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WO2009119723A1 - Copolymère séquencé à faible perméabilité au carburant - Google Patents

Copolymère séquencé à faible perméabilité au carburant Download PDF

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Publication number
WO2009119723A1
WO2009119723A1 PCT/JP2009/056084 JP2009056084W WO2009119723A1 WO 2009119723 A1 WO2009119723 A1 WO 2009119723A1 JP 2009056084 W JP2009056084 W JP 2009056084W WO 2009119723 A1 WO2009119723 A1 WO 2009119723A1
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WIPO (PCT)
Prior art keywords
fluorine
containing elastomer
segment
vinyl ether
copolymer
Prior art date
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PCT/JP2009/056084
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English (en)
Japanese (ja)
Inventor
昌二 福岡
恵子 鷲野
秀実 西井
大助 太田
充 岸根
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to JP2010505762A priority Critical patent/JP5353880B2/ja
Publication of WO2009119723A1 publication Critical patent/WO2009119723A1/fr
Anticipated expiration legal-status Critical
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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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • 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
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0284—Organic resins; Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a block copolymer of a fluorine-containing elastomer.
  • VdF vinylidene fluoride
  • PAVE perfluoroalkyl vinyl ether
  • Low fuel permeability is inferior to VdF / hexafluoropropylene (HFP) copolymer and VdF / HFP / tetrafluoroethylene (TFE) copolymer, and both cold resistance and low fuel permeability are desired. It is rare.
  • thermoplastic elastomer obtained by block polymerization of a fluororesin component in a fluorine-containing elastomer is excellent in low permeability of automobile fuel. This is considered because the resin component in the polymer suppresses the permeation of fuel.
  • the molded product obtained from this elastomer needs to increase the amount of the resin component in order to achieve low permeability, so that the hardness is increased or the cold resistance of the fluorine-containing elastomer is deteriorated. At the expense of Therefore, it cannot be a material having both low fuel permeability and cold resistance, which are the targets of the present application.
  • Patent Document 1 TFE and PAVE, perfluoromethyl vinyl ether (PMVE), are copolymerized in the presence of an iodine and / or bromine-containing compound, and this reaction is continued without releasing unreacted monomers.
  • a method for producing a fluorinated copolymer in which TFE and VdF are supplied to the system to continue the polymerization reaction is disclosed.
  • the production method in Patent Document 1 can produce a copolymer in high yield and increase productivity, but has not yet solved the problem of achieving both cold resistance and low fuel permeability.
  • the present invention uses a fluorine-containing elastomer, a composition for peroxide vulcanization, and a composition for peroxide vulcanization that are low in hardness and excellent in low fuel permeability while maintaining the cold resistance of the cold-resistant fluororubber.
  • An object of the present invention is to provide a fuel-based automobile part formed by molding.
  • the composition ratio of (1) vinylidene fluoride (VdF) / perfluoroalkyl vinyl ether (PAVE) copolymer is 50 to 85/15 to 50 mol%, or (2) VdF / tetrafluoroethylene (TFE)
  • the present invention relates to a fluorine-containing elastomer capable of peroxide vulcanization having iodine atoms.
  • the VdF / PAVE copolymer (1) in the fluorine-containing elastomer segment (A) is a VdF / perfluoromethyl vinyl ether (PMVE) copolymer
  • the VdF / TFE / PAVE copolymer (2) is VdF / TFE / PMVE.
  • a copolymer is preferred.
  • the fluorine-containing elastomer segment (B) has a composition ratio of (b1) tetrafluoroethylene / perfluoromethyl vinyl ether copolymer of 45 to 85/15 to 55 mol%, (b2) tetrafluoroethylene / ethylene / perfluoromethyl vinyl ether
  • the composition ratio of the copolymer is 15 to 85/1 to 30/14 to 55 mol%
  • the composition ratio of vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene is 25 to 85/0 to 40/15 to It is preferably at least one copolymer selected from the group consisting of 40 mol%.
  • the content of the fluorine-containing elastomer segment (A) is preferably 60 to 95% by mass in the fluorine-containing elastomer, and the content of the fluorine-containing elastomer segment (B) is preferably 5 to 40% by mass in the fluorine-containing elastomer. .
