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WO2025160041A1 - Compositions et procédés pour 2,2,4-trichloro-1,1,1-trifluorobutane - Google Patents

Compositions et procédés pour 2,2,4-trichloro-1,1,1-trifluorobutane

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Publication number
WO2025160041A1
WO2025160041A1 PCT/US2025/012357 US2025012357W WO2025160041A1 WO 2025160041 A1 WO2025160041 A1 WO 2025160041A1 US 2025012357 W US2025012357 W US 2025012357W WO 2025160041 A1 WO2025160041 A1 WO 2025160041A1
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WO
WIPO (PCT)
Prior art keywords
hcfc
composition
isomers
organic ligand
metal
Prior art date
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Pending
Application number
PCT/US2025/012357
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English (en)
Inventor
Andrew Jackson
Sigridur Soley Kristjansdottir
Viacheslav A. Petrov
John Joseph Hagedorn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemours Co FC LLC
Original Assignee
Chemours Co FC LLC
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Filing date
Publication date
Application filed by Chemours Co FC LLC filed Critical Chemours Co FC LLC
Publication of WO2025160041A1 publication Critical patent/WO2025160041A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons

Definitions

  • compositions comprising fluorinated compounds, processes of preparing such compositions and their use, particularly 2,2,4-trichloro-1 ,1 ,1-trifluorobutane, (HCFC-353maf, CH2CICH2CCI2CF3).
  • 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene may be useful in heat transfer fluid applications (e.g., immersion cooling systems, data-center cooling systems or thermal management solution for EV batteries). Accordingly, there is a need to develop new processes and intermediate compositions for preparing E- 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene.
  • the present invention relates to compositions comprising 2,2,4-trichloro- 1 ,1 ,1 -trifluorobutane (HCFC-353maf, CF3CCI2CH2CH2CI), processes of preparing such compositions and their use.
  • the present invention provides a process for preparing HCFC-353maf comprising contacting 1 ,1 ,1-trichloro-2,2,2-trifluoroethane (CFC-113a) with ethylene in the presence of a catalyst system comprising a metal and an organic ligand in a reactor to obtain a process mixture comprising HCFC-353maf.
  • the process is performed in the presence of an excess of CFC-113a and the process mixture comprises HCFC-353maf and CFC-113a.
  • the CFC-113a may be recovered from the process mixture and recycled to the process.
  • the process may be performed at a temperature of about 80°C to about 150°C, a pressure of about 50 to 150 psig.
  • the temperature is in the range of about 85°C to about 125°C, or in the range of about 95°C to about 115°C.
  • the present invention also provides a composition comprising HCFC- 353maf, and at least one additional compound chosen from ethylene, CF3CCI3 (CFC-113a), CF3CFCI2 (CFC-114a), CF3CHCI2 (HCFC-123), CHCI2CHCIF (HCFC- 131), C4H3F3CI4 isomers (HCFC-343 isomers), CF3CCI2CH2CH3 (HCFC-363maf), 1- chlorobutane, 1 -chlorobutene, 1 ,3-dichlorobutane, CF3CCI2CCI2CF3 (CFC-316maa), CFsCCkCCICFs (CFO-1316mxx), CeHsC Fs (trichlorotrifluorohexane isomers, HCFC-593 isomers), dichlorotrifluorooctene isomers (C8H11CI2F3 isomers), dichlorotri
  • the present invention provides a composition comprising HCFC-353maf and ethylene and CF3CFCI2 (CFC-114a), or HCFC- 353maf and CF3CFCI2 (CFC-114a) and CF3CHCI2 (HCFC-123), or HCFC-353maf and CF3CHCI2 (HCFC-123) and CF3CCI2CH2CH3 (HCFC-363maf), or HCFC-353maf and 1 -chlorobutene and dichlorotrifluorobutene, or HCFC-353maf and CeHsC Fs (trichlorotrifluorohexane isomers, HCFC-593 isomers) and CFO-1316mxx, or HCFC- 353maf and dichlorotrifluorooctene (C8H11CI2F3) and CF3CCI2CCI2CF3.
  • CFC-114a HCFC- 353maf and
  • the present invention also provides a composition comprising HCFC- 353maf, and at least one isomer of trichlorotrifluorohexane isomers, (HCFC-593 isomers).
  • Figure 1 illustrates a flow diagram for a process useful to prepare HCFC- 353maf according to an embodiment of this invention.
  • the present invention relates broadly to compositions comprising 2,2,4- trichloro-1 ,1 ,1-trifluorobutane (HCFC-353maf, CH2CICH2CCI2CF3), processes of preparing such compositions and their use.
