WO2022260138A1 - Procédé de production d'une dispersion aqueuse d'élastomère contenant du fluor, élastomère contenant du fluor et composition - Google Patents

Procédé de production d'une dispersion aqueuse d'élastomère contenant du fluor, élastomère contenant du fluor et composition Download PDF

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WO2022260138A1
WO2022260138A1 PCT/JP2022/023336 JP2022023336W WO2022260138A1 WO 2022260138 A1 WO2022260138 A1 WO 2022260138A1 JP 2022023336 W JP2022023336 W JP 2022023336W WO 2022260138 A1 WO2022260138 A1 WO 2022260138A1
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fluorine
group
mass
polymerization
carbon atoms
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PCT/JP2022/023336
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Japanese (ja)
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利奈 玉井
達也 森川
颯太 湯浅
光平 竹村
正樹 入江
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ダイキン工業株式会社
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Priority to JP2023527927A priority Critical patent/JPWO2022260138A1/ja
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    • 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
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • 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
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C08F14/22—Vinylidene fluoride
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents

Definitions

  • the present disclosure relates to a method for producing a fluorine-containing elastomer aqueous dispersion, a fluorine-containing elastomer, and a composition.
  • n OOM where n is an integer of 1 to 7 and M is NH 4 or an alkali metal
  • a method for producing a fluorine-containing elastomer is described, which is characterized in that it is carried out in an aqueous medium maintained at a liquid pH of 5 to 10 in the absence of a surfactant.
  • the method for producing a fluorine-containing elastomer according to claim 1 is described, wherein the copolymerization reaction is carried out in the presence of an acid alkali metal salt.
  • Patent Document 3 discloses a method for producing a partially fluorinated polymer dispersion, wherein one or more fluorinated monomers are polymerized by aqueous emulsion polymerization in the presence of a polymerizable fluorinated emulsifier to obtain partially fluorinated forming a fluorinated polymer, wherein the polymerizable fluorinated emulsifier has the formula: X 2 C ⁇ CX(CF 2 ) m (CH 2 ) n [O—(CX 2 ) p ] q —[O—(CX 2 ) r ] s —[O—(CX 2 —CX 2 )] t — [(O) w- (CX2) u ] v- [ CH2 ] z - Y (wherein X is independently selected from H, F, or CF3 ; Y is COOM or SO3M ; M is H, an alkali metal, or NH4
  • An object of the present disclosure is to provide a method for producing an aqueous fluoroelastomer dispersion that can generate a sufficient number of fluoroelastomer particles and greatly suppress adhesion of the fluoroelastomer to a polymerization tank. aim.
  • a fluorinated monomer in the presence of a fluorinated allyl ether (1) represented by the general formula (1), a fluorinated vinyl ether (2) represented by the general formula (2) and an aqueous medium, a fluorinated monomer
  • a method for producing an aqueous dispersion of a fluoroelastomer containing a methylene group in its main chain is provided by polymerizing a fluoroelastomer.
  • CX 11 2 CY 11 (-CZ 11 2 -O-Rf 11 -Y 12 ) (1) (Wherein, X 11 is the same or different and is -H or -F, Y 11 is -H, -F, an alkyl group or a fluorine-containing alkyl group, Z 11 is the same or different and - H, —F, alkyl group or fluorine-containing alkyl group Rf 11 is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond Y 12 is a hydrophilic group.)
  • CX 21 2 CY 21 (-O-Rf 21 -Y 22 ) (2) (Wherein, X 21 is the same or different and is -H or -F, Y 21 is -H, -F, alkyl group or fluorine-containing alkyl group, Rf 21 is C 1-40 A fluorine alkylene
  • Y 12 is —NH 2 , —P(O)(OM) 2 , —OP(O)(OM) 2 , —SO 3 M, —OSO 3 M, —COOM, —B (OM) 2 or —OB(OM) 2 (wherein M is H, a metal atom, NR 74 , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, R 7 is H or an organic group, which may be the same or different, any two of which may be combined to form a ring.) is preferably In the production method of the present disclosure, the production method according to claim 1 or 2, wherein all X 11 are -H, is preferred.
  • the amount of the fluorine-containing allyl ether (1) is preferably 3-5000 mass ppm with respect to the aqueous medium.
  • Y 22 is —NH 2 , —P(O)(OM) 2 , —OP(O)(OM) 2 , —SO 3 M, —OSO 3 M, —COOM, —B (OM) 2 or —OB(OM) 2 ( wherein M is H, a metal atom, NR 74 , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, R 7 is H or an organic group, which may be the same or different, any two of which may be combined to form a ring.) is preferably
  • the amount of the fluorine-containing vinyl ether (2) is preferably 3-5000 mass ppm with respect to the aqueous medium.
  • the fluorine-containing monomer in the presence of a chain transfer agent.
  • the fluorine-containing elastomer preferably contains vinylidene fluoride units.
  • the fluorine-containing elastomer preferably contains vinylidene fluoride units in an amount of 50 mol % or more with respect to all monomer units.
  • the Mooney viscosity (ML1+10 (100° C.)) of the fluorine-containing elastomer is preferably 10-130.
  • the main chain contains a methylene group
  • the monomer unit (1) based on the fluorine-containing allyl ether (1) represented by the general formula (1) and the general formula (2) A fluorine-containing elastomer containing monomer units (2) based on the fluorine-containing vinyl ether (2) represented is provided.
  • CX 11 2 CY 11 (-CZ 11 2 -O-Rf 11 -Y 12 ) (1) (Wherein, X 11 is the same or different and is -H or -F, Y 11 is -H, -F, an alkyl group or a fluorine-containing alkyl group, Z 11 is the same or different and - H, —F, alkyl group or fluorine-containing alkyl group Rf 11 is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond Y 12 is a hydrophilic group.)
  • CX 21 2 CY 21 (-O-Rf 21 -Y 22 ) (2) (Wherein, X 21 is the same or different and is -H or -F, Y 21 is -H, -F, alkyl group or fluorine-containing alkyl group, Rf 21 is C 1-40 A fluorine alkylene
  • the fluorine-containing elastomer of the present disclosure preferably contains vinylidene fluoride units.
  • a fluoroelastomer aqueous dispersion containing the above fluoroelastomer and an aqueous medium.
  • a method for producing a fluoroelastomer aqueous dispersion that can generate a sufficient number of fluoroelastomer particles and greatly suppress adhesion of the fluoroelastomer to a polymerization tank. be able to.
  • the fluorine-containing elastomer is an amorphous fluoropolymer.
  • “Amorphous” means a melting peak ( ⁇ H ) is 4.5 J/g or less.
  • Fluorine-containing elastomers exhibit elastomeric properties by cross-linking. By elastomeric properties is meant the property of being able to stretch a polymer and retain its original length when the force required to stretch the polymer is no longer applied.
  • a perfluoromonomer is a monomer that does not contain a carbon atom-hydrogen atom bond in its molecule.
  • the perfluoromonomer may be a monomer in which some of the fluorine atoms bonded to the carbon atoms are substituted with chlorine atoms in addition to carbon atoms and fluorine atoms, and in addition to carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, boron atoms or silicon atoms.
  • the above perfluoromonomer is preferably a monomer in which all hydrogen atoms are substituted with fluorine atoms.
  • the above perfluoromonomers do not include monomers that provide crosslinkable groups.
  • a monomer that provides a cross-linking site is a monomer (cure site monomer) that provides the fluoropolymer with a cross-linking site for forming cross-links with a curing agent.
  • a monomer that provides a cross-linking site includes a monomer that provides a cross-linkable group.
  • each monomer unit constituting the fluorine-containing elastomer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.
  • organic group means a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound.
  • organic groups are an alkyl group optionally having one or more substituents, an alkenyl group optionally having one or more substituents, an alkynyl group optionally having one or more substituents, a cycloalkyl group optionally having one or more substituents, a cycloalkenyl group optionally having one or more substituents, a cycloalkadienyl group optionally having one or more substituents, an aryl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, a non-aromatic heterocyclic group optionally having one or more substituents, a heteroaryl group optionally having one or more substituents, cyano group, formyl group, RaO-, RaCO-, RaSO2- , RaCOO-, Ra
  • substituteduent means a substitutable group.
  • substitutable group examples include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, an aliphatic oxycarbonyl group , aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, aromatic sulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, aromatic sulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aromatic sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic sulfonamide group, aromatic sulf
  • the above aliphatic group may be saturated or unsaturated, and may be a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group. , an acylamino group, a carbamoylamino group, and the like.
  • the aliphatic group include alkyl groups having a total carbon number of 1 to 8, preferably 1 to 4, such as methyl, ethyl, vinyl, cyclohexyl and carbamoylmethyl groups.
  • the aromatic group includes, for example, a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, and the like.
  • You may have The aromatic group includes an aryl group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms in total, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group and a 4-methanesulfonylphenyl group. etc.
  • the heterocyclic group has a halogen atom, a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, and the like.
  • the heterocyclic group include 5- to 6-membered heterocyclic rings having a total carbon number of 2 to 12, preferably 2 to 10, such as 2-tetrahydrofuryl group and 2-pyrimidyl group.
  • the acyl group includes an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a hydroxy group, a halogen atom, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, and an amino group. , an aliphatic amino group, an acylamino group, a carbamoylamino group, and the like.
  • the acyl group includes acyl groups having 2 to 8, preferably 2 to 4 carbon atoms in total, such as acetyl, propanoyl, benzoyl and 3-pyridinecarbonyl groups.
  • the acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group, and the like, and has, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, and the like.
  • the acylamino group include acylamino groups having a total number of carbon atoms of 2 to 12, preferably 2 to 8, and alkylcarbonylamino groups having a total number of carbon atoms of 2 to 8, such as acetylamino, benzoylamino and 2-pyridinecarbonylamino. groups, propanoylamino groups, and the like.
  • the aliphatic oxycarbonyl group may be saturated or unsaturated, and may be a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic It may have an amino group, an acylamino group, a carbamoylamino group, or the like.
  • Examples of the aliphatic oxycarbonyl group include alkoxycarbonyl groups having 2 to 8, preferably 2 to 4 carbon atoms in total, such as methoxycarbonyl, ethoxycarbonyl and (t)-butoxycarbonyl groups.
  • the carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, and the like.
  • Examples of the carbamoyl group include an unsubstituted carbamoyl group, an alkylcarbamoyl group having a total of 2 to 9 carbon atoms, preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having a total of 2 to 5 carbon atoms, such as an N-methylcarbamoyl group, N,N-dimethylcarbamoyl group, N-phenylcarbamoyl group and the like.
  • the aliphatic sulfonyl group may be saturated or unsaturated, and may be a hydroxy group, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group. , an aliphatic amino group, an acylamino group, a carbamoylamino group, and the like.
  • Examples of the aliphatic sulfonyl groups include alkylsulfonyl groups having 1 to 6 total carbon atoms, preferably 1 to 4 total carbon atoms, such as methanesulfonyl groups.
  • the aromatic sulfonyl group includes a hydroxy group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, and the like. You may have Examples of the aromatic sulfonyl group include arylsulfonyl groups having 6 to 10 carbon atoms in total, such as benzenesulfonyl groups.
  • the above amino group may have an aliphatic group, an aromatic group, a heterocyclic group, or the like.
  • the acylamino group may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, and the like.
  • the acylamino group includes acylamino groups having 2 to 12 total carbon atoms, preferably 2 to 8 carbon atoms, more preferably alkylcarbonylamino groups having 2 to 8 total carbon atoms, such as acetylamino and benzoylamino. group, 2-pyridinecarbonylamino group, propanoylamino group and the like.
  • the aliphatic sulfonamide group, aromatic sulfonamide group, and heterocyclic sulfonamide group may be, for example, a methanesulfonamide group, a benzenesulfonamide group, a 2-pyridinesulfonamide group, and the like.
  • the above sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, and the like.
  • the sulfamoyl group include a sulfamoyl group, an alkylsulfamoyl group having a total number of carbon atoms of 1 to 9, a dialkylsulfamoyl group having a total number of carbon atoms of 2 to 10, and an arylsulfamoyl group having a total number of carbon atoms of 7 to 13.
  • a heterocyclic sulfamoyl group having a total of 2 to 12 carbon atoms more preferably a sulfamoyl group, an alkylsulfamoyl group having a total of 1 to 7 carbon atoms, a dialkylsulfamoyl group having a total of 3 to 6 carbon atoms, a total carbon arylsulfamoyl group having 6 to 11 atoms, heterocyclic sulfamoyl group having 2 to 10 total carbon atoms, such as sulfamoyl group, methylsulfamoyl group, N,N-dimethylsulfamoyl group, phenylsulfamoyl group; group, 4-pyridinesulfamoyl group, and the like.
  • the aliphatic oxy group may be saturated or unsaturated, and may have a methoxy group, ethoxy group, i-propyloxy group, cyclohexyloxy group, methoxyethoxy group, and the like.
  • Examples of the aliphatic oxy group include alkoxy groups having a total carbon number of 1 to 8, preferably 1 to 6, such as methoxy, ethoxy, i-propyloxy, cyclohexyloxy and methoxyethoxy.
