WO2018019724A1 - Procédé de fabrication de perfluorovinyléthers - Google Patents

Procédé de fabrication de perfluorovinyléthers Download PDF

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Publication number
WO2018019724A1
WO2018019724A1 PCT/EP2017/068508 EP2017068508W WO2018019724A1 WO 2018019724 A1 WO2018019724 A1 WO 2018019724A1 EP 2017068508 W EP2017068508 W EP 2017068508W WO 2018019724 A1 WO2018019724 A1 WO 2018019724A1
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Prior art keywords
metal
halofe
group
equal
different
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PCT/EP2017/068508
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English (en)
Inventor
Manuel GREGORI
Stefano Millefanti
Giuseppe Marchionni
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Solvay Specialty Polymers Italy S.P.A.
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Publication of WO2018019724A1 publication Critical patent/WO2018019724A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/42—Halogen atoms or nitro radicals

Definitions

  • the present invention relates to a method for the hydrodehalogenation of halofluoroethers to perfluorovinylethers.
  • Perfluorovinylethers are useful monomers for the manufacture of various fluoropolymers, in particular of thermoprocessable tetrafluoroethylene- based plastics and fluoroelastomers.
  • liquid phase processes generally suffer from the disadvantage that significant amounts of metal halides solutions or muds are typically obtained as by-products (e.g. ZnC solutions/muds are produced when a chlorofluoroether is dechlorinated over zinc).
  • by-products e.g. ZnC solutions/muds are produced when a chlorofluoroether is dechlorinated over zinc.
  • perfluorovinylethers and their handling and disposal are time-consuming, costly and very burdensome from an industrial point of view, as the muds are highly corrosive and possibly have a detrimental environmental impact.
  • perfluorovinylether by hydrodehalogenation of a halofluoroether comprising contacting the halofluoroether with hydrogen in the presence of a catalyst comprising at least one transition metal of group VIII B at a temperature of at most 340°C.
  • WO 2012/104365 discloses a process for the manufacture of a perfluorovinylether by hydrodehalogenation of a halofluoroether, said process comprising contacting the halofluoroether with hydrogen in the presence of a catalyst comprising palladium and at least one transition metal selected from the group consisting of the metals of group VI 11 B, other than palladium, and of group IB.
  • a catalyst comprising palladium and at least one transition metal selected from the group consisting of the metals of group VI 11 B, other than palladium, and of group IB.
  • the presence of at least a second transition metal selected from group VI 11 B and group IB allows retaining the activity of the catalyst (i.e. its ability to transform the halofluoroether in the desired halofluoroether) for a longer period of time, thus increasing the economic profitability of the process.
  • WO 2012/104365 lead also to the formation of monohalo-fluorovinylethers (i.e. fluorovinylethers comprising one halogen other than fluorine) as side- products which, despite being in a relative low amount, are not desired in subsequent polymerization reactions and are difficult to remove from the desired perfluorovinylether.
  • monohalo-fluorovinylethers i.e. fluorovinylethers comprising one halogen other than fluorine
  • perfluorovinylethers that are not contaminated by halofluorovinylethers.
  • US 5089454 SOLVAY AND CIE 18/02/1992 relates to catalytic compositions for the hydrogenation of chlorofluoroalkenes to fluoroalkenes, said composition comprising a porous carrier impregnated with a metal of group VIII of the Periodic Table of the elements and with one or more compounds selected from the salts of an alkali metal or alkaline-earth metal, in particular from sodium, potassium, caesium, lithium, barium, calcium or rubidium chlorides, fluorides or hydroxides.
  • EP 0434408 (E.I.DU PONT DE NEMOURS AND COMPANY) 26/06/1991 discloses the use of a catalyst comprising CuO, NiO and Cr2O3 on CaF2, promoted on an alkali metal selected from K, Cs and Rb for the
  • 27/1 1/1997 discloses the use of fluorides of metals of Group IA in the reaction of of of hexafluoropropylene epoxide (HFPO) with a mixture of carbonyl fluoride (CF) and perfluoroacetyl fluoride (PAF) in a process for the production of perfluoromethyl perfluorovinyl ether (PMVE) and perfluoroethyl perfluorovinyl ether (PEVE).
