WO2019059318A1 - Composé contenant du fluor, et polymère contenant du fluor ainsi que procédé de fabrication de celui-ci - Google Patents

Composé contenant du fluor, et polymère contenant du fluor ainsi que procédé de fabrication de celui-ci Download PDF

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WO2019059318A1
WO2019059318A1 PCT/JP2018/034925 JP2018034925W WO2019059318A1 WO 2019059318 A1 WO2019059318 A1 WO 2019059318A1 JP 2018034925 W JP2018034925 W JP 2018034925W WO 2019059318 A1 WO2019059318 A1 WO 2019059318A1
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fluorine
atom
general formula
independently
polymer
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Japanese (ja)
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司 臼田
祐介 ▲高▼平
森澤　義富
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Ａｇｃ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
    • C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/18—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C43/192—Ethers having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F32/02—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
    • C08F32/04—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/20—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • 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

Definitions

  • the present invention relates to a fluorine-containing compound, a fluorine-containing polymer containing a constituent unit derived from the fluorine-containing compound, and a method for producing the fluorine-containing polymer.
  • norbornene derivative a compound having a norbornene skeleton
  • the polymer containing the structural unit based on the norbornene derivative and the hydrogenated product thereof are excellent in the balance of various properties such as high glass transition temperature (high heat resistance), low water absorption, high light transmittance, etc. It is used in a wide variety of fields such as materials, semiconductor materials, and optical materials.
  • the fluorine-containing norbornene derivative containing a fluorine atom in the norbornene derivative and the polymer thereof are expected to be excellent in chemical durability, weather resistance and light transmittance as compared to the norbornene derivative containing no fluorine and the polymer thereof (Patent Document 1).
  • Non-patent document 1 a polymer obtained by ring-opening polymerization of a disubstituted norbornene compound (Non-patent document 1) in which a perfluoromethyl group is bonded to a carbon atom directly bonded to a norbornene skeleton or a disubstituted norbornene compound containing no fluorine atom by a metathesis reaction.
  • Non-Patent Document 2 has been reported.
  • Non-Patent Document 2 has been reported.
  • an object of the present invention is to provide a novel fluorine-containing compound which is a polysubstituted norbornene derivative having two or more norbornene skeletons and which contains a fluorine atom between the norbornene skeletons.
  • Another object of the present invention is to provide a novel polymer containing the above-mentioned fluorine-containing compound as a monomer and a method for producing the same.
  • the present invention relates to the following ⁇ 1> to ⁇ 7> as configurations for achieving the above-mentioned problems.
  • ⁇ 1> A fluorine-containing compound represented by the following general formula a.
  • Y is each independently CR 14 R 15 , O, S, NR 16 or PR 17 ;
  • Q is an m-valent organic group containing a fluorine atom,
  • R 11 to R 13 are each independently a hydrogen atom, a halogen atom or a monovalent organic group,
  • R 14 to R 17 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, m is a natural number of 2 or more, n is 0 or 1.
  • Y is each independently CR 14 R 15 , O, S, NR 16 , PR 17 ;
  • Q is an m-valent organic group containing a fluorine atom,
  • R 11 to R 13 are each independently a hydrogen atom, a halogen atom or a monovalent organic group,
  • R 14 to R 17 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
  • m is a natural number of 2 or more, n is 0 or 1 and
  • Each of x and v is a natural number representing the number of repetitions of the repeating unit.
  • Y is each independently CR 14 R 15 , O, S, NR 16 or PR 17 ;
  • Q is an m-valent organic group containing a fluorine atom,
  • R 11 to R 13 are each independently a hydrogen atom, a halogen atom or a monovalent organic group,
  • R 14 to R 17 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, m is a natural number of 2 or more, n is 0 or 1 and u is a natural number representing the number of repetitions of the repeating unit.
  • Y is each independently CR 14 R 15 , O, S, NR 16 or PR 17 ;
  • Q is an m-valent organic group containing a fluorine atom,
  • R 11 to R 13 are each independently a hydrogen atom, a halogen atom or a monovalent organic group,
  • R 14 to R 17 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, m is a natural number of 2 or more, n is 0 or 1 and x is a natural number representing the number of repetitions of the repeating unit.
  • Y is each independently CR 14 R 15 , O, S, NR 16 or PR 17 ;
  • Q is an m-valent organic group containing a fluorine atom,
  • R 11 to R 13 are each independently a hydrogen atom, a halogen atom or a monovalent organic group,
  • R 14 to R 17 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, m is a natural number of 2 or more, n is 0 or 1 and v is a natural number representing the number of repetitions of the repeating unit.
  • Y is each independently CR 14 R 15 , O, S, NR 16 or PR 17 ;
  • Q is an m-valent organic group containing a fluorine atom,
  • R 11 to R 13 are each independently a hydrogen atom, a halogen atom or a monovalent organic group,
  • R 14 to R 17 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
  • m is a natural number of 2 or more, n is 0 or 1 and
  • Each of x and u is a natural number representing the number of repetitions of the repeating unit.
  • the fluorine-containing polymer can be easily produced by ring-opening polymerization or addition polymerization using a metathesis reaction, and the obtained fluorine-containing polymer has chemical durability and weather resistance. It is expected to have excellent conductivity, light transmission, transparency, liquid repellency, and a low dielectric constant.
  • the fluorine-containing compound according to the present invention is a fluorine-containing norbornene derivative represented by the general formula a.
  • Y is each independently CR 14 R 15 , O, S, NR 16 or PR 17 .
  • the fluorine-containing compound in the present invention can be synthesized, for example, by Diels-Alder reaction of a diene having a five-membered ring structure such as cyclopentadiene as described later and an olefin.
  • Y can be defined by the diene structure of the five-membered ring structure.
  • Y is preferably CH 2 , O or NH from the viewpoint of reactivity and availability, and CH 2 is particularly preferable.