  • Compounds may be referred to herein by the compound name (e.g., 2,2,4- trichloro-1 ,1 ,1-trifluorobutane) or ASHRAE designation (e.g., HCFC-353maf) or chemical formula (e.g., CF3CCI2CH2CH2CI) and optionally prefaced by “CFC”, “HCFC”, “HFC”, “CFO”, “HCFO”, or “HFO”, meaning “chlorofluorocarbon”, “hydrochlorofluorocarbon”, “hydrofluorocarbon”, “chlorofluoroolefin”, “hydrochlorofluoroolefins”, or “hydrofluoroolefin”.
  • the absence of the preface does not change the meaning of the compound.
  • the term “isomers” is used to represent one or more compounds having the recited chemical formula that are identified using standard analytical techniques (GC and GC-mass spectrometry).
  • the isomers may include one or more compounds having the recited chemical formula, such as linear, branched and cyclic compounds).
  • isomers may include unsaturated compounds (having a double bond) or cyclic compounds having the same chemical formula or multiple unsaturations (two or more double bonds) or combinations with cyclic structures.
  • the compound may have “E-” and “Z-” isomers. If neither “E-” nor “Z-” are identified, the compound disclosed may contain one or both isomers.
  • CFO-1316mxx may include one or both of E- CFO-1316mxx and Z-CFO-1316mxx, whereas specific isomers are identified as “E- CFO-1316mxx” and “Z-CFO-1316mxx”.
  • compositions comprising, “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • 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.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • transitional phrase "consisting essentially of” is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention.
  • the term “consisting essentially of” occupies a middle ground between “comprising” and “consisting of”.
  • a “catalyst system” comprises a metal and an organic ligand.
  • the catalyst system effects the addition of alkyl halides to olefins.
  • effects the addition of alkyl halides to olefins is meant herein the catalyst system catalyzes or initiates the reaction of an alkyl halide with an olefin.
  • the present invention describes processes for preparing a mixture or a composition comprising, consisting of, or consisting essentially of HCFC-353maf (CF3CCI2CH2CH2CI, 2,2,4-trichloro-1 ,1 ,1-trifluorobutane), and one or more additional compounds.
  • the present invention provides a process for preparing HCFC-353maf comprising contacting CFC-113a with ethylene in the presence of a catalyst system comprising a metal and an organic ligand in a reactor to obtain a process mixture comprising HCFC-353maf, wherein the process is performed at a temperature of about 80°C to about 150°C, a and a pressure of about 50 to 150 psig.
  • the temperature is in the range of about 85 to about 125°C, or in the range of about 95 to about 115°C.
  • the process of this invention is performed at a conversion of CFC-113a of less than 100%, such as from 30-80% conversion of CFC-113a.
  • the process is performed at a conversion of less than 80% of the CFC-113a. In one embodiment, the process is performed at a conversion of 30-80% of the CFC-113a. In one embodiment, the process is performed at a conversion of 40-70% of the CFC- 113a. In one embodiment, the process is performed at a conversion of 50-70% of the CFC-113a.
  • the process of this invention is performed in the presence of an excess of CFC-113a.
  • the process mixture comprises HCFC- 353maf and CFC-113a.
  • the CFC-113a present in the process mixture may be and is preferably separated from the process mixture and recycled to the process.
  • the process of this invention involves reaction of CFC-113a with ethylene to produce HCFC-353maf in the presence of a catalyst system comprising a metal and an organic ligand.
  • a catalyst system comprising a metal and an organic ligand.
  • Many metals have been found to promote the addition of haloalkanes to olefins with good selectivity.
  • systems based on iron, copper, ruthenium and nickel are systems based on iron or copper.
  • the metal of the catalyst system is or comprises iron or copper. In one embodiment of the process of this invention, the metal is or comprises iron. In one embodiment, the metal is or comprises copper.
  • the metal is or comprises iron powder, iron wire, iron screen or iron turnings or combinations of two or more thereof.
  • the metal comprises iron powder.
  • the metal comprises iron wire.
  • the metal comprises iron screen.
  • the metal comprises iron turnings.
  • the metal is or comprises an iron salt such as ferric chloride or ferrous chloride.
  • the metal comprises ferric chloride.
  • the metal comprises ferrous chloride.
  • the metal comprises ferric chloride and ferrous chloride.
  • the metal is or comprises copper.
  • the copper may be in the form of a copper salt such as copper(l) chloride or copper (II) chloride.