  • the fluorine-containing elastomer segment (B) at both ends of the fluorine-containing elastomer segment (A), and the fluorine content is preferably 64.0 to 70.0% by mass. Moreover, it is preferable to have two glass transition temperatures measured by a differential scanning calorimeter.
  • the present invention also relates to a composition for peroxide vulcanization comprising (i) the fluorine-containing elastomer, (ii) a polyfunctional unsaturated compound, and (iii) peroxide.
  • the present invention also relates to an automobile part that comes into contact with a fuel molded using the peroxide vulcanizing composition.
  • it is preferably used for parts having TR10 of ⁇ 20 ° C. or less as cold resistance.
  • the present invention relates to RI n , wherein n is an integer of 1 to 2, R is a saturated or unsaturated fluorohydrocarbon group or chlorofluorohydrocarbon group having 1 to 8 carbon atoms, or 1 carbon atom
  • R is a saturated or unsaturated fluorohydrocarbon group or chlorofluorohydrocarbon group having 1 to 8 carbon atoms, or 1 carbon atom
  • a fluorine-containing elastomer capable of peroxide vulcanization a composition for peroxide vulcanization, and the composition having low hardness and excellent fuel low permeability while maintaining the cold resistance of the cold resistant fluororubber. It is possible to provide a fuel-based automobile part molded by using the fuel system.
  • the composition ratio of (1) vinylidene fluoride (VdF) / perfluoroalkyl vinyl ether (PAVE) copolymer is 50 to 85/15 to 50 mol%, or (2) VdF / tetrafluoroethylene (TFE) / Fluorine-containing elastomer segment (A) having a composition ratio of 45 to 85/1 to 30/14 to 30 mol% of the composition ratio of the perfluoroalkyl vinyl ether (PAVE) copolymer, and fluorine-containing elastomer segment (A And a fluorine-containing elastomer that is substantially incompatible with the fluorine-containing elastomer segment (B), and is a peroxide-vulcanizable fluorine-containing elastomer having iodine atoms.
  • VdF vinylidene fluoride
  • PAVE perfluoroalkyl vinyl ether
  • the fluorine-containing elastomer of the present invention is a block copolymer consisting of only two types of elastomer segments, the fluorine-containing elastomer segment (A) and the fluorine-containing elastomer segment (B), the hardness of the vulcanizate can be kept low,
  • the compression set is also better than that of a block copolymer of a fluorine-containing elastomer segment and a fluorine-containing resin.
  • Fluorine-containing elastomer does not have a melting point derived from the elastomer.
  • a method for measuring the melting point for example, when the second scan heat balance is measured by DSC at a temperature rising speed of 10 ° C./min in the temperature range of 60 to 400 ° C., and the peak cannot be measured within the range. It can be confirmed that it is an elastomer.
  • Perfluoroalkoxy vinyl ether wherein Rf means a C 3-10 perfluoro ether group containing 1 to 2 ether bonds.
  • the fluorine-containing elastomer segment (A) is a VdF / PAVE copolymer (1)
  • the composition ratio of the VdF / PAVE copolymer (1) is 50 to 50 from the viewpoint of good cold resistance and flexibility. It is 85/15 to 50 mol%, preferably 55 to 80/20 to 45 mol%.
  • the fluorine-containing elastomer segment (A) is (2) VdF / TFE / PAVE copolymer
  • the composition ratio of VdF / TFE / PAVE copolymer (2) is good in cold resistance and flexibility. From that point, it is 45 to 85/1 to 30/14 to 30 mol%, preferably 50 to 80/5 to 25/16 to 28 mol%, more preferably 55 to 75/7 to 22/16 to 25 mol%.
  • the number average molecular weight (Mn) of the fluorine-containing elastomer segment (A) depends on the amount of the fluorine-containing elastomer segment (B) to be block copolymerized later, but the molding processability of the resulting block copolymer is good.
  • Mn number average molecular weight
  • 20,000 or more is preferable, and 30,000 or more is more preferable.
  • 300,000 or less is preferable and 200,000 or less is more preferable.
  • the Mooney viscosity at 100 ° C. of the fluorine-containing elastomer segment (A) is preferably 2 or more, and more preferably 5 or more, from the viewpoint that the moldability of the block copolymer obtained in the same manner as the molecular weight is good. Moreover, 200 or less is preferable and 150 or less is more preferable.