  • Q is an m-valent organic group containing a fluorine atom.
  • the structure of the organic group is not particularly limited as long as Q contains one or more fluorine atoms.
  • Examples of the organic group include a hydrocarbon group containing a fluorine atom, and a hydrocarbon group containing a fluorine atom and a hetero atom other than a fluorine atom.
  • the hetero atom means an atom other than a carbon atom and a hydrogen atom, and 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 chlorine atom It can be mentioned.
  • the fluorine-containing compound of the present invention is a compound having two or more norbornene skeletons.
  • the norbornene skeleton means a skeleton of bicyclo [2.2.1] hept-2-ene, but the position of Y in the general formula a may contain a hetero atom.
  • the hetero atom includes an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom.
  • a fluorine-containing compound having three or more norbornene skeletons can be obtained by appropriately having a quaternary carbon atom or a tertiary carbon atom in the structure of Q. Further, the fluorine-containing compound having three or more norbornene skeletons can be obtained not only by carbon atoms but also by containing, for example, Si and N in the main skeleton of Q.
  • a cyclic structure it may have an arenepolyyl group, a cycloalkanepolyyl group, and the like.
  • the arenepolyyl group means a polyvalent group corresponding to a residue obtained by removing two or more hydrogen atoms bonded to a carbon atom or the like forming an aromatic ring in an aromatic compound.
  • the aromatic compound may be either a homoarene which is a carbocyclic ring compound or a heteroarene which is a heterocyclic ring compound.
  • divalent groups such as phenylene group, biphenylene group and naphthylene group
  • trivalent groups such as benzenetriyl group and naphthalenetriyl group
  • tetravalent groups such as benzenetetrayl group and naphthalenetetrayl group
  • cycloalkanepolyyl group means a polyvalent group corresponding to a residue obtained by removing two or more hydrogen atoms bonded to a carbon atom forming a cycloalkane.
  • a divalent group such as a cyclopentadiyl group, a cyclohexanediyl group, a trivalent group such as a cyclopropanetriyl group, a cyclobutanetriyl group, a cyclobutanetriyl group, a cyclopentanetriyl group, a cyclohexanetriyl group, a cyclopropanetetrayl group
  • tetravalent groups such as cyclobutanetetrayl group, cyclopentanetetrayl group and cyclohexanetetrayl group.
  • the cyclic structure in the structure of Q is not limited to a single ring, and may be a polycyclic structure in which a plurality of rings are linked.
  • the polycyclic structure may be a fused ring or a spiro ring.
  • these cyclic structures are not limited to carbocyclic compounds, and may be heterocyclic compounds in which one or more carbon atoms are substituted with hetero atoms.
  • the hydrogen atoms forming the ring some or all of the hydrogen atoms may be substituted with halogen atoms.
  • one or more fluorine atoms may be contained in the structure of Q, and the number of fluorine atoms is not particularly limited as long as it is one or more. Also, the position of the fluorine atom is not particularly limited. Further, it may be a perfluoro compound in which all hydrogen atoms present in the structure of Q are substituted by fluorine atoms.
  • the carbon number of Q is preferably 1 to 100, and more preferably 2 to 60.
  • Q is preferably an m-valent organic group containing at least one of —CF 2 — and —CF 3 .
  • a plurality of these groups may be contained.
  • As the group further contained in Q for example, methylene group, fluoromethylene group, etheric oxygen atom, carbonyl group, ester group, thioether group, amino group, hydroxyl group, carboxyl group, alkoxy group, silyl group, nitrile group, and Although the group of these combination is mentioned, it is not limited to these.
  • the ends of the organic group represented by Q may all be bonded to the norbornene skeleton, or may be another structure.
  • the other structure is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, a hydroxyl group, a carboxyl group, a silanol group, a vinyl group, an aryl group, an ester group, an amino group and the like.
  • at least a part of hydrogen atoms in these groups may be substituted with a halogen atom.
  • R 11 to R 13 each independently represent a hydrogen atom, a halogen atom or a monovalent organic group.
  • R 11 to R 13 mean R 11 , R 12 and R 13 .
  • the halogen atom includes a fluorine atom, a chlorine atom and a bromine atom. Among them, a hydrogen atom or a fluorine atom is preferable from the viewpoint of easy availability.
  • a monovalent hydrocarbon group a monovalent hydrocarbon group containing a halogen atom, a monovalent hydrocarbon group containing a hetero atom, a monovalent hydrocarbon group containing a halogen atom and a hetero atomcan be mentioned.
  • the monovalent organic group a fluorine-containing hydrocarbon group having an etheric oxygen atom is preferable.
  • the carbon number of the monovalent organic group is preferably 1 to 200, more preferably 1 to 100, and still more preferably 1 to 20.
  • m is a natural number of 2 or more.
  • the value of m is determined by the structure of Q (the number of bonds).
  • m should be 2 or more, and the upper limit is not particularly limited, but is preferably 8 or less, more preferably 2 to 4 from the viewpoint of easy availability.
  • n 0 or 1.
  • a fluorine-containing compound is synthesized, for example, by a one-stage Diels-Alder reaction of a diene having a five-membered ring structure with an olefin, as shown in the following scheme, n is 0.
  • N can be made 1 by reacting the obtained compound again with a diene.
  • Y, Q, R 11 to R 13 and m are as described above.
  • R 14 to R 17 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • R 14 to R 17 means R 14 , R 15 , R 16 and R 17 .
  • the olefin to be a raw material may be an m-valent organic group in which Q is a fluorine atom, and R 11 to R 13 may be a hydrogen atom, a halogen atom or a monovalent organic group.
  • the monovalent organic group may be further converted to another monovalent organic group after the Diels-Alder reaction.
  • a ladder-type polymer has less conformational change than a normal polymer and has a rigid structure, so that new physical properties and functions can be expected.
