WO2016140201A1 - Procédé de fabrication d'un substrat dans lequel est introduit un groupe organique contenant un atome de fluor et une double liaison carbone-carbone - Google Patents

Procédé de fabrication d'un substrat dans lequel est introduit un groupe organique contenant un atome de fluor et une double liaison carbone-carbone Download PDF

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WO2016140201A1
WO2016140201A1 PCT/JP2016/056122 JP2016056122W WO2016140201A1 WO 2016140201 A1 WO2016140201 A1 WO 2016140201A1 JP 2016056122 W JP2016056122 W JP 2016056122W WO 2016140201 A1 WO2016140201 A1 WO 2016140201A1
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group
carbon
carbon atoms
double bond
atom
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PCT/JP2016/056122
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Japanese (ja)
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祐介 ▲高▼平
大輔 上牟田
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旭硝子株式会社
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Priority to JP2017503651A priority Critical patent/JP6593433B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a novel method for producing a base material into which an organic group containing a fluorine atom and a carbon-carbon double bond is introduced by a metathesis reaction.
  • a base material having an organic group containing a fluorine atom in its surface layer is industrially useful in applications where water repellency, oil repellency and antifouling properties are required, such as displays, glasses and touch panels.
  • the organic group containing a fluorine atom exhibits high lubricity, water / oil repellency, and the like, and thus is suitably used as a surface treatment agent for a substrate.
  • the surface treatment agent imparts water and oil repellency to the surface of the base material, it becomes easy to wipe off the dirt on the surface of the base material, and the dirt removability is improved.
  • Patent Document 1 discloses a surface treating agent that uses a compound having two or more silicon atoms in the molecule as the fluorine-containing silane compound.
  • olefin metathesis reaction which is a double bond recombination reaction using a metal catalyst
  • metal catalyst a metal catalyst
  • olefin metathesis reaction which is a double bond recombination reaction using a metal catalyst
  • olefin metathesis is widely used as a method for producing olefins having various substituents.
  • an electron-deficient olefin having an electron-withdrawing substituent has low reactivity, it is not easy to use it for olefin metathesis.
  • Non-Patent Document 1 examines the reactivity of olefins having various substituents, and describes that the reactivity of electron-deficient olefins is low.
  • the conventional surface treatment agent containing a fluorine-containing silane compound has a possibility of deterioration in performance due to long-term use, and there is room for improvement such as insufficient friction durability. Therefore, if a substrate having an organic group containing a fluorine atom on the surface layer using another fluorine-containing compound that is not a fluorine-containing silane compound and is easily available industrially can be easily and efficiently produced under mild conditions. It can be a highly durable base material compared to existing methods. On the other hand, it is not practical to use an olefin having a halogen atom for olefin metathesis.
  • tetrafluoroethylene and hexafluoropropylene are industrially easily available and useful compounds from the viewpoint of commercialization, but they are not only olefins that are extremely deficient in electrons, but are also olefins because of their difficulty in handling. No reports have been used for metathesis.
  • an organic group containing a fluorine atom and a carbon-carbon double bond is introduced by performing a metathesis reaction using another fluorine-containing compound that is industrially easily available as a raw material. It is an object of the present invention to easily and efficiently produce a base material under mild conditions.
  • the inventors of the present invention have developed a olefin containing a fluorine atom (fluorine-containing olefin) in the presence of a metal-carbene complex compound on the surface of a base material into which an organic group containing a carbon-carbon double bond has been introduced. And a metathesis reaction under mild conditions, it was found that a substrate into which an organic group containing a fluorine atom and a carbon-carbon double bond was introduced could be produced, and the present invention was completed.
  • the present invention relates to the following ⁇ 1> to ⁇ 11>.
  • ⁇ 1> In the presence of a metal-carbene complex compound (10) having an olefin metathesis reaction activity on the surface of a base material into which an organic group containing a carbon-carbon double bond has been introduced, the carbon-carbon double bond is represented by the following formula: A method for producing a base material into which an organic group containing a fluorine atom and a carbon-carbon double bond has been introduced by subjecting the olefin compound represented by (21) to a metathesis reaction.
  • R F is a fluorine atom, a (per) fluoroalkyl group having 1 to 12 carbon atoms, a (per) fluoroalkoxy group having 1 to 12 carbon atoms, or a (per) fluoroalkyl group having 1 to 200 carbon atoms containing an etheric oxygen atom. And a group selected from the group consisting of (per) fluoroalkoxy groups having 2 to 200 carbon atoms and containing an etheric oxygen atom.
  • X 11 to X 13 are each independently a group selected from the group consisting of the following group (i), group (ii), group (v) and group (vi).
  • ⁇ 2> The production method according to ⁇ 1>, wherein the substrate is glass or resin.
  • ⁇ 3> The production method according to ⁇ 1> or ⁇ 2>, wherein a carbon-carbon double bond introducing agent is reacted with the surface of the base material to introduce a carbon-carbon double bond onto the surface of the base material.
  • ⁇ 4> The production method according to ⁇ 3>, wherein the carbon-carbon double bond introducing agent is a silane coupling agent having a carbon-carbon double bond in the molecule.