  • the above aromatic amino group and heterocyclic amino group are an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic group condensed with the aryl group, an aliphatic oxycarbonyl group, preferably the total number of carbon atoms 1 to 4 aliphatic groups, 1 to 4 total carbon atom aliphatic oxy groups, halogen atoms, 1 to 4 total carbon atom carbamoyl groups, nitro groups, 2 to 4 total carbon atom aliphatic oxycarbonyls You may have a group.
  • the aliphatic thio group may be saturated or unsaturated, and an alkylthio group having 1 to 8 total carbon atoms, more preferably 1 to 6 total carbon atoms, such as a methylthio group and an ethylthio group. , carbamoylmethylthio group, t-butylthio group and the like.
  • the carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group, and the like.
  • Examples of the carbamoylamino group include a carbamoylamino group, an alkylcarbamoylamino group having 2 to 9 total carbon atoms, a dialkylcarbamoylamino group having 3 to 10 total carbon atoms, an arylcarbamoylamino group having 7 to 13 total carbon atoms, heterocyclic carbamoylamino group having 3 to 12 total carbon atoms, preferably carbamoylamino group, alkylcarbamoylamino group having 2 to 7 total carbon atoms, dialkylcarbamoylamino group having 3 to 6 total carbon atoms, 7-11 arylcarbamoylamino groups, heterocyclic carbamoylamino groups having 3-10 total carbon atoms, such as carbamoylamino, methylcar
  • ranges represented by endpoints include all numbers subsumed within that range (eg, 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9 .98, etc.).
  • reference to "at least 1" includes all numbers greater than or equal to 1 (eg, at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.) .
  • the fluorine-containing allyl ether (1) and the fluorine-containing vinyl ether (2) By using two types of compounds having different structures, the fluorine-containing allyl ether (1) and the fluorine-containing vinyl ether (2), it is possible to generate a sufficient number of fluorine-containing elastomer particles for the smooth progress of the polymerization reaction. At the same time, adhesion of the fluorine-containing elastomer to the polymerization tank can be greatly suppressed. Although the reason for this is not clear, the two types of compounds having different structures have different reactivities with fluorine-containing monomers. In the subsequent polymerization reaction, mainly the fluorine-containing vinyl ether (2) reacts with the fluorine-containing monomer to have a hydrophilic group. It is presumed that this is for the purpose of forming fluorine-containing elastomer particles with high stability.
  • Fluorine-containing allyl ether (1) is represented by general formula (1).
  • CX 11 2 CY 11 (-CZ 11 2 -O-Rf 11 -Y 12 ) (1) (Wherein, X 11 is the same or different and is -H or -F, Y 11 is -H, -F, an alkyl group or a fluorine-containing alkyl group, Z 11 is the same or different and - H, —F, alkyl group or fluorine-containing alkyl group Rf 11 is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond Y 12 is a hydrophilic group.)
  • X 11 is -H or -F. Both of X 11 may be -F, or at least one may be -H. For example, one may be -F and the other may be -H, or both may be -H. All of X 11 are preferably —H, since more fluorine-containing elastomer particles can be generated and adhesion of the fluorine-containing elastomer to the polymerization tank can be further suppressed.
  • Y 11 is —H, —F, an alkyl group or a fluorine-containing alkyl group.
  • the alkyl group is an alkyl group containing no fluorine atoms and may have 1 or more carbon atoms.
  • the number of carbon atoms in the alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
  • the fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and may have 1 or more carbon atoms.
  • the number of carbon atoms in the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
  • Y 11 is preferably -H, -F or -CF 3 , more preferably -F.
  • Z 11 are the same or different and are —H, —F, an alkyl group or a fluoroalkyl group.
  • the alkyl group is an alkyl group containing no fluorine atoms and may have 1 or more carbon atoms.
  • the number of carbon atoms in the alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
  • the fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and may have 1 or more carbon atoms.
  • the number of carbon atoms in the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
  • Z 11 is preferably -H, -F or -CF 3 , more preferably -F.
  • At least one of X 11 , Y 11 and Z 11 preferably contains a fluorine atom.
  • X 11 can be -H and Y 11 and Z 11 can be -F.
  • Rf 11 is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond.
  • a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group containing an ether bond between carbon atoms without a structure terminating with an oxygen atom.
  • the number of carbon atoms in the fluorine-containing alkylene group is preferably 2 or more.
  • the number of carbon atoms in the fluorine-containing alkylene group is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.
  • the fluorine-containing alkylene group includes -CF 2 -, -CH 2 CF 2 -, -CF 2 CF 2 -, -CF 2 CH 2 -, -CF 2 CF 2 CH 2 - , -CF (CF 3 )- , -CF(CF 3 )CF 2 -, -CF(CF 3 )CH 2 - and the like.
  • the fluorine-containing alkylene group is preferably a perfluoroalkylene group.
  • the number of carbon atoms in the fluorine-containing alkylene group having an ether bond is preferably 3 or more. Moreover, the carbon number of the fluorine-containing alkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, and even more preferably 12 or less.
  • Examples of the fluorine-containing alkylene group having an ether bond include the following formula: -(CFZ 12 CF 2 O) p1 -(CF 2 O) q1 - ( CZ 132 CF 2 CF 2 O) r1 -CZ 14 Z 15 -(CF 2 ) s1 - (CH 2 ) t1 - (Wherein, Z 12 is F or CF 3 ; Z 13 and Z 14 are each H or F; Z 15 is H, F or CF 3 ; p1+q1+r1 is an integer of 1 to 10; s1 is 0 or 1; It is also preferably a divalent group represented by an integer of up to 5).
  • fluorine-containing alkylene group having an ether bond examples include -CF(CF 3 )CF 2 -O-CF(CF 3 )-, -(CF(CF 3 )CF 2 -O) n -CF(CF 3 )-(wherein n is an integer of 1 to 10), -CF(CF 3 )CF 2 -O-CF(CF 3 )CH 2 -, -(CF(CF 3 )CF 2 -O) n -CF (CF 3 )CH 2 — (wherein n is an integer of 1 to 10), —CH 2 CF 2 CF 2 O—CH 2 CF 2 CH 2 —, —CF 2 CF 2 CF 2 O—CF 2 CF 2 -, -CF 2 CF 2 CF 2 O--CF 2 CF 2 CH 2 -, -CF 2 CF 2 O--CF 2 CF 2 CH 2 -, -CF 2 CF 2 O--CF 2 -, -CF 2 CF 2 O--
  • Y12 in general formula ( 1 ) is a hydrophilic group.
  • hydrophilic groups include -NH 2 , -P(O)(OM) 2 , -OP(O)(OM) 2 , -SO 3 M, -OSO 3 M, -COOM, -B(OM) 2 , —OB(OM) 2 (in each formula, M is H, a metal atom, NR 74 , imidazolium optionally having substituent ( s), pyridinium optionally having substituent(s) or substituent Phosphonium which may be present, R 7 is H or an organic group, which may be the same or different, any two of which may be bonded to each other to form a ring) is preferred.
  • the hydrophilic group is preferably an anionic group such as -P(O)(OM) 2 , -OP(O)(OM) 2 , -SO 3 M, -OSO 3 M, -COOM, -B(OM). 2 , -OB(OM) 2 are more preferred.
  • An alkyl group is preferred as the organic group for R7 .
  • R 7 is preferably H or a C 1-10 organic group, more preferably H or a C 1-4 organic group, still more preferably H or a C 1-4 alkyl group, most preferably H.
  • the metal atom includes a monovalent or divalent metal atom, preferably an alkali metal (group 1) or an alkaline earth metal (group 2), more preferably Na, K or Li.
  • —SO 3 can generate more fluorine-containing elastomer particles and can further suppress adhesion of the fluorine-containing elastomer to the polymerization tank.
  • M or —OSO 3 M M is H, a metal atom, NR 74 , imidazolium optionally having substituent ( s), pyridinium optionally having substituent(s) or good phosphonium, R 7 is H or an organic group, which may be the same or different, any two of which may be linked together to form a ring) is preferred.
  • R 7 is preferably H or a C 1-10 organic group, more preferably H or a C 1-4 organic group, and even more preferably H or a C 1-4 alkyl group.
  • metal atoms include alkali metals (group 1) and alkaline earth metals (group 2), with Na, K or Li being preferred.
  • M is preferably —H, a metal atom or —NR 74 , more preferably —H, an alkali metal (group 1 ), an alkaline earth metal (group 2 ) or —NR 74 , and —H, —Na, -K, -Li or -NH 4 is more preferred, -Na, -K or -NH 4 is even more preferred, -Na or -NH 4 is particularly preferred, and -NH 4 is most preferred.
  • Y 12 is preferably -COOM or -SO 3 M, more preferably -COOM.
  • the fluorine-containing allyl ether (1) is preferably a compound (1a) represented by general formula (1a). CH 2 ⁇ CF(—CF 2 —O—Rf 11 —Y 12 ) (1a) (In the formula, Rf 11 and Y 12 are the same as above.)
  • Compound (1a) is preferably a compound having —COOM as Y 12 in formula (1a), especially CH 2 ⁇ CFCF 2 OCF(CF 3 )COOM and CH 2 ⁇ CFCF 2 OCF(CF 3 )CF 2 At least one selected from the group consisting of OCF(CF 3 )COOM (wherein M is as defined above) is preferred.
  • the fluorine-containing allyl ether (1) is preferably a compound (1b) represented by general formula (1b).
  • CX 12 2 CFCF 2 -O-(CF(CF 3 )CF 2 O) n5 -CF(CF 3 )-Y 12 (1b) (In the formula, each X 12 is the same and represents F or H. n5 represents 0 or an integer of 1 to 10, and Y 12 is the same as defined above.)
  • n5 is preferably an integer of 0 or 1 to 5, more preferably 0, 1 or 2, from the viewpoint of the stability of the resulting aqueous dispersion. It is even more preferable to have Y 12 is preferably -COOM in terms of obtaining appropriate water solubility and stability of the aqueous dispersion, and M is less likely to remain as an impurity and improves the heat resistance of the obtained molded product. , H or NH4 .
  • examples of the fluorine-containing allyl ether (1) include the compound (1c) represented by the general formula (1c).
  • CF 2 CFCF 2 -O-Rf 11 -Y 12 (1c) (Wherein, Rf 11 and Y 12 are the same as above)
  • the amount of the fluorine-containing allyl ether (1) is preferably 3 to 5000 ppm by mass, more preferably 5 ppm by mass or more, and still more preferably 10 mass ppm or more, particularly preferably 20 mass ppm or more, most preferably 30 mass ppm or more, more preferably 1000 mass ppm or less, still more preferably 500 mass ppm or less, especially It is preferably 200 mass ppm or less, most preferably 100 mass ppm or less.
  • the amount of the fluorine-containing allyl ether (1) is preferably 3 to 300 mass ppm, preferably 3 to 150 mass ppm, relative to the aqueous medium. Weight ppm is more preferred, 5 to 100 weight ppm is more preferred, and 8 to 80 weight ppm is most preferred.
  • the amount of the fluorine-containing allyl ether (1) is preferably 3 to 500 ppm by mass with respect to the aqueous medium. ⁇ 200 ppm by weight is more preferred, 5 to 120 ppm by weight is more preferred, and 20 to 110 ppm by weight is most preferred.
  • a redox polymerization initiator is used as the polymerization initiator and the polymerization is carried out at 10° C.
  • the amount of the fluorine-containing allyl ether (1) is preferably 3 to 300 ppm by mass with respect to the aqueous medium, and 3 to 300 ppm by mass. 100 mass ppm is more preferred, 5 to 80 mass ppm is more preferred, and 10 to 70 mass ppm is most preferred.
  • the amount of the fluorine-containing allyl ether (1) is preferably 3 to 500 mass ppm, more preferably 5 to 300 mass ppm, relative to the aqueous medium.
  • the amount of the fluorine-containing allyl ether (1) is preferably 5 to 500 ppm by mass with respect to the aqueous medium, and 8 to 500 ppm by mass. 300 ppm by mass is more preferred, 15 to 200 ppm by mass is more preferred, and 20 to 150 ppm by mass is most preferred.
  • the amount of the fluorine-containing allyl ether (1) is within the above range, the adhesion rate can be further reduced and the polymerization time can be shortened.
  • the fluorine-containing allyl ether (1) is preferably added before starting the polymerization reaction by adding the polymerization initiator. Moreover, it is preferable to add only before starting the polymerization reaction and not to add it after starting the polymerization.
  • the fluorine-containing vinyl ether (2) is represented by general formula (2).
  • CX 21 2 CY 21 (-O-Rf 21 -Y 22 ) (2) (Wherein, X 21 is the same or different and is -H or -F, Y 21 is -H, -F, alkyl group or fluorine-containing alkyl group, Rf 21 is C 1-40 A fluorine alkylene group or a fluorine-containing alkylene group having an ether bond with 2 to 100 carbon atoms, and Y 22 is a hydrophilic group.)
  • X 21 is -H or -F. Both of X 21 may be -F, or at least one may be -H. For example, one may be -F and the other may be -H, or both may be -H. All of X 21 are preferably -F, since more fluorine-containing elastomer particles can be generated and adhesion of the fluorine-containing elastomer to the polymerization tank can be further suppressed.
  • Y 21 is —H, —F, an alkyl group or a fluorine-containing alkyl group.
  • the alkyl group is an alkyl group containing no fluorine atoms and may have 1 or more carbon atoms.
  • the number of carbon atoms in the alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
  • the fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and may have 1 or more carbon atoms.