  • Y in the formula is preferably each independently CH 2 , O or NH.
  • R 11 to R 13 are preferably a hydrogen atom, a fluorine atom or a monovalent organic group, and more preferably a hydrogen atom, a fluorine atom or a monovalent fluorine-containing hydrocarbon group having an etheric oxygen atom.
  • Q is preferably a completely fluorinated divalent organic group or a completely fluorinated divalent organic group having an etheric oxygen atom, and a completely fluorinated divalent hydrocarbon group, or A fully fluorinated divalent hydrocarbon group having an etheric oxygen atom is more preferable, and a completely fluorinated bivalent alkylene group having 1 to 20 carbon atoms, or a completely fluorinated having an etheric oxygen atom Particularly preferred is a divalent alkylene group having 1 to 20 carbon atoms.
  • Y in the formula is preferably each independently CH 2 , O or NH.
  • R 11 to R 13 are preferably a hydrogen atom, a fluorine atom or a monovalent organic group, and more preferably a hydrogen atom, a fluorine atom or a monovalent fluorine-containing hydrocarbon group having an etheric oxygen atom.
  • Q is preferably a completely fluorinated trivalent organic group having 5 to 15 carbon atoms, or a fully fluorinated trivalent organic group having 5 to 15 carbon atoms having an etheric oxygen atom.
  • Examples of the fluorine-containing compound represented by the general formula a include the following compounds.
  • l is 1 to 5.
  • the fluorine-containing compound represented by the general formula a is used as a monomer, and a polymerization reaction is carried out to obtain a fluorine-containing polymer including the structure represented by the general formula I or II.
  • the symbols in the formula have the same meanings as the symbols in the general formula a.
  • x and v are natural numbers representing the number of repetitions of the repeating unit.
  • the polymerization reaction may be ring-opening polymerization (ring-opening metathesis polymerization, ROMP) by metathesis reaction, or addition polymerization such as radical polymerization or coordination polymerization.
  • ROMP ring-opening metathesis polymerization
  • addition polymerization such as radical polymerization or coordination polymerization.
  • the main chain double bond of the fluorine-containing polymer represented by the general formula I may be converted into a hydrogenated product by hydrogenation.
  • the fluorine-containing polymer obtained at this time will contain the structure represented by said general formula I '. Details of the hydrogen additive will be described later.
  • the ring-opening metathesis polymerization of the fluorine-containing compound represented by the general formula a is a fluorine-containing fluorine-containing compound having a structure represented by the general formula I by polymerization in the presence of a metal-carbene complex catalyst as shown in the following scheme. Polymers can be obtained.
  • Y, Q, R 11 to R 13 , m, n and x are respectively the same as those described above.
  • Cat is a catalyst which shows metathesis reaction activity.
  • [L] is a ligand
  • M is ruthenium, molybdenum or tungsten
  • a 1 and A 2 are each independently a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may contain a hetero atom, Each means.
  • geometric isomers (cis and trans) are also present during polymerization.
  • a dimer compound is produced from each of the above reaction intermediates, from which the polymerization proceeds to obtain a polymer.
  • geometric isomers exist in the dimer.
  • the resulting polymer may be formed by only one of the two bond types, or may be formed by both bond types.
  • a homopolymer obtained by polymerization using one kind of fluorine-containing compound (monomer) as a raw material is used, but copolymerization may be performed using two or more kinds of monomers as a raw material.
  • the copolymerization it is not particularly limited as long as at least one of the two or more monomers is a fluorine-containing compound represented by the general formula a, and the other monomers are not particularly limited as long as they are cyclic olefins. It may or may not have.
  • the other monomers it is more preferable to have a norbornene skeleton which is considered to be close to ring strain energy and highly reactive with the main monomer.
  • the fluorine-containing compound represented by the general formula a may be used as a main monomer or may be used as a comonomer.
  • alternating copolymer, block copolymer and random copolymer can be synthesized, and a desired copolymer can be obtained depending on the preparation ratio of monomers as raw materials and polymerization conditions. it can.
  • the molecular weight of the polymer is preferably 1,000 to 5,000,000 in view of mechanical properties and physical properties.
  • the molecular weight is a weight average molecular weight, and is measured under conditions of a polymer solution using gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the repeating number of the repeating unit represented by x in the formula is preferably 2 to 10,000 from the viewpoint of mechanical properties and physical properties, more preferably 5 to It is 6,500.
  • the total number of repeating units present is preferably 2 to 10,000, more preferably 5 to 6,500.
  • the obtained polymer has properties such as high heat resistance, low water absorption, high light transmittance (transparency), high chemical durability, high weather resistance, high liquid repellency, etc., and the balance of these properties is also excellent. Therefore, it can be used in a wide variety of fields such as electric and electronic materials, semiconductor materials, optical materials, medical instruments and cell culture materials, liquid repellent materials, elastomeric materials, crosslinking agents, airgel materials and the like.
  • Metal-carbene complex compound Although the ring-opening metathesis polymerization reaction proceeds in the presence of a catalyst, it is not particularly limited as long as it is a catalyst that performs ring-opening metathesis polymerization.
  • the metal-carbene complex compound include a ruthenium-carbene complex, a molybdenum-carbene complex, or a tungsten-carbene complex (hereinafter, also collectively referred to as “metal-carbene complex”).
  • a metal-carbene complex compound having an olefin metathesis reaction activity plays a role as a catalyst in the process for producing a fluoropolymer, but means both those charged as a reagent and those generated in the reaction (catalytically active species) Do.
  • metal-carbene complex compounds are known to exhibit catalytic activity by dissociation of some of the ligands under reaction conditions, and to exhibit catalytic activity without dissociation of ligands.
  • the present invention is not limited in any way.
  • the metal in the metal-carbene complex compound is preferably ruthenium, molybdenum or tungsten.
