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WO2024203271A1 - Procédé de production d'élastomère contenant du fluor et élastomère contenant du fluor - Google Patents

Procédé de production d'élastomère contenant du fluor et élastomère contenant du fluor Download PDF

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Publication number
WO2024203271A1
WO2024203271A1 PCT/JP2024/009508 JP2024009508W WO2024203271A1 WO 2024203271 A1 WO2024203271 A1 WO 2024203271A1 JP 2024009508 W JP2024009508 W JP 2024009508W WO 2024203271 A1 WO2024203271 A1 WO 2024203271A1
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Prior art keywords
fluorine
diiodo compound
containing elastomer
fluoromonomer
monomer
Prior art date
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PCT/JP2024/009508
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English (en)
Japanese (ja)
Inventor
利奈 玉井
正樹 入江
綱之 奥村
志勇 王
志東 蔡
陸 山口
充 岸根
怡峰 ▲嚴▼
国良 王
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to CN202480021288.2A priority Critical patent/CN120958043A/zh
Priority to JP2024516983A priority patent/JP7759004B2/ja
Publication of WO2024203271A1 publication Critical patent/WO2024203271A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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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
    • C08F214/00—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
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—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
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F214/00—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
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • 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
    • C08F214/00—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
    • C08F214/18—Monomers containing fluorine
    • C08F214/28—Hexyfluoropropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or 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; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides

Definitions

  • This disclosure relates to a method for producing a fluorine-containing elastomer, a fluorine-containing elastomer, a crosslinkable composition, and a molded article.
  • Patent Document 1 describes a copolymer that does not contain bromine and/or iodine, which is obtained by copolymerizing a specific type of fluorine-containing vinyl compound with a specific type of alkenyl isocyanurate and/or alkenyl cyanurate, has reactive double bonds as side chains, and is essentially a non-crosslinked copolymer that can be crosslinked by free radicals under mild conditions.
  • Patent document 2 describes a method for producing liquid fluororubber that can be pumped at least at slightly elevated temperatures (60-120°C) and processed in conventional thermoplastic processing machines, in which a) vinylidene fluoride and optionally further fluorine-containing and/or fluorine-free monomers are polymerized by a free radical mechanism in the presence of b) at least one compound or a mixture thereof selected from the group consisting of diiodomethane, 1,2-diiodo-1,1-difluoroethane, 1-iodo-2-bromo-1,1-difluoroethane, 1-bromo-2-iodo-1,1-difluoroethane, 1,2-dibromo-1,1-difluoroethane, and in the presence of an initiator or further auxiliary or both, at a temperature of 0°C to 70°C.
  • the objective of this disclosure is to provide a new method for producing a fluorine-containing elastomer and a new fluorine-containing elastomer.
  • the present disclosure provides a method for producing a fluorine-containing elastomer by polymerizing a fluoromonomer and a polyfunctional non-fluorine-containing monomer in the presence of a diiodo compound to obtain a fluorine-containing elastomer.
  • the present disclosure provides a novel method for producing a fluorine-containing elastomer and a novel fluorine-containing elastomer.
  • the first manufacturing method of the present disclosure has such a configuration, and therefore can produce a fluorine-containing elastomer that can be crosslinked by peroxide crosslinking and that can be easily removed from a mold when a molded product is produced using the mold.
  • Patent Document 1 when a fluorine-containing elastomer is produced using a specific type of fluorine-containing vinyl compound and a specific type of alkenyl isocyanurate and/or alkenyl cyanurate, there is a problem in that it is difficult to produce a fluorine-containing elastomer that has sufficient crosslinking properties and gives a molded article with excellent compression set resistance.
  • Patent Document 2 when a fluorine-containing elastomer is produced using diiodomethane, there is a problem in that it is difficult to produce a fluorine-containing elastomer that gives a molded article with excellent demolding properties and compression set resistance.
  • Patent Document 3 when a fluoroelastomer is produced using a fluorovinyl ether containing a halogen atom, a fluoroelastomer with excellent properties can be produced.
  • the fluorovinyl ether described in Patent Document 3 has the problem that it is laborious to produce and expensive.
  • a method for producing a fluorine-containing elastomer it has been found that the problems of the prior art can be successfully solved by polymerizing a fluoromonomer and a polyfunctional fluorine-free monomer in the presence of a diiodo compound.
  • the fluorine-containing elastomer obtained by the first production method of the present disclosure can be crosslinked by peroxide crosslinking.
  • molded articles obtained by crosslinking the fluorine-containing elastomer obtained by the first production method of the present disclosure have excellent release properties, so that they can be produced with high productivity and also have excellent heat resistance and compression set resistance properties.
  • the diiodo compound used in the first production method may be a fluorine-containing diiodo compound (11) or a fluorine-free diiodo compound (12).
  • a diiodo compound iodine atoms can be introduced into the polymer terminals of a fluorine-containing elastomer.
  • crosslinkable iodine atoms By introducing crosslinkable iodine atoms into the polymer terminals, a fluorine-containing elastomer that can be efficiently crosslinked by peroxide crosslinking can be produced.
  • the fluorine-containing diiodo compound (11) is a compound having a fluorine atom and two iodine atoms.
  • Examples of the fluorine-containing diiodo compound (11) include 1,3-diiodoperfluoropropane, 1,4-diiodoperfluoro-n-butane, 1,3-diiodo-2-chloroperfluoropropane, 1,5-diiodo-2,4-dichloroperfluoro-n-pentane, 1,7-diiodoperfluoro-n-octane, 1,2-di(iododifluoromethyl)perfluorocyclobutane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, and 1,16-diio
  • fluorine-containing diiodo compound (11) a fluorine-containing diiodo compound having two or more carbon atoms is preferred, and 1,4-diiodoperfluoro-n-butane is more preferred.
  • the fluorine-free diiodo compound (12) is a compound that does not contain a fluorine atom and has two iodine atoms.
  • Examples of the fluorine-free diiodo compound (12) include diiodomethane, 1,2-diiodoethane, 1,3-diiodo-n-propane, and 1,2-diiodo-1,1-difluoroethane.
  • non-fluorine-containing diiodo compound (12) a non-fluorine-containing diiodo compound having one carbon atom is preferable, and diiodomethane is more preferable.
  • a non-fluorine-containing diiodo compound having a small carbon atom number is preferable, and the production cost of the fluorine-containing elastomer can be reduced.
  • both the fluorine-containing diiodo compound (11) and the fluorine-free diiodo compound (12) are used. This allows the fluorine-containing elastomer to be produced more cheaply than a manufacturing method that uses only a fluorine-containing diiodo compound as a chain transfer agent.
  • a fluoromonomer is polymerized in the presence of a diiodo compound (1), and then the fluoromonomer is polymerized in the presence of a non-fluorine-containing diiodo compound (12).
  • the diiodo compound (1) may be added all at once or continuously.
  • the timing of adding the diiodo compound (1) is not particularly limited, but it is preferable to add at least a portion of the diiodo compound (1) until a mass of the fluorine-containing elastomer equivalent to 10 mass% of the mass of the finally obtained fluorine-containing elastomer is produced.
  • the non-fluorine-containing diiodo compound (12) may be added all at once or continuously.
  • the timing of adding the non-fluorine-containing diiodo compound (12) is not particularly limited, but it is preferable to add at least a portion of the non-fluorine-containing diiodo compound (12) after a mass of the fluorine-containing elastomer equivalent to 30 to 90 mass% of the mass of the finally obtained fluorine-containing elastomer is produced.
  • a fluoromonomer is polymerized in the presence of diiodo compound (1) until a mass of fluoroelastomer equivalent to 30 to 90 mass% of the mass of the finally obtained fluoroelastomer is produced, and then the fluoromonomer is polymerized in the presence of non-fluorine-containing diiodo compound (12).
  • the polymerization of the fluoromonomer in the presence of the diiodo compound (1) is carried out until a mass of the fluoroelastomer corresponding to preferably 30 to 90 mass%, more preferably 40 mass% or more, and more preferably 80 mass% or less is produced, based on the mass of the final fluoroelastomer.
  • a fluoromonomer is polymerized in the presence of a fluorine-containing diiodo compound (11), and then the fluoromonomer is polymerized in the presence of a fluorine-free diiodo compound (12).
  • diiodomethane is known as a chain transfer agent used in the production method of a fluorine-containing elastomer, as described in Patent Document 2.
  • the reaction rate is low, especially in the early stage of the polymerization reaction, and it is difficult to produce the fluorine-containing elastomer with high productivity.
  • the amount of initiator is significantly increased to increase productivity, the iodine group at the polymer end is replaced by the initiator end, and the compression set resistance property is reduced.
  • a fluorine-containing diiodo compound (11) By polymerizing a fluoromonomer in the presence of a fluorine-containing diiodo compound (11), and then polymerizing the fluoromonomer in the presence of a fluorine-free diiodo compound (12), a fluorine-containing elastomer that can be crosslinked by peroxide crosslinking can be produced with high productivity, and the fluorine-containing elastomer can be produced more cheaply than a production method that uses only a fluorine-containing diiodo compound as a chain transfer agent.
  • a fluoromonomer is polymerized in the presence of a fluorine-containing diiodo compound (11) until a mass of a fluoroelastomer equivalent to 30 to 90 mass% of the mass of the finally obtained fluoroelastomer is produced, and then the fluoromonomer is polymerized in the presence of a fluorine-free diiodo compound (12).