  • Other copper salts may also be used including copper(l) bromide, copper (II) bromide, copper (I) iodide, copper (II) acetate and copper (II) sulfate.
  • the metal comprises copper (I) chloride.
  • the metal comprises copper (II) chloride.
  • the metal comprises copper(l) chloride and copper (II) chloride.
  • the organic ligand can be an organophosphorus compound or an organonitrogen compound.
  • the metal when the organic ligand is an organophosphorus compound, the metal is iron. In one embodiment, when the organic ligand is an organonitrogen compound, the metal is copper.
  • the organic ligand when the organic ligand is an organophosphorus compound, the organic ligand may be selected from the group consisting of a phosphine, phosphinite, phosphonate, phosphite, a phosphine oxide or a phosphate, and mixtures of two or more thereof.
  • the organic ligand when the organic ligand is an organonitrogen compound, the organic ligand may be selected from the group consisting of an amine, a nitrile, an amide, a thiamide, and mixtures of two or more thereof.
  • the metal is iron and the organic component comprises an organophosphorus compound.
  • the organophosphorus compound may be phosphine, phosphinite, phosphonate, phosphite, phosphine oxide or phosphate, each comprising one or more alkyl or aryl groups.
  • the organophosphorus compound includes compounds having a structural formula as follows: PR1R2R3 where each R1, R2, and R3 is independently aryl, alkyl, aryloxy or alkoxy.
  • the organophosphorus compound includes compounds having a structural formula as follows: OPR1R2R3 where each R1, R2, and R3 is independently aryloxy or alkoxy.
  • the metal of the catalyst system comprises iron and the organic ligand of the catalyst system comprises a trialkyl phosphate or trialkyl phosphine or triaryl phosphine.
  • the process is performed in the presence a catalyst system comprising iron and an alkyl phosphate, wherein the alkyl phosphate is a monoalkyl phosphate, a dialkyl phosphate or a trialkyl phosphate or a combination of two or more thereof.
  • the alkyl phosphate is a monoalkyl phosphate.
  • the alkyl phosphate is a dialkyl phosphate.
  • the alkyl phosphate is a trialkyl phosphate.
  • the alkyl phosphate is a combination of two or more of monoalkyl phosphate, dialkyl phosphate and trialkyl phosphate.
  • the metal of the catalyst system comprises iron and the organic ligand is trialkyl phosphate, wherein the trialkyl phosphate is a tris(Ci -6 alkyl)phosphate.
  • the metal of the catalyst system is iron and the organic ligand is tributyl phosphate.
  • the metal of the catalyst system is iron and the organic ligand of the catalyst system comprises a phosphine.
  • the phosphine comprises an alkylphosphine or arylphosphine.
  • the phosphine is chosen from tributyl phosphine and triphenyl phosphine.
  • the organic ligand is tributyl phosphine.
  • the organic ligand is triphenyl phosphine.
  • the process is performed in the presence of a catalyst system wherein the metal of the catalyst system comprises copper and the organic ligand of the catalyst system is a nitrogencontaining organic ligand.
  • the organic ligand of the catalyst system may comprise an organonitrogen compound.
  • the organonitrogen compound may be selected from the group consisting of an amine, a nitrile, or an amide, or combinations of two or more thereof.
  • the amine may be selected from the group consisting of monoalkyl amine, dialkylamine, trialkyl amine and cyclic amine.
  • the amine may be selected from the group consisting of tertbutylamine, n-butylamine, sec-butylamine, 2-propylamine, benzylamine, tri-n- butylamine, ethanolamine, piperidine and pyridine.
  • the amine is tert-butylamine.
  • the nitrile may be selected from the group consisting of acetonitrile, propionitrile, n-butyronitrile, benzonitrile, and phenylacetonitrile. In one embodiment, the nitrile is acetonitrile.
  • the amide may be selected from the group consisting of hexamethylphosphoramide and dimethylformamide. In one embodiment, the amide is hexamethylphosphoramide.
  • the organic ligand may comprise a nitrogencontaining heterocyclic compound.
  • Suitable heterocyclic compounds include those selected from the group consisting of imidazoles, imidazolines, oxadiazoles, oxazoles, oxazolines, isoxazoles, thiazoles, thiazolines, pyrrolines, pyridines, trihydropyrimidines, pyrazoles, triazoles, triazolium salts, isothiazoles, tetrazoles, tetrazolium salts, thiadiazoles, pyridazines, pyrazines, oxazines and dihydrooxazine.