  • the fluorine content of the fluorine-containing elastomer segment (A) is preferably 63.5% by mass or more, more preferably 64.0% by mass or more, and 64.5% by mass or more from the viewpoint of good low fuel permeability. Is more preferable. Further, the fluorine content of the fluorine-containing elastomer segment (A) is preferably 68.0% by mass or less, more preferably 67.5% by mass or less, and 67.0% by mass or less from the viewpoint of good cold resistance. Is more preferable.
  • the content ratio of the fluorine-containing elastomer segment (A) in the fluorine-containing elastomer is preferably 60% by mass or more, more preferably 65% by mass or more, and further preferably 70% by mass or more from the viewpoint of improving cold resistance. Further, the content of the fluorine-containing elastomer segment (A) is preferably 95% by mass or less, more preferably 90% by mass or less in the fluorine-containing elastomer, from the viewpoint of improving low fuel permeability.
  • the fluorine-containing elastomer segment (B) in the block copolymer of the present invention is an elastomer segment excellent in low fuel permeability and is a segment that is substantially incompatible with the fluorine-containing elastomer segment (A).
  • the fluorine-containing elastomer segment (B) is finely dispersed in the fluorine-containing elastomer segment (A) that forms a micro domain. Therefore, it is considered that a bypass effect is exhibited when the fuel permeates and low permeability can be realized.
  • the crosslinked product is a polymer having a low fuel permeability superior to the crosslinked product of the fluorine-containing elastomer segment (A), and the elastomer is compatible with the fluorine-containing elastomer (A).
  • Any low and phase-separating polymer may be used.
  • the phase separation means that, for example, glass transition temperatures due to the respective polymers are observed when both the fluorine-containing elastomer segments (A) and (B) are allowed to coexist.
  • fluorine-containing elastomers examples include fluorine-containing elastomers based on VdF, fluorine-containing elastomers based on TFE, and fluorine-containing elastomers based on ethylene (Et).
  • Et fluorine-containing elastomers based on ethylene
  • the polymer itself is excellent in low fuel permeability
  • the TFE / PMVE copolymer (b1) having a lower affinity (not including VdF) and the VdF / PMVE copolymer and the VdF / TFE / PMVE copolymer is more preferable.
  • composition ratio of the (b1) TFE / PMVE copolymer in the fluorine-containing elastomer segment (B) is preferably 50 to 85/15 to 50 mol% from the viewpoint of good flexibility and low fuel permeability. More preferably, it is 55 to 80/20 to 45 mol%.
  • composition ratio of the (b2) TFE / Et / PMVE copolymer in the fluorine-containing elastomer segment (B) is preferably from 15 to 85/1 in view of the good flexibility and low fuel permeability. 30/14 to 55 mol%, more preferably 20 to 75/5 to 25/20 to 50 mol%.
  • composition ratio of the (b3) VdF / TFE / HFP copolymer in the fluorine-containing elastomer segment (B) is preferably 25 to 85/0 to 40 from the viewpoint of good flexibility and low fuel permeability. / 15 to 40 mol%, more preferably 30 to 70/10 to 40/15 to 35 mol%.
  • the number average molecular weight (Mn) of the fluorine-containing elastomer segment (B) is not clear because it cannot be measured, but it needs to have fluidity that can be finely dispersed in the fluorine-containing elastomer (A).
  • the fluorine content of the fluorine-containing elastomer segment (B) is preferably 65.0% by mass or more, more preferably 68.0% by mass or more, and even more preferably 70% by mass or more from the viewpoint of good low fuel permeability. preferable. Further, the fluorine content of the fluorine-containing elastomer segment (B) is preferably 74.0% by mass or less, and more preferably 73.5% by mass or less from the viewpoint of good cold resistance and flexibility.
  • the content ratio of the fluorine-containing elastomer segment (B) in the fluorine-containing elastomer is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 12% by mass or more from the viewpoint of good low fuel permeability. preferable. Further, the content of the fluorine-containing elastomer segment (B) is preferably 40% by mass or less, more preferably 35% by mass or less in the fluorine-containing elastomer, from the viewpoint of improving cold resistance and good flexibility. A mass% or less is more preferable.
