetrachloride and / or vinyl chloride are recycled back to the feed of the reactor, optionally with a small amount of HCC- 240fa.

[0070] According to the olefin insertion process of the present invention, the conversion is between about 10% to about 80%. According to the olefin insertion process of the present invention, selectivity of HCC-240fa is between about 90% to about 99.5%. On the other hand, selectivity of unwanted byproducts, such astelomer, oligomers, dimers and / or other polymeric products, is less than about 10%, more preferably less than about 8%, more preferably less than about 6%, or less than about 5%, or less than about 4%, or less than about 3%, or less than about 2% or less than about 1%.

[0071] In one embodiment, for the process of producing HCC-240fa, a molar ratio of carbon tetrachloride to vinyl chloride is from about 0.5:1 to about 3:1 , preferably from about 1 : 1 to about 2: 1.

[0072] In one embodiment, for the process of producing HCC-240fa, a molar ratio of phosphate co-catalyst to vinyl chloride is from about 0.01 :1 to about 0.1 :1 , preferably from about 0.4:1 to about 0.8:1.

[0073] In one embodiment, the insertion reaction to produce HCC-240fa may be carried out at an elevated temperature. In another embodiment, the reaction may be carried out at a temperature of between about 90°C to about 130°C, or between about 100°C to about 120°C, preferably at a temperature of about 115°C.

[0074] In one embodiment, the reaction for producing HCC-240fa is conducted at a reduced pressure. In one embodiment, the reaction for producing HCC-240fa is conducted at a pressure of from about 25 psig to about 50 psig, preferably from about 25 psig to about 45 psig. The reduced pressure minimizes or suppresses the formation of unwanted byproducts, such as telomer, oligomers, dimers and / or other polymeric products, to be less than about 10 wt.%, more preferably less than about 8 wt.%, more preferably less than about 6 wt.%, or less than about 5 wt.%, or less than about 4 wt.%, or less than about 3 wt.%, or less than about 2 wt.% or less than about 1 wt.%, based on a total weight of the product stream (also referred to herein as reaction mixture or composition).

[0075] In one embodiment, the insertion reaction for producing HCC-240fa is carried out in the presence of a reduced amount of moisture. In one embodiment, the moisture content in the reactor is maintained or controlled to be about 500 ppm or less, or about 200 ppm or less, or about 100 ppm or less. The reduced moisture content minimizes the presence of free halides such as chloride in an acidic environment, therefore, leading to less corrosion.

[0076] In one embodiment, the carbon tetrachloride feed material for the reaction to produce HCC-240fa comprises carbon tetrachloride and one or more additional compounds selected from dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC-1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1 ,1 ,2-trichloroethane, 1 ,1 ,1 -trichloroethane, hexachloroethane, E-1 ,2-dichloroethene, Z-1 ,2 dichloroethene and 1 ,1- dichloroethene, or at least two additional compounds or at least three additional compounds or more. In one embodiment, a moisture content of the carbon tetrachloride feed is about 100 ppm or less, or about 50 ppm or less, or about 30 ppm or less, inclusive of all values and integers therebetween.

[0077] In one embodiment, the vinyl chloride feed material for the reaction to produce HCC-240fa comprises vinyl chloride and one or more additional compounds selected from C2H4 (FC-1150, ethylene), CsHs (propane), CH3CI, methanol, C2H3CI (FC-1140), C4H6(1-butyne), C4H4(1-buten-3-yne), C3H8O (CH3CH2OCH3), C2H5CI and C2HsBr, or at least two additional compounds or at least three additional compounds or more. In one embodiment, a moisture content of the vinyl chloride feed is about 100 ppm or less, or about 50 ppm or less, or about 30 ppm or less, inclusive of all values and integers therebetween.

[0078] In some embodiments, for the production of HCC-240fa, the reaction is carried out under conditions which suppress or minimize formation of byproduct telomers, oligomers, dimers and / or other polymeric products, particularly those of the formula CCl3(CH2CHCI)nCI, where n > 2. As such, according to the present invention, the formation of waste, such as byproduct telomers, oligomers, dimers and / or other polymeric products is minimized or suppressed by running the reaction at a pressure no greater than 50 psig, preferably no greater than 45 psig, and more preferably no greater than 40 psig. In some embodiments, for the production of HCC-240fa, the reaction is carried out under conditions, and more particularly reduced moisture content of about 500 ppm or less, preferably about 200 ppm or less, more preferably about 100 ppm or less, which suppress or minimize the presence of free halides such as chloride in an acidic environment, therefore, leading to less corrosion. In one embodiment, the catalyst comprises iron metal, iron oxide, iron hydrate, and / or iron hydroxide.

[0079] In some embodiments, the product stream of the process of the present invention, as described above for the production of HCC-240fa, comprises, consists essentially of, or consists of, HCC-240fa and less than about 10 wt.% byproduct telomers, oligomers, dimers and / or other polymeric products of the formula CCl3(CH2CHCI)nCI, where n > 2, more preferably less than about 8 wt.%, more preferably less than about 6 wt.%, or less than about 5 wt.%, or less than about 4 wt.%, or less than about 3 wt.%, or less than about 2 wt.% or less than about 1 wt.%, or less than about 0.5 wt.%, based on a total weight of the product stream (also referred to herein as reaction mixture or composition).

[0080] In one embodiment, the reaction mixture or product stream produced by the reaction of this embodiment comprises (i) HCC-240fa; and (ii) one or more additional compounds selected from 1 -chlorobutane; 1 ,2,3-trichloropropene (CHCI=CCI-CH2CI, HCO-1240xd); HCO-1230xd (CHCI=CCI-CHCI2, 1 ,2,3,3-tetrachloropropene);1.1.1.3- tetrachloropropane (CCI3-CH2-CH3, HCC-250fb); 1 ,4 dichlorobutane; 1 ,2- dichloro-cyclobutane, 1 ,1,4,4-tetrachlorobutadiene; 1,1, 3, 4 tetrachlorobutadiene;1.1.1.2.3-pentachloropropane (HCC-240db); 1 , 1 , 3, 3-tetrachloro-1 -propene (CCI2=CH-CHCI2); C5H7CI3 isomer(s); and C4H7CI3 isomer(s), or at least two additional compounds or at least three additional compounds or more; and (iii) less than about 10 wt.% byproduct (higher molecular weight) telomers, oligomers, dimers and other polymers of the formula CCl3(CH2CHCI)nCI, where n > 2, preferably less than about 5 wt.%, more preferably less than about 4 wt.% or less than about 3 wt.% or less than about 2 wt.% or less than about 1 wt.%, most preferably less than about 0.5%, inclusive of all values and ranges therebetween.