  • ⁇ 5> The production method according to ⁇ 3> or ⁇ 4>, wherein the base material is a resin film, and the carbon-carbon double bond introducer is a polyfunctional (meth) acrylate.
  • ⁇ 6> The production method according to any one of ⁇ 1> to ⁇ 5>, wherein the metal of the metal-carbene complex compound (10) is ruthenium.
  • the metal of the metal-carbene complex compound (10) is molybdenum or tungsten, and the metal-carbene complex compound (10) is used as a ligand [L] as an imide ligand and an oxygen atom.
  • ⁇ 8> The production method according to any one of ⁇ 1> to ⁇ 7>, wherein the olefin compound represented by the formula (21) is a 1,1-difluoroolefin.
  • R F of the olefin compound represented by the formula (21) is a (per) fluoroalkyl group having 1 to 200 carbon atoms containing an etheric oxygen atom, and 2 to 200 carbon atoms having an etheric oxygen atom (
  • ⁇ 10> The production method according to any one of ⁇ 1> to ⁇ 9>, wherein the temperature of the metathesis reaction is 0 to 150 ° C.
  • ⁇ 11> The production method according to any one of ⁇ 1> to ⁇ 10>, wherein no solvent is used in the metathesis reaction.
  • a substrate into which an organic group containing a fluorine atom and a carbon-carbon double bond has been introduced is produced simply and efficiently by a metathesis reaction using a fluorine-containing olefin.
  • the base material can be a highly durable base material compared to a conventional base material.
  • the present invention relates to a metathesis by a metal catalyst, and description of general features common to the prior art may be omitted.
  • the “compound represented by the formula (X)” may be simply referred to as “compound (X)”.
  • the perhalogenated alkyl group means a group in which all hydrogen atoms of the alkyl group are substituted with halogen atoms. The same applies to perhalogenated alkoxy groups, perhalogenated aryl groups, and perhalogenated aryloxy groups.
  • (per) halogenated alkyl group is used as a general term that combines a halogenated alkyl group and a perhalogenated alkyl group. That is, the group is an alkyl group having one or more halogen atoms.
  • the term “(per) fluoroalkyl group” is used as a general term that combines a fluoroalkyl group and a perfluoroalkyl group. That is, the group is an alkyl group having one or more fluorine atoms.
  • An aryl group means a monovalent group corresponding to a residue obtained by removing one hydrogen atom bonded to any one of carbon atoms forming an aromatic ring in an aromatic compound, and a carbocyclic compound
  • the aryl group derived from is combined with the heteroaryl group derived from a heterocyclic compound.
  • the number of carbon atoms of the hydrocarbon group means the total number of carbon atoms contained in the whole hydrocarbon group, and when the group has no substituent, the number of carbon atoms forming the hydrocarbon group skeleton is When the group has a substituent, the total number is obtained by adding the number of carbon atoms in the substituent to the number of carbon atoms forming the hydrocarbon group skeleton.
  • bonding in a chemical formula means that it is any one or a mixture of both among the isomers of E / Z.
  • the wavy line crossing the bond connecting the substrate and the atom means that the detailed bond from the substrate surface to the atom is omitted.
  • the heteroatom means an atom other than a carbon atom and a hydrogen atom, preferably one or more atoms selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, and a halogen atom. More preferably an oxygen atom or a nitrogen atom.
  • the present invention relates to a method for producing a base material into which an organic group containing a fluorine atom and a carbon-carbon double bond is introduced by a metathesis reaction.
  • the following schemes (a) to (d) show the procedures for producing a substrate into which an organic group containing a fluorine atom and a carbon-carbon double bond is introduced when the substrate is glass.
  • each X is independently a group selected from the group consisting of a halogen atom, an alkoxy group having 1 to 12 carbon atoms, and an aryl group having 5 to 20 carbon atoms
  • R F is a fluorine atom, 12 (per) fluoroalkyl groups, (per) fluoroalkoxy groups having 1 to 12 carbon atoms, (per) fluoroalkyl groups having 1 to 200 carbon atoms containing an etheric oxygen atom, and carbon atoms containing an etheric oxygen atom
  • a carbon-carbon double bond is introduced by reacting a silane coupling agent or the like there.
  • a base material into which an organic group containing a fluorine atom and a carbon-carbon double bond is introduced by subjecting the introduced carbon-carbon double bond portion to a metathesis reaction with a fluorine-containing olefin compound in the presence of a specific metal catalyst. Can be obtained.
  • the substrate in the present invention is not particularly limited. Specifically, glass, resin (natural or synthetic), metal, ceramic, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, building material, or a composite thereof A base material etc. are mentioned and it is comprised with arbitrary appropriate materials.
  • a glass substrate or a resin substrate is preferable.
  • soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, quartz glass, or chemically strengthened glass thereof is preferable, chemically strengthened soda lime glass, chemically strengthened Alkali aluminosilicate glass or chemically strengthened borosilicate glass is particularly preferred.
  • the material of the resin base material an acrylic resin or a polycarbonate resin is preferable. Among them, those having a hydroxyl group on the surface are preferable because they can easily introduce a carbon-carbon double bond.
  • the shape of the substrate is not particularly limited.