  • the number of carbon atoms in the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
  • Y 21 is preferably -H, -F or -CF 3 , more preferably -F.
  • At least one of X 21 and Y 21 preferably contains a fluorine atom.
  • X 21 can be -H and Y 21 and Z can be -F.
  • Rf 21 is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond.
  • a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group containing an ether bond between carbon atoms without a structure terminating with an oxygen atom.
  • the number of carbon atoms in the fluorine-containing alkylene group is preferably 2 or more.
  • the number of carbon atoms in the fluorine-containing alkylene group is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.
  • the fluorine-containing alkylene group includes -CF 2 -, -CH 2 CF 2 -, -CF 2 CF 2 -, -CF 2 CH 2 -, -CF 2 CF 2 CH 2 - , -CF (CF 3 )-, -CF(CF 3 )CF 2 -, -CF 2 CF(CF 3 )-, -CF(CF 3 )CH 2 - and the like.
  • the fluorine-containing alkylene group is preferably a perfluoroalkylene group.
  • Y22 in general formula ( 2) is a hydrophilic group.
  • hydrophilic groups include -NH 2 , -P(O)(OM) 2 , -OP(O)(OM) 2 , -SO 3 M, -OSO 3 M, -COOM, -B(OM) 2 , —OB(OM) 2 (in each formula, M is H, a metal atom, NR 74 , imidazolium optionally having substituent ( s), pyridinium optionally having substituent(s) or substituent Phosphonium which may be present, R 7 is H or an organic group, which may be the same or different, any two of which may combine with each other to form a ring).
  • the hydrophilic group is preferably an anionic group such as -P(O)(OM) 2 , -OP(O)(OM) 2 , -SO 3 M, -OSO 3 M, -COOM, -B(OM). 2 , -OB(OM) 2 are more preferred.
  • An alkyl group is preferable as the organic group for R7 .
  • R 7 is preferably H or a C 1-10 organic group, more preferably H or a C 1-4 organic group, still more preferably H or a C 1-4 alkyl group, and most preferably H.
  • the metal atom includes a monovalent or divalent metal atom, preferably an alkali metal (group 1) or an alkaline earth metal (group 2), more preferably Na, K or Li.
  • Y 22 can generate more fluorine-containing elastomer particles and can further suppress adhesion of the fluorine-containing elastomer to the polymerization tank.
  • 3 M or —OSO 3 M M is H, a metal atom, NR 74 , imidazolium optionally having substituents, pyridinium optionally having substituents, or phosphonium, R 7 is H or an organic group, which may be the same or different, any two of which may be combined with each other to form a ring) is preferred.
  • R 7 is preferably H or a C 1-10 organic group, more preferably H or a C 1-4 organic group, and even more preferably H or a C 1-4 alkyl group.
  • the metal atom include alkali metals (group 1) and alkaline earth metals (group 2), and Na, K, and Li are preferable.
  • the above M is preferably -H, a metal atom or -NR 7 4 , more preferably -H, an alkali metal (group 1), an alkaline earth metal (group 2) or -NR 7 4 , -H, -Na , -K, -Li or -NH 4 are more preferred, -Na, -K or -NH 4 are even more preferred, -Na or -NH 4 are particularly preferred, and -NH 4 is most preferred.
  • the above Y 22 is preferably -COOM or -SO 3 M.
  • the compound represented by general formula (2) is preferably at least one selected from the group consisting of compounds represented by general formulas (2a) to (2f).
  • CF 2 CF-O-(CF 2 ) n1 -Y 22 (2a) (Wherein, n1 represents an integer of 1 to 10, and Y 22 is the same as defined above)
  • CF 2 CF-O-(CF 2 C(CF 3 )F) n2 -Y 22 (2b) (Wherein, n2 represents an integer of 1 to 5, and Y 22 is the same as defined above.)
  • CF 2 CF-O-(CFX 22 ) n3 -Y 22 (2c) (Wherein, X 22 represents F or CF 3 , n3 represents an integer of 1 to 10, and Y 22 is the same as defined above.)
  • CF2 CF - O-( CF2CFX22O ) n4- ( CF2 ) n6 -Y22 ( 2d ) (In the formula, n4 represents an integer of
  • n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less.
  • Y 22 is preferably —COOM or —SO 3 M in terms of obtaining appropriate water solubility and stability of the aqueous dispersion, and M is easy to synthesize the fluorine-containing vinyl ether (2). Therefore, it is preferably Na, H, or NH4 , and M is preferably H or NH4 , since it hardly remains as an impurity and improves the heat resistance of the obtained molded product.
  • n2 is preferably an integer of 3 or less from the viewpoint of the stability of the resulting aqueous dispersion, and Y 22 provides appropriate water solubility and stability of the aqueous dispersion.
  • M is preferably Na or H or NH 4 because the synthesis of the fluorine-containing vinyl ether (2) is easy, and M is an impurity H or NH 4 is preferable in that it is less likely to remain as a residue and the heat resistance of the resulting molded product is improved.
  • n3 is preferably an integer of 5 or less in terms of water solubility
  • Y 22 is -COOM or - in terms of obtaining appropriate water solubility and stability of the aqueous dispersion.
  • SO 3 M is preferable, and M is preferably Na, H, or NH 4 in terms of improving dispersion stability.
  • X 22 is preferably —CF 3 from the viewpoint of stability of the aqueous dispersion
  • n4 is preferably an integer of 5 or less from the viewpoint of water solubility
  • Y 22 is preferably —COOM or —SO 3 M
  • M is preferably Na or H or NH 4 in terms of obtaining appropriate water solubility and stability of the aqueous dispersion.
  • CF2 CFOCF2CF ( CF3 ) OCF2CF2COOM
  • CF2 CFOCF2CF ( CF3 ) OCF2COOM
  • CF2 CFOCF2 CF ( CF3 ) OCF2CF2CF2COOM
  • CF2 CFOCF2CF ( CF3 ) OCF2SO3M
  • CF2 CFOCF2CF ( CF3 ) OCF2CF2SO3M
  • CF2 CFOCF2CF ( CF3 ) OCF2CF2CF2SO3M
  • CF2 CFOCF2CF ( CF3 ) OCF2CF2CF2SO3M ( wherein M represents H , NH4 or an alkali metal).
  • n5 is preferably an integer of 5 or less in terms of water solubility
  • Y 22 is -COOM or -SO in terms of obtaining moderate water solubility and stability of the aqueous dispersion.
  • 3 M preferably M is Na or H or NH 4 .
  • the amount of the fluorine-containing vinyl ether (2) is preferably 3 to 5000 mass ppm, more preferably 5 mass ppm or more, and still more preferably 10 mass ppm, relative to the aqueous medium.
  • mass ppm or more particularly preferably 20 mass ppm or more, most preferably 30 mass ppm or more, more preferably 1000 mass ppm or less, still more preferably 500 mass ppm or less, and particularly preferably is 200 mass ppm or less, most preferably 100 mass ppm or less.
  • the amount of the fluorine-containing vinyl ether (2) is preferably 3 to 300 mass ppm, more preferably 3 to 150 mass ppm, relative to the aqueous medium. ppm is more preferred, 5 to 100 ppm by weight is more preferred, and 8 to 80 ppm by weight is most preferred.
  • the amount of the fluorine-containing vinyl ether (2) is preferably 3 to 500 ppm by mass relative to the aqueous medium, and 3 to 500 ppm by mass. 200 mass ppm is more preferred, 5 to 120 mass ppm is more preferred, and 20 to 110 mass ppm is most preferred.
  • a redox polymerization initiator is used as the polymerization initiator and the polymerization is carried out at 10° C.
  • the amount of the fluorine-containing vinyl ether (2) is preferably 3 to 300 mass ppm, more preferably 3 to 100 mass ppm, relative to the aqueous medium. Weight ppm is more preferred, 5 to 80 weight ppm is more preferred, and 10 to 70 weight ppm is most preferred.
  • the amount of the fluorine-containing vinyl ether (2) is preferably 3 to 500 ppm by mass, more preferably 5 to 300 ppm by mass, relative to the aqueous medium.
  • the amount of the fluorine-containing vinyl ether (2) is preferably 5 to 500 mass ppm, more preferably 8 to 300 mass ppm, relative to the aqueous medium. Weight ppm is more preferred, 15 to 200 weight ppm is more preferred, and 20 to 150 weight ppm is most preferred.
  • the amount of the fluorine-containing vinyl ether (2) is within the above range, the adhesion rate can be further reduced and the polymerization time can be shortened.
  • the fluorine-containing vinyl ether (2) is preferably added before starting the polymerization reaction by adding the polymerization initiator. Moreover, it is preferable to add only before starting the polymerization reaction and not to add it after starting the polymerization.
  • the mass ratio ((1)/(2)) between the amount of the fluorine-containing allyl ether (1) and the amount of the fluorine-containing vinyl ether (2) used in the polymerization of the fluorine-containing monomer is preferably from 1/99. 99/1, more preferably 20/80 to 80/20, still more preferably 20/80 to 60/40.
  • the production method of the present disclosure can efficiently produce a fluorine-containing elastomer when at least the fluorine-containing allyl ether (1) and the fluorine-containing vinyl ether (2) are used in combination.
  • two or more fluorine-containing allyl ethers (1) may be used simultaneously
  • two or more fluorine-containing vinyl ethers (2) may be used simultaneously
  • those having volatility or Other compounds having surface activity may be used at the same time as long as they may remain in the molded article containing the fluorine-containing elastomer.
  • a fluorine-containing monomer is polymerized in the presence of a non-fluorine-containing surfactant (hydrocarbon-based surfactant).
  • the fluorine-containing monomer is polymerized in the absence of a non-fluorine-containing surfactant (hydrocarbon-based surfactant).
  • a fluorine-containing monomer is polymerized in the absence of a fluorine-containing surfactant (excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)). do.
  • a fluorine-containing surfactant excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2).
  • fluorine-containing surfactant examples include anionic fluorine-containing surfactants.
  • the anionic fluorine-containing surfactant may be, for example, a surfactant containing a fluorine atom having a total carbon number of 20 or less in the portion excluding the anionic group.
  • the fluorine-containing surfactant may also be a fluorine-containing surfactant having an anionic moiety with a molecular weight of 1000 or less, preferably 800 or less.
  • the "anionic portion” means the portion of the fluorine-containing surfactant excluding the cation. For example, in the case of F(CF 2 ) n1 COOM represented by formula (I) described later, it is the portion of “F(CF 2 ) n1 COO”.
  • the fluorine-containing surfactant also includes a fluorine-containing surfactant having a LogPOW of 3.5 or less.
  • the above LogPOW is the partition coefficient between 1-octanol and water, and LogP [wherein P is the octanol/water (1:1) mixture containing the fluorine-containing surfactant during phase separation. represents the concentration ratio of the fluorine-containing surfactant/the concentration of the fluorine-containing surfactant in water].
  • fluorine-containing surfactant examples include US Patent Application Publication No. 2007/0015864, US Patent Application Publication No. 2007/0015865, US Patent Application Publication No. 2007/0015866, and US Patent US2007/0276103, US2007/0117914, US2007/142541, US2008/0015319, US3250808 Specification, US Patent No. 3271341, JP 2003-119204, WO 2005/042593, WO 2008/060461, WO 2007/046377, JP 2007-119526 Publication, International Publication No. 2007/046482, International Publication No. 2007/046345, US Patent Application Publication No. 2014/0228531, International Publication No. 2013/189824, International Publication No. 2013/189826, etc. mentioned.
  • N 0 As the anionic fluorine-containing surfactant, the following general formula (N 0 ): X n0 ⁇ Rf n0 ⁇ Y 0 (N 0 ) (In the formula, X n0 is H, Cl or and F. Rf n0 has 3 to 20 carbon atoms and is chain, branched or cyclic, and some or all of H is replaced by F is an alkylene group, the alkylene group may contain one or more ether bonds, and some H may be substituted with Cl. Y 0 is an anionic group.) The compound represented by mentioned.
  • the anionic group of Y 0 may be -COOM, -SO 2 M, or -SO 3 M, and may be -COOM or -SO 3 M.
  • M is H, a metal atom, NR 74 , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium ; is H or an organic group.
  • the metal atom include alkali metals (group 1) and alkaline earth metals (group 2), such as Na, K, and Li.
  • R 7 may be H or a C 1-10 organic group, may be H or a C 1-4 organic group, or may be H or a C 1-4 alkyl group.
  • M may be H, a metal atom or NR 7 4 , may be H, an alkali metal (group 1), an alkaline earth metal (group 2) or NR 7 4 , H, Na, K, Li or NH4 .
  • Rf n0 50% or more of H may be substituted with fluorine.
  • N 1 As the compound represented by the general formula (N 0 ), the following general formula (N 1 ): X n0 ⁇ (CF 2 ) m1 ⁇ Y 0 (N 1 ) (Wherein, X n0 are H, Cl and F, m1 is an integer of 3 to 15, and Y 0 is as defined above.)
  • Rf n5 is a linear or branched partially or fully fluorinated alkylene group that may contain an ether bond of 1 to 3 carbon atoms, and L is a linking group; , Y 0 are as defined above, provided that the total number of carbon atoms of X n2 , X n3 , X n4 and Rf n5 is 18 or less.