[0081] In one embodiment, the total amount of additional compound(s) in any of the aforementioned compositions ranges from greater than 0 wt.% to less than or equal to about 5 wt.%, about 4 wt.%, about 3 wt.%, about 2 wt.%, about 1 wt.%, about 0.9 wt.%, about 0.8 wt.%, about 0.7 wt.%, about 0.6 wt.%, about 0.5 wt.%, about 0.4 wt.%, about 0.3 wt.%, about 0.2 wt.%, about 0.1 wt.%, based on the total weight of the composition. In another embodiment, the total amount of additional compound(s) ranges from 0.01 ppm (weight) to about 1 wt.%, or from 0.1 ppm (weight) to about 1 wt.%, or from 0.001 wt.% to about 1 wt.%, or from 0.001 wt.% to about 0.5 wt.%, or from 0.001 wt.% to 0.4 wt.% or less, or from 0.001 wt.% to 0.1wt.% or less, or about 0.1 wt.%, based on the total weight of the composition, and all values and integers between all such ranges.

[0082] In one embodiment, the HCC-240fa reaction product comprises at least about 95% by weight, at least about 96% by weight, at least about 97% by weight, at least about 98% by weight, at least about 99% by weight, at least 99.5% by weight, at least 99.6% by weight, at least 99.7% by weight, at least 99.8% by weight, or about 99.9% by weight of HCC-240fa and the one or more of the additional compounds.

[0083] In one embodiment, the HCC-240fa reaction product has a moisture content of less than about 500 ppm, or less than about 400 ppm, or less than about 300 ppm, or less than about 200 ppm, or less than about 100 pm, less than about 75 ppm. Preferably, the moisture content of the HCC-240fa reaction product is less than about 100 ppm, more preferably less than about 75 ppm.

[0084] In one embodiment, the HCC-240fa reaction product has an acidity content (as HCI) of less than about 100 ppm, less than about 75 ppm, or less than about 50 ppm, or less than about 25 ppm, or less than about 10 ppm. Preferably, the acidity content of the HCC-240fa reaction product is less than about 25 ppm, more preferably less than about 10 ppm.

[0085] The insertion reaction for the production of HCC-240fa is as follows:where n > 2.

[0086] In one embodiment, the HCC-240fa produced by this reaction is utilized as a feed material for subsequent reactions to produce HFCs such as 1, 1,1 , 3,3- pentafluoropropane (CF3CH2CHF2 or HFC-245fa), HCFOs such as 1-chloro-3,3,3- trifluoro-1 -propene (CF3CH=CHCI or HCFO-1233zd), and HFOs such as 1 , 3,3,3- tetrafluoro-1-propene (CF3CH=CHF or HFO-1234ze).

[0087] More particularly, HCC-240fa is a starting material for the production of HFC-245fa, a refrigerant and blowing agent, may be prepared by fluorination of HCC-240fa in the liquid phase (see for example, U.S. Pat. No. 6,291 ,730, the entire disclosure of which is incorporated herein by reference). HCFO-1233zd is useful asa chemical intermediate and may be prepared by fluorination of HCC-240fa as disclosed in U.S. Pat. No. 6,013,846, the entire disclosure of which is incorporated herein by reference. HFO-1234ze, useful as a refrigerant, has been prepared by dehydrofluorination of HFC-245fa using a strong base in aqueous or alcoholic solution or by means of chromium-containing catalyst in the presence of oxygen at elevated temperature as disclosed in U.S. Pat. No. 6,124,510, the entire disclosure of which is incorporated herein by reference, and from HCFO-1233zd as disclosed in U.S. Pat. No. 5,895,825, the entire disclosure of which is incorporated herein by reference. HFO-1234ze has also been prepared from HCC-240fa as disclosed in U.S. Pat. No. 6,111,150, the entire disclosure of which is incorporated herein by reference.

[0088] Certain of the compounds mentioned herein exist as different configurational isomers or stereoisomers. When the specific isomer is not designated, the present invention is intended to include all single configurational isomers, single stereoisomers, single geometric or any combination thereof. For instance, HFO-1234ze is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio.Embodiment for Production of HCC-230fa

[0089] In one embodiment, the invention provides a process for producing HCC- 230fa using carbon tetrachloride as the haloalkane feed material and vinylidene chloride as the olefin.

[0090] In one embodiment, for the production of HCC-230fa, the catalyst is selected from cuprous salts, organometallic cuprous compounds, iron wire, iron shavings, iron powder, iron chlorides, nickel powder, nickel shavings, nickel wire, nickel screen, nickel shots or nickel turnings.

[0091] In one embodiment, for the production of HCC-230fa, the co-catalyst is selected from organic amines, nitriles, amides, phosphates and combinations thereof.

[0092] In one embodiment, a moisture content of the catalyst system is about 1000 ppm or less, or about 750 ppm or less, or about 500 ppm or less, inclusive of all values and integers therebetween.

[0093] In one embodiment, the invention provides an olefin insertion process comprising contacting carbon tetrachloride with vinylidene chloride in the presence of a catalyst system that consists of metallic iron and a phosphate or phosphine to produce HCC-230fa under reaction conditions which suppress or minimize formation of byproduct telomers, oligomers, dimers and / or other polymeric products.

[0094] This process may be conducted in a liquid-phase reactor operating in batch, semi-batch, semi-continuous, or continuous modes.

[0095] In some embodiments, unreacted carbon tetrachloride and / or vinylidene chloride are recycled back to the feed of the reactor, optionally with a small amount of HCC-230fa.

[0096] According to this process, the conversion is between about 10% to about 80%. According to this process, selectivity of HCC-230fa is between about 90% to about 98%. On the other hand, selectivity of unwanted byproducts, such as telomer, oligomers, dimers and / or other polymeric products, is less than about 10%, more preferably less than about 8%, more preferably less than about 6%, or less than about 5%, or less than about 4%, or less than about 3%, or less than about 2% or less than about 1 %.

[0097] In one embodiment, a molar ratio of carbon tetrachloride to vinylidene chloride is from 0.5:1 to about 3:1 , preferably from about 1 :1 to about 2:1.

[0098] In one embodiment, a molar ratio of phosphate co-catalyst to vinylidene chloride is from 0.01 :1 to about 0.1 :1 , preferably from about 0.4:1 to about 0.8:1.

[0099] In one embodiment, the insertion reaction to produce HCC-230fa may be carried out at an elevated temperature. In another embodiment, the reaction may be carried out at a temperature of between about 90°C to about 130°C, or between about 100°C to about 120°C, preferably at a temperature of about 115°C.

[0100] In one embodiment, the reaction is conducted at a reduced pressure. In one embodiment, the reaction to produce HCC-230fa is conducted at a pressure of from about 15 psig to about 50 psig, preferably from about 20 psig to about 40 psig, more preferably about 15 psig to about 35 psig, most preferably about 35 psig. The reduced pressure minimizes or suppresses the formation of unwanted byproducts, such as telomer, oligomers, dimers and / or other polymeric products, to be less thanabout 10 wt.%, more preferably less than about 8 wt.%, more preferably less than about 6 wt.%, or less than about 5 wt.%, or less than about 4 wt.%, or less than about 3 wt.%, or less than about 2 wt.% or less than about 1 wt.%, or less than about 0.5 wt.%, based on a total weight of the product stream (also referred to herein as reaction mixture or composition).

