WO2002020445A1 - Procede de preparation de composes insatures fluores et procede de production de polymeres fluores - Google Patents

Procede de preparation de composes insatures fluores et procede de production de polymeres fluores Download PDF

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Publication number
WO2002020445A1
WO2002020445A1 PCT/JP2001/007496 JP0107496W WO0220445A1 WO 2002020445 A1 WO2002020445 A1 WO 2002020445A1 JP 0107496 W JP0107496 W JP 0107496W WO 0220445 A1 WO0220445 A1 WO 0220445A1
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group
organic group
compound
compound represented
formula
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PCT/JP2001/007496
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English (en)
Japanese (ja)
Inventor
Hidekazu Okamoto
Hirokazu Takagi
Takashi Okazoe
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Asahi Glass Company, Limited
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Priority to AU2001282559A priority Critical patent/AU2001282559A1/en
Publication of WO2002020445A1 publication Critical patent/WO2002020445A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides

Definitions

  • the present invention relates to a method for producing a fluorinated unsaturated compound that can be a useful resin raw material, and a method for producing a fluorinated polymer using the unsaturated compound.
  • Unsaturated compounds such as perfluoro (alkylalkenyl ether) are useful as raw material monomers for fluororesins. Fluororesins are used in a wide range of fields because of their excellent properties of heat resistance and chemical resistance.
  • perfluoro (alkyl alkenyl ether) is obtained by dimerization of perfluoroepoxides or reaction of perfluoroalkanoic acid fluoride with perfluoroepoxides in the presence of alkali metal fluoride. (2 alkoxyalkanoic acid) It is industrially manufactured by a reaction of heating after forming fluorides.
  • An object of the present invention is to provide a production method for obtaining a fluorine-containing unsaturated compound in a short step by using a compound that can be obtained at a low cost.
  • a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas.
  • the present invention provides a method for producing a fluorine-containing unsaturated compound (2), which comprises subjecting the following compound (1) to a thermal decomposition reaction.
  • R AF is a monovalent organic group which does not change by a thermal decomposition reaction
  • R BF is a monovalent organic group or a fluorine atom is not more changes to the thermal decomposition reaction
  • the thermal decomposition reaction jointly with R AF and R BF It may form a divalent organic group that does not change.
  • the present invention provides the following compound (3a) by reacting the following compound (5) with the following compound (6a), and fluorinating the compound (3a) in a liquid phase to obtain the following compound (4) a) wherein the following compound (1) is obtained from a reaction product obtained by decomposing the ester bond of the compound (4a), and the compound (1) is subjected to a heat component reaction. 2)
  • the manufacturing method is provided.
  • R AF and R BF have the same meaning as above.
  • R AH is a monovalent organic group that is the same or different from R AF, and when it is a different monovalent organic group, R AH is a monovalent organic group that becomes R AF by fluorination
  • R BH is a R BF is the same as or different monovalent organic group or a hydrogen atom
  • R BH is R BF in the case where a hydrogen atom is fluorine atom, formed by R AH and R BH may form a divalent organic group jointly
  • the divalent organic group R AF and R BF are jointly it is the same as the divalent organic group rather good even or different divalent organic group
  • R AH and R BH was formed jointly when it is different divalent organic groups to be off Tsu fluorinated Is a divalent organic group formed by R AF and R BF
  • the present invention provides a method for producing a polymerizable monomer comprising one or more of the fluorinated unsaturated compounds obtained by any one of the above-mentioned production methods, or one or more of the fluorinated unsaturated compounds and another polymerizable monomer copolymerizable therewith.
  • a method for producing a fluoropolymer which comprises polymerizing one or more kinds of polymers.
  • the organic group refers to a group having a carbon atom as an essential, and includes any of a saturated and unsaturated structure.
  • Examples of the organic group to be fluorinated include an organic group having an atom that can be fluorinated (for example, a hydrogen atom bonded to carbon), an atomic group that can be fluorinated (for example, a carbon-carbon unsaturated double bond, a carbon atom).
  • An organic group having a carbon-unsaturated triple bond was For example, when a carbon-carbon double bond exists in an organic group, fluorine can be added to the carbon-carbon double bond by fluorination in a liquid phase to form a carbon-carbon single bond. When a carbon-carbon triple bond is present in an organic group, fluorine is added to the carbon-carbon triple bond by fluorination in a liquid phase to form a carbon-carbon single bond or a carbon-carbon triple bond. A carbon double bond is formed.
  • the monovalent organic group is preferably a monovalent hydrocarbon group, a heteroatom-containing monovalent hydrocarbon group, a halogenated monovalent hydrocarbon group, or a halogenated (heteroatom-containing monovalent hydrocarbon) group.
  • the divalent organic group is preferably a divalent hydrocarbon group, a heteroatom-containing divalent hydrocarbon group, a halogenated divalent hydrocarbon group, or a halogenated (heteroatom-containing divalent hydrocarbon) group.
  • the organic group preferably has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, from the viewpoint of solubility in the liquid phase used during the fluorination reaction.
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group. Further, a single bond, a double bond, or a triple bond may be present as a carbon-carbon bond in the aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group may have any of a straight-chain structure, a branched structure, a ring structure, or a structure partially having a ring structure.
  • a saturated hydrocarbon group is preferable.
  • the monovalent saturated hydrocarbon group include an alkyl group, and the structure may be any of a linear structure, a branched structure, a cyclic structure, and a partially cyclic structure.