  • the compound represented by the general formula (N 0 ) includes perfluorocarboxylic acid (I) represented by the following general formula (I), ⁇ -H perm represented by the following general formula (II), Fluorocarboxylic acid (II), perfluoroethercarboxylic acid (III) represented by the following general formula (III), perfluoroalkylalkylenecarboxylic acid (IV) represented by the following general formula (IV), the following general formula ( V) represented by perfluoroalkoxyfluorocarboxylic acid (V), perfluoroalkylsulfonic acid (VI) represented by the following general formula (VI), ⁇ -H perfluoro represented by the following general formula (VII) Sulfonic acid (VII), perfluoroalkylalkylene sulfonic acid (VIII) represented by general formula (VIII) below, alkylalkylene carboxylic acid (IX) represented by general formula (IX) below, general formula (X) below A fluoro
  • the perfluorocarboxylic acid (I) has the following general formula (I) F( CF2 ) n1COOM (I) (Wherein, n1 is an integer of 3 to 14 , M is H, a metal atom, NR 74 , imidazolium optionally having substituents, pyridinium optionally having substituents or It is a phosphonium which may have a substituent, and R 7 is H or an organic group.).
  • the ⁇ -H perfluorocarboxylic acid (II) has the following general formula (II) H(CF2) n2COOM ( II ) (wherein n2 is an integer of 4 to 15, and M is as defined above).
  • the perfluoroether carboxylic acid (III) has the following general formula (III) Rf 1 -O-(CF(CF 3 )CF 2 O) n3 CF(CF 3 )COOM (III) (Wherein, Rf 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is as defined above.) .
  • the perfluoroalkylalkylenecarboxylic acid (IV) has the following general formula (IV) Rf2(CH2)n4Rf3COOM ( IV ) (In the formula, Rf 2 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf 3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, n4 is 1 to 3 and M is defined above).
  • the alkoxyfluorocarboxylic acid (V) has the following general formula (V) Rf4 - O - CY1Y2CF2 - COOM (V) (Wherein, Rf 4 is a linear or branched partially or fully fluorinated alkyl group that may contain an ether bond having 1 to 12 carbon atoms, and Y 1 and Y 2 are the same or different , H or F, where M is as defined above.
  • the perfluoroalkylsulfonic acid (VI) has the following general formula (VI) F( CF2)n5SO3M ( VI ) (wherein n5 is an integer of 3 to 14, and M is as defined above).
  • the ⁇ -H perfluorosulfonic acid (VII) has the following general formula (VII) H( CF2)n6SO3M ( VII ) (wherein n6 is an integer of 4 to 14, and M is as defined above).
  • the perfluoroalkylalkylene sulfonic acid (VIII) has the following general formula (VIII) Rf5 ( CH2 ) n7SO3M ( VIII) (Wherein, Rf 5 is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer of 1 to 3, and M is as defined above.) .
  • the alkylalkylenecarboxylic acid (IX) has the following general formula (IX) Rf6 ( CH2 ) n8COOM (IX) (wherein Rf 6 is a linear or branched partially or fully fluorinated alkyl group which may contain an ether bond with 1 to 13 carbon atoms, n8 is an integer of 1 to 3, M is defined above.).
  • the fluorocarboxylic acid (X) has the following general formula (X) Rf7 - O - Rf8 - O-CF2-COOM(X) (Wherein, Rf 7 is a linear or branched partially or fully fluorinated alkyl group that may contain an ether bond having 1 to 6 carbon atoms, and Rf 8 is a straight chain having 1 to 6 carbon atoms.
  • Rf 7 is a linear or branched partially or fully fluorinated alkyl group that may contain an ether bond having 1 to 6 carbon atoms
  • Rf 8 is a straight chain having 1 to 6 carbon atoms.
  • the alkoxyfluorosulfonic acid (XI) has the following general formula (XI) Rf9 -O - CY1Y2CF2 - SO3M (XI) (wherein Rf 9 is a linear or branched chained alkyl group which may contain an ether bond of 1 to 12 carbon atoms and which may contain chlorine and may be partially or fully fluorinated; Y 1 and Y 2 are the same or different and are H or F, and M is as defined above).
  • X 1 , X 2 and X 3 may be the same or different, and may contain H, F and an ether bond having 1 to 6 carbon atoms. is an alkyl group, Rf 10 is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a linking group, and Y 0 is an anionic group. ).
  • Y 0 can be -COOM, -SO 2 M, or -SO 3 M, and can be -SO 3 M, or COOM, where M is as defined above.
  • L include a single bond, a partially fluorinated alkylene group which may contain an ether bond having 1 to 10 carbon atoms, and the like.
  • the compound (XIII) has the following general formula (XIII) Rf 11 —O—(CF 2 CF(CF 3 )O) n9 (CF 2 O) n10 CF 2 COOM (XIII) (wherein Rf 11 is a chlorine-containing fluoroalkyl group having 1 to 5 carbon atoms, n9 is an integer of 0 to 3, n10 is an integer of 0 to 3, and M is the above-defined It is represented by Compound (XIII) includes CF2ClO ( CF2CF ( CF3 )O) n9 ( CF2O ) n10CF2COONH4 ( a mixture with an average molecular weight of 750, where n9 and n10 are as defined above). There is.)
  • a fluorine-containing monomer is polymerized in the presence of a fluorine-containing surfactant (excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)). .
  • a fluorine-containing monomer can be polymerized in the absence of a fluorine-containing compound represented by the general formula: X—(CF 2 ) m2 —Y.
  • a fluorine-containing surfactant excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)
  • the general formula: X-( The fluoromonomer can be polymerized in the absence of the fluorocompound represented by CF 2 ) m2 -Y.
  • fluorine-containing surfactants excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)
  • fluorine-containing surfactants general formula: X-(CF 2 ) m2 -Y (wherein X represents H or F, m2 represents an integer of 6 or more, Y represents -SO 3 M, -SO 4 M, -SO 3 R, -SO 4 R, -COOM , —PO 3 M 2 , —PO 4 M 2 (M represents H, NH 4 or an alkali metal, and R represents an alkyl group having 1 to 12 carbon atoms).
  • fluorine-containing surfactant that can be present during polymerization
  • fluorine-containing surfactants that are not present during polymerization
  • the general formula: X-(CF 2 ) m2 -Y In the formula, X represents H or F, m2 represents an integer of 6 or more, Y represents -SO 3 M, -SO 4 M, -SO 3 R, -SO 4 R, -COOM, -PO 3 M 2 , —PO 4 M 2 (M represents H, NH 4 or an alkali metal, and R represents an alkyl group having 1 to 12 carbon atoms). agents.
  • fluorine-containing surfactants that can be present during polymerization International Publication No. 2019/009248, International Publication No. 2007/120346, International Publication No. Examples include those described in Publication No. 2007/062059.
  • polymerization may be performed in the presence of a polymerization initiator.
  • the polymerization of the fluoromonomer is performed, for example, by charging a pressure-resistant polymerization tank equipped with a stirrer with the fluorinated allyl ether (1), the fluorinated vinyl ether (2), and an aqueous medium, and deoxidizing the reaction mixture. After that, a monomer is charged, the temperature is raised to a predetermined temperature, and a polymerization initiator is added to initiate the reaction. Since the pressure decreases as the reaction progresses, additional monomers are supplied continuously or intermittently so as to maintain the initial pressure, and the supply is stopped when a predetermined amount of monomers has been supplied. , purge the monomers in the reaction vessel and return the temperature to room temperature to complete the reaction.
  • the polymerization initiator includes a radical polymerization initiator.
  • the polymerization initiator is not particularly limited as long as it can generate radicals at the temperature at which the fluorine-containing monomer is polymerized, and oil-soluble polymerization initiators, water-soluble polymerization initiators, and the like can be used. , water-soluble polymerization initiators are preferred. Also, the polymerization initiator may be used in combination with a reducing agent or the like as a redox initiator.
  • the amount of the polymerization initiator when polymerizing the fluorine-containing monomer is appropriately determined according to the type of monomer, the molecular weight of the target fluorine-containing elastomer, and the reaction rate.
  • the amount of the polymerization initiator is appropriately determined depending on the molecular weight of the target fluorine-containing elastomer and the polymerization reaction rate, but is preferably 0.00001 to 10% by mass with respect to 100% by mass of the total amount of monomers. More preferably, it is 0.0001 to 1% by mass.
  • an oil-soluble radical polymerization initiator a water-soluble radical polymerization initiator, or an azo compound can be used.
  • Oil-soluble radical polymerization initiators may be known oil-soluble peroxides such as dialkylperoxycarbonates such as diisopropylperoxydicarbonate and disec-butylperoxydicarbonate; peroxy esters such as isobutyrate and t-butyl peroxypivalate; dialkyl peroxides such as di-t-butyl peroxide; ( ⁇ -hydro-tetradecafluorooctanoyl) peroxide, di( ⁇ -hydro-hexadecafluorononanoyl) peroxide, di(perfluorobutyryl) peroxide, di(perfluorovaleryl) peroxide, di (perfluorohexanoyl) peroxide, di (perfluoroheptanoyl) peroxide, di (perfluorooctanoyl) peroxide, di (perfluorononanoyl) peroxide, di ( ⁇ -chloro-he
  • Azo compounds include azodicarboxylate, azodicarboxyldiamide, 2,2'-azobisisobutyronitrile, 2,2'-azobis 2,4-dimethylvaleronitrile, 2,2'-azobis ( 2-methylpropionamidine) dihydrochloride, 4,4′-azobis(4-cyanovaleric acid).
  • the water-soluble radical polymerization initiator may be a known water-soluble peroxide, for example, persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, ammonium salts such as percarbonic acid, potassium salts, sodium salts , disuccinic acid peroxide, diglutaric acid peroxide, t-butyl permaleate, t-butyl hydroperoxide and the like.
  • a reducing agent such as sulfites may also be included, and the amount used may be 0.1 to 20 times that of the peroxide.
  • a salt of persulfate is preferable because it is easy to adjust the amount of generated radicals, and potassium persulfate (K 2 S 2 O 8 ), ammonium persulfate ((NH 4 ) 2 S 2 O 8 ), preferably sodium persulfate ( Na2S2O8 ), most preferably ammonium persulfate.
  • the polymerization temperature is 45°C or higher and the polymerization is carried out using a water-soluble peroxide, it is preferable to carry out the polymerization without using a reducing agent.
  • a redox initiator that combines an oxidizing agent and a reducing agent as the polymerization initiator. That is, the polymerization is preferably carried out in the presence of a redox initiator.
  • oxidizing agents include persulfates, organic peroxides, potassium permanganate, manganese triacetate, cerium ammonium nitrate, and bromates.
  • reducing agents include sulfites, bisulfites, bromates, diimine, oxalic acid, metal sulfinic acid salts, and the like.
  • Persulfates include ammonium persulfate, potassium persulfate and sodium persulfate.
  • Sulfites include sodium sulfite and ammonium sulfite. It is also preferred to add a copper salt, an iron salt to the redox initiator combination in order to increase the decomposition rate of the initiator.
  • Copper salts include copper (II) sulfate, and iron salts include iron (II) sulfate.
  • a chelating agent ethylenediaminetetraacetic acid disodium salt dihydrate is preferred.
  • redox initiators include potassium permanganate/oxalic acid, ammonium persulfate/bisulfite/iron(II) sulfate, ammonium persulfate/sulfite/iron(II) sulfate, ammonium persulfate/sulfite, ammonium persulfate/ Iron (II) sulfate, manganese triacetate/oxalic acid, cerium ammonium nitrate/oxalic acid, bromate/sulfite, bromate/bisulfite, ammonium persulfate/sodium hydroxymethanesulfinate dihydrate, etc. , ammonium persulfate/sodium hydroxymethanesulfinate dihydrate.
  • either the oxidizing agent or the reducing agent may be charged in advance into the polymerization tank, and then the other may be added continuously or intermittently to initiate polymerization.
  • the oxidizing agent or the reducing agent may be charged in advance into the polymerization tank, and then the other may be added continuously or intermittently to initiate polymerization.
  • ammonium persulfate/sodium hydroxymethanesulfinate dihydrate it is preferable to charge ammonium persulfate into a polymerization tank and continuously add sodium hydroxymethanesulfinate dihydrate thereto.
  • the amount of persulfate used in the redox initiator is preferably 0.001 to 2.0% by mass, more preferably 0.01 to 1.5% by mass, and 0.01 to 2.0% by mass, based on the aqueous medium used for polymerization. 05 to 1.0% by weight is particularly preferred.
  • the amount of the reducing agent used is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and particularly preferably 5 to 20% by mass, relative to the aqueous medium used for polymerization.
  • the amount of the third component (the copper salt, iron salt, etc.) used is preferably 0.001 to 0.5% by mass, more preferably 0.005 to 0.4% by mass, relative to the aqueous medium used for polymerization. is more preferable, and 0.01 to 0.3% by mass is particularly preferable.
  • the fluorine-containing monomer may be polymerized in the presence of a chain transfer agent.
  • chain transfer agents can be used, for example, hydrocarbons, esters, ethers, alcohols, ketones, halogen-containing compounds, carbonates and the like can be used.
  • isopentane , diethyl malonate and ethyl acetate are preferable from the viewpoint that the reaction rate is less likely to decrease.
  • the terminal of the polymer can be iodinated and it can be used as a reactive polymer.
  • a chain transfer agent it is particularly preferable to use a bromine compound or an iodine compound.