  • the surface region of the base material on which the surface treatment layer is to be formed may be at least part of the surface of the base material, and can be appropriately determined according to the use and specific specifications of the article to be manufactured.
  • the base material is an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a retardation film, or the like, depending on the specific specifications thereof. You may have a liquid crystal display module.
  • Carbon-carbon double bond introducing agent In order to introduce a carbon-carbon double bond to the substrate surface in the present invention, a known method can be used. Specifically, a method of introducing a carbon-carbon double bond to the substrate surface by reacting a carbon-carbon double bond introducing agent on the substrate surface is preferable.
  • the carbon-carbon double bond introducing agent is a functional group (having a carbon-carbon double bond) that has one or more carbon-carbon double bonds in the molecule and can react with a specific reaction site on the substrate surface. It may be a functional group).
  • a silane coupling agent having a carbon-carbon double bond in the molecule is preferably used as the carbon-carbon double bond introducing agent.
  • the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrichlorosilane, and allyltrimethoxysilane.
  • a polyfunctional acrylate or polyfunctional methacrylate (hereinafter, the acrylate and methacrylate are also collectively referred to as “(meth) acrylate”) or the like as a carbon-carbon double bond introducing agent.
  • (meth) acrylate a polyfunctional acrylate or polyfunctional methacrylate
  • Polyfunctional (meth) acrylates include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, and ethoxylated glycerin.
  • Examples include tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, and trimethylolpropane tri (meth) acrylate.
  • a thiol compound having a carbon-carbon double bond is preferably used as the carbon-carbon double bond introducing agent.
  • the reaction conditions for introducing the carbon-carbon double bond on the surface of the substrate may be any known conditions, and are not particularly limited.
  • a 11 to A 13 in the formula are each independently a group selected from the group consisting of the following group (i), group (ii), group (iii), and group (iv).
  • group (i) a hydrogen atom
  • group (ii) a halogen atom
  • Group (iii) a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • [L] is a ligand
  • M is ruthenium, molybdenum or tungsten.
  • R F is a fluorine atom, a (per) fluoroalkyl group having 1 to 12 carbon atoms, a (per) fluoroalkoxy group having 1 to 12 carbon atoms, or a (per) fluoroalkyl group having 1 to 200 carbon atoms containing an etheric oxygen atom.
  • X 11 to X 13 are each independently a group selected from the group consisting of the following group (i), group (ii), group (v) and group (vi). X 12 and X 13 may combine with each other to form a ring.
  • the compound (11) is described as a representative example of the metal-carbene complex compound (10).
  • the specific metal-carbene complex compound (10) include a ruthenium-carbene complex, a molybdenum-carbene complex, or a tungsten-carbene complex (hereinafter also collectively referred to as “metal-carbene complex”).
  • Metal-carbene complex compound (10) As the metal-carbene complex compound (10), the compound (11) is shown as an example in the above scheme (f), but the two groups bonded to the carbon atom forming a double bond with the metal are independent of each other. And a carbon number containing at least one atom selected from the group consisting of a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. Any monovalent hydrocarbon group of 1 to 20 may be used.
  • the compound (10) plays a role as a catalyst in the production method according to the present invention, it means both a substance to be charged as a reagent and a substance generated during the reaction (catalytically active species).
  • the compound (10) is known to show catalytic activity when some of the ligands dissociate under the reaction conditions, and to show catalytic activity without dissociation of the ligands.
  • any of them is not limited in the present invention.
  • the compound whose metal is ruthenium is generally referred to as “ruthenium-carbene complex”, for example, Vougioukalakis, G., et al. C. et al. Chem. Rev. , 2010, 110, 1746-1787.
  • the ruthenium-carbene complex described in 1) can be used.
  • a ruthenium-carbene complex commercially available from Aldrich or Umicore can be used.
  • the metal of the metal carbene complex compound is preferably ruthenium.
  • ruthenium-carbene complex examples include bis (triphenylphosphine) benzylidene ruthenium dichloride, bis (tricyclohexylphosphine) benzylidene ruthenium dichloride, bis (tricyclohexylphosphine) -3-methyl-2-butenylidene ruthenium dichloride, ( 1,3-diisopropylimidazol-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dicyclohexylimidazole-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dimesitylimidazole) -2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dimesitylimidazole
  • the ruthenium-carbene complex may be used alone or in combination of two or more. Further, if necessary, it may be supported on a carrier such as silica gel, alumina or polymer.
  • molybdenum-carbene complex compounds in which the metal is molybdenum or tungsten are generally referred to as “molybdenum-carbene complex” or “tungsten-carbene complex”.
  • the molybdenum-carbene complex or tungsten-carbene complex described in 1) can be used.
  • a molybdenum-carbene complex or a tungsten-carbene complex commercially available from Aldrich, Strem, and Ximo can be used.
  • the metal of the metal carbene complex compound is preferably molybdenum or tungsten from the viewpoint of availability of the catalyst.
  • the molybdenum-carbene complex or the tungsten-carbene complex may be used alone or in combination of two or more. Further, if necessary, it may be supported on a carrier such as silica gel, alumina or polymer.
  • R 1 include an alkyl group and an aryl group.