[0101] In one embodiment, the insertion reaction for producing HCC-230fa is carried out in the presence of a reduced amount of moisture. In one embodiment, the moisture content in the reactor is maintained or controlled to be about 500 ppm or less, or about 200 ppm or less, or about 100 ppm or less. The reduced moisture content minimizes the presence of free halides such as chloride in an acidic environment, therefore, leading to less corrosion.

[0102] In one embodiment, the carbon tetrachloride feed material for the reaction of this embodiment comprises carbon tetrachloride and one or more additional compounds selected from dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC-1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, chloroethane, dichloroethane, 1,1 ,2-trichloroethane, 1 ,1,1 -trichloroethane, hexachloroethane, E-1,2-dichloroethene, Z-1,2 dichloroethene and 1,1- dichloroethene, or at least two additional compounds or at least three additional compounds or more. In one embodiment, a moisture content of the carbon tetrachloride feed is about 100 ppm or less, or about 50 ppm or less, or about 30 ppm or less, inclusive of all values and integers therebetween.

[0103] In one embodiment, the vinylidene chloride feed material for the reaction of this embodiment comprises vinyl chloride and one or more additional compounds selected from vinyl chloride, dichloroethylene (both Z and E isomers), 1 ,1 ,1- trichloroethane and 1,2-dichloroethane, or at least two additional compounds or at least three additional compounds or more. In one embodiment, a moisture content of the vinylidene chloride feed is about 100 ppm or less, or about 50 ppm or less, or about 30 ppm or less, inclusive of all values and integers therebetween.

[0104] In some embodiments, for the production of HCC-230fa, the reaction is carried out under conditions which suppress or minimize formation of byproduct telomers, oligomers, dimers and / or other polymeric products, particularly those of theformula CCl3(CH2CCl2)nCI, where n > 2. As such, according to the present invention, the formation of waste, such as byproduct telomers, oligomers, dimers and / or other polymeric products is minimized or suppressed by running the reaction at a pressure no greater than 50 psig, preferably no greater than 40 psig, and more preferably no greater than 35 psig. In some embodiments, for the production of HCC-230fa, the reaction is carried out under conditions, and more particularly reduced moisture content of about 500 ppm or less, preferably about 200 ppm or less, more preferably about 100 ppm or less, which suppress or minimize the presence of free halides such as chloride in an acidic environment, therefore, leading to less corrosion.

[0105] In some embodiments, the product stream of the process of the present invention, as described above for the production of HCC-230fa, comprises, consists essentially of, or consists of, HCC-230fa and less than about 10 wt.% byproduct telomers, oligomers, dimers and / or other polymeric products of the formula CCl3(CH2CCl2)nCI, where n > 2 (e.g., CCI3CCI2CH2CI and CCI3CCIHCH2CI), more preferably less than about 8 wt.%, more preferably less than about 6 wt.%, or less than about 5 wt.%, or less than about 4 wt.%, or less than about 3 wt.%, or less than about 2 wt.% or less than about 1 wt.%, based on a total weight of the product stream (also referred to herein as reaction mixture or composition).

[0106] In one embodiment, the reaction mixture or product stream produced by the reaction of this embodiment comprises (i) HCC-230fa; (ii) one or more additional compounds selected from CCI3CCI2CH2CI, CCI3CCIHCH2CI and CCI3CH2CH2CI, or at least two additional compounds or at least three additional compounds or more; and (iii) less than about 10 wt.% of byproduct (higher molecular weight) telomers, such as telomers, oligomers, dimers and / or other polymeric products of the formula CCl3(CH2CCl2)nCI, where n > 2, preferably less than about 5 wt.%, more preferably less than about 4 wt.% or less than about 3 wt.% or less than about 2 wt.% or less than about 1 wt.%, most preferably less than about 0.5%, inclusive of all values and ranges therebetween.

[0107] In one embodiment, the total amount of additional compound(s) in any of the aforementioned compositions ranges from greater than 0 wt.% to less than or equal to about 5 wt.%, about 4 wt.%, about 3 wt.%, about 2 wt.%, about 1 wt.%, about 0.9 wt.%, about 0.8 wt.%, about 0.7 wt.%, about 0.6 wt.%, about 0.5 wt.%,about 0.4 wt.%, about 0.3 wt.%, about 0.2 wt.%, about 0.1 wt.%, based on the total weight of the composition. In another embodiment, the total amount of additional compound(s) ranges from 0.01 ppm (weight) to about 1 wt.%, or from 0.1 ppm (weight) to about 1 wt.%, or from 0.001 wt.% to about 1 wt.%, or from 0.001 wt.% to about 0.5 wt.%, or from 0.001 wt.% to 0.4 wt.% or less, or from 0.001 wt.% to 0.1 wt.% or less, or about 0.1 wt.%, based on the total weight of the composition, and all values and integers between all such ranges.

[0108] In one embodiment, the HCC-230fa reaction product comprises at least about 95% by weight, at least about 96% by weight, at least about 97% by weight, at least about 98% by weight, at least about 99% by weight, at least 99.5% by weight, at least 99.6% by weight, at least 99.7% by weight, at least 99.8% by weight, or about 99.9% by weight of HCC-230fa and the one or more of the additional compounds.

[0109] In one embodiment, the HCC-230fa reaction product has a moisture content of less than about 500 ppm, or less than about 400 ppm, or less than about 300 ppm, or less than about 200 ppm, or less than about 100 pm, less than about 75 ppm. Preferably, the moisture content of the HCC-240fa reaction product is less than about 100 ppm, more preferably less than about 75 ppm.

[0110] In one embodiment, the HCC-230fa reaction product has an acidity content (as HCI) of less than about 100 ppm, less than about 75 ppm, or less than about 50 ppm, or less than about 25 ppm, or less than about 10 ppm. Preferably, the acidity content of the HCC-240fa reaction product is less than about 25 ppm, more preferably less than about 10 ppm.

[0111] The insertion reaction for the production of HCC-230fa is as follows:

[0112] In one embodiment, the HCC-230fa produced by this reaction is utilized as a feed material for subsequent reactions to produce HFCs such as 1, 1,1 , 3,3,3- hexafluoropropane (HFC-236fa) and HFC-245fa, and HCFCs such as 1-chloro- 1 , 1 ,3,3,3-pentafluoropropane (HCFC-235fa).

[0113] More particularly, HCC-230fa can be reacted with HF in the liquid phase using halides, fluorosulfonates or triflates of antimony, molybdenum, niobium, tantalum, tin or titanium, or mixtures thereof as catalysts to produce HFC-236fa, a fire extinguishment reagent. HFC-236fa is also a starting material to make the fluoroelastomer curing site monomer 1 ,1 ,3,3,3-pentafluoropropene (CF3CH DF2 or HFO-1225zc). HCFC-235fa can also be prepared from HCC-230fa (e.g., by reacting said CCI3CH2CCI3 with HF). The reaction products may be separated by conventional techniques such as distillation. Azeotropic compositions of HCFC-235fa and HF can be produced in this manner; and the HCFC-235fa can be further reacted with HF to produce HFC-236fa. The HCFC-235fa product can also be hydrodechlorinated using a hydrodehalogenation catalyst to produce HFC-245fa.Palladium on acid-washed carbon is a preferred catalyst for the conversion of HCFC- 235fa to HFC-245fa.Embodiment for Production of HCFC-343mfn

[0114] In one embodiment, the invention provides a process for producing HCFC- 343mfn using CFC-113a as the haloalkane feed material and vinyl chloride as the olefin.