  • ruthenium-carbene complexes those in which the central metal is ruthenium are generally referred to as "ruthenium-carbene complexes", for example, those described in Vougioukalakis, G. et al. C. et al. Chem. Rev. , 2010, 110, 1746-1787.
  • the ruthenium-carbene complex described in can be utilized.
  • ruthenium-carbene complexes commercially available from Aldrich or Umicore can be used.
  • ruthenium-carbene complex examples include bis (triphenylphosphine) benzylideneruthenium dichloride, bis (tricyclohexylphosphine) benzylideneruthenium dichloride, bis (tricyclohexylphosphine) -3-methyl-2-butenylideneruthenium dichloride, 1,3-Diisopropylimidazole-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dicyclohexylimidazole-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dimesitylimidazole -2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dimesitylimidazole -2-ylid
  • the name starting with "Umicore” is a trade name of a product of Umicore.
  • the ruthenium-carbene complexes may be used alone or in combination of two or more. Furthermore, it may be supported on a carrier such as silica gel, alumina, polymer and the like as needed.
  • molybdenum-carbene complex or tungsten-carbene complex
  • tungsten-carbene complex for example, Grela, K. et al. (Ed) Olefin Metathesis: Theory and Practice, Wiley, 2014. Molybdenum-carbene complexes or tungsten-carbene complexes described in the above can be utilized.
  • a molybdenum-carbene complex or a tungsten-carbene complex commercially available from Aldrich, Strem, or Ximo can be used.
  • the molybdenum-carbene complex or the tungsten-carbene complex may be used alone or in combination of two or more. Furthermore, it may be supported on a carrier such as silica gel, alumina, polymer and the like as needed.
  • Me means methyl
  • i-Pr means isopropyl
  • t-Bu means tertiary butyl
  • Ph means phenyl
  • a degassed monomer as the raw material monomer.
  • the degassing operation is not particularly limited, but is usually in contact with a molecular sieve or the like.
  • the above degassing and dehydrating operations are usually performed before contacting with the metal-carbene complex.
  • the monomer used as a raw material may contain a trace amount impurities (for example, peroxide 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, W. L. F. et al., Purification of Laboratory Chemicals (Sixth Edition), 2009, Elsevier).
  • the molar ratio thereof is not particularly limited, but the compound which is the other monomer is usually 0.01 per 1 mol of the fluorine-containing compound represented by the general formula a as a standard. It is used in an amount of up to about 100 moles, preferably about 0.1 to 10 moles.
  • the metal-carbene complex may be introduced as a reagent or may be generated in situ.
  • a commercially available metal-carbene complex may be used as it is, or a non-commercially available metal-carbene complex synthesized from a commercially available reagent by a known method may be used.
  • metal-carbene complexes prepared from metal complexes which become precursors by known methods can be used in the present invention.
  • the amount of the metal-carbene complex to be used is not particularly limited, but it is usually 0.000001 (1 ppm) to 1 mol of the fluorine-containing compound represented by the general formula a as a reference among the monomers serving as a raw material
  • the amount is about 1 mole, preferably about 0.00001 (10 ppm) to 0.2 mole.
  • the metal-carbene complex to be used is generally charged as a solid into the reaction vessel, but may be charged or dissolved 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, part or all of the hydrogen atoms may be substituted with deuterium atoms.
  • the metal-carbene complex compound is preferably dissolved in the fluorine-containing compound represented by the general formula a.
  • 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 (THF), dioxane, diethyl ether, glyme, diglyme and the like 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 for example, hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, ⁇ , ⁇ , ⁇ -trifluoromethylbenzene, dichloropentafluoropropane and the like It can be used.
  • ionic liquid for example, various pyridinium salts, various imidazolium salts and the like can be used.
  • Hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, ⁇ , ⁇ , ⁇ -trifluoromethylbenzene and the like, and mixtures thereof are preferred.
  • the solvent that has been degassed and dehydrated there is no particular limitation on the degassing operation, but freeze degassing may be performed.
  • the dehydration operation is not particularly limited, but is usually in contact with a molecular sieve or the like.
  • the degassing and dehydrating operations are usually carried out before contacting with the metal-carbene complex.
  • an olefin or diene can be used as a chain transfer agent for the purpose of controlling molecular weight and its distribution.
  • the olefin for example, ⁇ -olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and the like, or fluorine-containing olefins thereof can be used.
  • diene examples include non-conjugated dienes such as 1,4-pentadiene, 1,5-hexadiene and 1,6-heptadiene, and fluorine-containing non-conjugated dienes thereof.
  • non-conjugated dienes such as 1,4-pentadiene, 1,5-hexadiene and 1,6-heptadiene
  • fluorine-containing non-conjugated dienes thereof examples include non-conjugated dienes such as 1,4-pentadiene, 1,5-hexadiene and 1,6-heptadiene, and fluorine-containing non-conjugated dienes thereof.
  • olefins, fluorine-containing olefins or dienes may be used alone or in combination of two or more.
  • the atmosphere in which the monomer and the metal-carbene complex are brought into contact with each other is not particularly limited, but in terms of prolonging the life of the catalyst, it is preferably under an inert gas atmosphere, and more preferably under a nitrogen or argon atmosphere. However, when a compound that becomes a gas under the reaction conditions is used as a raw material monomer, the reaction can be performed under these gas atmospheres.
  • the phase in which the monomer and the metal-carbene complex are brought into contact with each other is not particularly limited, but a liquid phase is usually used in terms of reaction rate. When the monomer used as a raw material is a gas under reaction conditions, it can be carried out in a gas-liquid two phase because it is difficult to carry out in the liquid phase.
  • a solvent when implementing in a liquid phase, a solvent can be used.
  • the same solvents as those used for dissolving or suspending the metal-carbene complex can be used.
  • the monomer used as a raw material contains the liquid thing under reaction conditions, it may be able to implement without a solvent (bulk polymerization).