  • the divalent saturated hydrocarbon group include an alkylene group, and the structure may be any of a linear structure, a branched structure, a ring structure, and a structure having a ring portion.
  • the alkyl group or the alkylene group preferably has 1 to 10 carbon atoms.
  • Examples of the alkyl group having a linear structure include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • Examples of the branched alkyl group include an isopropyl group, an isoptyl group, and a sec-butyl group. Examples include a tyl group and a tert-butyl group.
  • alkyl group having a ring structure examples include a cycloalkyl group, a bicycloalkyl group, a group having an alicyclic spiro structure, and a 3- to 6-membered cycloalkyl group is preferable, and a cyclopentyl group and a cyclohexyl group are preferred. And the like.
  • alkyl group having a ring portion examples include an alkyl group having an aromatic ring (eg, an aralkylene group such as a benzyl group and a phenethyl group) and an alkyl group having a heterocyclic ring (eg, a pyridylmethyl group, a furfuryl group, and the like).
  • an aromatic ring e.g, an aralkylene group such as a benzyl group and a phenethyl group
  • heterocyclic ring eg, a pyridylmethyl group, a furfuryl group, and the like.
  • alkylene group examples include groups in which one hydrogen atom of the above-mentioned alkyl group has a bond, and a linear or branched alkylene group is preferable.
  • halogen atom in the halogenated group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is preferred, and a fluorine atom, a chlorine atom, or a bromine atom is preferred. Or a fluorine atom and a chlorine atom are preferred.
  • halogenation means that one or more hydrogen atoms are replaced with a halogen atom.
  • Partial halogenation in halogenation means that part of a hydrogen atom is replaced with a halogen atom, and a hydrogen atom is present in the partially halogenated group.
  • Belha genogenesis means that all of the hydrogen atoms have been fluorinated. In Perno, there are no hydrogen atoms in the genogenated groups.
  • the meaning of halogenation, partial halogenation, perhalogenation is the same in the meaning of fluoro, partial fluoro, perfluorinated, and the like.
  • the halogenated hydrocarbon group refers to a group in which one or more of the hydrogen atoms present in the above hydrocarbon group has been replaced by a halogen atom.
  • a hydrogen atom may or may not be present in the halogenated hydrocarbon group.
  • a fluorine atom, a chlorine atom, or a fluorine atom and a chlorine atom are preferable.
  • the hydrogenated hydrocarbon group may have a linear structure or a branched structure, and may have a ring structure or a structure having a ring portion.
  • a partially halogenated hydrocarbon group refers to a group in which part of the hydrogen atoms present in the hydrocarbon group has been replaced by halogen atoms, and a hydrogen atom is present in the group.
  • the term “reno or halogenated hydrocarbon group” refers to a group in which all of the hydrogen atoms present in the hydrocarbon group have been replaced by halogen atoms, and there is no hydrogen atom in the group.
  • the halogen atom present in the halogenated group and the perhalogenated group may be one kind or two or more kinds.
  • a saturated group is preferable.
  • the monovalent saturated group include a fluoroalkyl group and a fluoro (partial cycloalkyl) group
  • examples of the divalent saturated group include a fluoroalkylene group and a fluoro (partial alkylene) group.
  • the saturated group preferably has 1 to 20 carbon atoms.
  • Perhalogenated monovalent saturated hydrocarbon groups include a perfluoroalkyl group or a perfluoro (partially alkyl) group (ie, a group in which all of the hydrogen atoms in the partially alkyl group are fluorinated). preferable.
  • the perhalogenated divalent saturated hydrocarbon group is preferably a perfluoroalkylene group or a perfluoro (partially-opened loanolealkylene) group (that is, a group in which all of the hydrogen atoms in the partially-closed alkylene group are fluorinated) .
  • the perfluoro (partial fluoroalkyl) group is the same as the perfluoroalkyl group, and the perfluoro (partial fluoroalkylene) group is the same as the perfluoroalkylene group.
  • the heteroatom-containing hydrocarbon group includes an oxygen atom, a nitrogen atom, or a sulfur atom.
  • a group consisting of a hetero atom such as a child, a carbon atom, and a hydrogen atom.
  • the hetero atom may be the hetero atom itself, or may be a hetero atom group formed by bonding hetero atoms to each other or a hetero atom to another atom. It is preferable that the hetero atom and the hetero atom group do not change even by thermal decomposition reaction.
  • the carbon number of the hetero atom-containing hydrocarbon group is preferably 1 to 20.
  • a saturated group is preferable, and a divalent heteroatom or a divalent heteroatom group is inserted between carbon-carbon atoms of the saturated hydrocarbon group, or A group in which a hetero atom is bonded to a carbon atom in a saturated hydrocarbon group, or a group in which a divalent heteroatom atom or a divalent heteroatom group is bonded to a carbon atom at the bonding terminal of the saturated hydrocarbon group is preferable.
  • the hetero atom-containing group a group containing an etheric oxygen atom is particularly preferable from the viewpoint of the usefulness of the compound.
  • the monovalent group is preferably an alkyl group containing an etheric oxygen atom (for example, an alkoxyalkyl group and the like), and divalent.
  • an alkylene group containing an ethereal oxygen atom for example, a polyoxyalkylene group
  • examples of the group having a ring portion containing an etheric oxygen atom include a group having a dioxolane skeleton.
  • alkoxyalkyl group a group in which one of the hydrogen atoms present in the alkyl group is substituted with an alkoxy group is preferable.