[0115] In one embodiment, for the production of HCFC-343mfn, the catalyst is selected from cuprous salts, organometallic cuprous compounds, iron wire, iron shavings, iron powder, iron chlorides, nickel powder, nickel shavings, nickel wire, nickel screen, nickel shots or nickel turnings.

[0116] In one embodiment, for the production of HCFC-343mfn, the co-catalyst is selected from organic amines, nitriles, amides, phosphates and combinations thereof.

[0117] In one embodiment, a moisture content of the catalyst system is about 1000 ppm or less, or about 750 ppm or less, or about 500 ppm or less, inclusive of all values and integers therebetween.

[0118] In one embodiment, the invention provides an olefin insertion process comprising contacting CFC-113a with vinyl chloride in the presence of a catalyst system that consists of metallic iron and a phosphine to produce HCFC-343mfnunder reaction conditions which suppress or minimize formation of byproduct telomers, oligomers, dimers and / or other polymeric products.

[0119] This process may be conducted in a liquid-phase reactor operating in batch, semi-batch, semi-continuous, or continuous modes.

[0120] In some embodiments, unreacted CFC-113a and / or vinyl chloride are recycled back to the feed of the reactor, optionally with a small amount of HCFC- 343mfn.

[0121] According to this process, the conversion is between about 10% to about 80%. According to this process, selectivity to HCFC-343mfn is between about 90% to about 99.5%. On the other hand, selectivity to unwanted byproducts, such as telomer, oligomers, dimers and other polymeric products, is less than about 10%, more preferably less than about 8%, more preferably less than about 6%, or less than about 5%, or less than about 4%, or less than about 3%, or less than about 2% or less than about 1%.

[0122] In one embodiment, a molar ratio of CFC-113a to vinyl chloride is from about 1 : 1 to about 3:1 , preferably from about 1 : 1 to about 2:1.

[0123] In one embodiment, a molar ratio of iron catalyst to vinyl chloride is from about 0.01 :1 to about 0.1:1 , preferably from about 0.07:1 to about 0.1:1. For example, the molar ratio of iron powder to vinyl chloride may be from 0.03-0.06 moles of iron to every one mole of olefin, while in another example, the molar ratio is from 0.07-0.1 moles of iron to every mole of vinyl chloride. In yet another example, a ratio of iron to vinyl chloride may be 0.0465:1, while in a further example, the ratio of iron to vinyl chloride may be 0.093:1.

[0124] In one embodiment, a molar ratio of phosphine ligand to vinyl chloride may be from about 0.01 :1 to about 0.04:1. In another embodiment, the molar ratio of phospine ligand to vinyl chloride may be from about 0.02:1 to about 0.06:1. For example, the molar ratio of phospine ligand to vinyl chloride may be about 0.023:1, while in another example, the molar ratio of ligand to vinyl chloride may be about 0.046:1. In one aspect of the invention, the molar ratio of triphenyl phosphine to vinyl chloride is about 0.023:1, while in another example, the molar ratio of triphenyl phosphine to vinyl chloride is about 0.046:1.

[0125] In one embodiment, the insertion reaction may be carried out at an elevated temperature. In another embodiment, the insertion reaction may be carried out at a temperature between about 50°C and 250°C, or between about 100°C and 200°C, or between about 120°C and 180°C, or between about 130°C and 170°C.

[0126] In one embodiment, the reaction is conducted at a reduced pressure. In one embodiment, the reaction is conducted at a pressure of from about 25 psig to about 50 psig, preferably from about 25 psig to about 45 psig. The reduced pressure minimizes or suppresses the formation of unwanted byproducts, such as telomer, oligomers, dimers and / or other polymeric products, to be less than about 10 wt.%, more preferably less than about 8 wt.%, more preferably less than about 6 wt.%, or less than about 5 wt.%, or less than about 4 wt.%, or less than about 3 wt.%, or less than about 2 wt.% or less than about 1 wt.%, based on a total weight of the product stream (also referred to herein as reaction mixture or composition).

[0127] In one embodiment, the insertion reaction for producing HCFC-343mfn is carried out in the presence of a reduced amount of moisture. In one embodiment, the moisture content in the reactor is maintained or controlled to be about 500 ppm or less, or about 200 ppm or less, or about 100 ppm or less. The reduced moisture content minimizes the presence of free halides such as chloride in an acidic environment, therefore, leading to less corrosion.

[0128] In one embodiment, the CFC-113a feed material for the reaction to produce HCFC-343mfn comprises CFC-113a and one or more additional compounds selected from CFC-113, HCFC-123, HCFC-123a, CFC-115, CFC-112, CFC-112a, CFC-113, CFC-114, CFC-114a, HCFC-122b,CFC-12, HCFC-124, CFC-216, CFC- 316, CFC-318, HCFC-122, CO-1110 and CFC-1317, or at least two additional compounds or at least three additional compounds or more. In one embodiment, a moisture content of the CFC-113a feed is about 100 ppm or less, or about 50 ppm or less, or about 30 ppm or less, inclusive of all values and integers therebetween.

[0129] In one embodiment, the vinyl chloride feed material for the reaction to produce HCFC-343mfn comprises vinyl chloride and one or more additional compounds selected from C2H4 (FC-1150, ethylene), CsHs (propane), CH3CI, methanol, C2H3CI (FC-1140), C4H6 (1-butyne), C4H4 (1-buten-3-yne), CsHsO (CH3CH2OCH3), C2H5CI and C2HsBr,, or at least two additional compounds or atleast three additional compounds or more. In one embodiment, a moisture content of the vinyl chloride feed is about 100 ppm or less, or about 50 ppm or less, or about 30 ppm or less, inclusive of all values and integers therebetween.

[0130] In some embodiments, for the production of HCFC-343mfn, the reaction is carried out under conditions which suppress or minimize formation of byproduct telomers, oligomers, dimers and other polymeric products, particularly those of the formula CF3CCl2(CH2CHCI)nCI, where n is > 2. As such, according to the present invention, the formation of waste, such as byproduct telomers, oligomers, dimers and / or other polymeric products, is minimized or suppressed by running the reaction at a pressure no greater than 50 psig, preferably no greater than 45 psig, and more preferably no greater than 40 psig. In some embodiments, for the production of HCFC-343mfn, the reaction is carried out under conditions, and more particularly reduced moisture content of about 500 ppm or less, preferably about 200 ppm or less, more preferably about 100 ppm or less, which suppress or minimize the presence of free halides such as chloride in an acidic environment, therefore, leading to less corrosion.