  • the heterocyclic compound is selected from the group having Formula (I) or Formula (II) as follows: where E is selected from O, S, Se, CH2 and N(R 8a ); R 5a is selected from the group consisting of CH3 and C2H5 (and is preferably CH3); R 6a and R 7a are selected from the group consisting of H, CH3, CeHs (i.e.
  • L is selected from the group consisting of O, S, Se, N(R 8a ), Ceb , 2,6-pyridyl-, -OCeb -Ceb O-, -CH2CH2OCH2CH2- and -(CH2)P-, where p is an integer from 0 to 6; and each R 8a is selected from the group consisting of H and CmH2m+i where m is an integer from 1 to
  • the metal of the catalyst system is copper and the organic ligand of the catalyst system comprises an organonitrogen compound.
  • the metal is or comprises copper and the organic ligand is an organonitrogen compound and the organonitrogen compound is an amine.
  • the concentration of the metal of the catalyst system as discussed herein refers to the concentration of the metal, based on ICP analysis of the process mixture.
  • the concentration of the metal from the catalyst system in the process mixture ranges from 300 ppmw to 3000 ppmw of metal and the metal is iron or copper.
  • the metal of the catalyst is iron and the concentration of the metal in the process mixture ranges from 300 ppmw to 3000 ppmw.
  • the metal of the catalyst system is copper and the concentration of the metal in the process mixture ranges from 300 ppmw to 3000 ppmw.
  • the concentration of the metal from the catalyst system in the process mixture ranges from 500 ppmw to 2500 ppmw of metal and the metal is iron or copper.
  • the metal of the catalyst system is iron and the concentration of the metal in the process mixture ranges from 500 ppmw to 2500 ppmw.
  • the metal of the catalyst system is copper and the concentration of the metal in the process mixture ranges from 500 ppmw to 2500 ppmw.
  • the concentration of the metal from the catalyst system in the process mixture ranges from 750 ppmw to 2000 ppmw of metal and the metal is iron or copper.
  • the metal of the catalyst system is iron and the concentration of the metal in the process mixture ranges from 750 ppmw to 2000 ppmw.
  • the metal of the catalyst system is copper and the concentration of the metal in the process mixture ranges from 750 ppmw to 2000 ppmw.
  • the concentration of the metal from the catalyst system in the process mixture ranges from 800 ppmw to 1800 ppmw of metal and the metal is iron or copper.
  • the metal of the catalyst system is iron and the concentration of the metal in the process mixture ranges from 800 ppmw to 1800 ppmw.
  • the metal of the catalyst system is copper and the concentration of the metal in the process mixture ranges from 800 ppmw to 1800 ppmw.
  • the concentration of the metal from the catalyst system in the process mixture ranges from 1000 ppmw to 1500 ppmw of metal and the metal is iron or copper.
  • the metal of the catalyst system is iron and the concentration of the metal in the process mixture ranges from 1000 ppmw to 1500 ppmw.
  • the metal of the catalyst system is copper and the concentration of the metal in the process mixture ranges from 1000 ppmw to 1500 ppmw.
  • the concentration of the metal from the catalyst system in the process mixture ranges from 1200 ppmw to 1400 ppmw of metal and the metal is iron or copper.
  • the metal of the catalyst system is iron and the concentration of the metal in the process mixture ranges from 1200 ppmw to 1400 ppmw. In one embodiment, the metal of the catalyst system is copper and the concentration of the metal in the process mixture ranges from 1200 ppmw to 1400 ppmw.
  • the concentration of the metal of the catalyst system in the process mixture ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises a trialkyl phosphate.
  • the concentration of the metal of the catalyst system in the process mixture ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises a trialkyl phosphate.
  • the concentration of the metal of the catalyst system in the process mixture ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises a tri(Ci-6 alkyl)phosphate.
  • the concentration of the metal of the catalyst system in the process mixture ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises tributyl phosphate.
  • the concentration of the metal of the catalyst system in the process mixture ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises a phosphine.
  • the concentration of the metal of the catalyst system in the process mixture ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises an alkylphosphine or arylphosphine.
  • the concentration of the metal of the catalyst system in the process mixture ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises triphenyl phosphine or tributyl phosphine.
  • the concentration of the metal of the catalyst system in the process mixture ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises triphenyl phosphine.
  • the concentration of the metal of the catalyst system in the process mixture ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises tributyl phosphine.
  • the concentration of the metal of the catalyst system in the process mixture ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises copper and the organic ligand of the catalyst system is an alkyl amine.