  • the alkoxy group preferably has 1 to 10 carbon atoms.
  • Examples of the alkoxyalkyl group include an ethoxymethyl group, an 11-propoxyshetyl group, a 2-propoxyshetinole group, and the like.
  • the halogenated (hetero atom-containing hydrocarbon) group may have a linear structure or a branched structure, and may be a fluoro (hetero atom-containing hydrocarbon) group or a fluoro (partial chroma (hetero atom-containing hydrocarbon) group. )) Groups are preferred.
  • Halogenated (containing hetero atoms The hydrocarbon group preferably has 1 to 20 carbon atoms.
  • perhalogenated (hetero atom-containing hydrocarbon) group a perfluoro (hetero atom-containing hydrocarbon) group or a perfluoro (partial opening (hetero atom-containing hydrocarbon)) group is preferable.
  • halogenated (hetero atom-containing hydrocarbon) group a saturated group is preferable.
  • a (hetero atom-containing alkyl) group or a fluoro (partial chloro (hetero atom-containing alkyl)) group is preferable, and a perfluoro (alkoxyl) group or a perfluoro (partial chloro (alkoxyl)) group is preferred. Groups are especially preferred.
  • a fluoro (hetero atom-containing alkylene) group is preferred, and a perfluoro (polyoxyalkylene) group is preferred.
  • the monovalent organic group which is not changed by the thermal decomposition reaction is a group having no structure such as one CF—CF 2 COF or one CF (CF 3 ) COF in the group.
  • the monovalent organic group R AF include a fluoro monovalent saturated organic group (for example, a fluoro monovalent saturated hydrocarbon group, a fluoro (hetero atom-containing monovalent saturated hydrocarbon) group, and a fluoro (partial chroma monovalent saturated hydrocarbon group).
  • a hydrocarbon) group or a fluoro (partial chroma (hetero atom-containing monovalent saturated hydrocarbon)) group is preferred.)
  • a perfluoro monovalent saturated organic group is particularly preferable, and a perfluoro monovalent saturated hydrocarbon group is particularly preferable.
  • a perfluoro mouth (a monovalent saturated hydrocarbon containing a hetero atom), a perfluoro (a partially saturated monovalent saturated hydrocarbon), or a perfluoro (a partially saturated hydrocarbon (monovalent saturated hydrocarbon containing a hetero atom)) group is preferable. .
  • the R BF is a monovalent organic group which does not change by a thermal decomposition reaction, the same groups as R AF is preferred.
  • R BF includes perfluoro monovalent saturated hydrocarbon group, perfluoro (monovalent saturated hydrocarbon containing a hydrogen atom) group, perfluoro (partially monovalent saturated hydrocarbon) group, and perfluoro (partially saturated hydrocarbon group containing heteroatom) A monovalent saturated hydrocarbon)) group or a fluorine atom is particularly preferred.
  • R AF and R BF jointly form a divalent organic group that does not change due to thermal decomposition In this case, there is no structure such as one CF—CF 2 COF or one CF (CF 3 ) COF in the divalent organic group.
  • the divalent organic group include a fluoro divalent saturated hydrocarbon group, a fluoro (hetero atom-containing divalent saturated hydrocarbon) group, a fluoro (partial chroma divalent saturated hydrocarbon) group and a fluoro (partial chroma hetero) Atom-containing divalent saturated hydrocarbon)) group, particularly perfluoro divalent saturated hydrocarbon group, perfluoro (divalent saturated hydrocarbon containing heteroatom) group, perfluoro (partially saturated divalent saturated hydrocarbon) group, or Perfluoro (partial chromato (heteroatom containing divalent saturated hydrocarbon)) radicals are preferred.
  • R AF is pel full O b alkyl group, Perufuruoro (ether oxygen atom-containing alkyl) group, Perufuruoro (partial black port alkyl) group, or Perufuruoro (partial black port (containing etheric oxygen atom Alkyl)) group.
  • R BF is pel full O b alkyl group, Perufuruoro (ether oxygen atom-containing alkyl) group, Perufuruoro (partial black port alkyl) group, per Furuoro (partial black port (etheric oxygen atom-containing alkyl )) Group or a fluorine atom.
  • R AF and R BF together form a divalent organic group include a perfluoroalkylene group, a perfluoro (alkylene containing an ethereal oxygen atom) group, and a perfluoro group. (Partially alkylene) or perfluoro (partially alkylene).
  • R AF and R BF are groups having an alkyl group as a skeleton
  • the alkyl groups are each independently preferably an alkyl group having 1 to 10 carbon atoms.
  • the alkyl group may have a straight-chain structure or a branched structure.
  • Examples of the alkyl group having a straight-chain structure include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • Examples of the alkyl group having a branched structure include an isopropyl group, a disoptyl group, a sec-butyl group, a tert-butyl group and the like.
  • R AF and R BF each have an etheric oxygen atom-containing alkyl group as a skeleton
  • the group may be an alkoxy group in which one of the hydrogen atoms present in the alkyl group is independently substituted with an alkoxy group.
  • Alkyl groups are preferred.
  • the alkoxy group preferably has 1 to 8 carbon atoms. Examples of the alkoxyalkyl group include an ethoxymethyl group, a 1-propoxyl group, and a 21-propoxyl group.
  • the group when the divalent organic group has an alkylene group as a skeleton, the group may be an alkylene group having 2 to 10 carbon atoms. I like it.