  • the ligand [L] of the metal catalyst preferably has a ligand in which an oxygen atom is bidentately coordinated.
  • the ligand in which the oxygen atom is bidentate is a ligand having two or more oxygen atoms in a ligand having two or more oxygen atoms, and oxygen This includes both cases where two monodentate ligands having atoms are coordinated (in this case, the monodentate ligands may be the same or different).
  • Me represents a methyl group
  • i-Pr represents an isopropyl group
  • t-Bu represents a tertiary butyl group
  • Ph represents a phenyl group.
  • tungsten-carbene complex examples include the following compounds.
  • ⁇ Olefin compound (21)> In the presence of the metal-carbene complex compound (10) having an olefin metathesis reaction activity on the surface of the base material into which an organic group containing a carbon-carbon double bond is introduced, the carbon-carbon double bond is converted into the olefin compound (21). And a metathesis reaction can produce a base material into which an organic group containing a fluorine atom and a carbon-carbon double bond is introduced.
  • X 11 to X 13 and R F in the compound (21) are as defined above. That is, X 11 to X 13 in the compound (21) are each independently a hydrogen atom; a halogen atom; an alkyl group having 1 to 12 carbon atoms; an alkoxy group having 1 to 12 carbon atoms; an aryl group having 5 to 20 carbon atoms; An aryloxy group having 5 to 20 carbon atoms; a (per) halogenated alkyl group having 1 to 12 carbon atoms; a (per) halogenated alkoxy group having 1 to 12 carbon atoms; a (per) halogenated aryl group having 5 to 20 carbon atoms And a (per) halogenated aryloxy group having 5 to 20 carbon atoms; a group selected from the group consisting of the alkyl group, alkoxy group, aryl group, aryloxy group, and (per) halogenated alkyl group.
  • a (per) halogenated alkoxy group, a (per) halogenated aryl group, and a (per) halogenated aryloxy group are oxygen atoms
  • Nitrogen atom, sulfur atom, phosphorus atom, and the atom selected from the group consisting of silicon atoms may have 1 or more containing substituent.
  • X 12 and X 13 may be bonded to each other as a divalent group in which one hydrogen atom or halogen atom is removed to form a ring.
  • a ring consisting of only a carbon atom or a ring consisting of a carbon atom and a hetero atom is preferable.
  • Examples of the ring size include a 3-membered ring to a 10-membered ring.
  • Examples of the ring partial structure include the following structures.
  • the group having a carbon atom may have an etheric oxygen atom between the carbon atoms as described later.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable from the viewpoint of availability.
  • the alkyl group having 1 to 12 carbon atoms the group having 1 to 8 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, or a propyl group is preferable from the viewpoint of easy availability.
  • the alkyl group chain may be linear, branched or cyclic.
  • the alkoxy group having 1 to 12 carbon atoms the group having 1 to 8 carbon atoms is preferable, and specifically, a methoxy group, an ethoxy group, or a propoxy group is preferable from the viewpoint of availability.
  • the alkoxy group chain may be linear, branched or cyclic.
  • the aryl group having 5 to 20 carbon atoms the group having 5 to 12 carbon atoms is preferable, and specifically, a phenyl group is preferable from the viewpoint of availability.
  • the aryloxy group having 5 to 20 carbon atoms the group having 5 to 12 carbon atoms is preferable. Specifically, a phenyloxy group is preferable from the viewpoint of availability.
  • the (per) halogenated alkyl group having 1 to 12 carbon atoms is preferably the group having 1 to 8 carbon atoms, particularly preferably a (per) fluoroalkyl group having 1 to 8 carbon atoms.
  • a trifluoromethyl group, a pentafluoroethyl group, or a heptafluoropropyl group is preferable from the viewpoint of availability.
  • the alkyl group chain may be linear, branched or cyclic.
  • the (per) halogenated alkoxy group having 1 to 12 carbon atoms is preferably the group having 1 to 8 carbon atoms, particularly preferably a (per) fluoroalkoxy group having 1 to 8 carbon atoms.
  • a trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoropropoxy group, a perfluoro (methoxymethoxy) group, or a perfluoro (propoxypropoxy) group is preferable, and in particular, a trifluoromethoxy group or a perfluoro (propoxypropoxy) group is available. It is preferable from the viewpoint of ease.
  • the alkoxy group chain may be linear, branched or cyclic.
  • the (per) halogenated aryl group having 5 to 20 carbon atoms is preferably the group having 5 to 12 carbon atoms, and particularly preferably a (per) fluoroaryl group having 5 to 12 carbon atoms.
  • a monofluorophenyl group or a pentafluorophenyl group is preferable, and a pentafluorophenyl group is particularly preferable from the viewpoint of availability.
  • the (per) halogenated aryloxy group having 5 to 20 carbon atoms is preferably the group having 5 to 12 carbon atoms, particularly preferably the (per) fluoroaryloxy group having 5 to 12 carbon atoms.
  • a monofluorophenyloxy group or a pentafluorophenyloxy group is preferable, and a pentafluorophenyloxy group is particularly preferable from the viewpoint of availability.
  • Examples of the substituent containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom include a nitrile group, a carboxyl group, and an ester group (acyloxy group or alkoxycarbonyl group). .