  • Polymerization methods using a bromine compound or an iodine compound include, for example, iodine transfer polymerization and bromine transfer polymerization.
  • Iodine compounds and bromine compounds are water-insoluble and difficult to emulsify. Therefore, emulsion polymerization was originally limited, and there was a tendency that a large amount of surfactant had to be used. According to the production method of the present disclosure, a fluorine-containing elastomer is obtained by polymerization using an iodine compound or a bromine compound, such as iodine transfer polymerization or bromine transfer polymerization, even in the absence of conventionally used surfactants. became possible.
  • Iodine transfer polymerization is radically active due to the low dissociation energy of the carbon-iodine bond, and the chain transfer reaction is involved in the process of the radical polymerization reaction. It's about how to Regarding the reaction conditions, known conditions can be used as appropriate, and are not particularly limited. The conditions described in Japanese Patent Application Laid-Open No. 53-3495 can be appropriately adopted. Similar polymerizations can be carried out using bromine compounds in place of iodine compounds, and in this disclosure such polymerizations are referred to as bromine transfer polymerizations.
  • iodine transfer polymerization is preferable from the viewpoint of polymerization reactivity and cross-linking reactivity.
  • bromine compounds or iodine compounds include, for example, the general formula: R 8 I x Br y (Wherein, x and y are each an integer of 0 to 2 and satisfy 1 ⁇ x + y ⁇ 2, and R 8 is a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or chlorofluoro a hydrocarbon group, or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom).
  • a bromine compound or an iodine compound iodine or bromine is introduced into the polymer and functions as a cross-linking point.
  • Bromine compounds and iodine compounds include, for example, 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodoperfluoropropane, 1,4-diiodoperfluorobutane, 1 ,5-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodine perfluorohexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo-n - propane, CF2Br2 , BrCF2CF2Br , CF3CFBrCF2Br , CFClBr2 , Br
  • compounds containing only iodine and not containing bromine are preferred, such as 1,4-diiodoperfluorobutane, 1,6-diiodine Perfluorohexane or 2-iodoperfluoropropane is preferably used.
  • the amount of chain transfer agent is preferably 0.2 ⁇ 10 ⁇ 3 to 2 mol %, more preferably 1.0 ⁇ 10 ⁇ 3 to 1 mol %, based on the total amount of monomers used in the polymerization. is.
  • Aqueous medium means a liquid containing water.
  • the aqueous medium is not particularly limited as long as it contains water.
  • water and fluorine-free organic solvents such as alcohols, ethers and ketones, and/or fluorine-containing organic solvents having a boiling point of 40° C. or less. may include.
  • Phosphate, sodium hydroxide, potassium hydroxide, aqueous ammonia, etc. may be used as a pH adjuster in the polymerization of the fluorine-containing monomer.
  • the aqueous medium is preferably acidic. Adhesion of the fluorine-containing polymer to the polymerization tank is further suppressed by polymerizing the fluorine-containing monomer in the presence of the fluorine-containing allyl ether (1) and the fluorine-containing vinyl ether (2) using an acidic aqueous medium. can.
  • the pH of the aqueous medium is preferably 7 or less, more preferably 6 or less, and preferably 3 or more.
  • the fluoromonomer may be polymerized in the presence or absence of the fluoromonomer polymerization seed particles.
  • fluorine-containing monomer polymerized seed particles are obtained by polymerizing a fluorine-containing monomer in an aqueous medium, and include monomers and additives (e.g., polymerization Initiator, etc.) are present during the second polymerization in which the types and proportions of components such as initiators, reaction conditions, etc. are different.
  • the fluoromonomer polymerized seed particles act as so-called seed particles during the polymerization of the fluoromonomer, and constitute the polymerization of the fluoromonomer in the presence of the seed particles, ie, the so-called seed polymerization. In the production method of the present disclosure, such seed polymerization may not be performed when polymerizing the fluorine-containing monomer.
  • the polymerization temperature for polymerizing the fluorine-containing monomer is preferably 10 to 120°C, more preferably 20 to 100°C.
  • the polymerization temperature is preferably 15 to 60°C, more preferably 18 to 55°C, and even more preferably 20 to 50°C, from the viewpoints of stability of the aqueous dispersion and reduction of adhesion rate.
  • the polymerization temperature is preferably 60 to 120° C., more preferably 60 to 100° C., more preferably 70 to 100° C., because the polymerization rate is high and a fluorine-containing elastomer that gives molded articles having excellent physical properties can be obtained. 90°C is more preferred.
  • the polymerization pressure for polymerizing the fluorine-containing monomer is preferably 0.5-10 MPaG, more preferably 1-7 MPaG.
  • the fluorine-containing monomer is polymerized in the presence of the fluorine-containing allyl ether (1), the fluorine-containing vinyl ether (2), and an aqueous medium, so that the polymer (fluorine-containing elastomer) is transferred to the polymerization tank. adhesion can be suppressed.
  • the polymer adhesion rate to the polymerization tank is preferably 8% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, and most preferably 2% by mass or less.
  • the polymer adhesion rate is the ratio of the mass of the polymer deposit adhering to the polymerization tank after the polymerization to the total amount of the polymer (fluorine-containing elastomer) after the polymerization (adhesion rate to the polymerization tank).
  • the polymer deposits include the polymer adhering to the inside of the polymerization vessel such as the inner wall of the polymerization vessel and the stirring blade after the aqueous dispersion is extracted from the polymerization vessel after the completion of polymerization, and the polymer that is released from the aqueous dispersion due to aggregation and Also included are polymers that are suspended or precipitated without being dispersed in a liquid.
  • the mass of the polymer deposit is the mass after removing moisture contained in the polymer deposit by drying at 120°C.
  • Polymer adhesion rate (% by mass) mass of polymer deposit/mass of obtained polymer (including deposit) x 100
  • Mass of polymer obtained mass of aqueous dispersion x solid content concentration (% by mass) of aqueous dispersion/100 + mass of polymer deposit
  • an aqueous dispersion of a fluorine-containing elastomer is obtained by polymerizing a fluorine-containing monomer.
  • the fluorine-containing monomer is preferably a fluorine-containing monomer (excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)), and more preferably does not contain a hydrophilic group.
  • PMVE perfluoro(methyl vinyl ether)
  • PEVE perfluoro(ethyl vinyl ether)
  • PPVE perfluoro(propyl vinyl ether)
  • PAVE has the formula: CF 2 ⁇ CFOCF 2 ORf c (wherein Rf c is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, or a cyclic perfluoroalkyl group having 5 to 6 carbon atoms). An alkyl group, or a linear or branched perfluorooxyalkyl group having 2 to 6 carbon atoms containing 1 to 3 oxygen atoms) can also be used.
  • Rf is a linear fluoroalkyl group
  • Rf is a linear perfluoroalkyl group
  • Rf preferably has 1 to 6 carbon atoms.
  • fluorine-free monomers may be polymerized together with fluorine-containing monomers.
  • fluorine-free monomers include ⁇ -olefin monomers having 2 to 10 carbon atoms such as ethylene, propylene, butene and pentene; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, butyl vinyl ether and alkyl vinyl ethers having 1 to 20 carbon atoms in the alkyl group such as , and these monomers and compounds can be used singly or in combination of two or more.
  • an aqueous dispersion containing a fluorine-containing elastomer can be produced.
  • the fluorine-containing elastomer obtained by the production method of the present disclosure contains methylene groups ( --CH.sub.2--) in its main chain.
  • the fluorine-containing elastomer containing —CH 2 — in the main chain is not particularly limited as long as it includes a chemical structure represented by —CH 2 —. Examples include —CH 2 —CF 2 — and —CH 2 —.
  • Fluorine-containing elastomers containing structures such as CH(CH 3 )—, —CH 2 —CH 2 —, —CH 2 —CF 2 —(CF 3 )—, such as vinylidene fluoride, propylene, It can be introduced into the main chain of the fluorine-containing elastomer by polymerizing ethylene, 2,3,3,3-tetrafluoropropylene, or the like.
  • the content of tetrafluoroethylene units in the fluorine-containing elastomer (the content of monomer units based on tetrafluoroethylene with respect to the total monomer units of the fluorine-containing elastomer) may be less than 40 mol %.
  • a partially fluorinated elastomer is preferable because it can generate more fluoroelastomer particles and can further suppress adhesion of the fluoroelastomer to the polymerization tank.
  • a partially fluorinated elastomer is a fluoropolymer containing fluorine-containing monomer units and having a perfluoromonomer unit content of less than 90 mol% with respect to the total monomer units, and having a glass transition temperature of 20°C or less. and a melting peak ( ⁇ H) magnitude of 4.5 J/g or less.
  • TFE tetrafluoroethylene
  • VdF vinylidene fluoride
  • CF 2 CF-Rf a
  • Rf a is —CF 3 or —OR
  • the fluorine-containing elastomer includes VdF-based fluorine-containing elastomer, TFE/propylene (Pr)-based fluorine-containing elastomer, TFE/Pr/VdF-based fluorine-containing elastomer, ethylene (Et)/HFP-based fluorine-containing elastomer, Et/ HFP/VdF fluorine-containing elastomer, Et/HFP/TFE fluorine-containing elastomer, Et/TFE/PAVE fluorine-containing elastomer, and the like.
  • VdF-based fluorine-containing elastomer TFE/Pr-based fluorine-containing elastomer, TFE/Pr/VdF-based fluorine-containing elastomer, or Et/TFE/PAVE-based fluorine-containing elastomer have good heat aging resistance and oil resistance. It is more suitable.
  • a VdF-based fluorine-containing elastomer is a fluorine-containing elastomer having VdF units.
  • the content of VdF units in the fluoroelastomer is preferably 20 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, relative to all monomer units, Particularly preferably, it is 60 mol % or more.
  • the VdF unit is preferably 20 mol% or more and 90 mol% or less, and preferably 40 mol% or more and 85 mol% of the total number of moles of the VdF unit and the monomer units based on other monomers. % or less, more preferably 45 mol % or more and 80 mol % or less, and particularly preferably 50 mol % or more and 80 mol % or less.
  • VdF-based fluorine-containing elastomer are not particularly limited as long as they are copolymerizable with VdF, and for example, the above-mentioned fluorine-containing monomers can be used.
  • VdF-based fluorine-containing elastomers include VdF/HFP copolymers, VdF/TFE/HFP copolymers, VdF/CTFE copolymers, VdF/CTFE/TFE copolymers, VdF/PAVE copolymers, and VdF/TFE.
  • /PAVE copolymer, VdF/HFP/PAVE copolymer, VdF/HFP/TFE/PAVE copolymer, VdF/TFE/Pr copolymer, VdF/Et/HFP copolymer and VdF/fluorinated monomer At least one copolymer selected from the group consisting of the copolymers of body (2) is preferred. Moreover, it is more preferable to have at least one monomer selected from the group consisting of TFE, HFP and PAVE as a monomer other than VdF.
  • VdF-based fluorine-containing elastomers include VdF/HFP copolymers, VdF/TFE/HFP copolymers, VdF/fluorine-containing monomer (2) copolymers, and VdF/PAVE copolymers.
  • VdF/TFE/PAVE copolymer, VdF/HFP/PAVE copolymer and at least one copolymer selected from the group consisting of VdF/HFP/TFE/PAVE copolymer is preferred, and VdF/HFP copolymer At least one copolymer selected from the group consisting of polymers, VdF/HFP/TFE copolymers, VdF/fluoromonomer (2) copolymers and VdF/PAVE copolymers is more preferred. .
  • the VdF/PAVE copolymer preferably has a VdF/PAVE composition of (65-90)/(35-10) (mol %).
  • the composition of VdF/PAVE is also one of the preferred forms in which it is (50 to 78)/(50 to 22) (mol %).
  • the VdF/TFE/PAVE copolymer preferably has a VdF/TFE/PAVE composition of (40-80)/(3-40)/(15-35) (mol %).
  • the VdF/HFP/PAVE copolymer preferably has a VdF/HFP/PAVE composition of (65-90)/(3-25)/(3-25) (mol %).
  • the composition of VdF/HFP/TFE/PAVE is (40-90)/(0-25)/(0-40)/(3-35) (mol%) is preferred, and (40 to 80)/(3 to 25)/(3 to 40)/(3 to 25) (mol%) is more preferred.
  • the copolymer of VdF/fluorine-containing monomer (2) has a VdF/fluorine-containing monomer (2) unit of (85 to 20)/(15 to 80) (mol %), and contains VdF and Monomer units other than the fluorine-containing monomer (2) are preferably 0 to 50 mol% of the total monomer units, and the mol% ratio of VdF/fluorine-containing monomer (2) units is (80 ⁇ 20)/(20-80) is more preferred.
  • the composition of VdF/fluorine-containing monomer (2) units is (78-50)/(22-50) (mol %).
  • the VdF/fluorine-containing monomer (2) unit is (85 to 50)/(15 to 50) (mol%), and VdF And it is also preferable that monomer units other than the fluorine-containing monomer (2) are 1 to 50 mol % of the total monomer units.
  • VdF and the fluorine-containing monomer (2) include TFE, HFP, PMVE, perfluoroethyl vinyl ether (PEVE), PPVE, CTFE, trifluoroethylene, hexafluoroisobutene, vinyl fluoride,
  • PEVE perfluoroethyl vinyl ether
  • CTFE trifluoroethylene
  • hexafluoroisobutene vinyl fluoride
  • the monomers exemplified as other monomers in the VdF fluorine-containing elastomer such as Et, Pr, alkyl vinyl ethers, and monomers that provide crosslinkable groups, are preferred, among which PMVE, CTFE, HFP, and TFE are preferred. more preferred.