  • the alkylene group may have a linear structure or a branched structure. Examples of the alkylene group having a straight-chain structure include an ethylene group, a trimethylene group, and a tetramethylene group. Examples of the alkylene group having a branched structure include groups in which one or more hydrogen atoms of an alkylene group having a linear structure are substituted with a methyl group, an ethyl group, or the like.
  • the divalent organic group has an etheric oxygen atom-containing alkyl group as a skeleton
  • the group includes a group in which one or more etheric oxygen atoms are interposed between carbon-carbon bonds of the alkylene group. Is preferred.
  • Specific examples of the compound (1) include the following compounds. However, the following odor Te C y F represents a cyclohexyl group Perufuruoroshiku port.
  • the compound (1) is subjected to a thermal decomposition reaction.
  • the thermal decomposition reaction is preferably carried out by a gas phase reaction or a liquid phase reaction, and is particularly preferably carried out by a gas phase reaction because it is efficient.
  • the method and reaction temperature of this thermal decomposition reaction are preferably selected depending on the boiling point and stability of compound (1).
  • the thermal decomposition reaction is carried out by a gas phase reaction
  • the vaporized compound (1) is passed through a heated reaction tube and formed by a decomposition reaction. It is preferable to obtain the fluorinated unsaturated compound (2) and COF 2 as an outlet gas, condense this, and continuously recover it.
  • the reaction temperature in the case of performing a thermal decomposition reaction in a gas phase reaction can be appropriately changed depending on the structure of the compound (1), but is generally preferably 50 ° C to 400 ° C, particularly preferably 100 ° C (to The temperature is preferably 350 ° C. If the reaction temperature is too high, the compound (2) to be produced may be further decomposed to lower the yield, and if the reaction temperature is too low, the reaction rate of the raw materials may be reduced. May decrease.
  • the residence time when a tubular reactor is used is preferably about 0.1 second to 10 minutes on an empty tower basis.
  • the reaction pressure is not particularly limited.
  • compound (1) is a high-boiling compound, it is preferable to carry out the reaction under reduced pressure.
  • the compound (1) is a low-boiling compound, it is preferable to carry out the reaction under pressure because decomposition of the product is suppressed and the reaction rate increases.
  • the gas phase reaction is carried out using a tubular reactor, it is preferable to fill the reaction tube with glass, an alkali metal salt, or an alkaline earth metal salt in order to promote the reaction.
  • an alkali metal salt or alkaline earth metal salt carbonate or fluoride is preferable.
  • the glass include common soda glass, and glass beads having a fluidity in the form of beads are particularly preferable.
  • the salts of alkali metal include sodium carbonate, sodium fluoride, potassium carbonate, lithium carbonate and the like.
  • the alkaline earth metal carbonate include calcium carbonate, calcium fluoride, magnesium carbonate, barium carbonate and the like.
  • reaction tube it is preferable to fill the reaction tube with calcium carbonate or barium carbonate, since the reaction yield is remarkably improved. Further, when the reaction tube is filled with glass, an alkali metal salt, or an alkaline earth metal salt, the reaction tube is made of glass beads, light ash of sodium carbonate, or the like, and has a particle size of 100 to 250. / zm, a fluidized bed type reaction system can be adopted. It is particularly preferable because of this.
  • the reaction is preferably carried out in the presence of an inert gas not directly involved in the thermal decomposition reaction in order to promote the vaporization of the compound (1).
  • the inert gas include nitrogen, carbon dioxide, helium, and argon.
  • the amount of the inert gas is preferably about 0.01 to 50% by volume based on the compound (1). If the amount of the inert gas is too large, the recovery amount of the compound (2) may be low.
  • a thermal decomposition reaction may be performed by a liquid phase reaction.
  • the heating temperature is preferably 50 ° C to 300 ° C because the residence time is long and side reactions are likely to occur.
  • the reactor for the liquid phase reaction it is preferable to use a usual autoclave, a usual tubular reactor, a fixed-bed reactor using a catalyst, or the like.
  • the catalyst it is preferable to use an alkali metal, an alkaline earth metal salt or the like.
  • carbonyl fluoride (COF 2 ) is generated together with the desired fluorine-containing unsaturated compound (2).
  • COF 2 carbonyl fluoride
  • These products are preferably separated and purified by an ordinary method.
  • the separation and purification method include a distillation method and silica gel column chromatography.
  • Carbonyl fluoride has a lower molecular weight than the fluorine-containing unsaturated compound (2) and usually has a low boiling point, so that it can be efficiently removed by distillation.
  • carbonyl fluoride is recovered as an alkaline product.
  • fluorinated unsaturated compound (2) include the following compounds.
  • the method for obtaining the compound (1) in the present invention is not particularly limited, and commercially available compounds and compounds manufactured by a known manufacturing method can be used.
  • the present invention Compound (1), the following compound (3) is fluorinated in the liquid phase to give the following compound (4), which is then separated from the reaction product obtained by decomposing the ester bond of this compound (4).
  • a compound having a desired structure is particularly preferable because the compound (1) having a desired structure can be easily obtained.
  • R AH, R BH R AH is a R AF is the same as or different monovalent organic group, R AH when a monovalent organic group that different and R AF is a R AF by being fluorinated 1 a Ataiyu machine group, R BH is R BF and the same or different monovalent organic group or a hydrogen atom, R by R BH when a monovalent organic group different from R BF is a fluorinated BF When R BH is a hydrogen atom, R BF is a fluorine atom, and R AH and R BH may form a divalent organic group together; group divalent or different and the same as the divalent organic group R AF and R BF are formed jointly, R AH and R BH when it is different from 2 Ataiyu machine group is formed jointly
  • the organic group is a group that becomes a divalent organic group formed by R AF and R BF together when fluorinated.