  • the total number of carbon atoms of the alkyl group, alkoxy group, (per) halogenated alkyl group, and (per) halogenated alkoxy group is 1 to 12
  • the aryl group, aryloxy group The total number of carbon atoms in the (per) halogenated aryl group and (per) halogenated aryloxy group is 5 to 20.
  • the alkyl group, alkoxy group, aryl group, aryloxy group, (per) halogenated alkyl group, (per) halogenated alkoxy group, (per) halogenated aryl group, or (per) halogenated aryloxy group are:
  • An etheric oxygen atom may be present between the carbon atoms. That is, the group (vi) is preferably a group (v) further containing one or more oxygen atoms, and the oxygen atom is more preferably an etheric oxygen atom. That is, the group (vi) is preferably the following group (vii).
  • Group (vii) Group (v) having an etheric oxygen atom between carbon atoms.
  • X 12 is preferably group (i), group (ii), group (v), or group (vii), and X 13 is group (ii) or group (v). Or a combination that is a group (vii). More preferably, X 12 is a hydrogen atom, a halogen atom, a (per) halogenated alkyl group having 1 to 12 carbon atoms, or a (per) halogen having 1 to 12 carbon atoms having an etheric oxygen atom between the carbon atoms.
  • Alkyl group (per) halogenated alkoxy group having 1 to 12 carbon atoms, (per) halogenated alkoxy group having 2 to 12 carbon atoms having an etheric oxygen atom between carbon atoms, carbon number 5 to 20 (per) halogenated aryl groups, 5 to 20 (per) halogenated aryl groups having an etheric oxygen atom between carbon atoms, (per) halogenated aryl having 5 to 20 carbon atoms oxy group, or a 5 to 20 carbon atoms having a carbon atom and an ether oxygen atom between carbon atoms (per) halogenated aryloxy group;
  • X 13 is a halogen atom, a carbon number 1 12 alkyl groups, an alkyl group having 2 to 12 carbon atoms having an etheric oxygen atom between carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an etheric oxygen atom between carbon atoms.
  • alkoxy group having 2 to 12 carbon atoms an aryl group having 5 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms having an etheric oxygen atom between the carbon atoms, ) Halogenated alkyl group, (per) halogenated alkyl group having 2 to 12 carbon atoms having an etheric oxygen atom between carbon atoms, (per) halogenated alkoxy group having 1 to 12 carbon atoms, carbon atom (Per) halogenated alkoxy group having 1 to 12 carbon atoms having an etheric oxygen atom between carbon atom and carbon atom, (per) halogenated aryl group having 5 to 20 carbon atoms, carbon atom and carbon atom A (per) halogenated aryl group having 5 to 20 carbon atoms having an etheric oxygen atom in between, a (per) halogenated aryloxy group having 5 to 20 carbon atoms, or an etheric oxygen atom between carbon atoms A
  • R F in the compound (21) is a fluorine atom, a (per) fluoroalkyl group having 1 to 12 carbon atoms, a (per) fluoroalkoxy group having 1 to 12 carbon atoms, or 1 to 200 carbon atoms containing an etheric oxygen atom ( It is a group selected from the group consisting of a per) fluoroalkyl group and a (per) fluoroalkoxy group having 2 to 200 carbon atoms containing an etheric oxygen atom.
  • the compound (21) is preferably 1,1-difluoroolefin or 1,2-difluoroolefin, more preferably 1,1-difluoroolefin or 1,2-difluoroolefin having 3 or more carbon atoms, particularly 1,1-difluoroolefin. Difluoroolefin is preferred.
  • R 2 F is derived from a (per) fluoroalkyl group having 1 to 200 carbon atoms containing an etheric oxygen atom, and a (per) fluoroalkoxy group having 2 to 200 carbon atoms containing an etheric oxygen atom.
  • Olefin which is a group selected from the group consisting of
  • an organic group containing a carbon-carbon double bond is introduced into the surface of the substrate, and the organic group containing a fluorine atom and a carbon-carbon double bond is further obtained by subjecting the carbon-carbon double bond to a metathesis reaction.
  • the present invention relates to a method for producing an introduced substrate.
  • a carbon-carbon double bond is introduced into the surface of the substrate by a known method.
  • a carbon-carbon double bond can be introduced by applying a silane coupling agent having an organic group containing a carbon-carbon double bond.
  • a coating method a known method can be appropriately used. Examples of the coating method include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, ink jet method, flow coating method, roll coating method, casting method, Langmuir-Blodgett method, gravure Examples thereof include a coating method.
  • a carbon-carbon double bond can be introduced under the conditions of heat curing or photocuring using polyfunctional (meth) acrylate or the like.
  • Photocuring is performed by irradiating active energy rays.
  • active energy rays include ultraviolet rays, electron beams, X-rays, radiation, high-frequency rays, etc., and ultraviolet rays having a wavelength of 180 to 500 nm are economically preferable.
  • Active energy ray sources include ultraviolet irradiation devices (xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps, ultraviolet LEDs, etc.), electron beam irradiation devices, X-ray irradiation devices, and high frequencies.
  • a generator or the like can be used.
  • heating may be performed after irradiation with active energy rays.