  • a fluoroelastomer that can be crosslinked by peroxide crosslinking with higher productivity, and also makes it possible to produce a fluoroelastomer at a lower cost than a production method that uses only a fluorine-containing diiodo compound as a chain transfer agent.
  • the polymerization of the fluoromonomer in the presence of the fluorine-containing diiodo compound (11) is carried out until a mass of the fluoroelastomer corresponding to preferably 30 to 90 mass%, more preferably 40 mass% or more, more preferably 80 mass% or less is produced, based on the mass of the final fluoroelastomer.
  • the amount of the diiodo compound (when both a fluorine-containing diiodo compound and a fluorine-free diiodo compound are used, the total amount of these) is preferably 0.2 ⁇ 10 ⁇ 3 to 2 mol %, more preferably 1.0 ⁇ 10 ⁇ 3 mol % or more, and more preferably 1 mol % or less, based on the total amount of monomers used in the polymerization.
  • the amount of the fluorine-containing diiodo compound (11) is preferably 0.2 ⁇ 10 ⁇ 3 to 2 mol %, more preferably 1.0 ⁇ 10 ⁇ 3 mol % or more, and more preferably 1 mol % or less, based on the total amount of monomers used in the polymerization.
  • the amount of the fluorine-free diiodo compound (12) is preferably 0.2 ⁇ 10 ⁇ 3 to 2 mol %, more preferably 1.0 ⁇ 10 ⁇ 3 mol % or more, and more preferably 1 mol % or less, based on the total amount of monomers used in the polymerization.
  • the polyfunctional fluorine-free monomer used in the first manufacturing method is a monomer having two or more functional groups and not containing a fluorine atom.
  • a polyfunctional fluorine-free monomer unit can be introduced into the fluorine-containing elastomer.
  • the polyfunctional fluorine-free monomer unit in the fluorine-containing elastomer gives the fluorine-containing elastomer a branched structure or functions as a site that can be crosslinked by peroxide crosslinking.
  • the polyfunctional non-fluorine-containing monomer has two or more functional groups.
  • the number of functional groups in the polyfunctional non-fluorine-containing monomer is preferably 2 to 6, more preferably 3 or more, more preferably 5 or less, and even more preferably 4 or less.
  • the number of functional groups in the polyfunctional non-fluorine-containing monomer is particularly preferably 3.
  • the polyfunctional non-fluorine-containing monomer preferably has an unsaturated functional group.
  • the unsaturated functional group is a functional group having an unsaturated bond such as a carbon-carbon double bond.
  • the unsaturated functional group is preferably at least one selected from the group consisting of a vinyl group, an isopropenyl group, an allyl group, and a methallyl group, and more preferably at least one selected from the group consisting of an allyl group and a methallyl group.
  • the polyfunctional non-fluorine-containing monomer preferably has a nitrogen-containing heterocycle.
  • the number of members of the nitrogen-containing heterocycle is preferably 4 to 10, and more preferably 6.
  • the number of nitrogen atoms forming the nitrogen-containing heterocycle is preferably 1 to 5, and more preferably 3.
  • the nitrogen-containing heterocycle is preferably a 6-membered ring formed by three carbon atoms and three nitrogen atoms, and more preferably a 1,3,5-triazine ring.
  • polyfunctional non-fluorine-containing monomers examples include triallyl cyanurate, triallyl isocyanurate (TAIC), trimethallyl isocyanurate, tris(diallylamine-s-triazine), triallyl phosphite, N,N-diallyl acrylamide, hexaallyl phosphoramide, N,N,N',N'-tetraallyl tetraphthalamide, N,N,N',N'-tetraallyl malonamide, trivinyl isocyanurate, 2,4,6-trivinylmethyltrisiloxane, and tri(5-norbornene-2-methylene) cyanurate.
  • TAIC triallyl isocyanurate
  • trimethallyl isocyanurate trimethallyl isocyanurate
  • triallyl phosphite examples include triallyl cyanurate, triallyl is
  • polyfunctional non-fluorine-containing monomer at least one selected from the group consisting of triallyl isocyanurate and trimethallyl isocyanurate is preferred.
  • the polyfunctional non-fluorine-containing monomer may be added all at once or continuously.
  • the timing of adding the polyfunctional non-fluorine-containing monomer is not particularly limited. In the case of polymerizing a fluoromonomer in the presence of a diiodo compound (1) and then polymerizing the fluoromonomer in the presence of a fluorine-free diiodo compound (12), it is preferable to add at least a part of the polyfunctional non-fluorine-containing monomer when polymerizing the fluoromonomer in the presence of the diiodo compound (1), and it is more preferable to add the polyfunctional non-fluorine-containing monomer after adding the diiodo compound (1) to the polymerization system. This makes it easy to produce a fluorine-containing elastomer having excellent mold releasability and excellent moldability.
  • the amount of polyfunctional non-fluorine-containing monomer is preferably 0.005 to 0.2 mol %, more preferably 0.01 mol % or more, and more preferably 0.1 mol % or less, based on the total amount of monomers used in the polymerization.
  • the molar ratio of the amount of the polyfunctional non-fluorine-containing monomer to the amount of the diiodo compound (polyfunctional non-fluorine-containing monomer/diiodo compound) is preferably 0.01 to 1.0, more preferably 0.05 or more, and more preferably 0.5 or less. If the amount of the polyfunctional non-fluorine-containing monomer used is too large compared to the amount of the diiodo compound used, the resulting fluorine-containing elastomer tends to gel. In addition, when the resulting fluorine-containing elastomer is crosslinked to produce a crosslinked sheet, the crosslinked sheet tends to warp, making it difficult to produce a molded product having the desired shape.
  • the fluoromonomer used in the first production method is a monomer containing a fluorine atom.
  • PMVE perfluoro(methyl vinyl ether)
  • PEVE perfluoro(ethyl vinyl ether)
  • PPVE perfluoro(propyl vinyl ether)
  • a perfluorovinyl ether represented by the formula: CF 2 ⁇ CFOCF 2 ORf c (wherein Rf c is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, or a linear or branched perfluorooxyalkyl group having 2 to 6 carbon atoms and containing 1 to 3 oxygen atoms).
  • Rf c is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, or a linear or branched perfluorooxyalkyl group having 2 to 6 carbon atoms and containing 1 to 3 oxygen atoms.
  • Rf c is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5
  • Rf 31 is a linear fluoroalkyl group
  • Rf 31 is a linear perfluoroalkyl group
  • Rf 31 preferably has 1 to 6 carbon atoms.
  • Examples of the fluoromonomer ( 2) include CH 2 ⁇ CFCF 3 , CH 2 ⁇ CFCF 2 CF 3 , CH 2 ⁇ CFCF 2 CF 2 CF 3 , CHF ⁇ CHCF 3 (1,3,3,3-tetrafluoropropene), CHF ⁇ CHCF 3 (E form), and CHF ⁇ CHCF 3 (Z form), and among these, 2,3,3,3 - tetrafluoropropylene represented by CH 2 ⁇ CFCF 3 is preferred.
  • the fluoromonomer used in the first manufacturing method preferably contains at least one selected from the group consisting of vinylidene fluoride and tetrafluoroethylene, and more preferably contains vinylidene fluoride.
  • the polymerization in the first production method can be carried out, for example, by charging a surfactant and an aqueous medium into a pressure-resistant polymerization tank equipped with a stirrer, deoxidizing, charging a monomer, bringing the temperature to a predetermined level, adding a polymerization initiator to start the reaction, and charging a diiodo compound during the polymerization reaction. Since the pressure decreases as the reaction proceeds, additional monomer is continuously or intermittently supplied to maintain the initial pressure, and when a predetermined amount of monomer has been supplied, the supply is stopped, the monomer in the reaction tank is purged, and the temperature is returned to room temperature to terminate the reaction.
  • the polymerization in the first manufacturing method can be carried out in the presence of a polymerization initiator.
  • the polymerization initiator include radical polymerization initiators.
  • radical polymerization initiators There are no particular limitations on the polymerization initiator as long as it can generate radicals at the polymerization temperature, and oil-soluble polymerization initiators, water-soluble polymerization initiators, etc. can be used, with water-soluble polymerization initiators being preferred.
  • the polymerization initiator may also be used as a redox initiator in combination with a reducing agent, etc.
  • the amount of polymerization initiator is appropriately determined depending on the type of monomer, the molecular weight of the desired fluorine-containing elastomer, and the reaction rate.
  • the amount of polymerization initiator is appropriately determined depending on the molecular weight of the desired fluorine-containing elastomer and the polymerization reaction rate, but is preferably 0.00001 to 10 mass%, and more preferably 0.0001 to 1 mass%, relative to 100 mass% of the total amount of monomers.
  • an oil-soluble radical polymerization initiator a water-soluble radical polymerization initiator, or an azo compound can be used.
  • the oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, for example, dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and disec-butyl peroxydicarbonate, peroxyesters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate, dialkyl peroxides such as di-t-butyl peroxide, and also di( ⁇ -hydro-dodecafluoroheptanoyl) peroxide, di( ⁇ -hydro-tetradecafluorooctanoyl) peroxide, di( ⁇ -hydro-hexadecafluorononanoyl) peroxide, di(perfluorobutyryl) peroxide, di(perfluorovaleryl) peroxide, di(perfluorohexanoyl) peroxide, di(perfluoroheptanoyl) peroxide, di(per
  • Azo compounds include azodicarboxylate, azodicarboxyldiamide, 2,2'-azobisisobutyronitrile, 2,2'-azobis2,4-dimethylvaleronitrile, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and 4,4'-azobis(4-cyanovaleric acid).