  • a TFE/Pr-based fluorine-containing elastomer refers to a fluorine-containing copolymer composed of 45 to 70 mol% of TFE and 55 to 30 mol% of Pr.
  • a specific third component may be included.
  • Specific third components include, for example, fluorine-containing olefins other than TFE (e.g., VdF, HFP, CTFE, perfluoro(butyl ethylene), etc.), fluorine-containing vinyl ethers (perfluoro(propyl vinyl ether), perfluoro(methyl vinyl ether) etc.); ⁇ -olefins (ethylene, 1-butene, etc.), vinyl ethers (ethyl vinyl ether, butyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl benzoate, crotonic acid (vinyl, vinyl methacrylate, etc.);
  • the specific third component may be used alone or in combination of two or more.
  • the TFE/Pr-based fluorine-containing elastomer preferably contains VdF, and among the TFE/Pr-based fluorine-containing elastomers, an elastomer composed of TFE, Pr, and VdF is called a TFE/Pr/VdF-based fluorine-containing elastomer.
  • the TFE/Pr/VdF fluorine-containing elastomer may further contain the above specific third component other than VdF.
  • the specific third component may be used alone or in combination of two or more.
  • the total content of the third component in the TFE/Pr fluorine-containing elastomer is preferably 35 mol% or less, more preferably 33 mol% or less, and even more preferably 31 mol% or less.
  • the Et/HFP copolymer preferably has an Et/HFP composition of (35 to 80)/(65 to 20) (mol %), (40 to 75)/(60 to 25) (mol %) is more preferred.
  • the Et/HFP/TFE copolymer preferably has an Et/HFP/TFE composition of (35 to 75)/(25 to 50)/(0 to 15) (mol%), and (45 to 75 )/(25-45)/(0-10) (mol %) is more preferred.
  • the Et/TFE/PAVE copolymer preferably has an Et/TFE/PAVE composition of (10 to 40)/(32 to 60)/(20 to 40) (mol%), and (20 to 40 )/(40 to 50)/(20 to 30) (mol %) is more preferable.
  • PMVE is preferred as PAVE.
  • the fluorine-containing elastomer is preferably a fluorine-containing elastomer containing VdF units, more preferably a VdF/HFP copolymer or a VdF/HFP/TFE copolymer, and the composition of VdF/HFP/TFE is (32 to 85)/( 10-34)/(0-40) (mol %) is particularly preferred.
  • the composition of VdF / HFP / TFE is more preferably (32-85) / (15-34) / (0-34) (mol%), (47-81) / (17-32) / (0- 26) (mol%) is more preferred.
  • the composition of VdF/HFP is preferably (45 to 85) / (15 to 55) (mol%), more preferably (50 to 83) / (17 ⁇ 50) (mol%), more preferably (55 to 81) / (19 to 45) (mol%), particularly preferably (60 to 80) / (20 to 40) (mol%) be.
  • the configuration described above is the configuration of the main monomer of the fluorine-containing elastomer, and in addition to the main monomer, a monomer that provides a crosslinkable group may be copolymerized.
  • a monomer that provides the crosslinkable group any monomer can be used as long as it can introduce an appropriate crosslinkable group into the fluorine-containing elastomer depending on the production method and the crosslinking system.
  • Known polymerizable compounds containing crosslinkable groups such as bonds, cyano groups, carboxyl groups, hydroxyl groups, amino groups, and ester groups can be mentioned.
  • CY 1 2 CY 2 R f 2 X 1 (3)
  • Y 1 and Y 2 are fluorine atoms, hydrogen atoms or —CH 3 ;
  • R f 2 may have one or more etheric oxygen atoms, may have an aromatic ring, a linear or branched fluorine-containing alkylene group in which some or all of the hydrogen atoms are substituted with fluorine atoms;
  • X 1 is an iodine atom or a bromine atom
  • the compound represented by can be mentioned.
  • linear or branched chain fluorine-containing alkylene group that is, a linear or branched chain fluorine-containing alkylene group in which some or all of the hydrogen atoms are substituted with fluorine atoms, some or all of the hydrogen atoms
  • R 1 is a hydrogen atom or a methyl group
  • CY 4 2 CY 4 (CF 2 ) n - X 1 (5)
  • Y 4 are the same or different, a hydrogen atom or a fluorine atom, n is an integer of 1 to 8)
  • CF2 CFCF2Rf4 -
  • iodine- or bromine-containing monomer represented by general formula (4) general formula (23): (Wherein, m is an integer of 1 to 5, n is an integer of 0 to 3)
  • An iodine-containing fluorinated vinyl ether represented by Among these, ICH 2 CF 2 CF 2 OCF CF 2 is preferred.
  • "(per)fluoropolyoxyalkylene group” means "fluoropolyoxyalkylene group or perfluoropolyoxyalkylene group”.
  • Z is preferably a (per)fluoroalkylene group having 4 to 12 carbon atoms, and R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are preferably hydrogen atoms.
  • Z is a (per)fluoropolyoxyalkylene group, the formula: -(Q) p -CF 2 O-(CF 2 CF 2 O) m -(CF 2 O) n -CF 2 -(Q) p - (In the formula, Q is an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having 2 to 10 carbon atoms, p is 0 or 1, and m and n have an m/n ratio of 0.2 to 5. and the molecular weight of the (per)fluoropolyoxyalkylene group is an integer in the range of 500 to 10,000, preferably 1,000 to 4,000.) is preferably a (per)fluoropolyoxyalkylene group represented by .
  • the number average molecular weight Mn of the fluorine-containing elastomer is preferably 1,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 20,000 to 300,000.
  • the fluorine content of the fluorine-containing elastomer is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more.
  • the upper limit of the fluorine content is preferably 75% by mass or less, more preferably 73% by mass or less.
  • the fluorine content is calculated based on the values measured by 19 F-NMR, 1 H-NMR, elemental analysis, and the like.
  • the fluorine-containing elastomer preferably has a Mooney viscosity at 100°C (ML1+10 (100°C)) of 130 or less.
  • the Mooney viscosity is more preferably 110 or less, even more preferably 90 or less.
  • the Mooney viscosity is more preferably 10 or more, and still more preferably 20 or more.
  • the Mooney viscosity is a value measured according to JIS K 6300-1.2013.
  • the fluorine-containing elastomer preferably has a glass transition temperature of -50 to 0°C.
  • the glass transition temperature is more preferably ⁇ 2° C. or lower, still more preferably ⁇ 3° C. or lower. Further, the glass transition temperature is more preferably ⁇ 45° C. or higher, further preferably ⁇ 40° C. or higher.
  • the glass transition temperature may be -10°C or higher, or -9°C or higher.
  • the glass transition temperature is measured using a differential scanning calorimeter (e.g., X-DSC7000 manufactured by Hitachi High-Tech Science) to obtain a DSC curve by heating 10 mg of the sample at 20 ° C./min, according to JIS K6240: 2011. , the glass transition temperature can be obtained from the DSC differential curve.
  • a differential scanning calorimeter e.g., X-DSC7000 manufactured by Hitachi High-Tech Science
  • the fluorine-containing elastomer preferably has an iodine content of 0.05 to 1.0% by mass.
  • the iodine content is more preferably 0.08% by mass or more, still more preferably 0.10% by mass or more, and more preferably 0.80% by mass or less, and even more preferably 0.60% by mass or less.
  • the iodine content can be determined by elemental analysis. Specifically, 12 mg of fluorine-containing elastomer was mixed with 5 mg of Na 2 SO 3 , and 30 mg of Na 2 CO 3 and K 2 CO 3 were mixed in 20 ml of pure water at a ratio of 1:1 (mass ratio) and dissolved in the absorbent. can be used, burned in oxygen in a quartz flask, allowed to stand for 30 minutes, and then measured using a Shimadzu 20A ion chromatograph. As a calibration curve, a KI standard solution, one containing 0.5 ppm by mass of iodine ions, and one containing 1.0 ppm by mass of iodine ions can be used.
  • the fluorine-containing elastomer preferably contains a —CH 2 I structure.
  • the inclusion of the —CH 2 I structure can be confirmed by the 1 H-NMR spectrum.
  • a fluorine-containing elastomer containing a —CH 2 I structure can be obtained by iodine transfer polymerization.
  • the fluorine-containing elastomer preferably contains 0.05 to 1.50 mol % of the --CH 2 I structure relative to 100 mol % of the --CH 2 -- structure.
  • the amount of the —CH 2 I structure is more preferably 0.08 mol% or more, still more preferably 0.12 mol% or more, more preferably 1.20 mol% or less, further preferably 1.00 mol% or less, and 0 0.80 mol % or less is particularly preferred.
  • the amount of —CH 2 I structure can be determined from the 1 H-NMR spectrum.
  • the fluorine-containing elastomer more preferably contains a —CF 2 CH 2 I structure.
  • a fluorine-containing elastomer containing a —CF 2 CH 2 I structure can be obtained by producing a VdF-based fluorine-containing elastomer by iodine transfer polymerization.
  • the fluorine-containing elastomer preferably contains 0.05 to 1.50 mol % of the -CF 2 CH 2 I structure with respect to 100 mol % of the -CH 2 - structure.
  • the amount of the —CF 2 CH 2 I structure is more preferably 0.08 mol % or more, still more preferably 0.12 mol % or more, more preferably 1.20 mol % or less, and even more preferably 1.00 mol % or less. , 0.80 mol % or less is particularly preferred.
  • the amount of the —CF 2 CH 2 I structure is the integrated value A of all peak intensities observed in the chemical shift region of 3.75 to 4.05 ppm derived from —CH 2 I in the 1 H-NMR spectrum, and —CH It is calculated by A/B*100 from the integrated value B of all peak intensities observed in the regions of 2.3 to 2.7 ppm and 2.9 to 3.75 ppm of chemical shift derived from 2- .
  • the fluoromonomers described for the fluoroelastomer can be appropriately used.
  • an aqueous dispersion of a fluorine-containing elastomer is obtained.
  • the solid content concentration (content of the fluoroelastomer) of the fluoroelastomer aqueous dispersion to be obtained is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, at the time of completion of polymerization, More preferably, it is 20 to 30% by mass.
  • the aqueous dispersion of the fluoroelastomer may contain fluoroelastomer particles.
  • the average particle size of the fluorine-containing elastomer particles is preferably 10 to 800 nm, more preferably 50 to 500 nm, still more preferably 70 to 300 nm.
  • the average particle size of the fluorine-containing elastomer particles is the cumulant average size, which can be measured by a dynamic light scattering method.
  • the number of fluorine-containing elastomer particles contained in the aqueous dispersion of the fluorine-containing elastomer is preferably 1.0 ⁇ 10 12 particles/cc or more, more preferably 5.0 ⁇ 10 12 particles/cc or more. More preferably, it is 1.0 ⁇ 10 13 particles/cc or more, particularly preferably 1.2 ⁇ 10 14 particles/cc or more, and most preferably 1.3 ⁇ 10 14 particles/cc or more.
  • the number of particles (the number of polymer particles) can be calculated according to the following formula.
  • the number of fluorine-containing elastomer particles obtained by the above formula is the number per 1 cc of water.
  • the specific gravity is the specific gravity of the fluorine-containing elastomer.
  • the specific gravity of the fluorine-containing elastomer can be obtained according to JIS Z 8807:2012.
  • the aqueous dispersion of the fluorine-containing elastomer may be subjected to treatments such as coagulation and heating.
  • the above coagulation can be carried out by adding alkaline earth and earth metal salts to the aqueous dispersion.
  • Alkaline earth and earth metal salts include sulfates, nitrates, hydrochlorides, acetates, etc. of calcium, magnesium, aluminum, and the like.
  • the coagulated fluorine-containing elastomer may be washed with water to remove impurities such as a small amount of buffer solution and salt present in the fluorine-containing elastomer, and then the washed fluorine-containing elastomer may be dried.
  • the drying temperature is preferably 40 to 200°C, more preferably 60 to 180°C, still more preferably 80 to 150°C.
  • the form of the fluorine-containing elastomer obtained after coagulation is not particularly limited, but may be gum, crumb, powder, pellet, etc., preferably gum or crumb. Gum is a small granular lump made of a fluorine-containing elastomer, and crumb is a fluorine-containing elastomer that cannot maintain its shape as a gum at room temperature and fuses with each other. It is in the shape of an amorphous mass.
  • the gum or crumb is preferably obtained from the aqueous dispersion obtained by the production method of the present disclosure by coagulation, drying, etc. by conventionally known methods.
  • a composition (crosslinkable composition) can be produced by adding a crosslinking agent or the like to the aqueous dispersion of the fluoroelastomer or the fluoroelastomer obtained by the production method of the present disclosure.
  • the type and amount of the cross-linking agent are not particularly limited, and can be used within a known range.
  • the crosslinked system includes, for example, a peroxide crosslinked system, a polyol crosslinked system, a polyamine crosslinked system, etc., and is selected from the group consisting of a peroxide crosslinked system and a polyol crosslinked system. At least one selected is preferred. From the viewpoint of chemical resistance, a peroxide crosslinked system is preferred, and from the viewpoint of heat resistance, a polyol crosslinked system is preferred.