  • the heating temperature is preferably 50 to 120 ° C.
  • an appropriate pretreatment may be applied to the surface of the substrate.
  • Specific examples include a method of pouring a solvent over the surface of the substrate, a method of wiping with a cloth soaked with a solvent, a corona treatment, a UV-ozone treatment, and the like.
  • compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as necessary.
  • Specific methods include, for example, a method of pouring a solvent over the surface layer and a method of wiping with a cloth soaked with a solvent.
  • An olefin containing a fluorine atom is used as the compound (21) for causing a metathesis reaction to a substrate having a carbon-carbon double bond introduced on the surface, and the compound can utilize both an internal olefin and a terminal olefin. it can.
  • a degassed and dehydrated compound (21) is used as a raw material.
  • the deaeration operation There is no particular limitation on the deaeration operation, but freeze deaeration and the like may be performed. Although there is no restriction
  • the degassing and dehydration operations are usually performed before contacting with the metal-carbene complex compound.
  • the compound (21) used as a raw material may contain a trace amount impurity (for example, hydrogen fluoride etc.), you may refine
  • the purification method There is no particular limitation on the purification method. For example, it can be carried out according to the method described in the literature (Armarego, WLF et al., Purification of Laboratory Chemicals (Sixth Edition), 2009, Elsevier).
  • C ⁇ C base material the base material into which the carbon-carbon double bond as a raw material is introduced
  • the other compound (21) or the C ⁇ C substrate may be contacted.
  • the compound (21) is used in an amount of about 0.01 to 100 mol, preferably about 0.1 to 10 mol, per 1 mol of the olefin moiety on the surface of the C ⁇ C substrate.
  • the metal-carbene complex compound may be added as a reagent or generated in the system.
  • a commercially available metal-carbene complex compound may be used as it is, or a commercially available metal-carbene complex compound synthesized by a known method from a commercially available reagent may be used.
  • a metal-carbene complex compound prepared from a metal complex as a precursor by a known method can be used in the present invention.
  • the metal-carbene complex compound to be used is usually charged into the reaction vessel as a solid, but may be charged after dissolving or suspending in a solvent.
  • the solvent used at this time is not particularly limited as long as it does not adversely affect the reaction, and an organic solvent, a fluorine-containing organic solvent, an ionic liquid, water and the like can be used alone or in combination. In these solvent molecules, some or all of the hydrogen atoms may be substituted with deuterium atoms.
  • the compound (21) is liquid (including the case where it is liquefied by heating), it is preferable not to use a solvent for the metathesis reaction. In this case, the metal-carbene complex compound is preferably dissolved in the compound (21).
  • organic solvent examples include aromatic hydrocarbon solvents such as benzene, toluene, o-, m-, p-xylene and mesitylene; aliphatic hydrocarbon solvents such as hexane and cyclohexane; dichloromethane, chloroform, 1, 2 -Halogen solvents such as dichloroethane, chlorobenzene and o-dichlorobenzene; ether solvents such as tetrahydrofuran, dioxane, diethyl ether, glyme and diglyme can be used.
  • aromatic hydrocarbon solvents such as benzene, toluene, o-, m-, p-xylene and mesitylene
  • aliphatic hydrocarbon solvents such as hexane and cyclohexane
  • dichloromethane, chloroform, 1, 2 -Halogen solvents such as dichloroethane, chlorobenzene and o-
  • fluorine-containing organic solvent examples include hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, ⁇ , ⁇ , ⁇ -trifluoromethylbenzene, dichloropentafluoropropane, and the like.
  • hexafluorobenzene examples include hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, ⁇ , ⁇ , ⁇ -trifluoromethylbenzene, dichloropentafluoropropane, and the like.
  • ionic liquid for example, various pyridinium salts, various imidazolium salts and the like can be used.
  • benzene, toluene, o-, m-, p-xylene, mesitylene, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, diethyl ether, dioxane, THF in terms of solubility of the metal-carbene complex, etc. Tetrahydrofuran
  • hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, ⁇ , ⁇ , ⁇ -trifluoromethylbenzene, and mixtures thereof are preferred.
  • a degassed and dehydrated solvent for improving the yield of the target product.
  • the deaeration operation freeze deaeration and the like may be performed.
  • dehydration operation Usually, it is made to contact with a molecular sieve etc.
  • the degassing and dehydration operations are usually performed before contacting with the metal-carbene complex compound.
  • the same solvents as those used for dissolving or suspending the metal-carbene complex compound can be used.
  • the same solvents as those used for dissolving or suspending the metal-carbene complex compound can be used.
  • the same solvents as those used for dissolving or suspending the metal-carbene complex compound can be used.
  • two or more compounds (21) as a raw material and at least one of these compounds is liquid under the reaction conditions, it may be carried out without a solvent.
  • a metal container or a glass container can be used.
  • the cross metathesis concerning this invention may handle the olefin in a gaseous state on reaction conditions, the pressure-resistant container in which high airtightness is possible is preferable.
  • the target olefin portion on the substrate surface is usually obtained as a mixture of a plurality of olefins.
  • compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as necessary. Specific methods include, for example, a method of pouring a solvent over the surface layer and a method of wiping with a cloth soaked with a solvent.