  • the water-soluble radical polymerization initiator may be a known water-soluble peroxide, such as ammonium, potassium, or sodium salts of persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, or percarbonic acid; organic peroxides such as disuccinic acid peroxide or diglutaric acid peroxide; t-butyl permaleate; or t-butyl hydroperoxide.
  • a reducing agent such as sulfites may also be included, and the amount used may be 0.1 to 20 times the amount of the peroxide.
  • a salt of persulfuric acid is preferable because the amount of radicals generated can be easily adjusted.
  • Potassium persulfate (K 2 S 2 O 8 ), ammonium persulfate ((NH 4 ) 2 S 2 O 8 ), and sodium persulfate (Na 2 S 2 O 8 ) are preferable, and ammonium persulfate is most preferable.
  • a redox initiator that combines an oxidizing agent and a reducing agent as the polymerization initiator.
  • Oxidizing agents include persulfates, organic peroxides, potassium permanganate, manganese triacetate, cerium ammonium nitrate, bromates, etc.
  • Reducing agents include sulfites, bisulfites, bromates, diimines, oxalic acid, and metal sulfinates.
  • Persulfates include ammonium persulfate, potassium persulfate, and sodium persulfate.
  • Sulfites include sodium sulfite and ammonium sulfite.
  • a copper salt or an iron salt to the combination of redox initiators.
  • copper salt copper(II) sulfate
  • iron salt iron(II) sulfate
  • a chelating agent is disodium ethylenediaminetetraacetate dihydrate.
  • 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, and hydrogen peroxide/ascorbic acid (described in JP-A-55-102615), with ammonium persulfate/sodium hydroxymethanesulfinate dihydrate being preferred.
  • either the oxidizing agent or the reducing agent may be charged in advance to 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 to 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 in the polymerization tank and continuously add sodium hydroxymethanesulfinate dihydrate to it.
  • 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 particularly preferably 0.05 to 1.0% by mass, based on the aqueous medium used in the polymerization.
  • the amount of the reducing agent used is preferably 0.01 to 30% by mass, more preferably 0.05 to 10% by mass, and particularly preferably 0.1 to 5% by mass, relative to the aqueous medium used in the 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, and particularly preferably 0.01 to 0.3% by mass, based on the aqueous medium used in the polymerization.
  • the polymerization in the first manufacturing method can be carried out in the presence of a surfactant.
  • the surfactant may be either a reactive surfactant or a non-reactive surfactant.
  • the surfactant may also be either a fluorine-containing surfactant or a non-fluorine-containing surfactant.
  • the surfactant may also be either an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant.
  • the polymerization in the first manufacturing method can also be carried out in the absence of a surfactant, as described in WO 2007/129735.
  • the polymerization in the first production method can be carried out in an aqueous medium.
  • the aqueous medium means a liquid containing water.
  • the aqueous medium is not particularly limited as long as it contains water, and may contain water and, for example, a fluorine-free organic solvent such as an alcohol, ether, or ketone, and/or a fluorine-containing organic solvent having a boiling point of 40°C or less.
  • the polymerization temperature in the first manufacturing method is preferably 10 to 120°C.
  • the polymerization pressure in the first manufacturing method is preferably 0.5 to 10 MPaG.
  • the first manufacturing method provides a fluorine-containing elastomer.
  • the fluorine-containing elastomer provided by the first manufacturing method has a multimodal molecular weight distribution.
  • the fluorine-containing elastomer provided by the first manufacturing method has a bimodal molecular weight distribution. It is preferable that the fluorine-containing elastomer has a bimodal molecular weight distribution in which the ratio ((A)/(B)) of the area of the peak on the high molecular weight side appearing in the GPC curve (A) to the area of the peak on the low molecular weight side (B) is 90/10 to 30/70.
  • the fluorine-containing elastomer has such a molecular weight distribution, it is possible to obtain a molded product having excellent releasability, heat resistance, and compression set resistance, and the moldability of the fluorine-containing elastomer is improved.
  • the ratio ((A)/(B)) of the fluorine-containing elastomer obtained by the first production method is preferably 90/10 to 30/70, more preferably 80/20 or less, and more preferably 40/60 or more.
  • an aqueous dispersion containing a fluorine-containing elastomer is usually obtained.
  • the aqueous dispersion of the fluorine-containing elastomer may be subjected to treatments such as coagulation and heating.
  • the 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, and acetates of calcium, magnesium, aluminum, etc.
  • the coagulated fluorine-containing elastomer may be washed with water to remove small amounts of impurities such as buffer solutions and salts 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, and even 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, pellets, etc., and is preferably gum or crumb.
  • Gum is a small granular mass of fluorine-containing elastomer
  • crumb is an amorphous mass formed when the fluorine-containing elastomer cannot maintain its small granular shape as a gum at room temperature and melts together.
  • Gum or crumb is preferably obtained by coagulating, drying, etc., the aqueous dispersion obtained by the manufacturing method disclosed herein using a conventional method.
  • a fluorine-containing elastomer According to the first production method, a fluorine-containing elastomer can be obtained.
  • the fluorine-containing elastomer has an iodine content of 0.1 to 1.0 mass % and contains a fluoromonomer unit and a polyfunctional non-fluorine-containing monomer unit.
  • the fluorine-containing elastomer according to one embodiment of the present disclosure has such a configuration, it can be crosslinked by peroxide crosslinking to obtain a molded article, and furthermore, when a molded article is produced using a mold, it can be easily removed from the mold. Therefore, by using the fluorine-containing elastomer of the present disclosure, beautiful molded articles can be produced with high productivity. Furthermore, molded articles obtained from the fluorine-containing elastomer of the present disclosure also have excellent heat resistance and compression set resistance properties.
  • the iodine content in the fluorine-containing elastomer is 0.05 to 2.0% by mass, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 1.5% by mass or less, more preferably 1.0% by mass or less.
  • the iodine content in fluorine-containing elastomers can be measured by elemental analysis.
  • the polyfunctional non-fluorine-containing monomer unit in the fluorine-containing elastomer is a repeating unit based on a polyfunctional non-fluorine-containing monomer.
  • Examples of the polyfunctional non-fluorine-containing monomer include the polyfunctional non-fluorine-containing monomer used in the first production method, and similar ones are preferred.
  • the content of the polyfunctional non-fluorine-containing monomer units is preferably 0.005 to 0.2 mol %, more preferably 0.01 mol % or more, and more preferably 0.1 mol % or less, based on the total monomer units.
  • the fluorine-containing elastomer may be obtained by polymerizing a polyfunctional non-fluorine-containing monomer in an amount corresponding to preferably 0.005 to 0.2 mol %, more preferably 0.01 mol % or more, more preferably 0.1 mol % or less, based on the total monomer units of the fluorine-containing elastomer.
  • the content of polyfunctional non-fluorine-containing monomer units in a fluorine-containing elastomer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of monomer.
  • the fluoromonomer units in the fluorine-containing elastomer are repeating units based on a fluoromonomer.
  • Examples of the fluoromonomer include the fluoromonomers used in the first production method, and similar ones are preferred.
  • the fluorine-containing elastomer has a multimodal molecular weight distribution. In another embodiment, the fluorine-containing elastomer has a bimodal molecular weight distribution. It is preferable that the fluorine-containing elastomer has a bimodal molecular weight distribution in which the ratio ((A)/(B)) of the area of the peak on the high molecular weight side appearing in the GPC curve (A) to the area of the peak on the low molecular weight side (B) is 90/10 to 30/70.
  • the fluorine-containing elastomer has such a molecular weight distribution, it is possible to obtain a molded product having excellent releasability, heat resistance, and compression set resistance, and the moldability of the fluorine-containing elastomer is improved.
  • the ratio of the fluorine-containing elastomers ((A)/(B)) is preferably 90/10 to 30/70, more preferably 80/20 or less, and more preferably 40/60 or more.
  • the fluorine-containing elastomer may be a fully fluorinated elastomer or a partially fluorinated elastomer. In one embodiment, the fluorine-containing elastomer is a partially fluorinated elastomer.
  • a partially fluorinated elastomer is a fluoropolymer that contains fluoromonomer units and has a perfluoromonomer unit content of less than 90 mol% relative to the total monomer units, has a glass transition temperature of 20°C or less, and has a melting peak ( ⁇ H) magnitude of 4.5 J/g or less.
  • a perfluoromonomer is a monomer that does not contain a carbon atom-hydrogen atom bond in the molecule.
  • perfluoromonomers may be monomers in which some of the fluorine atoms bonded to carbon atoms have been replaced with chlorine atoms, and may also have nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, boron atoms, or silicon atoms in addition to carbon atoms.
  • a perfluoromonomer is preferably a monomer in which all hydrogen atoms have been replaced with fluorine atoms. Perfluoromonomers do not include monomers that provide crosslinkable groups.