  • the container for bringing the monomer into contact with the metal-carbene complex is not particularly limited as long as the reaction is not adversely affected.
  • a metal container or a glass container can be used.
  • a pressure-tight container capable of high airtightness is preferable.
  • the temperature at which the monomer and the metal-carbene complex are brought into contact with each other is not particularly limited, but the temperature can be usually in the range of -100 to 200 ° C., and 0 to 150 ° C. is preferable in terms of reaction rate.
  • the reaction does not start at low temperature, and rapid decomposition of the complex may occur at high temperature, so it is necessary to set the lower limit and the upper limit of the temperature appropriately. It is usually carried out at a temperature below the boiling point of the solvent used.
  • the time for contacting the monomer with the metal-carbene complex is not particularly limited, but it is usually carried out in the range of 1 minute to 48 hours.
  • the pressure at which the monomer and the metal-carbene complex are brought into contact with each other is not particularly limited, but may be under pressure, normal pressure or reduced pressure. Usually, it is about 0.001 to 10 MPa, preferably about 0.01 to 1 MPa.
  • the molecular weight of the obtained polymer can be made into a target one by appropriately adjusting reaction conditions such as the preparation ratio of monomers, the above-mentioned reaction temperature, reaction time, reaction pressure and the like.
  • an inorganic salt, an organic compound, a metal complex or the like may be coexistent as long as the reaction is not adversely affected.
  • the mixture of the monomer and the metal-carbene complex may be stirred to such an extent that the reaction is not adversely affected.
  • a mechanical stirrer, a magnetic stirrer or the like can be used as a method of stirring.
  • the target polymer may be isolated by a known method.
  • an isolation method for example, in the case of a solution, the reaction solution is drained into a poor solvent under stirring to precipitate a hydrogenated polymer to form a slurry, which is recovered by filtration, centrifugation, decantation, etc.
  • the steam stripping method which blows in steam to solution and precipitates a polymer, the method of removing a solvent directly from the reaction solution by heating etc., etc. are mentioned, and, in the case of a slurry, it is filtration method, centrifugation, decantation method etc Methods of recovery etc. may be mentioned.
  • column chromatography, recycle preparative HPLC, etc. may be mentioned, and these can be used alone or in combination as needed.
  • the target substance obtained by this reaction can be identified by the same known method as a general polymer compound.
  • a general polymer compound For example, 1 H-, 19 F-, 13 C-NMR, GPC, static light scattering, SIMS, GC-MS and the like can be mentioned, and these can be used alone or in combination as needed.
  • SIMS SIMS
  • GC-MS GC-MS and the like
  • two or more monomers as a copolymer, it is possible to impart various properties as compared to homopolymers.
  • the ratio of the two or more unit structures constituting the copolymer depends on the preparation ratio of the monomers, but is generally represented by the general formula a as a standard Assuming that the number of repeating units derived from fluorine-containing is 1, the number of repeating units derived from other cyclic olefins is about 0.01 to 100, and preferably about 0.1 to 10.
  • the hydrogenated product of the fluorine-containing polymer (ring-opening metathesis polymer) represented by the general formula I in the present invention is obtained by hydrogenating the main chain double bond of the fluorine-containing polymer containing the structure represented by the general formula I And includes the structure represented by the general formula I ′.
  • the conversion (hydrogenation) of hydrogenation of the constituent unit of the fluorine-containing polymer represented by the general formula I to the constituent unit of the fluorine-containing polymer represented by the general formula I ′ is preferably 50% or more It is 100% or less, more preferably 80% or more and 100% or less.
  • the symbols in the formulas are as described above.
  • the fluorine-containing polymer represented by the general formula I contains a large number of main chain double bonds which absorb light at a particular wavelength, particularly at a wavelength in the ultraviolet range, the light transmission to the wavelength in the ultraviolet range is obtained. There is a risk that the optical characteristics may be impaired.
  • the light transmittance can be controlled to the required transmittance by adding (adding) a hydrogen atom to the main chain double bond of the ring-opening metathesis polymer to form a saturated bond. Further, when the amount of double bonds contained in the fluorine-containing polymer represented by the general formula I is large, the refractive index of the polymer is increased, and when the amount of saturated bonds is increased by hydrogenation, the refractive index is decreased. it can.
  • the refractive index can be arbitrarily adjusted by increasing or decreasing the rate of addition of hydrogen atoms (hereinafter sometimes referred to as the hydrogen addition rate).
  • these main chain double bonds limit the free movement of the polymer by having a geometrically planar structure. That is, if there are many double bonds, the glass transition temperature becomes high, and the heat resistance property is improved.
  • the double bond may deteriorate the stability against oxidation, and in order to prevent oxidation, the problem is solved by appropriately adding an antioxidant etc. which can be generally used for an olefin polymer. be able to.
  • the double bond may be oxidized to have an epoxide structure.
  • the amount of these double bonds also affects the mechanical strength and impact resistance of the polymer, and if the amount is large, the rigidity is enhanced, and if double bonds are converted to saturation bonds, flexibility is achieved. And impact resistance can be increased.
  • the hydrogenation ratio of the main chain double bond can be arbitrarily determined by the balance of polymer physical properties such as light transmittance, heat resistance, weather resistance, mechanical strength, and impact resistance.
  • the molecular weight of the ring-opened metathesis polymer hydrogenated substance is preferably 1,000 to 5,000,000 from the viewpoint of mechanical properties and physical properties.
  • the said molecular weight is a value represented by a weight average molecular weight, and is measured on conditions of a polymer solution using GPC.
  • the number of repeating units of the repeating unit represented by u in the formula is 2 to 10,000, in terms of mechanical properties and physical properties. And more preferably 5 to 6,500.
  • the total number of repeating numbers of a plurality of repeating units is preferably 2 to 10,000, more preferably 5 to 6,500. .