  • the surface of the substrate obtained by this reaction can be identified by a known method similar to a normal organic compound. For example, 1 H-, 19 F-, 13 C-NMR, GC-MS and the like can be mentioned, and these can be used alone or in combination.
  • Example 1 Manufacture of a glass substrate into which an organic group containing fluorine atoms and carbon-carbon double bonds has been introduced by cross-metathesis. A clean glass substrate is obtained by washing a 60 ⁇ 60 mm glass substrate in the order of dilute hydrochloric acid and ion-exchanged water. Obtained (base material A1). Next, a dimethylacetamide solution of allyltrichlorosilane was applied to the substrate A1 by spin coating.
  • Example 2 Manufacture of glass substrate introduced with organic group containing fluorine atom and carbon-carbon double bond by ring-opening cross metathesis Clean glass substrate by washing 60 ⁇ 60mm glass substrate in order of dilute hydrochloric acid and ion-exchanged water A material is obtained (base material A2). Next, a dimethylacetamide solution of 5-[(2-trimethoxysilyl) ethyl] bicyclo [2.2.1] -2-heptene is applied to the substrate A2 by spin coating. This is dried in a desiccator and the surface is washed with methanol to obtain a glass substrate (substrate B2) having a carbon-carbon double bond introduced on the surface.
  • Example 3 Production of glass substrate into which organic group containing fluorine atom and carbon-carbon double bond is introduced by ring-opening metathesis polymerization. Clean glass substrate by washing 60 ⁇ 60mm glass substrate in order of dilute hydrochloric acid and ion-exchanged water. A material is obtained (base material A3). Next, a dimethylacetamide solution of 5-[(2-trimethoxysilyl) ethyl] bicyclo [2.2.1] -2-heptene is applied to the substrate A3 by spin coating. This is dried in a desiccator and the surface is washed with methanol to obtain a glass substrate (substrate B3) having a carbon-carbon double bond introduced on the surface.
  • n is a positive integer representing a repeating unit.
  • Example 4 Manufacture of glass substrate into which organic group containing fluorine atom and carbon-carbon double bond is introduced by chain diene metathesis polymerization Clean glass by washing 60 ⁇ 60mm glass substrate in order of dilute hydrochloric acid and ion-exchanged water A base material is obtained (base material A4). Next, a dimethylacetamide solution of allyltrichlorosilane is applied to the substrate A4 by spin coating. This is dried in a desiccator, and the surface is washed with methanol to obtain a glass substrate (substrate B4) having a carbon-carbon double bond introduced on the surface.
  • Grubbs second generation catalyst (0.01 mmol) similar to Example 1 and 10 mL of methylene chloride are weighed into a pressure-tight airtight container, and the substrate B4 is submerged in the resulting solution, and the inside of the pressure-tight airtight container is replaced with hexafluorobutadiene. To do. After leaving at room temperature for 24 hours, the substrate is taken out and washed with methanol to obtain a glass substrate (substrate C4) into which an organic group containing fluorine atoms and carbon-carbon double bonds has been introduced. A series of reactions is shown below. In the formula, n is a positive integer representing a repeating unit.
  • Example 5 Production of Glass Substrates Introduced Organic Groups Containing Fluorine Atoms and Carbon-Carbon Double Bonds by Molybdenum Catalyst Cross-Metathesis
  • Examples of known molybdenum catalysts DG represented by the following formulas as Grubbs second generation catalyst of Example 1 The glass substrate (C1) in which an organic group containing the same fluorine atom and carbon-carbon double bond as in Example 1 was introduced was obtained by changing to
  • Example 9 Production of glass substrate into which organic group containing fluorine atom and carbon-carbon double bond is introduced by tungsten catalyst cross metathesis.
  • Grubbs second generation catalyst in Example 1 is changed to known tungsten catalyst H represented by the following formula Then, the same reaction is performed to obtain a glass substrate (C1) into which an organic group containing the same fluorine atom and carbon-carbon double bond as in Example 1 is introduced.
  • Example 10 Production of glass base material into which organic group containing fluorine atom and carbon-carbon double bond is introduced by cross-metathesis
  • Glass base material B1 obtained in the same manner as Example 1 in a pressure-resistant container, same as Example 1 Of Grubbs second generation catalyst (0.01 mmol) and 10 mL of methylene chloride. After replacing the inside of the pressure vessel with tetrafluoroethylene (1 mmol), after leaving it to stand at room temperature for 24 hours, the base material is taken out and washed with methanol to introduce organic groups containing fluorine atoms and carbon-carbon double bonds. A glass substrate (substrate C10) is obtained. A series of reactions are shown below.
  • Examples 11 to 14 Production of Glass Substrate Introduced Organic Group Containing Fluorine Atom and Carbon-Carbon Double Bond by Cross-Metathesis Reaction was carried out by changing the tetrafluoroethylene of Example 10 to the compound (21) shown in the following table. carry out. As a product, glass substrates (substrates C11 to C14) into which organic groups containing fluorine atoms and carbon-carbon double bonds shown in Table 4 are introduced are obtained.