  • HFPO hexafluoropropylene epoxide
  • CF carbonyl fluoride
  • PAF perfluoroacetyl fluoride
  • a catalyst comprising a transition metal of group VIIIB and an alkali metal of group IA is able to promote the hydrodechlorination reaction of halofluoroethers to provide perfluorovinylethers without giving rise to halofluorovinylethers as byproducts.
  • the present invention relates to a method for
  • HaloFE halofluoroether
  • Rf represents a C1-C6 perfluoro(oxy)alkyl group
  • Rf', Rf" and Rf' equal or different from each other, independently represent fluorine atoms or C1-C5 perfluoro(oxy)alkyl groups
  • X and X' equal or different from each other, are independently selected from CI, Br or I;
  • Rf* and Rf*' equal or different from each other, independently represent fluorine atoms or C1-C3 perfluoro(oxy)alkyl groups;
  • said method comprising contacting said halofluoroether (HaloFE) with hydrogen in the presence of a catalyst comprising at least one transition metal of group VI 11 B and at least one alkali metal of group IA.
  • a catalyst comprising at least one transition metal of group VI 11 B and at least one alkali metal of group IA.
  • the method of the present invention enables to selectively provide compounds (herein after referred to as "perfluorovinylethers") of formulae (A*) and (B*), respectively:
  • Rf, Rf', Rf", Rf'", Yi , Y2, Rf* and Rf*' have same meanings as above defined
  • the method is carried out at temperatures generally not exceeding 340°C; thus, poisoning from HF, sintering or coking phenomena otherwise known as significantly reducing the life of group VI 11 B transition metal catalysts can be essentially avoided.
  • hydrodehalogenation is intended to denote the selective elimination of two halogen atoms, X, X' in formulae (l-A) an (l-B), selected from CI, Br or I, from two adjacent fluorine-substituted carbon atoms of said halofluoroether (HaloFE), in the presence of hydrogen, to yield the corresponding perfluorovinylethers, i.e.
  • perfluoro(oxy)alkyl group is intended to indicate either a perfluoroalkyl group or a perfluorooxyalkyl group, that is a perfluoroalkyl group comprising one or more than one catenary oxygen atom.
  • the halofluoroether [0019] According to a first embodiment of the invention, the halofluoroether
  • HaloFE of the invention is a chlorofluoroether (HaloFE-1 ) having general formula (l-A) as described above, wherein X and X', equal or different from each other, are independently selected from CI, Br or I, with the proviso that at least one of X and X' in said formula (l-A) is a chlorine atom.
  • halofluoroether (HaloFE) of this first embodiment is preferably a
  • HaloFE-2 having general formula (l-A) as described above, wherein X and X' are equal to each other and are chlorine atoms, that is to say that chlorofluoroether (HaloFE-2) complies with formula (ll-A) here below:
  • Rf represents a C1-C6 perfluoro(oxy)alkyl group, preferably a Ci-C 4 perfluoroalkyl group, more preferably a C1-C3 perfluoroalkyl group;
  • Rf', Rf" and Rf' equal or different from each other, independently represent fluorine atoms or C1-C5 perfluoro(oxy)alkyl groups, preferably fluorine atoms or C1-C3 perfluoroalkyl groups, more preferably fluorine atoms or C1-C2 perfluoroalkyl groups, even more preferably fluorine atoms.
  • the chlorofluoroether (HaloFE-2) of the present invention is typically a gaseous compound under process conditions.
  • HaloFE-2 chlorofluoroethers
  • formula (ll-A) Representative compounds of chlorofluoroethers (HaloFE-2) described by formula (ll-A) useful in the present invention include, but are not limited to, the following compounds: CF3OCFCICF2CI, CF3CF2OCFCICF2CI,
  • the halofluoroether (HaloFE) of the invention is a chlorofluorodioxolane (HaloFE-3) having general formula (l-B) as described above, wherein X and X', equal or different from each other, are independently selected from CI, Br or I, with the proviso that at least one of X and X' in said formula (l-B) is a chlorine atom.
  • the halofluoroether (HaloFE) of this second embodiment is preferably a chlorofluorodioxolane (HaloFE-4) having general formula (l-B) as described above, wherein X and X' are equal to each other and are chlorine atoms, that is to say that chlorofluorodioxolane (HaloFE-4) complies with formula ( I l-B) here below:
  • Rf * and Rf * ' equal or different from each other, independently represent fluorine atoms or C1-C3 perfluoro(oxy)alkyl groups, preferably fluorine atoms or C1-C3 perfluorooxyalkyl groups, more preferably fluorine atoms or -OCF3 groups; Yi and Y2, equal or different from each other, independently represent fluorine atoms or C1-C3 perfluoroalkyl groups, preferably fluorine atoms.