  • the concentration of the metal of the catalyst system in the process mixture ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises copper and the organic ligand of the catalyst system is tributyl amine.
  • the process is performed with a molar excess of 1,1,1 - trichloro-2,2,2-trifluoroethane.
  • a molar excess of 1,1 ,1-trichloro-2,2,2-trifluoroethane used is based on 1 molar equivalent of ethylene, for example, greater than 1 molar equivalent, greater than 2 molar equivalents, greater than 5 molar equivalents, or greater than 10 molar equivalents of 1,1 ,1-trichloro-2,2,2-trifluoroethane is used based on 1 molar equivalent of ethylene.
  • a reaction system comprising a reactor and a distillation system downstream of the reactor.
  • the reaction system includes feed lines to introduce reactants to the reactor.
  • the feed lines include a feed line for a reactant ethylene feed, and a fresh reactant CFC-113a feed, an organic ligand feed and a recycled CFC-113a feed.
  • fresh reactant CFC-113a feed and recycled CFC-113a feed are combined in a single feed for CFC-113a to be introduced to the reactor.
  • the organic ligand is combined with the fresh reactant CFC-113a feed or the recycled CFC-113a feed prior to introducing the reactor.
  • the reaction system further comprises an exit stream from the reactor, which provides the process mixture.
  • the reaction system comprises a distillation system to separate the desired product from the reactor process mixture.
  • the distillation system may comprise multiple distillation columns, evaporator (reboiler)/condenser to facilitate separating reactants, components of the catalyst system, and by-products from the reactor process mixture.
  • the reactor process mixture may proceed through a mechanism to separate a portion of the reaction process mixture, which is preferably cooled and then recycled to the reactor.
  • the distillation system comprises a distillation column to separate a stream comprising reactants from the process mixture.
  • the separated reactants comprise CFC-113a and optionally, ethylene.
  • the distillation system comprises one or more additional distillation columns to separate the desired product (HCFC-353maf) from the remaining process mixture.
  • the distillation system comprises a distillation column to remove compounds having boiling points below ethylene from the process mixture.
  • the distillation system comprises a distillation column to remove compounds having boiling points above the boiling point of HCFC-353maf.
  • the reaction system provides a purified product comprising HCFC-353maf.
  • the reaction system may comprise a storage tank to store the purified HCFC-353maf.
  • the purified HCFC-353maf product may be used as a starting material to produce 3,3,4,4,4-pentafluorobut-1-ene (HFO-1345zf), and optionally subsequently, 3,5,5-trichloro-1 ,1 ,1 ,2,2,6,6,6-octafluorohexane (HCFC- 548mafd) and E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene (E-HFO-153-10mczz).
  • composition comprising HCFC-353maf, and at least one additional compound chosen from ethylene, CF3CCI3 (CFC-113a), CF3CFCI2 (CFC-114a), CF3CHCI2 (HCFC-123), CHCI2CHCIF (HCFC-131), C4H3F3CI4 (HCFC-343 isomers), CF3CCI2CH2CH3 (HCFC-363maf), 1- chlorobutane, 1 -chlorobutene, 1 ,3-dichlorobutane, CF3CCI2CCI2CF3 (CFC-316maa), CFsCCkCCICFs (CFO-1316mxx), CeHsC Fs (trichlorotrifluorohexane, HCFC-593 isomers), dichlorotrifluorooctene (C8H11CI2F3 isomers), dichlorotrifluorobutene (HCFC-113a), CF3CFCI2 (C
  • composition comprising HCFC-353maf, ethylene and CFC-113a.
  • composition comprising HCFC-353maf, ethylene and CFC-113a and further comprising CFC-114a.
  • composition comprising HCFC-353maf, ethylene and CFC-113a and further comprising CFC-114a and/or HCFC-363maf.
  • compositions comprising HCFC-353maf, ethylene and CFC-113a and further comprising CFC-114a and/or HCFC-363maf and/or 1 -chlorobutane, and/or CFC-316maa, and/or CFO-1316mxx.
  • composition comprising HCFC-353maf, ethylene and CFC-113a and further comprising CFC-114a and/or HCFC-363maf and/or 1 -chlorobutane and/or dichlorotrifluorooctene.
  • a composition comprising HCFC-353maf, ethylene and CFC-113a and further comprising CFC-114a and/or HCFC-363maf and/or 1 -chlorobutane and/or dichlorotrifluorooctane and/or organic ligand.
  • the organic ligand is tributylphosphate.
  • the organic ligand is triphenylphosphine.
  • composition comprising HCFC-353maf, andHCFC-593 isomers.