  • the fluorine-containing elastomer preferably contains a monomer unit based on at least one monomer selected from the group consisting of tetrafluoroethylene (TFE), vinylidene fluoride (VdF), and a perfluoroethylenically unsaturated compound represented by the general formula: CF 2 ⁇ CF-Rf a (wherein Rf a is -CF 3 or -ORf b (Rf b is a perfluoroalkyl group having 1 to 5 carbon atoms)) (e.g., hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE) etc.).
  • the fluorine-containing elastomer preferably contains a VdF unit or a TFE unit, and more preferably contains a VDF unit.
  • fluorine-containing elastomers include VdF-based fluorine-containing elastomers, TFE/propylene (Pr)-based fluorine-containing elastomers, TFE/Pr/VdF-based fluorine-containing elastomers, ethylene (Et)/HFP-based fluorine-containing elastomers, Et/HFP/VdF-based fluorine-containing elastomers, Et/HFP/TFE-based fluorine-containing elastomers, and Et/TFE/PAVE-based fluorine-containing elastomers.
  • VdF-based fluorine-containing elastomers are more preferred in terms of good heat aging resistance and oil resistance.
  • the VdF-based fluorine-containing elastomer is a fluorine-containing elastomer having VdF units.
  • the content of VdF units in the fluorine-containing elastomer is preferably 20 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, and particularly preferably 60 mol% or more, based on the total number of monomer units.
  • the VdF units preferably account for 20 mol% or more and 90 mol% or less of the total number of moles of VdF units and monomer units based on other monomers, more preferably 40 mol% or more and 85 mol% or less, even more preferably 45 mol% or more and 80 mol% or less, and particularly preferably 50 mol% or more and 80 mol% or less.
  • the other monomers in the VdF-based fluorine-containing elastomer are not particularly limited as long as they are copolymerizable with VdF, and for example, the fluoromonomers mentioned above can be used.
  • the VdF-based fluorine-containing elastomer is preferably at least one copolymer selected from the group consisting of VdF/HFP copolymer, VdF/TFE/HFP copolymer, VdF/CTFE copolymer, VdF/CTFE/TFE copolymer, VdF/PAVE copolymer, VdF/TFE/PAVE copolymer, VdF/HFP/PAVE copolymer, VdF/HFP/TFE/PAVE copolymer, VdF/TFE/Pr copolymer, VdF/Et/HFP copolymer, and VdF/fluoromonomer (2) copolymer.
  • the fluoromonomer other than VdF has at least one fluoromonomer selected from the group consisting of TFE, HFP, and PAVE.
  • the VdF-based fluorine-containing elastomer is preferably at least one copolymer selected from the group consisting of VdF/HFP copolymer, VdF/TFE/HFP copolymer, VdF/fluoromonomer (2) copolymer, VdF/PAVE copolymer, VdF/TFE/PAVE copolymer, VdF/HFP/PAVE copolymer, and VdF/HFP/TFE/PAVE copolymer, and more preferably at least one copolymer selected from the group consisting of VdF/HFP copolymer, VdF/HFP/TFE copolymer, VdF/fluoromonomer (2) copolymer, and VdF/PAVE copolymer.
  • the VdF/PAVE copolymer preferably has a VdF/PAVE composition of (65 to 90)/(35 to 10) (mol %). In addition, it is also one of the preferred embodiments that the VdF/PAVE composition is (50 to 78)/(50 to 22) (mol %).
  • VdF/TFE/PAVE copolymer one having a VdF/TFE/PAVE composition of (40-80)/(3-40)/(15-35) (mol%) is preferred.
  • VdF/HFP/PAVE copolymer one having a VdF/HFP/PAVE composition of (65-90)/(3-25)/(3-25) (mol%) is preferred.
  • VdF/HFP/TFE/PAVE copolymer one having a VdF/HFP/TFE/PAVE composition of (40-90)/(0-25)/(0-40)/(3-35) (mol%) is preferred, and one having a VdF/HFP/TFE/PAVE composition of (40-80)/(3-25)/(3-40)/(3-25) (mol%) is more preferred.
  • VdF/fluoromonomer (2) As a copolymer of VdF/fluoromonomer (2), it is preferable that the VdF/fluoromonomer (2) units are (85-20)/(15-80) (mol%) and that monomer units other than VdF and fluoromonomer (2) account for 0-50 mol% of the total monomer units, and it is more preferable that the molar ratio of VdF/fluoromonomer (2) units is (80-20)/(20-80). In addition, one preferred embodiment is that the composition of VdF/fluoromonomer (2) units is (78-50)/(22-50) (mol%).
  • VdF/fluoromonomer (2) one in which the VdF/fluoromonomer (2) units are (85-50)/(15-50) (mol%) and the other monomer units other than VdF and fluoromonomer (2) are 1-50 mol% of the total monomer units is also preferred.
  • VdF and fluoromonomer (2) preferred are the monomers exemplified as other monomers in the VdF-based fluorine-containing elastomer, such as TFE, HFP, PMVE, perfluoroethyl vinyl ether (PEVE), PPVE, CTFE, trifluoroethylene, hexafluoroisobutene, vinyl fluoride, Et, Pr, alkyl vinyl ether, and monomers that provide crosslinkable groups, and among these, PMVE, CTFE, HFP, and TFE are more preferred.
  • TFE/Pr-based fluorine-containing elastomer refers to a fluorine-containing copolymer consisting of 45-70 mol% TFE and 55-30 mol% Pr. In addition to these two components, it may contain a specific third component.
  • the specific third component may include, for example, fluoromonomers such as 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.); hydrocarbon monomers such as ⁇ -olefins (ethylene, 1-butene, etc.), vinyl ethers (ethyl vinyl ether, butyl vinyl ether, hydroxybutyl vinyl ether, etc.), and vinyl esters (vinyl acetate, vinyl benzoate, vinyl crotonate, vinyl methacrylate, etc.); and the like.
  • the specific third component may be one type, or two or more types may be used in combination.
  • TFE/Pr-based fluorine-containing elastomers preferably contain VdF, and among TFE/Pr-based fluorine-containing elastomers, elastomers consisting of TFE, Pr, and VdF are called TFE/Pr/VdF-based fluorine-containing elastomers.
  • the TFE/Pr/VdF-based fluorine-containing elastomer may further contain the specific third component other than VdF.
  • the specific third component may be one type or a combination of two or more types.
  • the total content of the third components in the TFE/Pr-based 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 (35-80)/(65-20) (mol%), and more preferably has an Et/HFP composition of (40-75)/(60-25) (mol%).
  • the Et/HFP/TFE copolymer preferably has an Et/HFP/TFE composition of (35-75)/(25-50)/(0-15) (mol%), and more preferably has an Et/HFP/TFE composition of (45-75)/(25-45)/(0-10) (mol%).
  • the Et/TFE/PAVE copolymer preferably has a composition of Et/TFE/PAVE of (10-40)/(32-60)/(20-40) (mol%), and more preferably (20-40)/(40-50)/(20-30) (mol%). PMVE is preferred as the PAVE.
  • a fluorine-containing elastomer containing VdF units is preferred, a VdF/HFP copolymer or a VdF/HFP/TFE copolymer is more preferred, and a VdF/HFP/TFE composition of (32-85)/(10-34)/(0-40) (mol%) is particularly preferred.
  • the VdF/HFP/TFE composition is more preferably (32-85)/(15-34)/(0-34) (mol%), and even more preferably (47-81)/(17-32)/(0-28) (mol%).
  • the VdF/HFP composition is preferably (45-85)/(15-55) (mol%), more preferably (50-83)/(17-50) (mol%), even more preferably (55-81)/(19-45) (mol%), and particularly preferably (60-80)/(20-40) (mol%).
  • the above-mentioned structure is the structure of the main monomer of the fluorine-containing elastomer, and does not include the content of polyfunctional non-fluorine-containing monomer units.
  • a monomer that provides a crosslinkable group (excluding polyfunctional non-fluorine-containing monomers) may be copolymerized.
  • the monomer that provides a crosslinkable group may be any monomer that can introduce an appropriate crosslinkable group into the fluorine-containing elastomer depending on the production method and crosslinking system, and examples of such monomers include known polymerizable compounds that include crosslinkable groups such as iodine atoms, bromine atoms, carbon-carbon double bonds, cyano groups, carboxyl groups, hydroxyl groups, amino groups, and ester groups.
  • R f 3 is a linear or branched fluorine-containing alkylene group which may have one or more ether-bonded oxygen atoms and in which some or all of the hydrogen atoms are substituted with fluorine atoms, i.e., a linear or branched fluorine-containing alkylene group in which some or all of the hydrogen atoms are substituted with fluorine atoms, a linear or branched fluorine-containing oxyalkylene group in which some or all of the hydrogen atoms are substituted with fluorine atoms, or a linear or branched fluorine-containing polyoxyalkylene group in which some or all of the hydrogen atoms are substituted with fluorine atoms; R 1 is
  • CF 2 CFCF 2 R f 4 -X 1 (6)
  • R 4 is -(OCF 2 ) n - or -(OCF(CF 3 )) n -, where n is an integer of 0 to 5.
  • CF 2 CFCF 2 (OCF(CF 3 )CF 2 ) m (OCH 2 CF 2 CF 2 ) n OCH 2 CF 2 -X 1 (7)
  • m is an integer from 0 to 5, and n is an integer from 0 to 5).