[0131] In some embodiments, the product stream of the process of the present invention, as described above for the production of HCFC-343mfn, comprises, consists essentially of, or consists of, HCFC-343mfn and less than about 10 wt.% byproduct telomers, oligomers, dimers and / or other polymeric products of the formula CF3CCl2(CH2CHCI)nCI, where n is > 2, more preferably less than about 8 wt.%, more preferably less than about 6 wt.%, or less than about 5 wt.%, or less than about 4 wt.%, or less than about 3 wt.%, or less than about 2 wt.% or less than about 1 wt.%, or less than about 0.5 wt.%, based on a total weight of the product stream (also referred to herein as reaction mixture or composition).

[0132] In one embodiment, the reaction mixture or product stream produced by the reaction of this embodiment comprises (i) HCFC-343mfn; (ii) one or more additional compounds selected from CF3CCI2CHCICH2CI, CF3CH2CHCICH2CI and CF3CHCICHCICH2CI, or at least two additional compounds or at least three additional compounds or more; and (iii) less than about 10 wt.% of byproduct (higher molecular weight) telomers, such as telomers, oligomers, dimers and / or other polymeric products of the formula CF3CCl2(CH2CHCI)nCI, where n is > 2, preferablyless than about 5 wt.%, more preferably less than about 4 wt.% or less than about 3 wt.% or less than about 2 wt.% or less than about 1 wt.%, most preferably less than about 0.5%, inclusive of all values and ranges therebetween.

[0133] In one embodiment, the total amount of additional compound(s) in any of the aforementioned compositions ranges from greater than 0 wt.% to less than or equal to about 5 wt.%, about 4 wt.%, about 3 wt.%, about 2 wt.%, about 1 wt.%, about 0.9 wt.%, about 0.8 wt.%, about 0.7 wt.%, about 0.6 wt.%, about 0.5 wt.%, about 0.4 wt.%, about 0.3 wt.%, about 0.2 wt.%, about 0.1 wt.%, based on the total weight of the composition. In another embodiment, the total amount of additional compound(s) ranges from 0.01 ppm (weight) to about 1 wt.%, or from 0.1 ppm (weight) to about 1 wt.%, or from 0.001 wt.% to about 1 wt.%, or from 0.001 wt.% to about 0.5 wt.%, or from 0.001 wt.% to 0.4 wt.% or less, or from 0.001 wt.% to 0.1 wt.% or less, or about 0.1 wt.%, based on the total weight of the composition, and all values and integers between all such ranges.

[0134] In one embodiment, the HCFC-343mfn reaction product comprises at least about 95% by weight, at least about 96% by weight, at least about 97% by weight, at least about 98% by weight, at least about 99% by weight, at least 99.5% by weight, at least 99.6% by weight, at least 99.7% by weight, at least 99.8% by weight, or about 99.9% by weight of HCFC-343mfn and the one or more of the additional compounds.

[0135] In one embodiment, the HCFC-343mfn reaction product has a moisture content of less than about 500 ppm, or less than about 400 ppm, or less than about 300 ppm, or less than about 200 ppm, or less than about 100 pm, less than about 75 ppm. Preferably, the moisture content of the HCC-240fa reaction product is less than about 100 ppm, more preferably less than about 75 ppm.

[0136] In one embodiment, the HCFC-343mfn reaction product has an acidity content (as HCI) of less than about 100 ppm, less than about 75 ppm, or less than about 50 ppm, or less than about 25 ppm, or less than about 10 ppm. Preferably, the acidity content of the HCC-240fa reaction product is less than about 25 ppm, more preferably less than about 10 ppm.

[0137] The insertion reaction for the production of HCFC-343mfn is as follows:

[0138] In one embodiment, the HCFC-343mfn produced by this reaction is utilized as a feed material for subsequent reactions to produce compounds such as 1 ,1,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0139] Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present invention to its fullest extent. The following specific embodiments are, therefore, to be construed as merely illustrative, and do not constrain the remainder of the disclosure in any way whatsoever.

[0140] The invention will be described in greater detail below by way of specific examples. The following examples are offered for illustrative purposes and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of non-critical parameters which can be changed or modified to yield essentially the same results.EXAMPLESComparative Example 1

[0141] Vinyl chloride (38.5 g, 0.616 mol) was added to a mixture of CCL (159 g, 1.03 mol), chopped Fe wire (1.27 g, 0.023 mol) and tributyl phosphate (2.7 g, 0.01 mol) in a 400 mL Hastelloy reactor. The reactor was heated up to 110°C for 5 hours. The highest pressure of the reaction was 150 psig. HCC-240fa was produced along with telomer byproducts. The mixture was transferred to a container and analyzed by GC to determine the conversion and selectivity. The results are shown in Table 1.Example 1

[0142] Vinyl chloride (7.4 g, 0.118 mol) was added to a mixture of CCk (159 g, 1.03 mol), chopped Fe wire (1.27 .62 g, 0.011 mol) and tributyl phosphate (2.7 g, 0.01 mol) in a 210 mL Hastelloy reactor. The reactor was heated up to 110°C for 5 hours. The pressure of the reaction was controlled to be no higher than 40 psig. HCC-240fa was produced along with a small amount of telomer byproducts. Themixture was transferred to a container and analyzed by GC to determine the conversion and selectivity. The results are shown in Table 1 .Comparative Example 2

[0143] Vinylidene chloride (59.8 g, 0.616 mol) is added to a mixture of CCU (159 g, 1.03 mol), chopped Fe wire (1.27 g, 0.023 mol) and tributyl phosphate (2.7 g, 0.01 mol) in a 400 mL Hastelloy reactor. The reactor is heated up to 100°C for 5 hours. The highest pressure of the reaction is 60 psig. HCC-230fa is produced along with telomer byproducts. The mixture is transferred to a container and analyzed by GC to determine the conversion and selectivity. The results are shown in Table 1 .Example 2

[0144] Vinylidene chloride (60 g, 0.616 mol) is added to a mixture of CCU (159 g, 1.03 mol), chopped Fe wire (1.27 g, 0.023 mol) and tributyl phosphate (2.7 g, 0.01 mol) in a 400 mL Hastelloy reactor. The reactor is heated up to 100°C for 5 hours. The pressure of the reaction is controlled to be no higher than 30 psig. HCC-230fa is produced along with a small amount of telomer byproducts. The mixture is transferred to a container and analyzed by GC to determine the conversion and selectivity. The results are shown in Table 1.Comparative Example 3

[0145] Trifluoropropene (59.2 g, 0.616 mol) is added to a mixture of CCI4 (159 g, 1.03 mol) chopped Fe wire (1.27 g, 0.023 mol) and tributyl phosphate (2.7 g, 0.01 mol) in a 400 mL Hastelloy reactor. The reactor is heated up to 105°C for 5 hours. The highest pressure of the reaction is 247 psig. CCI3CH2CHCICF3 (HCC-343jfd) is produced along with telomer byproducts, such as CCl3(CH2CHCF3)nCI, where n > 2, or CI(CHCF3CH2)mCCl2(CH2CHCF3)mCI, where each of m and m' is > 1 . The mixture is transferred to a container and analyzed by GC to determine the conversion and selectivity. The results are shown in Table 1.Example 3