  • Examples 15 to 18 Production of glass base material into which organic group containing fluorine atom and carbon-carbon double bond is introduced by molybdenum catalyst cross metathesis.
  • the Grubbs second generation catalyst of Example 10 was changed to molybdenum catalysts D to G, and similarly Reaction is performed to obtain glass substrates (C15 to C18) into which organic groups containing the same fluorine atom and carbon-carbon double bond as in Example 10 are introduced.
  • Example 19 Production of a glass substrate into which an organic group containing a fluorine atom and a carbon-carbon double bond is introduced by tungsten catalyst cross-metathesis.
  • the Grubbs second generation catalyst of Example 10 is changed to tungsten catalyst H, and the reaction is similarly performed.
  • the glass substrate (C19) having the same fluorine atom and carbon-carbon double bond as in Example 10 introduced therein is obtained.
  • Example 20 Production of glass substrate into which organic group containing fluorine atom and carbon-carbon double bond is introduced by ring-opening metathesis polymerization
  • Glass substrate B3 obtained by the same method as Example 3, Grubbs similar to Example 1
  • a second generation catalyst (0.01 mmol), perfluoro-2,2-dimethyl-1,3-dioxole (1 mmol), and 10 mL of methylene chloride are metered in to proceed with the desired ring-opening metathesis polymerization.
  • the substrate is taken out and washed with methanol to obtain a glass substrate (substrate C20) into which an organic group containing a fluorine atom and a carbon-carbon double bond is introduced.
  • a series of reactions are shown below.
  • n is a positive integer indicating a repeating unit.
  • Example 21 Production of gold base material into which organic groups including fluorine atoms and carbon-carbon double bonds are introduced by cross-metathesis
  • Gold base material is first deposited on a clean silicon wafer washed with ethanol and ion-exchanged water under reduced pressure. Next, by treatment with an ethanol solution of 4-mercapto-1-butanol, a gold substrate having a hydroxyl group terminal is obtained (A21).
  • a dimethylacetamide solution of allyltrichlorosilane is applied to the substrate A21 by spin coating. This is dried in a desiccator and the surface is washed with methanol to obtain a gold base material (base material B21) having a carbon-carbon double bond introduced on the surface.
  • a base material into which an organic group containing a fluorine atom and a carbon-carbon double bond is introduced can be easily and efficiently produced by a metathesis reaction using a fluorine-containing olefin.

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Abstract

La présente invention aborde le problème de la fabrication facile et efficace, dans des conditions douces, d'un substrat dans lequel est introduit un groupe organique contenant un atome de fluor et une double liaison carbone-carbone à l'aide, en tant que matière première, d'un composé contenant du fluor qui est facilement disponible à l'échelle industrielle. La présente invention concerne le procédé de fabrication d'un substrat dans lequel est introduit un groupe organique contenant un atome de fluor et une double liaison carbone-carbone par métathèse, sur une surface d'un substrat dans lequel est introduit un groupe organique contenant une double liaison carbone-carbone, la double liaison carbone-carbone muni d'un composé d'oléfine représenté par la formule (21) en présence d'un composé complexe métal-carbène.
PCT/JP2016/056122 2015-03-03 2016-02-29 Procédé de fabrication d'un substrat dans lequel est introduit un groupe organique contenant un atome de fluor et une double liaison carbone-carbone WO2016140201A1 (fr)

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WO2018159641A1 (fr) * 2017-03-02 2018-09-07 Ａｇｃ株式会社 Procédé de production d'un composé de silane contenant du fluor, et composé de silane contenant du fluor
CN110294704A (zh) * 2018-03-24 2019-10-01 复旦大学 一种制备含单氟烷基烯烃化合物的方法

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WO2006046699A1 (fr) * 2004-10-28 2006-05-04 Asahi Glass Company, Limited Procédé de fabrication de substrats possédant en surface des films hydrophiles ayant un effet hydrofuge

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EP1301458B1 (fr) * 2000-06-23 2015-09-09 California Institute Of Technology Synthese d'olefines fonctionnalisees et non fonctionnalisees par metathese croisee et metathese a fermeture de cycle
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JPH04363386A (ja) * 1990-09-28 1992-12-16 Ppg Ind Inc 表面撥水性物品及びその製造方法
JP2002517372A (ja) * 1998-06-10 2002-06-18 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド 撥水性表面処理
JP2003064348A (ja) * 2001-08-28 2003-03-05 Sony Corp 防汚性表面処理剤及び防汚性表面処理用組成物
WO2006046699A1 (fr) * 2004-10-28 2006-05-04 Asahi Glass Company, Limited Procédé de fabrication de substrats possédant en surface des films hydrophiles ayant un effet hydrofuge

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018159641A1 (fr) * 2017-03-02 2018-09-07 Ａｇｃ株式会社 Procédé de production d'un composé de silane contenant du fluor, et composé de silane contenant du fluor
JPWO2018159641A1 (ja) * 2017-03-02 2019-12-19 Ａｇｃ株式会社 含フッ素シラン化合物の製造方法及び含フッ素シラン化合物
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CN110294704A (zh) * 2018-03-24 2019-10-01 复旦大学 一种制备含单氟烷基烯烃化合物的方法

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