  • CF 2 CFCF 2 (OCH 2 CF 2 CF 2 ) m (OCF(CF 3 )CF 2 ) n OCF(CF 3 )-X 1 (8) (In the formula, m is an integer from 0 to 5, and n is an integer from 0 to 5).
  • CF 2 CF (OCF 2 CF (CF 3 )) m O (CF 2 ) n ⁇ X 1 (9) (wherein m is an integer from 0 to 5, and n is an integer from 1 to 8).
  • CF 2 CF (OCF 2 CF (CF 3 )) m ⁇ X 1 (10) (wherein m is an integer from 1 to 5).
  • CF 2 CFOCF 2 (CF(CF 3 )OCF 2 ) n CF(-X 1 )CF 3 (11) (wherein n is an integer from 1 to 4).
  • CF 2 CFO(CF 2 ) n OCF(CF 3 )-X 1 (12) (wherein n is an integer from 2 to 5).
  • CF 2 CFO(CF 2 ) n -(C 6 H 4 )-X 1 (13) (wherein n is an integer from 1 to 6)
  • CF 2 CF(OCF 2 CF(CF 3 )) n OCF 2 CF(CF 3 ) ⁇ X 1 (14) (wherein n is an integer of 1 to 2).
  • CH2 CFCF2OCF ( CF3 )OCF( CF3 ) -X1 (17)
  • CH2 CFCF2OCH2CF2 - X1 ( 18 )
  • CF 2 CFO(CF 2 CF (CF 3 )O) m CF 2 CF (CF 3 )-X 1 (19) (In the formula, m is an integer of 0 or more).
  • CF 2 CFOCF(CF 3 )CF 2 O(CF 2 ) n ⁇ X 1 (20) (In the formula, n is an integer of 1 or more).
  • CF 2 CFOCF 2 OCF 2 CF(CF 3 )OCF 2 -X 1 (21)
  • CH 2 CH-(CF 2 ) n X 1 (22) (wherein n is an integer from 2 to 8).
  • X1 is the same as above.
  • the iodine- or bromine-containing monomer represented by the general formula (4) may be a monomer represented by the general formula (23): (wherein m is an integer from 1 to 5, and n is an integer from 0 to 3).
  • Preferred examples of the iodine-containing fluorinated vinyl ethers include those represented by the following formula: Among these, ICH 2 CF 2 CF 2 OCF ⁇ CF2 is preferred.
  • preferred examples of the iodine- or bromine-containing monomer represented by the general formula (5) include ICF 2 CF 2 CF ⁇ CH 2 and I(CF 2 CF 2 ) 2 CF ⁇ CH 2 .
  • a more specific example of the iodine- or bromine-containing monomer represented by the general formula (9) is I(CF 2 CF 2 ) 2 OCF ⁇ CF 2 .
  • preferred examples of the iodine- or bromine-containing monomer represented by the general formula (22) include CH 2 ⁇ CHCF 2 CF 2 I and I(CF 2 CF 2 ) 2 CH ⁇ CH 2 .
  • R 2 R 3 C ⁇ CR 4 -Z—CR 5 ⁇ CR 6 R 7 (wherein R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and all are H or an alkyl group having 1 to 5 carbon atoms; Z is a linear or branched alkylene or cycloalkylene group which may contain an oxygen atom and is preferably at least partially fluorinated having 1 to 18 carbon atoms, or a (per)fluoropolyoxyalkylene group) is also preferred as a monomer which provides a crosslinkable group.
  • the term "(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 - (wherein 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 are integers such that the m/n ratio is 0.2 to 5 and the molecular weight of the (per)fluoropolyoxyalkylene group is in the range of 500 to 10,000, preferably 1,000 to 4,000.)
  • 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-containing elastomer preferably has a fluorine content of 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, and more preferably 73% by mass or less.
  • the fluorine content is calculated based on values measured by 19 F-NMR, 1 H-NMR, elemental analysis, etc.
  • the Mooney viscosity (ML1+10(121°C)) of the fluorine-containing elastomer at 121°C is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, and particularly preferably 10 or more. It is also preferably 200 or less, more preferably 170 or less, even more preferably 150 or less, even more preferably 130 or less, and particularly preferably 100 or less. Mooney viscosity is measured in accordance with ASTM D1646 and JIS K6300-1.
  • the number average molecular weight of the fluorine-containing elastomer is preferably 1,000 to 300,000, and more preferably 10,000 to 200,000.
  • the number average molecular weight is measured by gel permeation chromatography (GPC).
  • the weight average molecular weight of the fluorine-containing elastomer is preferably 1,500 to 450,000, and more preferably 15,000 to 300,000.
  • the weight average molecular weight is measured by gel permeation chromatography (GPC).
  • the glass transition temperature of the fluorine-containing elastomer is preferably -50 to 0°C.
  • the glass transition temperature is more preferably -2°C or lower, and even more preferably -3°C or lower.
  • the glass transition temperature is more preferably -45°C or higher, and even more preferably -40°C or higher.
  • the glass transition temperature may be -10°C or higher, or may be -9°C or higher.
  • the glass transition temperature can be determined from the DSC differential curve by heating 10 mg of a sample at 20°C/min using a differential scanning calorimeter (e.g., X-DSC7000 manufactured by Hitachi High-Tech Science Corporation).
  • a fluoromonomer is polymerized in the presence of a fluorine-containing diiodo compound (11), and then the fluoromonomer is polymerized in the presence of a fluorine-free diiodo compound (12) to obtain a fluorine-containing elastomer.
  • Diiodomethane has been known as a chain transfer agent used in the production method of fluorine-containing elastomers, as described in Patent Document 2.
  • fluorine-containing elastomers are produced using diiodomethane, there is a problem that the reaction rate is low, particularly in the early stages of the polymerization reaction, making it difficult to produce fluorine-containing elastomers with high productivity.
  • fluorine-containing elastomers that give molded articles with excellent compression set resistance.
  • the second manufacturing method of the present disclosure has the above-mentioned configuration, and therefore can produce a fluorine-containing elastomer that can be crosslinked by peroxide crosslinking with high productivity, and can produce a fluorine-containing elastomer more cheaply than a manufacturing method that uses only a fluorine-containing diiodo compound as a chain transfer agent. Furthermore, the molded article obtained by crosslinking the fluorine-containing elastomer obtained by the first manufacturing method of the present disclosure also has excellent heat resistance and compression set resistance.
  • the fluorine-containing diiodo compound (11) used in the second manufacturing method is a compound having a fluorine atom and two iodine atoms.
  • Examples of the fluorine-containing diiodo compound (11) include the fluorine-containing diiodo compound (11) used in the first manufacturing method, and similar compounds are preferred.
  • the fluorine-containing diiodo compound (11) may be added all at once or continuously.
  • the timing of adding the fluorine-containing diiodo compound (11) is not particularly limited, but it is preferable to add at least a portion of the fluorine-containing diiodo compound (11) until a mass of the fluorine-containing elastomer equivalent to 10 mass% of the mass of the finally obtained fluorine-containing elastomer is produced.
  • the fluorine-free diiodo compound (12) used in the second manufacturing method is a compound that does not contain a fluorine atom and has two iodine atoms.
  • Examples of the fluorine-free diiodo compound (12) include the fluorine-free diiodo compound (12) used in the first manufacturing method, and similar compounds are preferred.
  • the non-fluorine-containing diiodo compound (12) may be added all at once or continuously.
  • the timing of adding the non-fluorine-containing diiodo compound (12) is not particularly limited, but it is preferable to add at least a portion of the non-fluorine-containing diiodo compound (12) after a mass of the fluorine-containing elastomer equivalent to 30 to 90 mass% of the mass of the finally obtained fluorine-containing elastomer is produced.
  • a fluoromonomer is polymerized in the presence of a fluorine-containing diiodo compound (11) until a mass of a fluoroelastomer corresponding to 30 to 90 mass% of the mass of the finally obtained fluoroelastomer is produced, and then the fluoromonomer is polymerized in the presence of a fluorine-free diiodo compound (12).
  • a fluoroelastomer that can be crosslinked by peroxide crosslinking with higher productivity, and also makes it possible to produce a fluoroelastomer at a lower cost than a production method that uses only a fluorine-containing diiodo compound as a chain transfer agent.
  • the polymerization of the fluoromonomer in the presence of the fluorine-containing diiodo compound (11) is carried out until a mass of the fluoroelastomer corresponding to preferably 30 to 90 mass%, more preferably 40 mass% or more, and more preferably 80 mass% or less is produced, based on the mass of the final fluoroelastomer.
  • the amount of the fluorine-containing diiodo compound (11) is preferably 0.2 ⁇ 10 ⁇ 3 to 2 mol %, more preferably 1.0 ⁇ 10 ⁇ 3 mol % or more, and more preferably 1 mol % or less, based on the total amount of monomers used in the polymerization.
  • the amount of the fluorine-free diiodo compound (12) is preferably 0.2 ⁇ 10 ⁇ 3 to 2 mol %, more preferably 1.0 ⁇ 10 ⁇ 3 mol % or more, and more preferably 1 mol % or less, based on the total amount of monomers used in the polymerization.
  • a polyfunctional non-fluorine-containing monomer may be further polymerized in addition to the fluoromonomer.
  • a polyfunctional non-fluorine-containing monomer By using a polyfunctional non-fluorine-containing monomer, a polyfunctional non-fluorine-containing monomer unit can be introduced into the fluoroelastomer.