  • R c , R CF The same or different monovalent organic groups, and in different cases, R CF is a monovalent organic group in which R c is fluorinated.
  • the above method is also preferable in that compound (3) can be obtained at low cost and various structures can be obtained.
  • R AH and R BH is a monovalent organic group containing a hydrogen atom.
  • R AH is a group corresponding to R AF
  • R AH is a monovalent hydrocarbon group, a hetero atom-containing monovalent hydrocarbon group, a partially halogenated monovalent hydrocarbon group, or a partially halogenated (hetero atom containing A monovalent hydrocarbon) group.
  • R BH corresponds to R BF and is monovalent It is preferably a hydrocarbon group, a heteroatom-containing monovalent hydrocarbon group, a partially halogenated monovalent hydrocarbon group, a partially halogenated (heteroatom-containing monovalent hydrocarbon) group, or a hydrogen atom.
  • R AH is particularly preferably an alkyl group, an etheric oxygen atom-containing alkyl group, a partial chloroalkyl group, or a partial cycloalkyl (etheric oxygen atom-containing alkyl) group.
  • R BH represents an alkyl group, an etheric oxygen atom-containing alkyl group, part component Kuroroaruki group, partial black port (etheric oxygen atom-containing alkyl) group or the hydrogen atom, is particularly preferred.
  • RBH is a hydrogen atom
  • R BF is a fluorine atom.
  • the base when R AH and R BH form a divalent organic group jointly is a group R AF and R BF corresponds to the divalent organic group that forms jointly, a divalent hydrocarbon It is preferably a hydrogen group, a hetero atom-containing divalent hydrocarbon group, a partially halogenated divalent hydrocarbon group, or a partially halogenated (hetero atom-containing divalent hydrocarbon) group, and an alkylene group or an etheric oxygen atom.
  • An alkylene group, a partial alkylene group or a partial alkylene (etheric oxygen atom-containing alkylene) group is particularly preferred.
  • Compound (3) is preferably a compound in which R c is a perfluoro monovalent saturated organic group from the viewpoint of ease of availability and ease of carrying out the continuous production method described below.
  • Perfluoro (monovalent saturated hydrocarbon containing heteroatom), perfluoro (partially halogenated monovalent saturated hydrocarbon), or perfluoro (partially halogenated (monovalent saturated hydrocarbon containing heteroatom)) Particularly preferred are a perfluoroalkyl group, a perfluoro (alkyl containing an etheric oxygen atom) group, a perfluoro (a partially substituted alkyl) group, and a perfluoro (a partially substituted (alkyl containing an etheric oxygen atom)) group. .
  • R c a perfluoroalkyl group, a perfluoro (partial chloroalkyl) group, a perfluoro (alkoxyalkyl) group, or a perfluoro (partially chloroalkyl (alkoxyalkyl)) group is preferable.
  • the structure of R c is preferably adjusted in relation to the structure of R AH R BH so that compound (3) is easily dissolved in the liquid phase during fluorination.
  • the compound (3) include the following compounds.
  • Cy in the present specification means a cyclohexyl group.
  • compound (3) is fluorinated in a liquid phase to obtain compound (4).
  • Fluorination The reaction can theoretically be carried out by electrochemical fluorination, cobalt fluorination, or a method of reacting with fluorine in the gas phase, but compound (3) has an etheric oxygen atom in the molecule.
  • the fluorination can be carried out while preventing the decomposition reaction of the C—O bond, and the liquid phase fluorination method of reacting with fluorine (elemental fluorine) in the liquid phase for producing the compound (4) with high yield (so-called, Liquid phase fluorination) is preferred.
  • the fluorine content in compound (3) should be 30% by mass in order to improve the solubility of compound (3) in the liquid phase.
  • the fluorine content in the compound (3) is particularly preferably 30% by mass to 80% by mass.
  • the molecular weight of the compound (3) is preferably from 200 to 100.
  • liquid phase fluorination method it is preferable to adopt a method of introducing the compound (3) into the liquid phase.
  • Fluorine may be previously present in the liquid phase, fluorine gas may be introduced into the reaction system sequentially, and the latter is preferred because the amount of compound (3) with respect to fluorine gas can be adjusted.
  • solvent 1 a known organic solvent having perfluoroalkanes or one or more atoms selected from a chlorine atom, a nitrogen atom, and an oxygen atom in its structure are preferred.
  • a solvent having high solubility of the compound (3) particularly a solvent capable of dissolving the compound (3) by 1% by mass or more, particularly a solvent capable of dissolving the compound (3) by 5% by mass or more. Is preferred.
  • solvent 1 used as the liquid phase it is preferable to select from solvents that dissolve fluorine gas and are inert to fluorine gas.
  • Perfluoroalkanes (trade name: FC-72, etc.)
  • Perfluoroethers (trade names: FC-75, FC-77, etc.)
  • perfluoropolyethers (trade names: Kryttustus, Fomblin, Galden, Demnum and others.
  • Chlorofluorocarbons (trade name: CFC), chlorofluoropolyethers, perfluoroalkylamines (eg, perfluorotrialkylamine, etc.), inert fluids (trade name: florinate), perhalogen Solvents in which the terminal is a COF group such as a chemical compound, a perfluoroether, and a perfluoroether are preferred.