  • composition comprising HCFC-353maf and 1 , 1 , 1-trifluoro-2,2,6-trichlorohexane (HCFC-593mafff).
  • composition comprising HCFC-353maf and 1 ,3,6-trichloro-3-trifluoromethylpentane.
  • composition comprising HCFC-353maf, andHCFC-593 isomers and further comprising ethylene and CFC- 113a.
  • composition comprising HCFC-353maf, HCFC-593 isomers, ethylene and CFC-113a and further comprising CFC-114a.
  • composition comprising HCFC-353maf, HCFC-593 isomers, ethylene and CFC-113a and further comprising CFC-114a and/or HCFC-363maf.
  • composition comprising HCFC-353maf, HCFC-593 isomers, ethylene and CFC-113a and further comprising CFC-114a and/or 363maf and/or 1 -chlorobutane and/or CFC-316maa, and/or CFO- 1316mxx.
  • composition comprising HCFC-353maf, CFC-316maa and CFO-1316mxx.
  • a composition comprising HCFC-353maf, HCFC-593 isomers, ethylene and CFC-113a and further comprising CFC-114a and/or HCFC-363maf and/or 1 -chlorobutane and/or dichlorotrifluorooctene.
  • composition comprising HCFC-353maf, and at least one of ethylene, 1,1,1-trichloro-2,2,2trifluoroethane, 1- chlorobutane, 2,2,3,3-tetrachloro-1 ,1 ,1 ,4,4,4-hexafluorobutane, 2,3-dichloro-
  • composition comprising HCFC-353maf, and at least two of ethylene, 1,1,1-trichloro-2,2,2trifluoroethane, 1- chlorobutane, 2, 2, 3, 3-tetrachloro-1 ,1 ,1 ,4,4,4-hexafluorobutane, 2,3-dichloro-
  • composition comprising HCFC-353maf, and at least three of ethylene, 1,1 ,1-trichloro-2,2,2trifluoroethane, 1- chlorobutane, 2, 2, 3, 3-tetrachloro-1 ,1 ,1 ,4,4,4-hexafluorobutane, 2,3-dichloro-
  • composition comprising HCFC-353maf, and at least four of ethylene, 1 ,1 ,1-trichloro-2,2,2trifluoroethane, 1- chlorobutane, 2, 2, 3, 3-tetrachloro-1 ,1 ,1 ,4,4,4-hexafluorobutane, 2,3-dichloro-
  • composition comprising HCFC-353maf, and ethylene, 1,1,1-trichloro-2,2,2trifluoroethane, 1 -chlorobutane, 2,2,3,3-tetrachloro-1 ,1 ,1 ,4,4,4-hexafluorobutane, 2,3-dichloro-1 ,1,1 ,4,4,4-hexafluoro- 2-butene, trichlorotrifluorohexane, 1 ,5,5-trichloro-6,6,6-trifluorohexane, and 2,2,4- trich loro- 1 , 1 , 1 -trifluorobutane.
  • composition comprising HCFC-353maf, and at least one of 1 ,1-dichloro-1,2,2,2-tetrafluoroethane, 2,2- dichloro-1 , 1 , 1 -trifluoroethane, 1,1 ,1-trichloro-2,2,2trifluoroethane, 1 -chlorobutane,
  • composition comprising HCFC-353maf, and at least two of 1 ,1 -dichloro- 1,2, 2, 2-tetrafluoroethane, 2,2- dichloro-1,1,1-trifluoroethane, 1,1 ,1-trichloro-2,2,2trifluoroethane, 1 -chlorobutane,
  • composition comprising HCFC-353maf, and at least three of 1,1 -dichloro-1, 2, 2, 2-tetrafluoroethane, 2,2- dichloro-1,1,1-trifluoroethane, 1,1 ,1-trichloro-2,2,2trifluoroethane, 1 -chlorobutane,
  • composition comprising HCFC-353maf, and at least four of 1,1 -dichloro-1 , 2, 2, 2-tetrafluoroethane, 2,2- dichloro-1,1,1-trifluoroethane, 1,1 ,1-trichloro-2,2,2trifluoroethane, 1 -chlorobutane,
  • composition comprising HCFC-353maf, and 1 ,1 -dichloro- 1,2, 2, 2-tetrafluoroethane, 2,2-dichloro-1 , 1 , 1 - trifluoroethane, 1,1,1-trichloro-2,2,2trifluoroethane, 1 -chlorobutane, 1 , 1 -dichloro- 1 ,2,2,2-tetrafluoroethane, 2,2-dichloro-1 , 1 , 1 -trifluorobutane, 1 , 5, 5-trich loro-6 , 6 ,6- trifluorohexane, 1,3,6-trichloro-3-trifluoromethylpentane, dichlorotrifluorooctene, and tributylphosphate.