  • the polyfunctional non-fluorine-containing monomer unit in the fluoroelastomer gives the fluoroelastomer a branched structure or functions as a site that can be crosslinked by peroxide crosslinking.
  • the polyfunctional non-fluorine-containing monomer used in the second manufacturing method is a monomer that has two or more functional groups and does not contain a fluorine atom.
  • Examples of the polyfunctional non-fluorine-containing monomer include the polyfunctional non-fluorine-containing monomer used in the first manufacturing method, and the same ones are preferable and can be used in the same amounts.
  • the fluoromonomer used in the second manufacturing method is a monomer containing a fluorine atom.
  • Examples of the fluoromonomer include the fluoromonomer used in the first manufacturing method, and the same ones are preferable and can be used in the same amounts.
  • polymerization can be carried out, for example, by charging a surfactant and an aqueous medium into a pressure-resistant polymerization tank equipped with an agitator, deoxidizing, charging the monomer, bringing the temperature to a predetermined level, adding a polymerization initiator to start the reaction, and charging a diiodo compound during the polymerization reaction.
  • a pressure-resistant polymerization tank equipped with an agitator
  • deoxidizing charging the monomer
  • bringing the temperature to a predetermined level adding a polymerization initiator to start the reaction
  • charging a diiodo compound during the polymerization reaction.
  • additional monomer is continuously or intermittently supplied to maintain the initial pressure, and when a predetermined amount of monomer has been supplied, the supply is stopped, the monomer in the reaction vessel is purged, and the temperature is returned to room temperature to terminate the reaction.
  • the polymerization in the second manufacturing method can be carried out in the presence of a polymerization initiator.
  • a polymerization initiator examples include the polymerization initiator used in the first manufacturing method, and the same initiators are preferable and can be used in the same amounts.
  • the polymerization in the second manufacturing method can be carried out in the presence of a surfactant.
  • a surfactant examples include those used in the first manufacturing method, and the same surfactants are preferable.
  • the polymerization in the second manufacturing method can be carried out in an aqueous medium.
  • the aqueous medium include the aqueous medium used in the first manufacturing method, and the same is preferable.
  • the polymerization temperature in the second manufacturing method is preferably 10 to 120°C.
  • the polymerization pressure in the first manufacturing method is preferably 0.5 to 10 MPaG.
  • the second production method produces a fluorine-containing elastomer.
  • the fluorine-containing elastomer produced by the second production method has a multimodal molecular weight distribution.
  • the fluorine-containing elastomer produced by the second production method has a bimodal molecular weight distribution. It is preferable that the fluorine-containing elastomer has a bimodal molecular weight distribution in which the ratio ((A)/(B)) of the area of the peak on the high molecular weight side appearing in the GPC curve (A) to the area of the peak on the low molecular weight side (B) is 90/10 to 30/70.
  • the fluorine-containing elastomer has such a molecular weight distribution, it is possible to produce a molded product having excellent heat resistance and compression set resistance, and the moldability of the fluorine-containing elastomer is improved.
  • the ratio ((A)/(B)) of the fluorine-containing elastomer obtained by the second production method is preferably 90/10 to 30/70, more preferably 80/20 or less, and more preferably 40/60 or more.
  • the fluorine-containing elastomer obtained by the second manufacturing method may have the same structure as the fluorine-containing elastomer obtained by the first manufacturing method, except that the inclusion of polyfunctional non-fluorine-containing monomer units is optional.
  • a crosslinkable composition can be produced by adding a crosslinking agent or the like to the fluorine-containing elastomer obtained by the first production method, the fluorine-containing elastomer according to one embodiment of the present disclosure, or the fluorine-containing elastomer obtained by the second production method.
  • a molded article can be obtained by crosslinking the crosslinkable composition containing the fluorine-containing elastomer and the peroxide crosslinking agent.
  • the type and amount of the crosslinking agent are not particularly limited and may be within the known range.
  • a peroxide crosslinking agent is preferred, and an organic peroxide is more preferred.
  • the organic peroxide may be any organic peroxide that can easily generate peroxy radicals in the presence of heat or an oxidation-reduction 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-butylperoxyisopropylcarbonate, and t-
  • the amount of organic peroxide to be blended is preferably 0.1 to 15 parts by mass, and more preferably 0.3 to 5 parts by mass, per 100 parts by mass of the fluorine-containing elastomer.
  • the crosslinkable composition further contains a crosslinking aid.
  • crosslinking aids include triallyl cyanurate, triallyl isocyanurate (TAIC), triacrylformal, triallyl trimellitate, N,N'-m-phenylene bismaleimide, dipropargyl 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-tetramethylphenyl)propanediol, and tetramethylphenyl ether.
  • lion tris(diallylamine)-S-triazine, N,N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallyl phosphoramide, N,N,N',N'-tetraallylphthalamide, N,N,N',N'-tetraallylmalonamide, trivinyl isocyanurate, 2,4,6-trivinylmethyltrisiloxane, tri(5-norbornene-2-methylene) cyanurate, triallyl phosphite, trimethallyl isocyanurate, etc.
  • triallyl isocyanurate (TAIC) is preferred because of its excellent crosslinkability, mechanical properties, and flexibility.
  • the amount of cross-linking aid is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 7.0 parts by mass, and even more preferably 0.1 to 5.0 parts by mass, per 100 parts by mass of fluorine-containing elastomer. If the amount of cross-linking aid is less than 0.01 parts by mass, the mechanical properties and flexibility will decrease. If the amount exceeds 10 parts by mass, the heat resistance will be poor and the durability of the molded product will also tend to decrease.
  • the crosslinkable composition may contain various additives, such as typical additives that are blended into elastomers as necessary, such as fillers (carbon black, barium sulfate, etc.), processing aids (wax, etc.), plasticizers, colorants, stabilizers, tackifiers (coumarone resin, coumarone-indene resin, etc.), release agents, electrical conductivity agents, thermal conductivity agents, surface non-tackifiers, flexibility agents, heat resistance improvers, and flame retardants, and may also contain one or more commonly used crosslinking agents and crosslinking accelerators other than those mentioned above.
  • additives such as typical additives that are blended into elastomers as necessary, such as fillers (carbon black, barium sulfate, etc.), processing aids (wax, etc.), plasticizers, colorants, stabilizers, tackifiers (coumarone resin, coumarone-indene resin, etc.), release agents, electrical conductivity agents, thermal conductivity agents, surface non
  • 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, even more preferably 2 to 100 parts by mass, and particularly preferably 2 to 75 parts by mass, per 100 parts by mass of the fluorine-containing elastomer.
  • the content of processing aids such as wax is preferably 0 to 10 parts by mass, and more preferably 0 to 5 parts by mass, per 100 parts by mass of the fluoroelastomer.
  • processing aids, plasticizers, and release agents tends to reduce the mechanical properties and sealing properties of the resulting molded product, so it is necessary to adjust the content of these agents within a range that allows for the desired properties of the resulting molded product.
  • the method for preparing the crosslinkable composition there are no particular limitations on the method for preparing the crosslinkable composition, so long as it is a method that can uniformly mix the fluorine-containing elastomer and the crosslinking agent.
  • a method can be used in which a powder of the fluorine-containing elastomer coagulated alone is kneaded with other additives and compounding agents, if necessary, in a kneader such as an open roll.
  • a molded article can be obtained by crosslinking the crosslinkable composition.
  • a molded article can also be obtained by molding and crosslinking the composition.
  • the composition can be molded by a conventionally known method.
  • the molding and crosslinking methods and conditions may be within the range of known methods and conditions for the molding and crosslinking employed.
  • the order of molding and crosslinking is not limited, and molding may be followed by crosslinking, crosslinking may be followed by molding, or molding and crosslinking may be performed simultaneously.
  • molding methods include, but are not limited to, compression molding, casting, injection molding, extrusion molding, and roto-cure molding.
  • cross-linking methods that can be used include steam cross-linking, heat cross-linking, and radiation cross-linking, with steam cross-linking and heat cross-linking being preferred.
  • Specific cross-linking conditions which are not limited to, are usually within a temperature range of 140 to 250°C and a cross-linking time of 1 minute to 24 hours, and can be determined appropriately depending on the types of cross-linking accelerator, cross-linking agent, and acid acceptor.
  • Specific crosslinking 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, and can be appropriately determined depending on the type of crosslinking agent, etc.
  • the obtained molded products can be used as various parts in various fields such as the automotive industry, the aircraft industry, and the semiconductor industry.
  • the molded products can be used for applications similar to those of the crosslinked rubber molded products described in JP 2013-216915 A and the fluororubber molded products described in JP 2019-94430 A, such as sealing materials, sliding parts, and non-adhesive parts.
  • Examples of uses for the 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 that require excellent non-stickiness and low friction. It is particularly suitable for use as various sealing materials in the automotive industry, etc.
  • tubes can also be used for tubes, hoses, rolls, various rubber rolls, flexible joints, rubber sheets, coatings, belts, dampers, valves, valve seats, valve bodies, chemical-resistant coating materials, laminating materials, lining materials, etc.
  • the present invention provides a method for producing a fluorine-containing elastomer, comprising polymerizing a fluoromonomer and a polyfunctional non-fluorine-containing monomer in the presence of a diiodo compound to obtain a fluorine-containing elastomer.