  • the amount of the solvent 1 used in the liquid phase is preferably at least 5 times, more preferably 10 to 100 times the mass of the compound (3).
  • the amount of fluorine used in the fluorination reaction is preferably such that fluorine gas is charged so that the amount of fluorine atoms is always in excess equivalent to the amount of hydrogen atoms in compound (3).
  • the fluorine gas is used in an amount of 1.5 times equivalent or more (ie, 1.5 times or more moles) with respect to the hydrogen atom in it. Further, in the fluorination reaction of the present invention, it is preferable to always make the amount of fluorine excessively equivalent from the start of the reaction to the end of the reaction.
  • an alkali metal fluoride preferably NaF or KF
  • a trialkylamine may be present in the reaction system as an HF scavenger.
  • the yield of the fluorination reaction product can be increased by adding a compound capable of generating a fluorine radical or irradiating the reaction system with ultraviolet rays at a later stage of the fluorination reaction.
  • the compound capable of generating a fluorine radical include aromatic compounds such as benzene and toluene.
  • Fluorination of compound (3) in the liquid phase produces compound (4).
  • the crude product containing the compound (4) may be used as it is in the next step, or may be purified to obtain a highly pure compound (4).
  • Examples of the purification method include a method of distilling the crude product as it is under normal pressure or reduced pressure.
  • R CF in compound (4) is a monovalent saturated compound in which R c of compound (3) has no hydrogen atom.
  • R CF when it is machine group are the same monovalent organic group and R c, when having a case or a hydrogen atom R c has an unsaturated bond a group RG is fluorinated.
  • Specific examples of the compound (4) include the following compounds.
  • Compound (1) is obtained by decomposing the ester bond of compound (4).
  • Ester bond decomposition reactions include thermal decomposition reactions in the gas or liquid phase, the presence of electrophiles or nucleophiles The decomposition reaction below.
  • the thermal decomposition reaction can be carried out by heating compound (4).
  • the reaction type of the thermal decomposition reaction is preferably selected depending on the boiling point of the compound (4) and its stability.
  • the reaction temperature of the thermal decomposition reaction in the gas phase is preferably from 50 to 350 ° C, particularly preferably from 50 to 300 ° C, particularly preferably from 150 to 250 ° C.
  • an inert gas which is not directly involved in the reaction may be allowed to coexist.
  • the inert gas include nitrogen, carbon dioxide, oxygen and the like. It is preferable to add about 0.01 to 50% by volume of the inert gas to the compound (4). If the amount of inert gas added is large, the amount of product recovered may be reduced.
  • the compound (4) is a compound that is difficult to degas
  • a method in which the ester bond is decomposed by heating in the liquid phase, or the presence of a nucleophile or an electrophile in the liquid phase It is preferable to use a method of decomposing an ester bond below.
  • the thermal decomposition in the liquid phase is preferably carried out by heating the solution of compound (4) as it is in the reactor.
  • the reaction pressure in this case is not limited. Since the compound (1) is usually obtained as a product having a lower boiling point than the compound (4), the liquid phase ester thermal decomposition method carries out a reaction while performing distillation in a reactor having a distillation column, and performs the reaction. Is preferably carried out by a method of continuously extracting as a distillation fraction (also called a reactive distillation method). Further, the method may be carried out by a method of collectively extracting the product from the reactor after the completion of the heating.
  • the reaction temperature of the reaction is preferably from 50 to 300 ° C, particularly preferably from 100 to 250 ° C.
  • the decomposition reaction of the ester bond When the decomposition reaction of the ester bond is performed by a liquid phase method, it may be performed without a solvent or in the presence of a solvent (hereinafter, referred to as solvent 2).
  • the solvent 2 does not react with the compound (4) and is compatible with the compound (4), and is incompatible with the formed compound (1). There is no particular limitation as long as it does not respond.
  • the solvent 2 include an inert solvent such as perfluorotrialkylamine, and a chlorofluoroethylene oligomer having a high boiling point, such as chlorofluorocarbons (for example, trade name: Freonlube) Is preferred.
  • the amount of the solvent 2 is preferably 10 to 1000% by mass based on the compound (4).
  • the ester bond decomposition reaction When the ester bond decomposition reaction is performed in a liquid phase using a nucleophile or an electrophile, the reaction may be performed without a solvent or in the presence of a solvent (hereinafter, referred to as solvent 3).
  • the solvent 3 is preferably the same as the solvent 2.
  • the nucleophile is preferably fluoridion-one (F-I), and particularly preferably fluoridion-one derived from alkali metal fluoride.
  • F-I fluoridion-one
  • the fluoride of an alkali metal, Na F, NaHF 2, KF , C s F selfishness, N a F are particularly preferred in view of economy of these.
  • the nucleophile used at the beginning of the reaction may be a catalytic amount or may be used in excess. That 1-500 mole 0/0 are preferred amount of the nucleophilic agent for the compound (4), such as F-, particularly preferably 10 to 100 mole 0/0, Toriwa only 5-50 mole% is preferred.
  • the lower limit of the reaction temperature is preferably 130 ° C, and the upper limit is preferably the temperature between the boiling point of the solvent and the boiling point of the compound (4), and particularly preferably -20 ° C to 250 ° C.
  • This reaction is also preferably carried out using a reactor equipped with a distillation column.
  • Compound (1) is contained in the decomposition reaction product of the ester bond of compound (4).