[0146] Trifluoropropene (59.2 g, 0.616 mol) is added to a mixture of CCI4 (159 g, 1.03 mol) chopped Fe wire (1.27 g, 0.023 mol) and tributyl phosphate (2.7 g, 0.01mol) in a 400 mL Hastelloy reactor. The reactor is heated up to 105°C for 5 hours. The pressure of the reaction is controlled to be no higher than 70 psig.CCI3CH2CHCICF3 (HCC-343jfd) is produced along with a small amount of telomer byproducts, such as CCl3(CH2CHCF3)nCI, where n > 2, orCI(CHCF3CH2)mCCl2(CH2CHCF3)mCI, where each of m and m' is > 1. The mixture is transferred to a container and analyzed by GC to determine the conversion and selectivity. The results are shown in Table 1.Table 1

[0147] The results surprisingly indicate that carrying out the olefin insertion reactions of the present invention at a reduced pressure can minimize the formation of telomer by products, and more particularly that running the olefin insertion reactions at reduced pressure leads to higher conversion and selectivity to the target hydrochloro(fluoro)carbon compound. Although the vapor pressure of vinyl chloride is greater than 300 psi at 110°C, the reaction prefers low pressure to achieve greater selectivity and conversion, which is surprising as one would expect that higher pressure not lower pressure would accelerate the reaction rate to achieve higher conversion. Similarly, the vapor pressure of vinylidene chloride is greater than 90 psi, and the vapor pressure of trifluoropropene is greater than 500 psig, and thus one would expect that higher pressure not lower pressure would accelerate the reaction rate to achieve higher conversion, but instead the Examples show that the reactions prefer lower pressure to achieve greater selectivity and conversion.OTHER EMBODIMENTS

[0148] Embodiment 1. A process comprising contacting a haloalkane reactant with an olefin in the presence of a catalyst system to produce a product stream comprising a haloalkane insertion product, wherein the product stream contains less than about 10 wt.% of byproduct telomers, oligomers, dimers and / or other polymeric products.

[0149] Embodiment 2. A process comprising contacting a haloalkane reactant with an olefin in the presence of a catalyst system to produce a product stream comprising a haloalkane insertion product, wherein selectivity of the haloalkane insertion product is between about 90% to about 99.5% and wherein selectivity of byproduct telomers, oligomers, dimers and / or other polymeric products is less than 10%.

[0150] Embodiment 3. The process of Embodiment 1 , wherein said haloalkane reactant is an alkane substituted with at least one halogen selected from the group consisting of F, Cl, and combinations thereof.

[0151] Embodiment 4. The process of any of Embodiments 1 to 3, wherein the haloalkane reactant is selected from the group consisting of chlorocarbons and chlorofluorocarbons.

[0152] Embodiment 5. The process of any of Embodiments 1 to 3, wherein the haloalkane reactant is a C1, C2 or C3 compound, preferably carbon tetrachloride (CCk) or 1,1 ,1-trichloro-2,2,2-trifluoroethane (CFC-113a, CF3CCI3).

[0153] Embodiment 6. The process of any of Embodiments 1 to 5, wherein a moisture content of the haloalkane reactant is less than about 100 ppm, or less than about 50 ppm, or less than about 30 ppm.

[0154] Embodiment 7. The process of any of Embodiments 1 to 6, wherein the olefin is an unsaturated hydrocarbon, with at least one double bond optionally substituted with Cl, F or combinations thereof, excluding ethylene.

[0155] Embodiment 8. The process of any of Embodiments 1 to 7, wherein the olefin is selected from the group consisting of vinyl chloride, 3,3,3-trifluoropropene,vinyl fluoride, vinylidene chloride, and allyl chloride, preferably vinyl chloride, vinylidene chloride or 3,3,3-trifluoropropene.

[0156] Embodiment 9. The process of any of Embodiments 1 to 8, wherein a moisture content of the olefin is less than about 100 ppm, or less than about 50 ppm, or less than about 30 ppm.

[0157] Embodiment 10. The process of any of Embodiments 1 to 9, wherein the haloalkane insertion product preferably comprises at least one hydrochloro(fluro)carbon.

[0158] Embodiment 11. The process of any of Embodiments 1 to 10, wherein the haloalkane insertion product is represented by the formula R1CH2R2, where R1is a halogenated or partially halogenated C1 to C4 compound, optionally branched, and where R2is one of (i) CHxCh-x, where x is an integer from 0 to 1 ; (ii) CHxFyCh, where x is an integer from 0 to 1 and y is an integer from 0 to 1 ; or (iii) CHCICF3.

[0159] Embodiment 12. The process of any of Embodiments 1 to 11 , wherein the process is carried out at a reduced pressure.

[0160] Embodiment 13. The process of Embodiment 12, wherein the reduced pressure is in the range of about 15 psig to about 50 psig, or about 25 psig to about 50 psig, or about 20 psig, or about 25 psig, or about 30 psig, or about 35 psig, or about 40 psig, or about 45 psig, or about 50 psig.

[0161] Embodiment 14. The process of any of Embodiments 1 to 13, wherein process is carried out in the presence of a moisture content of less than about 1000 ppm, or less than about 750 ppm, or less than about 500 ppm.

[0162] Embodiment 15. The process of any of Embodiments 1 to 14, wherein the haloalkane reactant is carbon tetrachloride (CCI4), the olefin is vinyl chloride (CH2=CHCI), and the haloalkane insertion product is 1 ,1 ,1 ,3,3-pentachloropropane (HCC-240fa, CCI3CH2CHCI2).

[0163] Embodiment 16. The process of Embodiment 15, wherein the process is carried out at a pressure from about 25 psig to about 50 psig, preferably from about 25 psig to about 45 psig.

[0164] Embodiment 17. The process of any of Embodiments 15 to 16, wherein a composition produced by the process comprises the HCC-240fa, and one or more additional compounds selected from the group consisting of 1 -chlorobutane; 1 ,2,3- trichloropropene (CHCI=CCI-CH2CI, HCO-1240xd); HCO-1230xd (CHCI=CCI- CHCI2, 1,2,3,3-tetrachloropropene); 1 ,1 ,1 ,3-tetrachloropropane (CCI3-CH2-CH3, HCC-250fb); 1 ,4 dichlorobutane; 1 ,2-dichloro-cyclobutane, 1 , 1 ,4,4- tetrachlorobutadiene; 1,1 , 3, 4 tetrachlorobutadiene; 1 ,1 ,1 ,2,3-pentachloropropane (HCC-240db); 1 ,1,3,3-tetrachloro-1-propene (CCI2=CH-CHCI2); C5H7CI3 isomer(s); C4H7CI3 isomer(s) and byproduct (higher molecular weight) telomers, oligomers, dimers and other polymers of the formula CC (CH2CHCI)nCI, where n > 2, wherein the composition contains less than about 10 wt% of the CCl3(CH2CHCI)nCI byproducts. In one embodiment, the HCC-240fa composition has a moisture content of less than about 500 ppm, or less than about 400 ppm, or less than about 300 ppm, or less than about 200 ppm, or less than about 100 pm, less than about 75 ppm. Preferably, the moisture content of the HCC-240fa composition is less than about 100 ppm, more preferably less than about 75 ppm. In one embodiment, the HCC-240fa composition has an acidity content (as HCI) of less than about 100 ppm, less than about 75 ppm, or less than about 50 ppm, or less than about 25 ppm, or less than about 10 ppm. Preferably, the acidity content of the HCC-240fa composition is less than about 25 ppm, more preferably less than about 10 ppm.