  • the cross-linking agent is preferably at least one cross-linking agent selected from the group consisting of a polyol cross-linking agent and a peroxide cross-linking agent, more preferably a peroxide cross-linking agent.
  • the amount of the cross-linking agent to be blended may be appropriately selected according to the type of the cross-linking agent, etc., but it is preferably 0.2 to 6.0 parts by mass, more preferably 0.3 parts by mass, per 100 parts by mass of the fluorine-containing elastomer. ⁇ 5.0 parts by mass.
  • Peroxide crosslinking can be performed by using an uncrosslinked elastomer capable of peroxide crosslinking as the fluorine-containing elastomer and an organic peroxide as the crosslinking agent.
  • the uncrosslinked elastomer that can be peroxide-crosslinked is not particularly limited as long as it has a site that can be peroxide-crosslinked.
  • the peroxide-crosslinkable site is not particularly limited, and examples thereof include a site having an iodine atom, a site having a bromine atom, and the like.
  • the organic peroxide may be any organic peroxide that can easily generate peroxy radicals in the presence of heat or a redox system, such as 1,1-bis(t-butylperoxy)-3, 5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, ⁇ , ⁇ -bis(t- Butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)-hexyne -3, benzoyl peroxide, t-butylperoxybenzene, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, t-buty
  • the blending amount of the organic peroxide is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 5 parts by mass, per 100 parts by mass of the fluorine-containing elastomer.
  • the fluorine-containing elastomer composition preferably further contains a cross-linking aid.
  • crosslinking aids include triallyl cyanurate, triallyl isocyanurate (TAIC), triacrylformal, triallyl trimellitate, N,N'-m-phenylenebismaleimide, dipropagyl terephthalate, diallyl phthalate, Tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris(2,3,3-trifluoro-2-propenyl)-1,3,5-triazine-2 ,4,6-trione), tris(diallylamine)-S-triazine, N,N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallylphosphoramide, N,N,N',N'-te
  • the amount of the cross-linking aid compounded is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 7.0 parts by mass, and still more preferably 0 parts by mass with respect to 100 parts by mass of the fluorine-containing elastomer. .1 to 5.0 parts by mass. If the cross-linking coagent is less than 0.01 part by mass, the mechanical properties and the flexibility may deteriorate. If the amount exceeds 10 parts by mass, the heat resistance tends to be poor and the durability of the molded product tends to decrease.
  • Polyol crosslinking can be performed by using an uncrosslinked elastomer that can be polyol-crosslinked as a fluorine-containing elastomer and a polyhydroxy compound as a crosslinking agent.
  • the blending amount of the polyhydroxy compound in the polyol cross-linkable system is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the uncrosslinked elastomer capable of being polyol-crosslinked.
  • the polyol crosslinking can be sufficiently advanced. More preferably, it is 0.02 to 8 parts by mass. More preferably, it is 0.03 to 4 parts by mass.
  • the polyol-crosslinkable uncrosslinked elastomer is not particularly limited as long as it has a polyol-crosslinkable site.
  • the polyol-crosslinkable site is not particularly limited, and examples thereof include sites having vinylidene fluoride (VdF) units.
  • Examples of the method for introducing the cross-linking site include a method of copolymerizing a monomer that provides the cross-linking site during polymerization of the uncrosslinked elastomer.
  • polyhydroxy compound a polyhydroxy aromatic compound is preferably used because of its excellent heat resistance.
  • the polyhydroxyaromatic compound is not particularly limited, and examples thereof include 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A), 2,2-bis(4-hydroxyphenyl)perfluoropropane. (hereinafter referred to as bisphenol AF.
  • Bisphenol AF is available from, for example, Fuji Film Wako Pure Chemical Industries, Ltd., Central Glass Co., Ltd., etc.), 1,3-dihydroxybenzene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene , 1,6-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxystilbene, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2-bis(4-hydroxyphenyl)butane (hereinafter referred to as bisphenol B), 4,4-bis(4-hydroxyphenyl)valeric acid, 2,2-bis(4-hydroxyphenyl)tetrafluorodichloropropane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy diphenyl ketone, tri(4-hydroxyphenyl)methane, 3,3′,5,5′-tetrachlorobisphenol A, 3,3
  • polyhydroxyaromatic compounds may be alkali metal salts, alkaline earth metal salts, etc. However, when the copolymer is coagulated using an acid, it is preferable not to use the above metal salts.
  • the blending amount of the polyhydroxyaromatic compound is 0.1 to 15 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the uncrosslinked elastomer.
  • the fluorine-containing elastomer composition preferably further contains a cross-linking accelerator.
  • the cross-linking accelerator promotes the formation of intramolecular double bonds in the dehydrofluoric acid reaction of the polymer main chain and the addition of the polyhydroxy compound to the generated double bonds.
  • the cross-linking accelerator may be used in combination with an acid acceptor such as magnesium oxide, or a cross-linking aid.
  • crosslinking accelerator examples include onium compounds.
  • onium compounds ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, and 1 It is preferably at least one selected from the group consisting of functional amine compounds, more preferably at least one selected from the group consisting of quaternary ammonium salts and quaternary phosphonium salts.
  • the quaternary ammonium salt is not particularly limited, and examples include 8-methyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride, 8-methyl-1,8-diazabicyclo[5, 4,0]-7-undecenium iodide, 8-methyl-1,8-diazabicyclo[5,4,0]-7-undecenium hydroxide, 8-methyl-1,8-diazabicyclo[5 ,4,0]-7-undecenium methyl sulfate, 8-ethyl-1,8-diazabicyclo[5,4,0]-7-undecenium bromide, 8-propyl-1,8-diazabicyclo[5 ,4,0]-7-undecenium bromide, 8-dodecyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride, 8-dodecyl-1,8-diazabicyclo[5,4 ,
  • DBU-B is, for example, available from Fuji Film Wako Pure Chemical Industries, Ltd.), 8-benzyl-1,8-diazabicyclo[5,4,0]-7-undecenium hydroxide, 8-phenethyl-1,8-diazabicyclo[5 ,4,0]-7-undecenium chloride, 8-(3-phenylpropyl)-1,8-diazabicyclo[5,4,0]-7-undecenium chloride, tetrabutylammonium hydrogen sulfate, tetra butylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide and the like.
  • DBU-B is preferable from the viewpoint of crosslinkability, mechanical properties and flexibility.
  • the quaternary phosphonium salt is not particularly limited, and examples thereof include tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl -2-methoxypropyl phosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride, and the like.
  • BTPPC benzyltriphenylphosphonium chloride
  • BTPPC benzyltriphenylphosphonium chloride
  • cross-linking accelerator a solid solution of a quaternary ammonium salt and bisphenol AF, a solid solution of a quaternary phosphonium salt and bisphenol AF, and a chlorine-free cross-linking accelerator disclosed in JP-A-11-147891 are used.
  • a cross-linking accelerator a solid solution of a quaternary ammonium salt and bisphenol AF, a solid solution of a quaternary phosphonium salt and bisphenol AF, and a chlorine-free cross-linking accelerator disclosed in JP-A-11-147891 are used.
  • the amount of the crosslinking accelerator to be blended is preferably 0.01 to 8.00 parts by mass, more preferably 0.02 to 5.00 parts by mass, per 100 parts by mass of the uncrosslinked elastomer. More preferably, it is 0.03 to 3.00 parts by mass. If the amount of the cross-linking accelerator is less than 0.01 parts by mass, the cross-linking of the uncross-linked elastomer may not proceed sufficiently, and the resulting molded article may have reduced heat resistance. If it exceeds 8.00 parts by mass, there is a possibility that the molding processability of the fluorine-containing elastomer composition will be deteriorated, the elongation in mechanical properties will be deteriorated, and the flexibility will also tend to be deteriorated.
  • Acid acceptors are used to neutralize acidic substances generated during polyol cross-linking. #2000, CALDIC #1000 (manufactured by Ohmi Chemical Industry Co., Ltd.)), calcium oxide, litharge (lead oxide), zinc white, dibasic lead phosphite, hydrotalcite, etc., and highly active magnesium oxide and low It is preferably at least one selected from the group consisting of active magnesium.
  • Polyamine crosslinking can be performed by using a polyamine-crosslinkable fluorine-containing elastomer as a fluorine-containing elastomer and a polyamine compound as a crosslinking agent.
  • the polyamine-crosslinkable fluorine-containing elastomer is not particularly limited as long as it has a polyamine-crosslinkable site.
  • the polyamine-crosslinkable site is not particularly limited, and examples thereof include sites having vinylidene fluoride (VdF) units.
  • Examples of the method for introducing the cross-linking site include a method of copolymerizing a monomer that provides the cross-linking site during polymerization of the fluorine-containing elastomer.
  • polyamine compounds examples include hexamethylenediamine carbamate, N,N'-dicinnamylidene-1,6-hexamethylenediamine, and 4,4'-bis(aminocyclohexyl)methane carbamate. Among these, N,N'-dicinnamylidene-1,6-hexamethylenediamine is preferred.
  • the method for obtaining the composition containing the cross-linking agent is not particularly limited as long as the method is capable of uniformly mixing the fluorine-containing elastomer obtained by the production method of the present disclosure and the cross-linking agent.
  • the method is capable of uniformly mixing the fluorine-containing elastomer obtained by the production method of the present disclosure and the cross-linking agent.
  • the present disclosure contains a methylene group in the main chain and further contains a monomer unit (1) based on a fluorine-containing allyl ether (1) and a monomer unit (2) based on a fluorine-containing vinyl ether (2). It also relates to fluoroelastomers.
  • the fluorine-containing elastomer of the present disclosure can be suitably produced by the production method of the present disclosure.
  • composition of the present disclosure is not particularly limited, and may be, for example, an aqueous dispersion, gum, crumb, powder, pellet, or the like.
  • An aqueous dispersion is a dispersion system containing an aqueous medium as a dispersion medium and a fluorine-containing elastomer as a dispersoid.
  • the aqueous medium is not particularly limited as long as it is a liquid containing water, and in addition to water, it may contain, for example, an organic solvent such as alcohol, ether, ketone, or paraffin wax.
  • a suitable configuration of the fluorine-containing elastomer is the same as the configuration of the fluorine-containing elastomer obtained by the production method of the present disclosure.
  • Suitable configurations of the fluorine-containing allyl ether (1) and the fluorine-containing vinyl ether (2) are the same as the configurations of the fluorine-containing allyl ether (1) and the fluorine-containing vinyl ether (2) used in the production method of the present disclosure.
  • the content of the monomer units (1) based on the fluorine-containing allyl ether (1) in the fluorine-containing elastomer is preferably 0.0009 to 1.5% by mass with respect to the total monomer units, and more It is preferably 0.0015% by mass or more, more preferably 0.0030% by mass or more, particularly preferably 0.0060% by mass or more, most preferably 0.0090% by mass or more, and more preferably It is 0.30% by mass or less, more preferably 0.15% by mass or less, particularly preferably 0.09% by mass or less, and most preferably 0.06% by mass or less. If the content of the monomer units (1) based on the fluorine-containing allyl ether (1) is too high, the properties required for the fluorine-containing elastomer may be impaired.
  • the content of the monomer units (2) based on the fluorine-containing vinyl ether (2) in the fluorine-containing elastomer is preferably 0.0009 to 1.5% by mass, more preferably 0.0009 to 1.5% by mass, based on the total monomer units. is 0.0015% by mass or more, more preferably 0.0030% by mass or more, particularly preferably 0.0060% by mass or more, most preferably 0.0090% by mass or more, more preferably 0 0.30% by mass or less, more preferably 0.15% by mass or less, particularly preferably 0.09% by mass or less, and most preferably 0.06% by mass or less. If the content of the monomer units (2) based on the fluorine-containing vinyl ether (2) is too high, the properties required for the fluorine-containing elastomer may be impaired.
  • the content of monomer unit (1) and monomer unit (2) in the fluorine-containing elastomer is calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer. can.
  • the composition and the aqueous dispersion to be described later contains a fluorosurfactant (excluding the fluorinated allyl ether (1) and the fluorinated vinyl ether (2)).
  • a fluorine-containing surfactant-containing fluorine-containing elastomer, composition, and aqueous dispersion can be obtained by using a fluorine-containing surfactant (except for the fluorine-containing allyl ether (1) and the fluorine-containing vinyl ether (2)). There is an advantage that it can be manufactured stably with productivity.
  • fluorine-containing surfactant examples include fluorine-containing surfactants (provided that fluorine-containing allyl ether (1), fluorine-containing vinyl ether (2) and fluorine-containing compounds represented by the general formula: X—(CF 2 ) m2 —Y ) are preferred, and those exemplified as fluorine-containing surfactants that can be present during polymerization can be mentioned.
  • fluorine-containing surfactant a fluorine-containing surfactant (excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)) is more preferred.
  • the aqueous dispersion may not contain a fluorine-containing compound represented by the general formula: X-(CF 2 ) m2 -Y.
  • An embodiment of the fluorine-containing elastomer, composition and aqueous dispersion does not substantially contain a fluorine-containing surfactant (excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)).
  • Fluorine-containing surfactants excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)
  • fluorine-containing surfactants are used for fluorine-containing elastomers, compositions and aqueous dispersions that do not substantially contain fluorine-containing surfactants.