  • the product usually contains the compound (1) and the following compound (6).
  • RGF has the same meaning as above.
  • the compound (1) it is preferable to obtain the compound (1) by separating it from the reaction product. Further, it is preferable that the compound (6) is separated from the reaction product, if necessary. Les ,. As a separation method, a distillation method is preferable.
  • the continuous production method can be preferably carried out on the compound (6a) in which R CF in the compound (6) is a perfluoro monovalent saturated organic group (RCF 1 ° below).
  • RCF 1 ° below perfluoro monovalent saturated organic group
  • R AF OCR BF CF 2 (2) That is, the compound (5) is reacted with the compound (6a) to give the compound (3a), and the compound (3a) is fluorinated in a liquid phase. To obtain the above compound (4a), and obtain a compound (1) and a compound (6a) from a reaction product obtained by decomposing an ester bond of the compound (4a). A part of the obtained compound (6a) Or a method for continuously producing compound (1) by using all or all of them as compound (6a) to be reacted with compound (5). Further, the compound (1) is thermally decomposed and converted into a target compound (2).
  • R AF , R BF , R AH , R BH , and R CF10 are as described above.
  • Specific examples of the compound (6a) include the following compounds.
  • the reaction between compound (5) and compound (6a) may be carried out in the presence of a solvent (hereinafter, referred to as solvent 4). However, it is preferable to carry out the reaction in the absence of solvent 4 in terms of volumetric efficiency. Preferred from. If solvent 4 is used, preference is given to dichloromethane, chloroform 13 form, triethylamine or a mixed solvent of triethylamine and tetrahydrofuran! / ,.
  • the amount of the solvent 4 is preferably 50 to 500% by mass based on the total amount of the compound (5) and the compound (6a).
  • metal fluoride such as sodium fluoride
  • trialkylamine is present in the reaction system as an HF scavenger. May be. It is particularly preferable to use an HF scavenger when compound (5) or compound (6a) is acid-labile. When the HF scavenger is not used, it is preferable to discharge HF out of the reaction system by accompanying the HF with a nitrogen gas stream. When the alkali metal fluoride is used, the amount is preferably 1 to 10 times the mole of the compound (6a).
  • the reaction temperature of the reaction of the compound (5) with the compound (6a) is preferably 150 ° C. or higher, more preferably + 100 ° C. or lower or the boiling point of the solvent 4 or lower.
  • the reaction time of the reaction depends on the feed rate of the raw materials and the amount of the compound used in the reaction. It can be changed as appropriate.
  • the reaction pressure gauge pressure, hereinafter the same is preferably from 0 (atmospheric pressure) to 2 MPa.
  • compound ( 3a ) in which R c of compound (3) is R CF1G is generated.
  • the crude product containing the compound (3a) may be purified according to the intended purpose to obtain a high-purity product, or may be used as it is in the next reaction, etc., but the fluorination reaction in the next step can be carried out safely. From the viewpoint of performing, it is desirable to purify the crude product. Purification methods include distillation of the crude product as it is, treatment of the crude product with diluted alkaline water, etc., separation of the crude product, extraction with an appropriate organic solvent, and distillation. Chromatography and the like.
  • the polymerizable monomer capable of polymerizing with the compound (2) is not particularly limited, and may be selected from known polymerizable monomers. Known polymerization techniques can be applied as they are to the polymerization reaction.
  • Examples include butyl ethers having a possible group, and olefins such as ethylene, propylene, and isobutylene.
  • the fluoropolymer obtained by the present invention is useful as a fluororesin. Fluororesins are used in a wide range of fields because of their excellent properties of heat resistance and chemical resistance.
  • Example 1 inner diameter 2 Omm, Na 2 C0 3 and 280 g packed inside diameter 45mm of 1 m long made of SUS column with an average particle diameter 160 mu m, a height of 400 mm S US made fluidized bed reaction
  • the vessels were connected in series and placed in a salt bath, and the temperature in the salt bath was adjusted to 270 ° C.
  • Nitrogen gas was passed through the reactor at 152 OmL / min, and CF 3 CF 2 CF 2 OCF 2 CF 2 C ⁇ F (purity 99%) was fed using a metering pump for 60.2 ⁇ hours for 1.8 hours. did.
  • a dry ice / ethanol trap was installed at the reactor outlet to collect the product.
  • the crude liquid was concentrated by an evaporator and then distilled under reduced pressure to obtain 57.4 g of a fraction containing the title compound at a purity of 99%.
  • Example 4 Example of production of CF 3 CF 2 CF 2 OCF (CF 3 ) COO (CF 2 ) 3 OCF 2 CF 2 CF 3 by fluorination reaction
  • Example 3 19.5 ⁇ of the fraction obtained in Example 3 was dissolved in 1,1,2_ trichloro mouth trifluorobenzene (hereinafter referred to as R-113; 250 g) to obtain a fraction solution. Meanwhile, 50 OmL Na F (26.1 g) was placed in a nickel autoclave, and R-113 (324 g) was added thereto, followed by stirring and cooling to 110 ° C. After blowing nitrogen gas for 1 hour, fluorine gas diluted to 20% with nitrogen gas is blown at a flow rate of 5.66 LZh for 1 hour, and while blowing at the same flow rate, the distillate solution is applied for 19.4 hours. And injected.