  • the fluorine-containing elastomer segment (A) and the fluorine-containing elastomer segment (B) are not compatible with each other, two glass transition temperatures are observed. If the fluorine-containing elastomer segment (A) and the fluorine-containing elastomer segment (B) are compatible with each other, the low fuel permeability is improved, but the glass transition temperature is significantly increased, and the target cold resistance cannot be obtained. Since the fluorine-containing elastomer segment (A) and the fluorine-containing elastomer segment (B) are not compatible with each other, the cold resistance characteristic of the cold-resistant fluororubber of the fluorine-containing elastomer segment (A) serving as a matrix is exhibited. Further, the low fuel permeability is realized by microscopic dispersion of the fluorine-containing elastomer segment (B) having low fuel permeability.
  • the glass transition temperature of the block copolymer of the fluorine-containing elastomer segment (A) and the fluorine-containing elastomer segment (B) is measured by, for example, a differential scanning calorimetry (DSC) apparatus.
  • DSC differential scanning calorimetry
  • the heat balance of the second scan is measured in the temperature range of ⁇ 50 ° C. to 150 ° C. at a temperature rising speed of 10 ° C./min, and what is detected as the inflection point can be obtained by the midpoint method.
  • the glass transition temperature derived from the fluorine-containing elastomer segment (A) is preferably lower than the glass transition temperature derived from the fluorine-containing elastomer segment (B) from the viewpoint of good cold resistance.
  • the temperature is preferably ⁇ 33 ° C. to ⁇ 20 ° C., more preferably ⁇ 32 ° C. to ⁇ 24 ° C.
  • the glass transition temperature derived from the fluorine-containing elastomer segment (B) is preferably higher than the glass transition temperature derived from the fluorine-containing elastomer segment (A) from the viewpoint of good fuel low permeability. Specifically, ⁇ 20 ° C. to + 10 ° C. is preferable, and ⁇ 15 ° C. to + 5 ° C. is more preferable.
  • the number average molecular weight (Mn) of the block copolymer of the fluorine-containing elastomer segment (A) and the fluorine-containing elastomer segment (B) is often 20,000 to 300, If it is in the range of 000, there is no problem.
  • the Mooney viscosity at 100 ° C. of the block copolymer comprising the fluorine-containing elastomer segment (A) and the fluorine-containing elastomer segment (B) is preferably 5 or more, and preferably 10 or more, from the viewpoint of good molding processability. More preferred. Further, the Mooney viscosity at 100 ° C. of the block copolymer is preferably 150 or less, more preferably 120 or less, and even more preferably 100 or less, from the viewpoint that the molding processability is also good.
  • the fluorine content of the block copolymer comprising the fluorine-containing elastomer segment (A) and the fluorine-containing elastomer segment (B) is preferably 64.0% by mass or more from the viewpoint of good fuel low permeability. 0 mass% or more is more preferable. Further, the fluorine content of the block copolymer is preferably 70.0% by mass or less, more preferably 69.0% by mass or less, from the viewpoint of good low fuel permeability.
  • the fluorine-containing elastomer segment (A) and the fluorine-containing elastomer segment (B) are composed of AB type, BAB type, ABA type,-(B -A) n -type.
  • the fluorine-containing elastomer segment (B) is provided at both ends of the fluorine-containing elastomer segment (A) from the viewpoint that the fluorine-containing elastomer segment (B) excellent in fuel low permeability is easily finely dispersed.
  • the block copolymer which is the fluorine-containing elastomer of the present invention has iodine atoms and can be peroxide vulcanized.
  • a method for producing a fluorine-containing elastomer having an iodine atom the molecular weight distribution of the obtained polymer is narrow, the molecular weight can be easily controlled, and an iodine atom can be introduced at the terminal, so that a known iodine transfer weight can be introduced. Legal is preferred.
  • a radical initiator in the presence of a radical initiator while stirring the monomer constituting the elastomer segment under pressure in the presence of an iodine compound, preferably a diiodine compound, in the absence of oxygen.
  • an iodine compound preferably a diiodine compound
  • iodine compound used include, for example, RI n (wherein n is an integer of 1 to 2 and R is a saturated or unsaturated fluorohydrocarbon group having 1 to 8 carbon atoms or a chlorofluorohydrocarbon). Group or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom).