[0165] Embodiment 18. The process of any of Embodiments 1 to 14, wherein the haloalkane reactant is carbon tetrachloride (CCI4), the olefin is vinylidene chloride (CH2=CCl2), and the haloalkane insertion product is 1 ,1,1,3,3,3-hexachloropropane (HCC-230fa, CCI3CH2CCI3).

[0166] Embodiment 19. The process of Embodiment 18, wherein the process is carried out at a pressure from about 15 psig to about 50 psig, preferably from about 20 psig to about 40 psig.

[0167] Embodiment 20. The process of any of Embodiments 18 to 19, wherein a composition produced by the process comprises the HCC-230fa, and one or more additional compounds selected from the group consisting of from CCI3CCI2CH2CI, CCI3CCIHCH2CI and CCI3CH2CH2CI, and byproduct (higher molecular weight) telomers, oligomers, dimers and other polymers of the formula CC (CH2CCl2)nCI,where n > 2, wherein the composition contains less than about 10 wt% of the CCl3(CH2CCl2)nCI byproducts. In one embodiment, the HCC-230fa composition has a moisture content of less than about 500 ppm, or less than about 400 ppm, or less than about 300 ppm, or less than about 200 ppm, or less than about 100 pm, less than about 75 ppm. Preferably, the moisture content of the HCC-230fa composition is less than about 100 ppm, more preferably less than about 75 ppm. In one embodiment, the HCC-230fa composition has an acidity content (as HCI) of less than about 100 ppm, less than about 75 ppm, or less than about 50 ppm, or less than about 25 ppm, or less than about 10 ppm. Preferably, the acidity content of the HCC-230fa composition is less than about 25 ppm, more preferably less than about 10 ppm.

[0168] Embodiment 21. The process of any of Embodiments 1 to 20, wherein the catalyst system comprises, consists essentially of or consists of a catalyst and a cocatalyst, wherein the catalyst is preferably selected from the group consisting of cuprous salts, organometallic cuprous compounds, metallic iron components, metallic nickel components and iron chlorides, and wherein the co-catalyst is preferably organic ligand aselected from the group consisting of organic amines, nitriles, amides, amines, phosphates and phosphines.

[0169] Embodiment 22. The process of Embodiment 21 , wherein a moisture content of the catalyst system is about 1000 ppm or less, preferably about 750 ppm or less, more preferably about 500 ppm or less.

[0170] Embodiment 23. A composition comprising (i) HCC-240fa, (ii) one or more additional compounds selected from the group consisting of 1 -chlorobutane; 1 ,2,3- trichloropropene (CHCI=CCI-CH2CI, HCO-1240xd); HCO-1230xd (CHCI=CCI- CHCI2, 1 ,2,3,3-tetrachloropropene); 1 ,1 ,1 ,3-tetrachloropropane (CCI3-CH2-CH3, HCC-250fb); 1 ,4 dichlorobutane; 1 ,2-dichloro-cyclobutane, 1 , 1 ,4,4- tetrachlorobutadiene; 1 ,1 , 3, 4 tetrachlorobutadiene; 1 ,1 ,1 ,2,3-pentachloropropane (HCC-240db); 1 ,1 ,3,3-tetrachloro-1-propene (CCI2=CH-CHCI2); C5H7CI3 isomer(s); C4H7CI3 isomer(s), and (iii) byproduct (higher molecular weight) telomers, oligomers, dimers and other polymers of the formula CC (CH2CHCI)nCI, where n > 2, wherein the composition contains less than about 10 wt% of the CCl3(CH2CHCI)nCI byproducts.

[0171] Embodiment 24. The composition of Embodiment 23, wherein the composition has a moisture content of less than about 500 ppm, or less than about 400 ppm, or less than about 300 ppm, or less than about 200 ppm, or less than about 100 pm, less than about 75 ppm.

[0172] Embodiment 25. The composition of Embodiment 23 or 24, wherein the composition has an acidity content (as HCI) of less than about 100 ppm, less than about 75 ppm, or less than about 50 ppm, or less than about 25 ppm, or less than about 10 ppm.

[0173] Embodiment 26. A composition comprising (i) HCC-230fa, (ii) one or more additional compounds selected from the group consisting of from CCI3CCI2CH2CI, CCI3CCIHCH2CI and CCI3CH2CH2CI, and (iii) byproduct (higher molecular weight) telomers, oligomers, dimers and other polymers of the formula CC (CH2CCl2)nCI, where n > 2, wherein the composition contains less than about 10 wt% of the CCl3(CH2CCl2)nCI byproducts.

[0174] Embodiment 27. The composition of Embodiment 26, wherein the composition has a moisture content of less than about 500 ppm, or less than about 400 ppm, or less than about 300 ppm, or less than about 200 ppm, or less than about 100 pm, less than about 75 ppm.

[0175] Embodiment 28. The composition of Embodiment 26 or 27, wherein the composition has an acidity content (as HCI) of less than about 100 ppm, less than about 75 ppm, or less than about 50 ppm, or less than about 25 ppm, or less than about 10 ppm.

[0176] It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.

Claims

CLAIMSWhat is claimed is:

1. A process comprising contacting a haloalkane reactant with an olefin in the presence of a catalyst system to produce a product stream comprising a haloalkane insertion product, wherein the product stream contains less than about 10 wt.% of byproduct telomers, oligomers, dimers and / or other polymeric products.

2. A process comprising contacting a haloalkane reactant with an olefin in the presence of a catalyst system to produce a product stream comprising a haloalkane insertion product, wherein selectivity of the haloalkane insertion product is between about 90% to about 99.5% and wherein selectivity of byproduct telomers, oligomers, dimers and / or other polymeric products is less than 10%.

3. The process of claim 1, wherein said haloalkane reactant is an alkane substituted with at least one halogen selected from the group consisting of F, Cl, and combinations thereof.

4. The process of any of claims 1 to 3, wherein the haloalkane reactant is selected from the group consisting of chlorocarbons and chlorofluorocarbons.

5. The process of any of claims 1 to 3, wherein the haloalkane reactant is a C1 , C2 or C3 compound, preferably carbon tetrachloride (CCU) or 1 ,1 , 1-trichloro- 2,2,2-trifluoroethane (CFC-113a, CF3CCI3).

6. The process of any of claims 1 to 5, wherein a moisture content of the haloalkane reactant is less than about 100 ppm, or less than about 50 ppm, or less than about 30 ppm.

7. The process of any of claims 1 to 6, wherein the olefin is an unsaturated hydrocarbon, with at least one double bond optionally substituted with Cl, F or combinations thereof, excluding ethylene.