  • R-113 1,1,2_ trichloro mouth trifluorobenzene
  • the operation was repeated four times while the temperature was raised from 110 ° C. to room temperature, and then five times at room temperature. During this time, a total of 0.291 g of benzene and a total of 45.0 g of R-113 were injected. Thereafter, nitrogen gas was blown for 2 hours, and the reaction mixture was taken out by decantation. The obtained crude liquid was concentrated by an evaporator, and the product was quantified by 19 F-NMR. The yield was 69%. A part of the crude liquid was distilled under reduced pressure to obtain a purified title compound.
  • Example 5 From the crude liquid obtained in Example 5, CF 3 CF 2 CF 2 OCF (CF 3 ) COF was obtained. Using this, the reaction was carried out in the same manner as in Example 3, Example 4, and Example 5 to obtain CF 3 CF 2 CF 2 OCF 2 CF 2 COF and CF 3 CF 2 CF 2 OCF (CF 3 ) COF.
  • a fluorinated unsaturated compound (2) which has been difficult to synthesize or a fluorinated unsaturated compound (2) which has been synthesized by an economically disadvantageous method can be converted from a compound (1) It can be manufactured in a short process and in high yield.
  • the compound (1) which is the raw material for the thermal decomposition reaction, is generally easily available, and can be easily synthesized from an easily available and inexpensive compound. Unsaturated compound (2) can be produced.
  • compound (1) is produced by fluorinating compound (3)
  • solubility in the solvent during fluorination is increased, and the fluorination reaction is reduced. Can be carried out in high yield.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé au cours duquel on peut préparer, durant une étape courte et avec un rendement élevé, des composés insaturés fluorés difficilement synthétisables ou préparés au moyen de procédés de synthèse coûteux, à partir de matières premières bon marché et facilement disponibles. On peut préparer des composés insaturés fluorés (2): R?AFOCRBF=CF¿2 par pyrolyse des composés (1): R?AFOCFRBFCF¿2COF, RAF étant un groupe organique monovalent stable à la pyrolyse, et RBF étant un groupe organique monovalent stable à la pyrolyse ou au fluor ou selon une autre possibilité, R?AF et RBF¿ pouvant être unis pour former un groupe organique divalent stable à la pyrolyse.
PCT/JP2001/007496 2000-09-01 2001-08-30 Procede de preparation de composes insatures fluores et procede de production de polymeres fluores WO2002020445A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6586626B2 (en) 1999-03-23 2003-07-01 Asahi Glass Company, Limited Process for producing a fluorine-containing compound by liquid phase fluorination
US6956138B2 (en) 2000-07-11 2005-10-18 Asahi Glass Company, Limited Method for producing a fluorine-containing compound
US7247757B2 (en) 2004-10-06 2007-07-24 Fujifilm Corporation Method of producing a fluorine-containing vinyl ether compound
CN105046090A (zh) * 2015-08-18 2015-11-11 中国科学院地质与地球物理研究所兰州油气资源研究中心 气体质谱和色谱质谱数据处理的径向基函数方法
JPWO2016092900A1 (ja) * 2014-12-12 2017-04-27 株式会社Moresco フルオロポリエーテルの製造方法
KR20220005775A (ko) * 2020-07-07 2022-01-14 한국화학연구원 높은 전환율을 갖는 퍼플루오로프로필비닐에테르의 제조방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0090498A2 (fr) * 1982-03-02 1983-10-05 E.I. Du Pont De Nemours And Company Polyéthers fluorinés et dérivés
JPH069474A (ja) * 1992-06-26 1994-01-18 Daikin Ind Ltd フッ素化ビニルエーテルの製造方法
JP2001139509A (ja) * 1999-08-31 2001-05-22 Asahi Glass Co Ltd 熱分解反応による不飽和化合物の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0090498A2 (fr) * 1982-03-02 1983-10-05 E.I. Du Pont De Nemours And Company Polyéthers fluorinés et dérivés
JPH069474A (ja) * 1992-06-26 1994-01-18 Daikin Ind Ltd フッ素化ビニルエーテルの製造方法
JP2001139509A (ja) * 1999-08-31 2001-05-22 Asahi Glass Co Ltd 熱分解反応による不飽和化合物の製造方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6586626B2 (en) 1999-03-23 2003-07-01 Asahi Glass Company, Limited Process for producing a fluorine-containing compound by liquid phase fluorination
US6951957B2 (en) 1999-03-23 2005-10-04 Asahi Glass Company, Limited Process for producing a fluorine-containing compound by liquid phase fluorination
US7083705B2 (en) 1999-03-23 2006-08-01 Asahi Glass Company, Limited Process for producing a fluorine-containing compound by liquid phase fluorination
US6956138B2 (en) 2000-07-11 2005-10-18 Asahi Glass Company, Limited Method for producing a fluorine-containing compound
US7247757B2 (en) 2004-10-06 2007-07-24 Fujifilm Corporation Method of producing a fluorine-containing vinyl ether compound
JPWO2016092900A1 (ja) * 2014-12-12 2017-04-27 株式会社Moresco フルオロポリエーテルの製造方法
US10053538B2 (en) 2014-12-12 2018-08-21 Moresco Corporation Method for producing fluoropolyether
CN105046090A (zh) * 2015-08-18 2015-11-11 中国科学院地质与地球物理研究所兰州油气资源研究中心 气体质谱和色谱质谱数据处理的径向基函数方法
KR20220005775A (ko) * 2020-07-07 2022-01-14 한국화학연구원 높은 전환율을 갖는 퍼플루오로프로필비닐에테르의 제조방법

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