  • compositions comprising HCFC-353maf, and at least one isomer of trichlorotrifl uorohexane, HCFC-593 isomers, ethylene and CFC-113a and further comprising 114a and/or 363maf and/or 1 -chlorobutane and/or tributylphosphate.
  • compositions comprising HCFC-353maf, and at least one isomer of trichlorotrifl uorohexane, HCFC-593 isomers, ethylene, CFC-113a and further comprising tributylphosphate.
  • this disclosure provides a composition comprising HCFC-353maf and at least one of CHCI2CHCIF (HCFC-131), C4H3F3CI4 (HCFC-343 isomers), dichlorotrifluorobutene (HCFO-1343 isomers), 1 -chlorobutene, C6H2CI3F7 isomers, and 1 ,3-dichlorobutane.
  • this disclosure provides a composition comprising HCFC-353maf and at least two of CHCI2CHCIF (HCFC-131), C4H3F3CI4 (HCFC-343 isomers), dichlorotrifluorobutene (HCFO-1343 isomers), 1 -chlorobutene, C6H2CI3F7 isomers, and 1 ,3-dichlorobutane.
  • this disclosure provides a composition comprising HCFC-353maf and at least three of CHCI2CHCIF (HCFC-131), C4H3F3CI4 (HCFC- 343 isomers), dichlorotrifluorobutene (HCFO-1343 isomers), 1 -chlorobutene, C6H2CI3F7 isomers, and 1 ,3-dichlorobutane.
  • this disclosure provides a composition comprising HCFC-353maf and at least four of CHCI2CHCIF (HCFC-131), C4H3F3CI4 (HCFC-343 isomers), dichlorotrifluorobutene (HCFO-1343 isomers), 1 -chlorobutene, C6H2CI3F7 isomers, and 1 ,3-dichlorobutane.
  • this disclosure provides a composition comprising HCFC-353maf, CHCI2CHCIF (HCFC-131), C4H3F3CI4 (HCFC-343 isomers), and dichlorotrifluorobutene (HCFO-1343 isomers).
  • this disclosure provides a composition comprising HCFC-353maf, CHCI2CHCIF (HCFC-131), C4H3F3CI4 (HCFC-343 isomers), and dichlorotrifluorobutene (HCFO-1343 isomers) and further comprises 1 -chlorobutene, C6H2CI3F7 isomers, or 1 ,3-dichlorobutane.
  • this disclosure provides a composition comprising HCFC-353maf, CHCI2CHCIF (HCFC-131), C4H3F3CI4 (HCFC-343 isomers), and dichlorotrifluorobutene (HCFO-1343 isomers) and further comprises 1 -chlorobutene, C6H2CI3F7 isomers, and 1 ,3-dichlorobutane.
  • Compounds disclosed herein are provided in Table 1.
  • Figure 1 provides a flow diagram for a process useful to prepare 2,2,4- trichloro-1 ,1,1-trifluorobutane according to an embodiment of this invention.
  • a reaction system 100 which includes reactor 101 and distillation system downstream of reactor 101.
  • reactant ethylene 102 and fresh reactant CFC-113a feed 103 are introduced to reactor 101.
  • organic ligand 104 component of the catalyst system described herein is also introduced to reactor 101.
  • a cooled recycled process stream 110 is also introduced to reactor 101.
  • Reactor 101 may be pre-loaded with metal component of the catalyst system (iron or copper based), which is not illustrated in Figure 1.
  • reactants ethylene, fresh and recycled CFC-113a and organic ligand
  • reactants ethylene, fresh and recycled CFC-113a and organic ligand
  • two or more of the reactants can be combined, including combining into a single feed stream along with cooled recycled process stream 110 from metal solids bed 105.
  • Metal component of the catalyst system described herein may be fed from metal bed 105 to reactor 101.
  • Metal solids bed 105 contains additional metal (iron or copper).
  • the additional metal may be any form of solid, metal (0) or metal salt.
  • the metal bed contains iron (0) which not only serves as a source of metal, but also is able to reduce Fe 3+ that may be produced in reactor 101 to Fe 2+ .
  • a vent condenser (not shown) may be attached to reactor 101 to remove inert materials.
  • the vent condenser may be operated periodically.