  • the chlorofluorodioxolane (HaloFE-4) of the present invention is typically a gaseous compound under process conditions.
  • HaloFE-4 chlorofluorodioxolanes described by formula ( I l-B) useful in the present invention include, but are not limited to, the following compounds:
  • the method of the present invention is carried out in the presence of a catalyst comprising at least one transition metal selected from group VIIIB [metal (M1 )] and at least one alkali metal of group IA [metal (M2)].
  • the term "transition metal of group VIIIB” is hereby intended to denote the following metals: Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt.
  • the catalyst comprises one metal of group VIIIB [metal (M1 )], preferably one of Rh, Ir, Pd and Pt; more preferably, the metal (M1 ) is Pd.
  • alkali metal of group IA is intended to denote Li, Na, K, Rb, Cs and Fr; preferably, the alkali metal of group IA [metal (M2)] is K or Cs; more preferably, the alkali metal of group IA is Cs.
  • the catalyst comprises one transition metal of group VIII B
  • the catalyst comprises Pd as metal (M1) and K as metal (M2).
  • the catalyst comprises Pd as metal (M1 ) and Cs as metal (M2).
  • Catalysts comprising Pd and Cs are particularly preferred because, in addition to avoiding the formation of halofluorovinylethers, they provide the desired perfluorovinylethers with higher selectivities.
  • the molar ratio between metal (M1) and metal (M2) typically ranges from 0.50 to 1.50; preferably, the molar ratio ranges from 0.90 to 1.10.
  • the catalyst of the invention is typically a supported catalyst, that is to say that it comprises metals (M1) and (M2) as above described and an inert carrier.
  • the inert carrier is generally selected from activated carbon, silica and alumina; preferably, the carrier is activated carbon.
  • Suitable inert carriers generally have a BET surface area of from 800 to 1600 m 2 /g, preferably from 1000 to 1600 m 2 /g, even more preferably from 1 100 to 1500 m 2 /g.
  • the BET surface area is measured by N2 adsorption as per the Brunauer, Emmett and Teller method of calculation, according to ISO 9277.
  • the catalyst When supported, the catalyst generally comprises metal (M1 ), preferably Pd, in an amount of from 0.1 wt% to 2 wt%, preferably from 0.3 wt % to 1.8 wt %, more preferably from 0.5 wt % to 1.5 wt % with respect to the inert carrier.
  • M1 metal
  • Pd metal
  • the amount of metal (M2), preferably K or Cs, in the supported catalyst is determined, on the basis of the weight of metal (M1), in order to obtain a (M1 ):(M2) molar ratio falling within the above identified ranges of from 0.50 to 1.50.
  • the catalyst can be advantageously prepared by the incipient wetness impregnation method. In such a method an aqueous solution of a suitable metal precursor is added to the inert carrier and dried. The metal is then typically reduced by treatment with h .
  • Suitable precursors of metal (M1 ) are halides, preferably chlorides, and
  • Suitable metal precursors of metal (M2) are organic and inorganic salts of such metals.
  • Organic salts can be selected from carboxylates, alcoholates and acetylacetonates whose alkyl chain usually contains from 1 to 10 carbon atoms.
  • Inorganic salts can be halides, hydroxides or nitrates.
  • an inorganic salt of metal (M2) is used, more preferably a chloride.
  • impregnation of the inert carrier with the precursor of the at least one metal (M1 ) and the at least one metal (M2) can be carried out either sequentially or simultaneously.
  • the inert carrier is first impregnated with a solution of the precursor of the at least one metal (M1 ), optionally dried and then impregnated with a solution of the precursor of metal (M2).
  • the inert carrier is impregnated with a solution comprising both the at least one metal (M1 ) and the precursor of the at least one metal (M2), followed by drying and reduction, if needed.
  • Catalysts used in the method of the invention are generally activated
  • temperatures comprised between 250°C and 450°C, more preferably between 250°C and 400°C, even more preferably between 300°C and 400°C.
  • regeneration of the catalyst is also carried out under hydrogen at temperatures comprised between 300°C and 500°C, more preferably between 350°C and 500°C, even more preferably between 400°C and 500 °C.