  • the obtained polymer has properties such as high heat resistance, low water absorption, high light transmittance (transparency), high chemical durability, high weather resistance, high liquid repellency, etc., and the balance of these properties is also excellent. Therefore, it can be used in a wide variety of fields such as electric and electronic materials, semiconductor materials, optical materials, medical instruments and cell culture materials, liquid repellent materials, elastomer materials, airgel materials and the like.
  • the fluorine-containing compound represented by the general formula a can be obtained by addition polymerization to obtain a fluorine-containing polymer including the structure represented by the general formula II.
  • the symbols in the formula are as described above.
  • polymerization as in the ring opening metathesis polymerization, it may be a homopolymer using only one kind of the fluorine-containing compound represented by the general formula a, or may be copolymerized using two or more kinds of monomers as a raw material Good.
  • the type of repeating unit to be a structural moiety not represented by General Formula II when carrying out the copolymerization is not particularly limited as long as it does not excessively inhibit the effect of the present invention.
  • Such a repeating unit is usually preferably a repeating unit derived from a copolymerizable vinyl compound, and preferable examples of the vinyl compound include ⁇ such as ethylene, propylene, 1-butene, 1-hexene and the like.
  • cyclic olefins styrenes, cyclic olefins etc.
  • styrenes cyclic olefins etc.
  • it is preferable to adopt a cyclic olefin and in particular, it is preferable to adopt a cyclic olefin which can form the same cyclic skeleton as that of the general formula II after polymerization.
  • alternating copolymer, block copolymer and random copolymer can be synthesized, and a desired copolymer can be obtained depending on the preparation ratio of monomers as raw materials and polymerization conditions. it can.
  • the molecular weight of the polymer is preferably 1,000 to 5,000,000 in view of mechanical properties and physical properties.
  • the molecular weight is a weight average molecular weight, and is measured under the conditions of a polymer solution using GPC.
  • the repeating number of the repeating unit represented by v in the formula is preferably 2 to 10,000 from the viewpoint of mechanical properties and physical properties, more preferably 5 to It is 6,500.
  • the total number of repeating units of a plurality of repeating units is preferably 2 to 10,000, more preferably 5 to 6,500.
  • the obtained polymer has properties such as high heat resistance, low water absorption, high light transmittance (transparency), high chemical durability, high weather resistance, high liquid repellency, etc., and the balance of these properties is also excellent. Therefore, it can be used in a wide variety of fields such as electric and electronic materials, semiconductor materials, optical materials, medical instruments and cell culture materials, liquid repellent materials, elastomer materials, airgel materials and the like.
  • a fluorine-containing polymer including a structure represented by the general formula II can be obtained.
  • the fluorine-containing polymer obtained is a fluorine-containing polymer (homopolymer) represented by the general formula II when the monomer is only the fluorine-containing compound represented by the general formula a, and plural kinds of monomers are used.
  • a fluorine-containing copolymer (copolymer) containing the structure represented by the general formula II is obtained.
  • one kind of fluorine-containing compound represented by the general formula a may be used, or a plurality of compounds having different structures may be used in combination as another monomer, which may be appropriately determined according to the desired polymer structure.
  • the polymerization method may, for example, be radical polymerization, cationic polymerization, anionic polymerization or coordination polymerization, among which radical polymerization or coordination polymerization is preferred.
  • the fluorine-containing polymer containing the structure represented by the general formula II can be obtained by a known method using the fluorine-containing compound represented by the general formula a. Among them, the method of addition polymerizing the above-mentioned fluorine-containing compound. As the conditions for addition polymerization, conditions well known to those skilled in the art can be appropriately optimized and adopted.
  • the ratio of the two or more unit structures constituting the copolymer depends on the preparation ratio of the monomers, but is generally represented by the general formula a as a standard Assuming that the number of repeating units derived from fluorine is one, the number of repeating units derived from other olefins is about 0.01 to 100, and preferably about 0.1 to 10.
  • the mass average molecular weight (Mw) and number average molecular weight (Mn) of the fluorine-containing polymer are determined using a standard polymethyl methacrylate sample of known molecular weight from the chromatogram obtained by the GPC apparatus (HLC-8220 manufactured by Tosoh Corporation). It calculated
  • Example 1-1 Diels-Alder reaction of fluorine-containing diene (1) and cyclopentadiene Dicyclopentadiene (5.20 g, 39.4 mmol) in a stainless steel (SUS 316) high-pressure miniature bomb, Table 1 below The fluorinated diene (10.0 g, 39.4 mmol) and hydroquinone (0.13 g, 1.18 mmol) were charged. Next, after 0.20 MPaG of nitrogen was pressured into the bomb, the operation of returning to normal pressure was repeated three times, and nitrogen substitution was performed, and heating was performed at 200 ° C. for 3 hours.
  • reaction contents were dissolved in dichloromethane and transferred to a 50 mL round bottom flask and then the solvent was evaporated under reduced pressure. After adding 20 mL of methanol to the concentrate and dissolving under heating and refluxing, it was ice-cooled. The precipitated crystals were filtered under reduced pressure and dried at 60 ° C. under reduced pressure to obtain 6.70 g of a compound represented by 2N-PF4 in a yield of 44%.
  • Example 1-2 Diels-Alder reaction of fluorine-containing diene (2) and cyclopentadiene Dicyclopentadiene (2.99 g, 22.6 mmol) in a stainless steel (SUS 316) high-pressure miniature bomb, Table 2 below The fluorinated diene (8.0 g, 22.6 mmol) and hydroquinone (0.075 g, 0.68 mmol) were charged. Next, after 0.20 MPaG of nitrogen was pressured into the bomb, the operation of returning to normal pressure was repeated three times, and nitrogen substitution was performed, and heating was performed at 180 ° C. for 5 hours.