  • the fluoromonomer comprises at least one selected from the group consisting of vinylidene fluoride and tetrafluoroethylene.
  • a process according to the first or second aspect wherein the polyfunctional fluorine-free monomer has from 2 to 6 functional groups.
  • the polyfunctional fluorine-free monomer has an unsaturated functional group.
  • the polyfunctional fluorine-free monomer has at least one unsaturated functional group selected from the group consisting of a vinyl group, an isopropenyl group, an allyl group and a methallyl group.
  • a production method according to any one of the first to fifth aspects, in which the polyfunctional fluorine-free monomer has a nitrogen-containing heterocycle.
  • the polyfunctional fluorine-free monomer is at least one selected from the group consisting of triallyl isocyanurate and trimethallyl isocyanurate.
  • the diiodo compound is both a fluorine-containing diiodo compound and a fluorine-free diiodo compound.
  • the diiodo compound is both a fluorine-containing diiodo compound having two or more carbon atoms and a fluorine-free diiodo compound having one carbon atom.
  • a production method according to any one of the first to ninth aspects, wherein the diiodo compound is both 1,4-diiodoperfluoro-n-butane and diiodomethane.
  • the diiodo compound is both 1,4-diiodoperfluoro-n-butane and diiodomethane.
  • a production process according to any of the first to tenth aspects, in which a fluoromonomer is polymerized in the presence of a diiodo compound (1), and then the fluoromonomer is polymerized in the presence of a fluorine-free diiodo compound (12), thereby obtaining a fluorine-containing elastomer.
  • a fluoromonomer is polymerized in the presence of a diiodo compound (1) until a fluoroelastomer is produced in an amount corresponding to 30 to 90 mass% of the mass of the finally obtained fluoroelastomer, and then the fluoromonomer is polymerized in the presence of a fluorine-free diiodo compound (12), thereby obtaining a fluoroelastomer.
  • a production method according to any of the first to twelfth aspects, in which the molar ratio of the amount of the polyfunctional non-fluorine-containing monomer to the amount of the diiodo compound (polyfunctional non-fluorine-containing monomer/diiodo compound) is 0.05 to 0.5.
  • the iodine content is 0.1 to 1.0% by mass, A fluorine-containing elastomer containing a fluoromonomer unit and a polyfunctional fluorine-free monomer unit is provided.
  • a fluorine-containing elastomer wherein the content of the polyfunctional non-fluorine-containing monomer unit is 0.01 to 0.2 mol % based on the total monomer units.
  • a fluorine-containing elastomer wherein the fluoromonomer comprises at least one selected from the group consisting of vinylidene fluoride and tetrafluoroethylene.
  • a fluorine-containing elastomer wherein the polyfunctional fluorine-free monomer has 2 to 6 functional groups.
  • a fluorine-containing elastomer according to any of the fourteenth to seventeenth aspects, wherein the polyfunctional non-fluorine-containing monomer has an unsaturated functional group.
  • a fluorine-containing elastomer according to any of the fourteenth to eighteenth aspects, wherein the polyfunctional fluorine-free monomer has at least one unsaturated functional group selected from the group consisting of a vinyl group, an isopropenyl group, an allyl group and a methallyl group.
  • the polyfunctional fluorine-free monomer has at least one unsaturated functional group selected from the group consisting of a vinyl group, an isopropenyl group, an allyl group and a methallyl group.
  • a fluorine-containing elastomer wherein the polyfunctional fluorine-free monomer is at least one selected from the group consisting of triallyl isocyanurate and trimethallyl isocyanurate.
  • the fluorine-containing elastomer according to any one of the fourteenth to twenty-first aspects, which has a multimodal molecular weight distribution.
  • a fluorine-containing elastomer according to any of the fourteenth to twenty-second aspects, which has a bimodal molecular weight distribution, and in which the ratio ((A)/(B)) of the area of a peak on the high molecular weight side appearing in a GPC curve to the area (B) of a peak on the low molecular weight side is 90/10 to 30/70.
  • a crosslinkable composition comprising the fluorine-containing elastomer and a peroxide crosslinking agent.
  • a molded article obtainable by crosslinking the crosslinkable composition.
  • a process for producing a fluorine-containing elastomer which comprises polymerizing a fluoromonomer in the presence of a fluorine-containing diiodo compound (11), and then polymerizing the fluoromonomer in the presence of a fluorine-free diiodo compound (12), thereby obtaining a fluorine-containing elastomer.
  • the twenty-sixth or twenty-seventh aspect of the present invention provides a production method in which the fluorine-containing diiodo compound (11) is 1,4-diiodoperfluoro-n-butane.
  • ⁇ 29> According to a twenty-ninth aspect of the present disclosure, The production method according to any one of the twenty-sixth to twenty-eighth aspects is provided, wherein the fluorine-free diiodo compound (12) has one carbon atom. ⁇ 30> According to a thirtieth aspect of the present disclosure, The production method according to any one of the twenty-sixth to twenty-ninth aspects is provided, wherein the fluorine-free diiodo compound (12) is diiodomethane.
  • a thirty-first aspect of the present disclosure there is provided a production process according to any of the twenty-sixth to thirtieth aspects, in which a fluoromonomer is polymerized in the presence of a fluorine-containing diiodo compound (11) until a fluoroelastomer having a mass corresponding to 30 to 90 mass% of the mass of the finally obtained fluoroelastomer is produced, and then the fluoromonomer is polymerized in the presence of a fluorine-free diiodo compound (12), thereby obtaining a fluoroelastomer.
  • a fluoromonomer is polymerized in the presence of a fluorine-containing diiodo compound (11) until a fluoroelastomer having a mass corresponding to 30 to 90 mass% of the mass of the finally obtained fluoroelastomer is produced, and then the fluoromonomer is polymerized in the presence of a fluorine-free diiodo compound
  • ⁇ 32> According to a thirty-second aspect of the present disclosure, The production process according to any of the twenty-sixth to thirty-first aspects is provided, wherein the finally obtained fluorine-containing elastomer has a bimodal molecular weight distribution, and the ratio ((A)/(B)) of the area of the peak on the high molecular weight side appearing in a GPC curve to the area (B) of the peak on the low molecular weight side is 90/10 to 30/70.
  • a thirty-third aspect of the present disclosure There is provided a production method according to any one of the twenty-sixth to thirty-second aspects, in which a polyfunctional non-fluorine-containing monomer is further polymerized in addition to the fluoromonomer.
  • TAIC unit content> The TAIC used for copolymerization was dissolved uniformly in acetone to give concentrations of 0.02 mol%, 0.04 mol%, and 0.06 mol% in the polymer A obtained in Comparative Experimental Example 1 in which TAIC was not copolymerized, and the solution was applied to an aluminum cup, and the acetone was dried in an electric furnace at 90°C until a constant weight was reached. Each sample obtained was measured in the ATR mode of an infrared spectrophotometer.
  • HLC-8320 manufactured by Tosoh Corporation
  • GPC KF-806M x 2 GPC KF-801 x 1
  • GPC KF-802 x 1 Detector: differential refractometer
  • Developing solvent tetrahydrofuran Temperature: 40°C
  • Sample concentration 0.2% by weight
  • APS ammonium persulfate
  • DI 1,4-diiodoperfluoro-n-butane
  • the iodine content was 0.37% by weight by the combustion ion method, and the copolymerization amount of TAIC was 0.022 mol% by IR.
  • the number average molecular weight Mn and Mw measured by GPC were 65600 and 128700, respectively, and the Mooney viscosity ML 121°C measured at 121°C was 23.0.
  • Experimental Example 2 Polymerization was carried out in the same manner as in Experimental Example 1, except that the amount of TAIC added was changed to 0.067 g. The amount of the obtained emulsion was 3012 g, and the solid content of this emulsion was 26.8%. The time required for polymerization was 10 hours and 41 minutes.
  • the iodine content was 0.54% by weight by the combustion ion method, and the amount of copolymerization of TAIC measured by IR was 0.036 mol%. GPC could not be measured because it was insoluble in the solvent, but the Mooney viscosity ML 121°C measured at 121°C was 12.7.
  • Experimental Example 3 Polymerization was carried out in the same manner as in Experimental Example 1, except that the amount of TAIC added was changed to 1.005 g. The amount of the obtained emulsion was 3039 g, and the solid content of this emulsion was 27.1%. The time required for polymerization was 13 hours and 40 minutes.
  • the iodine content was 0.53% by weight by the combustion ion method, and the amount of copolymerization of TAIC measured by IR was 0.057 mol%. GPC could not be measured because it was insoluble in the solvent, but the Mooney viscosity ML 121°C measured at 121°C was 22.8.
  • Experimental Example 4 Polymerization was carried out in the same manner as in Experimental Example 1, except that the amount of TAIC added was changed to 1.340 g. The amount of the obtained emulsion was 3076 g, and the solid content of this emulsion was 26.8%. The time required for polymerization was 10 hours and 41 minutes.
  • the iodine content was 0.49% by weight by the combustion ion method, and the amount of copolymerization of TAIC measured by IR was 0.060 mol%. GPC could not be measured because it was insoluble in the solvent, but the Mooney viscosity ML 121°C measured at 121°C was 23.4.