  • regeneration refers to the process of restoring the catalytic activity of the catalyst which has been deactivated by use in the
  • catalysts comprising Pd as metal (M1 ) and K or Cs as metal (M2) supported on carbon, wherein the molar ratio between (M1) and (M2) ranges from 0.50 to 1.50, preferably from 0.90 to 1.10, in particular in a method for the hydrodechlorination of chlorofluoroethers (HaloFE-2) of formula (ll-A) as described above.
  • HaloFE-2 chlorofluoroethers
  • the desired perfluorovinylether was obtained without formation of chlorofluorovinylethers.
  • Catalysts comprising Pd as metal (M1 ) and Cs as metal (M2) supported on carbon are particularly advantageous in that they allow obtaining the desired perfluorovinylether with selectivities of at least 80%.
  • the method of the present invention is preferably carried out at a
  • HaloFE halofluoroether
  • Lower limits of temperatures suitable for achieving efficient conversion of halofluoroethers to perfluorovinylethers are not particularly limited.
  • Temperatures of advantageously at least 170°C, preferably at least 200°C, more preferably at least 210°C, and even more preferably at least 230°C are generally used. Best results can be obtained at temperatures comprised between 230°C and 320°C.
  • the method of the present invention is advantageously carried out in gas- phase, that is to say in conditions wherein hydrogen and both the halofluoroether (HaloFE) and the corresponding perfluorovinylether are in gaseous state.
  • the catalyst is generally used as a solid, so that the reaction takes place between the reactants in the gas phase and the catalyst in the solid state.
  • Hydrogen can be fed either as neat reactant or diluted with an inert gas, e.g. nitrogen, helium or argon.
  • an inert gas e.g. nitrogen, helium or argon.
  • the inert gas is nitrogen.
  • the method of the invention is carried out in any suitable reactor, including fixed and fluidized bed reactors.
  • the method is generally carried out in continuous using a plug flow reactor comprising a fixed bed of catalyst.
  • the reaction pressure is not critical to the method.
  • the method of the invention is typically carried out under atmospheric pressure, even though pressures between 1 and 3 bar can be employed.
  • Contact time between the halofluoroether (HaloFE) and the catalyst is not particularly limited and will be chosen by the skilled in the art in relation, notably, with the reaction temperature and other process parameters.
  • Contact time which, for continuous processes, is defined as the ratio of the catalyst bed volume to the gas flow rate in standard conditions at 0°C and 1 bar, may vary between a few seconds and several hours.
  • this contact time is generally comprised between 2 and 200 seconds, preferably between 5 and 150 seconds, more preferably between 5 and 50 seconds.
  • time-on-stream may vary between 5 and 500 hours, preferably between 20 and 200 hours.
  • a time-on-stream of at least 50 hours without a significant decrease of conversion may generally be advantageous. Even more advantageous might be a time-on- stream of at least 50 hours without a significant decrease of both conversion and selectivity.
  • time-on-stream means the period of time in which the catalyst is contacted with the HaloFE to provide the desired perfluorovinylether. It is also understood that the spent catalyst can be advantageously regenerated as above mentioned and recycled in the method of the invention.
  • HaloFE hydrogen/halofluoroether
  • HaloFE hydrogen/halofluoroether
  • HaloFE halofluoroether
  • HaloFE-1 chlorofluoroether
  • HaloFE-2 chlorofluoroether
  • HaloFE-3 chlorofluorodioxolane
  • HaloFE-4 chlorofluorodioxolane
  • hydrogen chloride is typically obtained; halogenidric acids can be easily recovered by neutralization in an aqueous alkaline solution or by absorption in water.
  • the catalyst was subsequently dried at 120°C in a nitrogen flow for 6
  • CF3OCFCICF2CI manufactured according to US 2007203368 (SOLVAY SOLEXIS SPA) 30/08/2007 was fed in the reactor at a space velocity of 7.4 g/h; the residence time was 5 seconds.
  • Conversion and selectivity were calculated by gas-chromatography (GC) on an HP 5890 gas chromatographer equipped with a J&W Agilent Parabond Q semi-capillary column according to the internal standard method using nitrogen as internal standard and an autosampled calibrated injection loop.
  • Example 1 was repeated with the sole difference that Catalyst B was used.