  • reaction contents were dissolved in dichloromethane and transferred to a 50 mL round bottom flask and then the solvent was evaporated under reduced pressure. After adding 10 mL of methanol to the concentrate and dissolving under heating and refluxing, it was ice-cooled. The precipitated crystals were filtered under reduced pressure and dried at 60 ° C. under reduced pressure to obtain 7.51 g of a compound represented by 2N-PF6 in a yield of 68%.
  • Example 1-3 Diels-Alder reaction of fluorine-containing diene (3) and cyclopentadiene Dicyclopentadiene (7.13 g, 54.0 mmol) in a stainless steel (SUS 316) high-pressure miniature cylinder, Table 3 below
  • the fluorinated diene (15.0 g, 54.0 mmol) and hydroquinone (0.18 g, 1.62 mmol) were charged. Then, after 0.20 MPaG of nitrogen was pressured into the bomb, the operation of returning to normal pressure was repeated three times, and nitrogen substitution was performed, and heating was performed at 200 ° C. for 7 hours.
  • the reaction contents were transferred to a 30 mL round bottom flask, and then the monomer was purified by distillation under reduced pressure.
  • the compound represented by 2N-BVE was obtained in a yield of 6.85 g, 31%.
  • Example 1-6 Synthesis of Fluorine-Containing Norbornene (H) (1) Compound D is synthesized according to the procedure of Example 1-5.
  • Example 2-1 ROMP Homopolymerization of 2N-PF4 Under nitrogen atmosphere, Grubbs second generation catalyst (22 mg, 0.026 mmol) was weighed into a 10 mL screw tube and dissolved in dichloromethane (5 mL) to prepare a catalyst solution did. Next, the compound (2N-PF4) (2.0 g, 5.18 mmol) obtained in Example 1-1 and dichloromethane (19 mL) were charged into a 100 mL screw tube and dissolved, and then the catalyst prepared above was prepared. The solution was added to 1 mL (corresponding to 0.1 mol% of the catalyst) and allowed to react at room temperature for 3 hours.
  • Example 2-2 ROMP Homopolymerization of 2N-PF4 in the Presence of a Chain Transfer Agent Under a nitrogen atmosphere, a Grubbs second generation catalyst (8.07 mg, 0.0095 mmol) was weighed into a 6 mL screw tube and dichloromethane ( The catalyst solution was prepared by dissolving in 0.59 mL). Next, the compound (2N-PF4) (1.0 g, 2.59 mmol) obtained in Example 1-1, dichloromethane (11 mL) and 1-hexene (323 ⁇ L, 2.58 mmol) were added to a 50 mL screw tube bottle.
  • Example 2-3 Addition Polymerization of 2N-PF4 Under nitrogen atmosphere, tricyclohexylphosphine (6.85 mg, 0.024 mmol) was weighed into a 6 mL screw tube bottle, dissolved in toluene (0.5 mL), and then tricyclohexyl phosphine was dissolved. The solution was prepared. Next, weigh palladium (II) acetylacetonate (Pd (acac) 2 , 7.72 mg, 0.025 mmol) into a 6 mL screw-tube bottle, add all the tricyclohexylphosphine solution prepared above, and then add toluene. The catalyst solution was prepared by washing with (0.5 mL).
  • Example 2-4 ROMP Homopolymerization of 2N-PF6 in the Presence of Chain Transfer Agent
  • Grubbs 1st generation catalyst (1.86 g, 2.3 mmol) was weighed in a 300 mL round bottom flask and each dichloromethane was used. The catalyst solution was prepared by dissolving in (186 mL).
  • 2N-PF6 (27.5 g, 56.6 mmol)
  • dichloromethane (832 mL) and hexafluorobenzene (113 mL) were charged into a 2 L round bottom flask and cooled with ice water.
  • Example 2-5 Addition polymerization of 2N-PF6 Under nitrogen atmosphere, tricyclohexylphosphine (6.98 mg, 0.024 mmol) is weighed into a 6 mL screw tube bottle and dissolved in toluene (0.4 mL) to obtain tricyclohexyl phosphine The solution was prepared. Next, weigh Pd (acac) 2 (7.70 mg, 0.025 mmol) in a 6 mL screw-tube, add all the tricyclohexylphosphine solution prepared above, and wash with toluene (0.1 mL) A catalyst solution was prepared.
  • the whole solidified reaction mixture was transferred to a 50 mL screw tube bottle, acetone (20 mL) was added, and the whole was vigorously stirred overnight.
  • the crushed and washed polymer was recovered by vacuum filtration and dried at 60 ° C. under reduced pressure.
  • the yield of the target polymer (PA-2N-PF6) was 56%.
  • the conversion of the raw material monomer (2N-PF4) was 70% from the 1 H-NMR measurement of the filtrate obtained by filtration of the polymer.
  • Example 2-6 ROMP Homopolymerization of 2N-BVE Under nitrogen atmosphere, Grubbs second generation catalyst (22 mg, 0.026 mmol) was weighed into a 10 mL screw tube and dissolved in dichloromethane (5 mL) to prepare a catalyst solution did. Next, the compound (2N-BVE) (2.0 g, 4.87 mmol) obtained in Example 1-3 and dichloromethane (19 mL) were charged into a 100 mL screw tube and dissolved, and then the catalyst prepared above was prepared. The solution was added to 1.1 mL (corresponding to 0.1 mol% of the catalyst) and allowed to react at room temperature for 3 hours.
  • Example 2-7 ROMP Homopolymerization of 2N-BVE Diethyl aluminum chloride (0.87 M hexane solution, 0.5 mL) and toluene (4.5 mL) were weighed into a 10 mL screw tube under a nitrogen atmosphere, and then 0. A 087 M solution of diethylaluminum chloride was prepared. Next, molybdenum pentachloride (3.5 mg, 0.013 mmol) was weighed into a 6 mL screw tube bottle and dissolved in toluene (0.8 mL) to prepare a molybdenum pentachloride solution.