  • Process stream 106 exits reactor 101 proceeds through pump 130.
  • Process stream 106 is split following pump 130 into a first portion 107 and a second portion 108.
  • First portion 107 of process stream 106 proceeds through heat exchanger 109 to cool first portion 107 of process stream 106.
  • After cooling first portion 107 of process stream 106 proceeds through metal solids bed 105, allowing introducing additional metal to the stream, which exits metal solids bed 105 as recycled process stream 110.
  • a second portion 108 of process stream 106 comprising unreacted starting materials, product and byproducts proceeds to first distillation column 112a.
  • Low boilers are removed overhead from column 112a, providing separated stream 111.
  • “Low boilers” may comprise ethylene and components having a boiling point below the boiling point of ethylene.
  • Separated stream 111 proceeds through heat exchanger 113 to evaporator 114 then condenser 115.
  • a purge 116 may be removed from evaporator 114. Purge 116 may comprise undissolved metal, metal chlorides.
  • Noncondensables may comprise nitrogen, ethylene, anhydrous HCI, hydrogen, and low boiling fluorinated compounds.
  • distillation column 112b condensed stream 118 is separated into stream 119 comprising CFC-113a and components having a boiling point below HCFC- 353maf and a stream 120 comprising HCFC-353maf and components having a boiling point above HCFC-353maf.
  • Stream 119 proceeds to third distillation column 112c, from which CFC- 113a is separated from components having a boiling point below HCFC-353maf to provide recycle CFC-113a stream 121. A purge may be removed from the bottom of third distillation column 112c.
  • stream 120 comprising HCFC-353maf and components having a boiling point above HCFC-353maf is separated into stream 122 comprising purified HCFC-353maf from the column.
  • a purge stream 124 of high boilers is removed from distillation column 112d and purified stream comprising HCFC-353maf is removed as product stream 122 as final product.
  • the final product comprising HCFC-353maf may be stored in tank 123 for future use, such as, for example, in the manufacture of 3,3,4,4,4-pentafluorobut-1-ene (HFO-1345zf).
  • Additional components not shown in Figure 1 may include heat exchangers, pumps, vacuum equipment for distillation columns and evaporator.
  • Example 2 was repeated except ethylene was continuously added via a submerged dip tube as required to maintain the autoclave internal pressure at 125 psig.
  • conversion of CFC-113a and HCFC-353maf selectivity were similar (less than 5% difference). Thus, operating at a pressure of 125 psig showed consistently good results.
  • Example 2 was repeated except ethylene was continuously added via a submerged dip tube as required to maintain the autoclave internal pressure at 175 psig.
  • conversion of CFC-113a decreased by about 10% and the HCFC-353maf selectivity decreased by about 20%.

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Abstract

La présente invention concerne des compositions contenant du 2,2,4-trichloro-1,1,1-trifluorobutane (HCFC-353maf, CH2ClCH2CCl2CF3), des procédés de préparation de telles compositions et leur utilisation.
PCT/US2025/012357 2024-01-22 2025-01-21 Compositions et procédés pour 2,2,4-trichloro-1,1,1-trifluorobutane Pending WO2025160041A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996028404A1 (fr) * 1995-03-16 1996-09-19 Alliedsignal Inc. Nouveaux intermediaires pour la synthese de composes organiques
JPH08291088A (ja) * 1995-04-17 1996-11-05 A G Technol Kk ヒドロフルオロカーボンの製造方法
WO1997005089A1 (fr) * 1995-08-01 1997-02-13 E.I. Du Pont De Nemours And Company Procedes de fabrication d'halocarbures et de composes selectionnes, et azeotropes formes avec hf

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996028404A1 (fr) * 1995-03-16 1996-09-19 Alliedsignal Inc. Nouveaux intermediaires pour la synthese de composes organiques
JPH08291088A (ja) * 1995-04-17 1996-11-05 A G Technol Kk ヒドロフルオロカーボンの製造方法
WO1997005089A1 (fr) * 1995-08-01 1997-02-13 E.I. Du Pont De Nemours And Company Procedes de fabrication d'halocarbures et de composes selectionnes, et azeotropes formes avec hf

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MICHEAL VAN DER PUY ET AL: "Preparation,fluorination and synthetic utility of a CFC-olefin adduct", JOURNAL OF FLUORINE CHEMISTRY, ELSEVIER, NL, vol. 76, no. 1, 1 January 1996 (1996-01-01), pages 49 - 54, XP002112687, ISSN: 0022-1139, DOI: 10.1016/0022-1139(95)03326-2 *

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