  • Example 1 was repeated with the differences that catalyst C was used and CF3OCFCICF2CI was fed in the reactor at a space velocity of 7.7 g/h. The results are reported in Table 4 below.
  • Example 4 (comparative) - Hydrodechlorination of CF3OCFCICF2CI on catalyst D
  • Example 1 was repeated with the differences that catalyst D was used, and CF3OCFCICF2CI was fed in the reactor at a space velocity of 1.4 g/h with a residence time of about 10 seconds. The results are reported in Table 5 below.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé pour l'hydrodéshalogénation d'un halofluoroéther (HaloFE) ayant la formule générale (I-A) ou (I-B) : (I-A) RfO-CRf'X-CRf"Rf"'X' où -Rf représente un perfluoroalkyle C1-C6 ou un groupe perfluorooxyalkyle C1-C6; - Rf', Rf" et Rf'", égaux ou différents les uns des autres, représentent indépendamment un atome de fluor ou un perfluoroalkyle C1-C5 ou un groupe perfluorooxyalkyle C1-C5; X et X', égaux ou différents les uns des autres, sont indépendamment sélectionnés parmi CI, Br, ou I; (I-B) où : -Rf* et Rf*', égaux ou différents les uns des autres, représentent indépendamment un atome de fluor ou un perfluoroalkyle C1-C3 ou un groupe perfluorooxyalkyle C1-C3; -Y1 et Y2, égaux ou différents les uns des autres, représentent indépendamment un atome de fluor ou un groupe perfluoroalkyle C1-C3; X et X' sont comme définis précédemment; le procédé comprend la mise en contact dudit halofluoroéther (HaloFE) avec l'hydrogène en présence d'un catalyseur comprenant au moins un métal de transition du groupe VI 11 B et au moins un métal alcali du groupe IA.
PCT/EP2017/068508 2016-07-26 2017-07-21 Procédé de fabrication de perfluorovinyléthers WO2018019724A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0434408A1 (fr) 1989-12-19 1991-06-26 E.I. Du Pont De Nemours And Company Procédé à plusiers stades successis pour la préparation du hexafluoropropylène
US5089454A (en) 1988-05-24 1992-02-18 Solvay & Cie (Societe Anonyme) Catalytic composition for hydrogenation of chlorofluoroalkenes
WO1997044303A1 (fr) 1996-05-24 1997-11-27 E.I. Du Pont De Nemours And Company Production simultanee d'ether de perfluoromethyle perfluorovinyle et d'ether de perfluoroethyle perfluorovinyle
US20070203368A1 (en) 2005-12-22 2007-08-30 Solvay Solexis S.P.A. Process for preparing fluorohalogenethers
WO2009150091A1 (fr) 2008-06-09 2009-12-17 Solvay Solexis S.P.A. Procédé de fabrication d’éthers vinyliques perfluorés
WO2012104365A2 (fr) 2011-02-04 2012-08-09 Solvay Specialty Polymers Italy S.P.A. Procédé pour la fabrication d'éthers de perfluorovinyle

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5089454A (en) 1988-05-24 1992-02-18 Solvay & Cie (Societe Anonyme) Catalytic composition for hydrogenation of chlorofluoroalkenes
EP0434408A1 (fr) 1989-12-19 1991-06-26 E.I. Du Pont De Nemours And Company Procédé à plusiers stades successis pour la préparation du hexafluoropropylène
WO1997044303A1 (fr) 1996-05-24 1997-11-27 E.I. Du Pont De Nemours And Company Production simultanee d'ether de perfluoromethyle perfluorovinyle et d'ether de perfluoroethyle perfluorovinyle
US20070203368A1 (en) 2005-12-22 2007-08-30 Solvay Solexis S.P.A. Process for preparing fluorohalogenethers
WO2009150091A1 (fr) 2008-06-09 2009-12-17 Solvay Solexis S.P.A. Procédé de fabrication d’éthers vinyliques perfluorés
WO2012104365A2 (fr) 2011-02-04 2012-08-09 Solvay Specialty Polymers Italy S.P.A. Procédé pour la fabrication d'éthers de perfluorovinyle

Non-Patent Citations (1)

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Title
MADDILA, SURESH ET AL.: "Dechlorination of tetrachloro-o-benzoquinone by ozonation catalyzed by cesium loaded metal oxides", APPLIED CATALYSIS B: 138-139, 2013, pages 149 - 160

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