  • Example 2-8 ROMP homopolymerization of 2N-BVE in the presence of a chain transfer agent Under nitrogen atmosphere, Grubbs second generation catalyst (27 mg, 0.032 mmol) was weighed into a 10 mL screw tube and dichloromethane (2 mL) The catalyst solution was prepared by Next, the compound (2N-BVE) (5.0 g, 12.19 mmol) obtained in Example 1-3, dichloromethane (50 mL) and 1-hexene (760 ⁇ L, 6.10 mmol) were added to a 100 mL screw tube bottle.
  • Example 2-9 ROMP Copolymerization of 2N-BVE Under nitrogen atmosphere, Grubbs second generation catalyst (11 mg, 0.013 mmol) was weighed into a 10 mL screw tube and dissolved in dichloromethane (5 mL) to prepare a catalyst solution. did. Next, the compound (2N-BVE) (0.1 g, 0.24 mmol) obtained in Example 1-3, NPF4 (0.69 g, 2.20 mmol), dichloromethane (10 mL) and 1-hexene (1. h).
  • each of v and z is a positive integer indicating the number of repetition of the repeating unit (hereinafter, the same applies).
  • AK-225 (30 mL, dichloropentafluoropropane: manufactured by AGC) was added and stirred, and then the organic phase was separated. AK-225 (30 mL) was added to the aqueous layer of the pre-liquid separation to re-extract, and the obtained organic phase was combined with the previously obtained organic phase. Anhydrous sodium sulfate was added to the organic phase and stirred, and then insoluble matter was removed by filtration under reduced pressure. The obtained organic phase was concentrated by an evaporator and then purified by silica gel column chromatography (mobile phase: n-hexane) to obtain a compound represented by NDM-2PHVE. The yield was 16.0 g, and the yield was 81%.
  • ethyl vinyl ether 80 ⁇ L was added to the reaction solution to terminate the polymerization, and then 10 mL of dichloromethane was added to dilute the polymerization suspension.
  • the polymer suspension was continuously introduced into methanol (100 mL), and the precipitated polymer was recovered by vacuum filtration and dried at 60 ° C. under reduced pressure. The yield was 100%.
  • ROMP Homopolymerization of Fluorine-Containing Norbornene C Under a nitrogen atmosphere, a Grubbs second generation catalyst (5.7 mg, 0.0068 mmol) was weighed into a 10 mL screw tube and dissolved in dichloromethane (5 mL) to be a catalyst Prepare a solution. Next, Compound C (2.0 g, 1.35 mmol) obtained in Example 1-4 and dichloromethane (19 mL) were charged into a 100 mL screw tube and dissolved, and then 1 mL of the catalyst solution prepared above ( Add catalyst (equivalent to 0.1 mol%) and react at room temperature for 3 hours.
  • ethyl vinyl ether (422 ⁇ L) is added to the reaction solution to terminate the polymerization, and then 40 mL of chloroform is added to dilute the polymerization suspension.
  • the polymer suspension is continuously introduced into methanol (250 mL), and the precipitated polymer is recovered by filtration under reduced pressure and dried at 50 ° C. under reduced pressure to obtain the target polymer.
  • ROMP Homopolymerization of Fluorine-Containing Norbornene E Under a nitrogen atmosphere, a Grubbs second generation catalyst (5.7 mg, 0.0068 mmol) was weighed into a 10 mL screw tube and dissolved in dichloromethane (5 mL) to be a catalyst Prepare a solution. Next, Compound E (2.0 g, 1.35 mmol) obtained in Example 1-5 and dichloromethane (19 mL) were charged into a 100 mL screw tube and dissolved, and then 1 mL of the catalyst solution prepared above ( Add catalyst (equivalent to 0.1 mol%) and react at room temperature for 3 hours.
  • ethyl vinyl ether (422 ⁇ L) is added to the reaction solution to terminate the polymerization, and then 40 mL of chloroform is added to dilute the polymerization suspension.
  • the polymer suspension is continuously introduced into methanol (250 mL), and the precipitated polymer is recovered by filtration under reduced pressure and dried at 50 ° C. under reduced pressure to obtain the target polymer.
  • ethyl vinyl ether (422 ⁇ L) is added to the reaction solution to terminate the polymerization, and then 40 mL of chloroform is added to dilute the polymerization suspension.
  • the polymer suspension is continuously introduced into methanol (250 mL), and the precipitated polymer is recovered by filtration under reduced pressure and dried at 50 ° C. under reduced pressure to obtain the target polymer.
  • a fluorine-containing compound having two or more novel norbornene skeletons is obtained, and a fluorine-containing polymer having a desired structure or molecular weight is simply and efficiently obtained by ring-opening metathesis polymerization or addition polymerization of the compound.
  • a fluorine-containing polymer having a desired structure or molecular weight is simply and efficiently obtained by ring-opening metathesis polymerization or addition polymerization of the compound.

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Abstract

L'invention concerne un composé contenant du fluor qui est représenté par la formule générale (a). Dans la formule, Y représentent chacun indépendamment ＣＲ１４Ｒ１５, Ｏ, Ｓ, ＮＲ１６ ou ＰＲ１７, Q représente un groupe fonctionnel de valence m contenant un atome de fluor, Ｒ１１ à Ｒ１３ représentent chacun indépendamment un atome d'hydrogène, un atome d'halogène ou un groupe organique monovalent, Ｒ１４ à Ｒ１７ représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle de 1 à 20 atomes de carbone, m représente un entier naturel supérieur ou égal à 2, et n représente 0 ou 1.
PCT/JP2018/034925 2017-09-21 2018-09-20 Composé contenant du fluor, et polymère contenant du fluor ainsi que procédé de fabrication de celui-ci WO2019059318A1 (fr)

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