8. The process of any of claims 1 to 7, wherein the olefin is selected from the group consisting of vinyl chloride, 3,3,3-trifluoropropene, vinyl fluoride,vinylidene chloride, and allyl chloride, preferably selected from the group consisting of vinyl chloride, vinylidene chloride or 3,3,3-trifluoropropene.

9. The process of any of claims 1 to 8, wherein a moisture content of the olefin is less than about 100 ppm, or less than about 50 ppm, or less than about 30 ppm.

10. The process of any of claims 1 to 9, wherein the haloalkane insertion product preferably comprises at least one hydrochloro(fluro)carbon.

11. The process of any of claims 1 to 10, wherein the haloalkane insertion product is represented by the formula R1CH2R2, where R1is a halogenated or partially halogenated C1 to C4 compound, optionally branched, and where R2is one of (i) CHxCh-x, where x is an integer from 0 to 1 ; (ii) CHxFyC , where x is an integer from 0 to 1 and y is an integer from 0 to 1 ; or (iii) CHCICF3.

12. The process of any of claims 1 to 11 , wherein the process is carried out at a reduced pressure.

13. The process of claim 12, wherein the reduced pressure is in the range of about 15 psig to about 50 psig, or about 25 psig to about 50 psig, or about 20 psig, or about 25 psig, or about 30 psig, or about 35 psig, or about 40 psig, or about 45 psig, or about 50 psig.

14. The process of any of claims 1 to 13, wherein process is carried out in the presence of a moisture content of less than about 1000 ppm, or less than about 750 ppm, or less than about 500 ppm.

15. The process of any of claims 1 to 14, wherein the haloalkane reactant is carbon tetrachloride (CCI4), the olefin is vinyl chloride (CH2=CHCI), and the haloalkane insertion product is 1 ,1 ,1 ,3,3-pentachloropropane (HCC-240fa, CCI3CH2CHCI2).

16. The process of claim 15, wherein the process is carried out at a pressure from about 25 psig to about 50 psig, preferably from about 25 psig to about 45 psig.

17. The process of any of claims 15 to 16, wherein a composition produced by the process comprises the HCC-240fa, and one or more additional compounds selected from the group consisting of 1 -chlorobutane; 1 ,2,3-trichloropropene (CHCI=CCI-CH2CI, HCO-1240xd); HCO-1230xd (CHCI=CCI-CHCI2, 1 ,2, 3, 3-tetrachloropropene); 1 ,1 ,1 ,3-tetrachloropropane (CCI3-CH2-CH3, HCC-250fb);1.4 dichlorobutane; 1 ,2-dichloro-cyclobutane, 1 ,1 ,4,4-tetrachlorobutadiene;1.1.3.4 tetrachlorobutadiene; 1 ,1 ,1 ,2,3-pentachloropropane (HCC-240db);1 ,1 , 3, 3-tetrachloro-1 -propene (CCI2=CH-CHCI2); C5H7CI3 isomer(s); C4H7CI3 isomer(s) and byproduct (higher molecular weight) telomers, oligomers, dimers and other polymers of the formula CCl3(CH2CHCI)nCI, where n > 2, wherein the composition contains less than about 10 wt% of the CCl3(CH2CHCI)nCI byproducts.

18. The process of any of claims 1 to 14, wherein the haloalkane reactant is carbon tetrachloride (CCI4), the olefin is vinylidene chloride (CH2=CCl2), and the haloalkane insertion product is 1 ,1 ,1 ,3,3,3-hexachloropropane (HCC-230fa, CCI3CH2CCI3).

19. The process of claim 18, wherein the process is carried out at a pressure from about 15 psig to about 50 psig, preferably from about 20 psig to about 40 psig.

20. The process of any of claims 18 to 19, wherein a composition produced by the process comprises the HCC-230fa, and one or more additional compounds selected from the group consisting of from CCI3CCI2CH2CI, CCI3CCIHCH2CI and CCI3CH2CH2CI, and byproduct (higher molecular weight) telomers, oligomers, dimers and other polymers of the formula CCl3(CH2CCl2)nCI, where n > 2, wherein the composition contains less than about 10 wt% of the CCl3(CH2CCl2)nCI byproducts.

21. The process of any of claims 1 to 20, wherein the catalyst system comprises, consists essentially of or consists of a catalyst and a co-catalyst, wherein the catalyst is preferably selected from the group consisting of cuprous salts, organometallic cuprous compounds, metallic iron components, metallic nickel components and iron chlorides, and wherein the co-catalyst is preferably an organic ligand selected from the group consisting of organic amines, nitriles, amides, amines, phosphates and phosphines.

22. The process of claim 21 , wherein a moisture content of the catalyst system is about 1000 ppm or less, preferably about 750 ppm or less, more preferably about 500 ppm or less.

23. A composition comprising (i) HCC-240fa, (ii) one or more additional compounds selected from the group consisting of 1 -chlorobutane; 1 ,2,3-trichloropropene (CHCI=CCI-CH2CI, HCO-1240xd); HCO-1230xd (CHCI=CCI-CHCI2, 1 ,2,3,3- tetrachloropropene); 1 ,1 ,1 ,3-tetrachloropropane (CCI3-CH2-CH3, HCC-250fb);1.4 dichlorobutane; 1 ,2-dichloro-cyclobutane, 1 ,1 ,4,4-tetrachlorobutadiene;1.1.3.4 tetrachlorobutadiene; 1 ,1 ,1 ,2,3-pentachloropropane (HCC-240db);1 ,1 , 3, 3-tetrachloro-1 -propene (CCI2=CH-CHCI2); C5H7CI3 isomer(s); C4H7CI3 isomer(s), and (iii) byproduct (higher molecular weight) telomers, oligomers, dimers and other polymers of the formula CCl3(CH2CHCI)nCI, where n > 2, wherein the composition contains less than about 10 wt% of the CCl3(CH2CHCI)nCI byproducts.

24. The composition of claim 23, wherein the composition has a moisture content of less than about 500 ppm, or less than about 400 ppm, or less than about 300 ppm, or less than about 200 ppm, or less than about 100 pm, less than about 75 ppm.

25. The composition of claim 23 or 24, wherein the composition has an acidity content (as HCI) of less than about 100 ppm, less than about 75 ppm, or less than about 50 ppm, or less than about 25 ppm, or less than about 10 ppm.

26. A composition comprising (i) HCC-230fa, (ii) one or more additional compounds selected from the group consisting of from CCI3CCI2CH2CI, CCI3CCIHCH2CI and CCI3CH2CH2CI, and (iii) byproduct (higher molecular weight) telomers, oligomers, dimers and other polymers of the formula CCl3(CH2CCl2)nCI, where n > 2, wherein the composition contains less than about 10 wt% of the CCl3(CH2CCl2)nCI byproducts.

27. The composition of claim 26, wherein the composition has a moisture content of less than about 500 ppm, or less than about 400 ppm, or less than about 300 ppm, or less than about 200 ppm, or less than about 100 pm, less than about 75 ppm.

28. The composition of claim 26 or 27, wherein the composition has an acidity content (as HCI) of less than about 100 ppm, less than about 75 ppm, or less than about 50 ppm, or less than about 25 ppm, or less than about 10 ppm.

Images