  • the method for producing a fluorine-containing elastomer aqueous dispersion of the present disclosure which uses the fluorine-containing allyl ether (1) and the fluorine-containing vinyl ether (2), can be produced. It has become possible.
  • substantially free of fluorine-containing surfactant means the fluorine-containing elastomer, the composition, and the fluorine-containing surfactant in the aqueous dispersion (however, the fluorine-containing allyl ether (1) and fluorine-containing (excluding vinyl ether (2)) is 10 mass ppm or less, preferably 1 mass ppm or less, more preferably 100 mass ppb or less, still more preferably 10 mass ppb or less. more preferably 1 mass ppb or less, and particularly preferably less than the detection limit of the fluorine-containing surfactant as measured by liquid chromatography-mass spectrometry (LC/MS).
  • LC/MS liquid chromatography-mass spectrometry
  • the content of the fluorine-containing surfactant (excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)) can be quantified by a known method, for example, by LC/MS analysis.
  • methanol is added to the fluoroelastomer, the composition or the aqueous dispersion for extraction, and the resulting extract is subjected to LC/MS analysis.
  • a treatment such as Soxhlet extraction, ultrasonic treatment, or the like may be performed.
  • Molecular weight information is extracted from the obtained LC/MS spectrum, and conformity with the structural formula of the candidate fluorine-containing surfactant is confirmed.
  • aqueous solutions with five or more levels of content of the confirmed fluorosurfactant were prepared, and the aqueous solutions with each content were analyzed by LC/MS to determine the content and the relationship between the area area and the content. Plot and draw a standard curve. Then, using the calibration curve, the area area of the LC/MS chromatogram of the fluorine-containing surfactant in the extract can be converted to the content of the fluorine-containing surfactant.
  • the present disclosure also relates to compositions containing fluorine-containing elastomers.
  • the composition of the present disclosure may be an aqueous dispersion containing a fluorine-containing elastomer and an aqueous medium.
  • the upper limit of the solid content concentration of the aqueous dispersion is preferably 50% by mass, more preferably 40% by mass, still more preferably 35% by mass, and particularly preferably 30% by mass, relative to the aqueous dispersion.
  • the lower limit of the solid content concentration of the aqueous dispersion is preferably 5% by mass, more preferably 10% by mass, still more preferably 15% by mass, and particularly preferably 20% by mass.
  • the solid content concentration of the aqueous dispersion can be adjusted by diluting or concentrating the aqueous dispersion obtained by polymerization.
  • the solid content concentration of the aqueous dispersion is the concentration of the solid content contained in the aqueous dispersion.
  • a fluorine-containing elastomer etc. are mentioned as solid content.
  • the solid content concentration of the aqueous dispersion may be the content of the fluorine-containing elastomer in the aqueous dispersion.
  • the solid content concentration of the aqueous dispersion is obtained by drying 1 g of the aqueous dispersion under the conditions of 150 ° C. for 180 minutes, measuring the mass of the heating residue, and calculating the ratio of the mass of the heating residue to the mass of the aqueous dispersion. can be identified by
  • the aqueous dispersion can further contain a cross-linking agent, a filler, and the like.
  • a preferred configuration of the cross-linking agent is the same as the configuration of the composition (crosslinkable composition) obtained by the production method of the present disclosure.
  • the aqueous dispersion can be made into a dispersion suitable for rubber molding by adding a dispersion stabilizer such as a hydrocarbon surfactant or by concentrating it.
  • the dispersion is processed by pH adjustment, coagulation, heating, and the like.
  • the composition of the present disclosure may be a coagulate, gum, crumb, powder, pellet, etc. obtained by coagulating the fluorine-containing elastomer contained in the aqueous dispersion, and may be gum or crumb.
  • Gum is a small granular lump made of a fluorine-containing elastomer
  • crumb is a fluorine-containing elastomer that cannot maintain its shape as a gum at room temperature and fuses with each other. It is in the shape of an amorphous mass.
  • the gum or crumb is preferably obtained from the aqueous dispersion obtained by the production method of the present disclosure by coagulation, drying, etc. by conventionally known methods.
  • the water content of the composition is not particularly limited, but is preferably 1% by mass or less, more preferably 0.1% by mass or less, and still more preferably 0.01% by mass or less, relative to the mass of the composition. is.
  • the moisture content of the composition can be determined, for example, by sufficiently drying the composition by heating it to 120°C or higher, measuring the weight of the composition before and after heating, and dividing the weight loss by the weight before heating. can be calculated.
  • the composition can contain a cross-linking agent.
  • a preferred configuration of the cross-linking agent is the same as the configuration of the composition (crosslinkable composition) obtained by the production method of the present disclosure.
  • the composition may contain at least one polyfunctional compound.
  • a polyfunctional compound is a compound having two or more functional groups with the same or different structures in one molecule.
  • Functional groups possessed by polyfunctional compounds include functional groups generally known to have reactivity, such as carbonyl groups, carboxyl groups, haloformyl groups, amide groups, olefin groups, amino groups, isocyanate groups, hydroxy groups, and epoxy groups. Any group can be used.
  • the composition may contain usual additives that are blended into elastomers, such as fillers (carbon black, barium sulfate, etc.), processing aids (wax, etc.), plasticizers, colorants, stabilizers, tackifiers, etc., if necessary.
  • additives such as imparting agents (coumarone resin, cumarone-indene resin, etc.), release agents, conductivity imparting agents, thermal conductivity imparting agents, surface non-adhesive agents, flexibility imparting agents, heat resistance improving agents, flame retardants, etc. and one or more commonly used cross-linking agents and cross-linking accelerators different from those described above may be blended.
  • the content of the filler such as carbon black is not particularly limited, but is preferably 0 to 300 parts by mass, more preferably 1 to 150 parts by mass, relative to 100 parts by mass of the fluorine-containing elastomer. It is more preferably 2 to 100 parts by mass, and particularly preferably 2 to 75 parts by mass.
  • processing aids such as wax is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, per 100 parts by mass of the fluorine-containing elastomer.
  • processing aids, plasticizers and release agents tends to reduce the mechanical properties and sealability of the resulting molded product. need to be adjusted.
  • a molded product can be obtained by molding the composition.
  • a molded article can also be obtained by molding the composition and cross-linking it.
  • the composition can be molded by a conventionally known method.
  • the method and conditions for molding and crosslinking may be within the range of known methods and conditions for molding and crosslinking to be employed.
  • the order of molding and crosslinking is not limited, and crosslinking may be performed after molding, molding may be performed after crosslinking, or molding and crosslinking may be performed simultaneously.
  • molding methods include compression molding, injection molding, injection molding, extrusion molding, and molding using a roto-curing method, but are not limited to these.
  • a steam cross-linking method, a cross-linking method by heating, a radiation cross-linking method, or the like can be employed.
  • the steam cross-linking method and the cross-linking method by heat are preferable.
  • Specific cross-linking conditions which are not limited, are usually within a temperature range of 140 to 250° C. and a cross-linking time of 1 minute to 24 hours.
  • Specific cross-linking conditions which are not limited, are usually in the temperature range of 140 to 300° C. and in the range of 30 minutes to 72 hours.
  • the resulting molded products can be used as various parts in various fields such as the automobile industry, aircraft industry, and semiconductor industry. Molded products include, for example, sealing materials, sliding members, non-adhesive members, crosslinked rubber molded products described in JP-A-2013-216915, and fluororubber molded products described in JP-A-2019-94430. can be used for
  • Examples of usage forms of molded products include various sealing materials and packings such as rings, packings, gaskets, diaphragms, oil seals, and bearing seals.
  • As a sealing material it can be used in applications requiring excellent non-adhesiveness and low friction properties. In particular, it can be suitably used for various sealing materials in the automobile industry and the like.
  • tubes hoses, rolls, various rubber rolls, flexible joints, rubber plates, coatings, belts, dampers, valves, valve seats, valve bodies, chemical-resistant coating materials, laminating materials, lining materials, etc. can.
  • Mooney viscosity was measured according to JIS K 6300-1.2013 at 100° C. using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES.
  • the mass of the polymer deposit is the mass after removing moisture contained in the polymer deposit by drying at 120°C.
  • the average particle diameter is the cumulant average diameter calculated by the method described above, the number of polymer particles (the number of fluorine-containing elastomer particles) is the number per 1 cc of water, and all fluorine-containing particles of Examples and Comparative Examples The specific gravity of the elastomer was set to 1.8.
  • the monomer (initial monomer) was pressurized so that the internal pressure of the tank was 2.03 MPaG.
  • an aqueous polymerization initiator solution prepared by dissolving 0.030 g of ammonium persulfate (APS) in deionized water was pressurized with nitrogen gas to initiate polymerization.
  • APS ammonium persulfate
  • Table 1 shows the polymer adhesion rate, the solid content concentration of the aqueous dispersion, the mass of the aqueous dispersion, the average particle size and the number of particles.
  • Table 1 shows the polymer adhesion rate, the solid content concentration of the aqueous dispersion, the mass of the aqueous dispersion, the average particle size and the number of particles.
  • Example 3 In the same manner as in Example 1, except that 0.750 g of a 10% by mass aqueous solution of CF 2 ⁇ CFOCF 2 CF 2 COONH 4 was added instead of the aqueous solution of CF 2 ⁇ CF—O—CF 2 CF 2 SO 3 Na. Polymerization was carried out.
  • Table 1 shows the polymer adhesion rate, the solid content concentration of the aqueous dispersion, the mass of the aqueous dispersion, the average particle size and the number of particles.
  • Table 1 shows the polymer adhesion rate, the solid content concentration of the aqueous dispersion, the mass of the aqueous dispersion, the average particle size and the number of particles.
  • Comparative example 1 Same as Example 1, except that the aqueous solution of CH 2 ⁇ CF—CF 2 OCF(CF 3 )COONH 4 was not added, and 0.030 g of APS aqueous solution of polymerization initiator was injected with nitrogen gas 6.0 hours after the initiation of polymerization. Polymerization was carried out with
  • Table 1 shows the polymer adhesion rate, the solid content concentration of the aqueous dispersion, the mass of the aqueous dispersion, the average particle size and the number of particles.
  • Table 1 shows the polymer adhesion rate, the solid content concentration of the aqueous dispersion, the mass of the aqueous dispersion, the average particle size and the number of particles.
  • MT carbon Thermax N-990 Cancarb TAIC: triallyl isocyanurate, Tyke Nippon Kasei Co., Ltd.
  • Perhexa 25B 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, NOF Corporation
  • a monomer (initial monomer) was injected so that the internal pressure of the tank was 1.47 MPaG.
  • an aqueous polymerization initiator solution prepared by dissolving 0.0255 g of ammonium persulfate (APS) in deionized water was pressurized with nitrogen gas to initiate polymerization.
  • APS ammonium persulfate
  • Table 3 shows the polymer adhesion rate, the solid content concentration of the aqueous dispersion, the mass of the aqueous dispersion, the average particle size and the number of particles.
  • Table 3 shows the polymer adhesion rate, the solid content concentration of the aqueous dispersion, the mass of the aqueous dispersion, the average particle size and the number of particles.
  • Example 5 and Comparative Example 3 Using the fluorine-containing elastomers obtained in Example 5 and Comparative Example 3, in the same manner as in Example 1, minimum viscosity (ML), maximum torque level (MH), induction time (T10) and optimum vulcanization time ( T90) was determined. Further, using the fluoroelastomers obtained in Example 5 and Comparative Example 3, a fluoroelastomer composition and a crosslinked molding sheet were produced in the same manner as in Example 1, and the physical properties, hardness and compression durability in the normal state were measured. Strain was measured.
  • ML minimum viscosity
  • MH maximum torque level
  • T10 induction time
  • T90 optimum vulcanization time

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Abstract

La présente invention concerne un procédé de production d'une dispersion aqueuse d'élastomère contenant du fluor dans laquelle une dispersion aqueuse d'un élastomère contenant du fluor qui comprend un groupe méthylène dans la chaîne principale est produite par polymérisation de monomères contenant du fluor en présence : d'un éther allylique contenant du fluor (1) représenté par la formule générale (1) CX11 2=CY11(-CZ11 2-O-Rf11-Y12) ; d'un éther vinylique contenant du fluor (2) représenté par la formule générale (2) CX21 2=CY21(-O-Rf21-Y22) ; et d'un milieu aqueux.
PCT/JP2022/023336 2021-06-11 2022-06-09 Procédé de production d'une dispersion aqueuse d'élastomère contenant du fluor, élastomère contenant du fluor et composition WO2022260138A1 (fr)

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WO2009119487A1 (fr) * 2008-03-26 2009-10-01 ダイキン工業株式会社 Composition d'élastomère contenant du fluor réticulable et articles moulés de celle-ci
JP2016515662A (ja) * 2013-04-22 2016-05-30 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． スルホン酸官能基を含む架橋性ポリマー
JP2021046531A (ja) * 2019-07-16 2021-03-25 ダイキン工業株式会社 含フッ素エラストマーの製造方法および組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210179861A1 (en) * 2019-12-16 2021-06-17 GM Global Technology Operations LLC Precursors for forming heterophasic odor-absorbing and anti-fouling polymeric coatings
US11674044B2 (en) * 2019-12-16 2023-06-13 GM Global Technology Operations LLC Precursors for forming heterophasic odor-absorbing and anti-fouling polymeric coatings

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