  • Experimental Example 5 Polymerization was carried out in the same manner as in Experimental Example 1, except that 7.392 g of DI was changed to 3.490 g of CH 2 I 2 and the method of feeding the initiator APS after feeding CH 2 I 2 was changed as follows. When the amount of mixed gas B fed reached 16 g, 3.490 g of CH 2 I 2 was fed, and the polymerization behavior was observed to temporarily stop, and 10 g of a 0.45% aqueous solution of the initiator APS was added. Thereafter, the same amount of a 0.45% aqueous solution of the initiator APS was fed every hour until the polymerization rate recovered. In this polymerization, the polymerization rate recovered after 12 feedings, so the method of feeding APS described in Experimental Example 1 was used again thereafter.
  • the amount of the obtained emulsion was 2984 g, and the solid content of this emulsion was 27.0%.
  • the time required for polymerization was 9 hours and 28 minutes.
  • the iodine content was 0.39% by weight as determined by the combustion ion method, and the copolymerization amount of TAIC was 0.025 mol% as measured by IR.
  • the number average molecular weight Mn and weight average molecular weight Mw were measured by GPC as 60,500 and 156,600, respectively, and the Mooney viscosity ML 121°C measured at 121° C was 26.0.
  • DI 1,4-diiodoperfluoro-n-butane
  • the iodine content was 0.57% by weight by the combustion ion method, and the copolymerization amount of TAIC measured by IR was 0.041 mol%.
  • the number average molecular weight Mn measured by GPC was 53,700, the weight average molecular weight Mw was 177,800, and the Mooney viscosity ML 121° C. measured at 121° C. was 28.4.
  • Experimental Example 7 Polymerization was carried out in the same manner as in Experimental Example 6, except that TAIC was not charged when the amount of mixed gas B charged reached 553 g. The amount of the obtained emulsion was 3072 g, and the solid content of this emulsion was 27.2%. The time required for polymerization was 11 hours and 58 minutes.
  • the iodine content was 0.52% by weight by the combustion ion method, and the copolymerization amount of TAIC measured by IR was 0.021 mol%.
  • the number average molecular weight Mn measured by GPC was 47300, the weight average molecular weight Mw was 161100, and the Mooney viscosity ML 121°C measured at 121°C was 22.0.
  • Experimental Example 8 Polymerization was carried out in the same manner as in Experimental Example 6, except that 2.867 g of DI was charged when the amount of mixed gas B was 16 g, but was changed to 1.701 g of CH 2 I 2 .
  • CH 2 I 2 was charged twice, and the method of charging the initiator APS after charging CH 2 I 2 described in Experimental Example 5 was carried out each time. After the first charging, five charges of the initiator were carried out, and after the second charging, four charges of the initiator were carried out.
  • the obtained emulsion was 3152 g, and the solid content of this emulsion was 26.6%.
  • the time required for polymerization was 14 hours and 6 minutes.
  • the iodine content was 0.52% by weight as measured by the combustion ion method, and the amount of copolymerization of TAIC was 0.030 mol% as measured by IR.
  • the number average molecular weight Mn was 54,900 and the weight average molecular weight Mw was 184,700 as measured by GPC, and the Mooney viscosity ML 121°C was 33.8 as measured at 121°C.
  • Comparative Example 1 In a stainless steel reaction tank with an internal volume of 3.0 L, 2012 ml of pure water, 4.457 g of C 5 F 11 CHOONH 4 as an emulsifier, and 0.224 g of 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2-trifluoroallyloxy)propoxy]propionic acid ammonium salt were placed, and the internal space was fully replaced with nitrogen gas, after which a mixed gas A with a molar ratio of VdF/TFE/HFP of 19/11/70 was charged, and the reaction tank temperature was raised to 80° C. under stirring, and then the pressure was adjusted to 2.0 MPa.
  • Comparative Experimental Example 2 Polymerization was carried out in the same manner as in Comparative Experimental Example 1, except that the amount of DI charged was changed to 4.332 g. The amount of the obtained emulsion was 3079 g, and the solid content of this emulsion was 26.7%. The time required for polymerization was 7 hours and 24 minutes.
  • the number average molecular weight Mn measured by GPC was 62700, the weight average molecular weight Mw was 102200, and the Mooney viscosity ML 121°C measured at 121°C was 22.0.
  • Comparative Example 3 Polymerization was carried out in the same manner as in Comparative Experimental Example 1, except that 7.392 g of DI was replaced by 3.514 g of CH 2 I 2 , and the method of feeding APS described in Experimental Example 5 was adopted after the feeding of CH 2 I 2. In this polymerization, APS was charged 10 times until the polymerization rate recovered. The obtained emulsion was 3217 g, and the solid content of this emulsion was 25.9%. The time required for polymerization was 16 hours and 52 minutes.
  • the number average molecular weight Mn measured by GPC was 49800, the weight average molecular weight Mw was 95100, and the Mooney viscosity ML 121°C measured at 121°C was 13.0.
  • Comparative Example 4 Polymerization was carried out in the same manner as in Experimental Example 6, except that TAIC was not charged twice during polymerization. In this polymerization, APS was charged four times after CH 2 I 2 was charged. The obtained emulsion was 3037 g, and the solid content of this emulsion was 27.1%. The time required for polymerization was 8 hours and 59 minutes.
  • the number average molecular weight Mn measured by GPC was 42100, the weight average molecular weight Mw was 83300, and the Mooney viscosity ML 121°C measured at 121°C was 11.6.
  • Comparative Experimental Example 5 Polymerization was carried out in the same manner as in Experimental Example 8, except that TAIC was not charged during polymerization. In this polymerization, APS was charged 9 times after the first charge of CH 2 I 2 , and 3 times after the second charge. The obtained emulsion was 3142 g, and the solid content of this emulsion was 26.0%. The time required for polymerization was 14 hours and 22 minutes.
  • the number average molecular weight Mn measured by GPC was 35043
  • the weight average molecular weight Mw was 66900
  • the crosslinking curve of the crosslinkable composition at 170°C was obtained using a rheometer (Premier MDR, manufactured by Alpha Technology Co., Ltd.), and the minimum viscosity minimum torque (ML), maximum degree of vulcanization torque (MH), induction time (T10) and optimum crosslinking time (T90) were determined.
  • a rheometer Premier MDR, manufactured by Alpha Technology Co., Ltd.
  • ML minimum viscosity minimum torque
  • MH maximum degree of vulcanization torque
  • T10 induction time
  • T90 optimum crosslinking time
  • Modulus (M100)> The crosslinkable composition was subjected to primary press crosslinking and secondary oven crosslinking under the above-mentioned crosslinking conditions to prepare a sheet having a thickness of 2 mm, and the 100% modulus at 23° C. of the obtained sheet was measured in accordance with JIS-K6251.
  • Tb tensile strength at break
  • Eb tensile elongation at break
  • CS Compression set
  • the crosslinkable composition was subjected to primary press crosslinking and secondary oven crosslinking under the above-mentioned crosslinking conditions to prepare a JIS block, and the compression set (CS) was measured in accordance with JIS-K6301 (the JIS block was held at 200°C for 72 hours under 25% compression and then left in a thermostatic chamber at 25°C for 30 minutes, and then the measurement was performed).
  • the crosslinkable composition was subjected to primary press crosslinking and secondary oven crosslinking under the above-mentioned crosslinking conditions to prepare a sheet having a thickness of 2 mm, and the obtained sheet was left for 30 minutes in a thermostatic chamber at 25° C. After leaving the sheet, the four corners of the sheet were visually observed and evaluated according to the following criteria. Yes: The four corners of the sheet are warped. No: The four corners of the sheet are not warped.

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Abstract

L'invention concerne un procédé de production d'un élastomère contenant du fluor par polymérisation d'un fluoromonomère et d'un monomère polyfonctionnel exempt de fluor en présence d'un composé diiodo.
PCT/JP2024/009508 2023-03-30 2024-03-12 Procédé de production d'élastomère contenant du fluor et élastomère contenant du fluor Pending WO2024203271A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63304009A (ja) * 1987-06-04 1988-12-12 Nippon Mektron Ltd パ−オキサイド加硫可能な含フッ素エラストマ−の製造方法
JP2001233918A (ja) * 2000-02-22 2001-08-28 Daikin Ind Ltd 加硫性が改善された含フッ素エラストマーおよび加硫成形体
WO2016072397A1 (fr) * 2014-11-07 2016-05-12 旭硝子株式会社 Élastomère contenant du fluor, composition d'élastomère contenant du fluor, et article réticulé d'élastomère contenant du fluor
JP2019534372A (ja) * 2016-11-09 2019-11-28 スリーエム イノベイティブ プロパティズ カンパニー 過酸化物硬化性部分フッ素化ポリマー

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63304009A (ja) * 1987-06-04 1988-12-12 Nippon Mektron Ltd パ−オキサイド加硫可能な含フッ素エラストマ−の製造方法
JP2001233918A (ja) * 2000-02-22 2001-08-28 Daikin Ind Ltd 加硫性が改善された含フッ素エラストマーおよび加硫成形体
WO2016072397A1 (fr) * 2014-11-07 2016-05-12 旭硝子株式会社 Élastomère contenant du fluor, composition d'élastomère contenant du fluor, et article réticulé d'élastomère contenant du fluor
JP2019534372A (ja) * 2016-11-09 2019-11-28 スリーエム イノベイティブ プロパティズ カンパニー 過酸化物硬化性部分フッ素化ポリマー

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