  • n I monoiodomethane, 1-iodomethane, 1-iodo-n-propane, isopropyl iodide, diiodomethane, 1,2-diiodoethane, 1,3-diiodo-n-propane, I (CF 2 CF 2 ) (in the formula, n a is an integer of 1 or more) n I are preferably used include compounds represented by.
  • An iodine atom is introduced into a fluorine-containing elastomer obtained using such an iodine compound (see, for example, JP-A-53-125491 and JP-A-63-30409).
  • the fluorine-containing elastomer of the present invention can be produced by a conventional method including an iodine transfer polymerization method, and can be produced by a polymerization method such as an emulsion polymerization method, a suspension polymerization method, or a solution polymerization method. What is necessary is just to determine suitably polymerization conditions, such as temperature at the time of superposition
  • a wide range of emulsifiers can be used for the emulsion polymerization. From the viewpoint of suppressing chain transfer reaction to the emulsifier molecules that occur during the polymerization, a carboxylic acid having a fluorocarbon chain or a fluoropolyether chain is used. Salts are desirable. It is also desirable to use a reactive emulsifier.
  • the radical polymerization initiator used for polymerization is not particularly limited, and known organic and inorganic peroxides can be used.
  • oil-soluble organic peroxides include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and disec-butyl peroxydicarbonate, and perfluorocarbons such as t-butyl peroxybutyrate and t-butyl peroxypivalate.
  • examples thereof include oxyesters and dialkyl peroxides such as di-t-butyl peroxide.
  • the inorganic peroxide examples include a carboxyl group or a group capable of generating a carboxyl group (for example, acid fluoride, acid chloride, CF 2 OH, etc., all of which generate a carboxyl group in the presence of water).
  • a carboxyl group or a group capable of generating a carboxyl group for example, acid fluoride, acid chloride, CF 2 OH, etc., all of which generate a carboxyl group in the presence of water.
  • Those which can be present at the end of the elastomer are preferred, and specific examples include ammonium persulfate (APS), potassium persulfate (KPS), and the like.
  • pH adjuster in the polymerization system examples include electrolyte substances having buffering ability such as phosphate, carbonate, borate, sodium hydroxide, potassium hydroxide, ammonium hydroxide and the like.
  • Examples of the molecular weight modifier include the iodine compounds mentioned above.
  • Examples of a method for isolating the polymerization product from the polymerization reaction mixture include a method in which a metal salt such as magnesium chloride, calcium chloride, sodium chloride, magnesium sulfate, barium sulfate is added and coagulated.
  • a metal salt such as magnesium chloride, calcium chloride, sodium chloride, magnesium sulfate, barium sulfate is added and coagulated.
  • a block copolymer can be produced by polymerizing the fluorine-containing elastomer segment (B). It is preferable at the point which improves property.
  • the present invention also relates to a peroxide vulcanizing composition
  • a peroxide vulcanizing composition comprising (i) the fluorine-containing elastomer, (ii) a polyfunctional unsaturated compound, and (iii) a peroxide.
  • the polyfunctional unsaturated compound (ii) may be any compound that has a reactive activity with respect to peroxy radicals and polymer radicals.
  • a reactive activity with respect to peroxy radicals and polymer radicals.
  • polyfunctional compounds having a functional group such as-.
  • triallyl cyanurate triallyl isocyanurate (TAIC), trimethallyl isocyanurate, TAIC prepolymer, triacryl formal, triallyl trimellitate, N, N′-n-phenylenebismaleimide , 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-trione), tris (diallylamine) -S-triazine, triallyl phosphite, N, N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallyl phosphor Amide, N, N, N ′, N′-tetraallylte
  • the content of the polyfunctional unsaturated compound (ii) is 0.5 parts by mass with respect to 100 parts by mass of the fluorine-containing elastomer (i) from the viewpoint that the compression set and strength properties of the vulcanizate are good.
  • the above is preferable, and 1.0 mass part or more is more preferable.
  • the content of the polyfunctional unsaturated compound (ii) is preferably 6.0 parts by mass or less with respect to 100 parts by mass of the fluorine-containing elastomer (i) from the viewpoint of preventing mold contamination, and is 5.0 masses. Part or less is more preferable.
  • the peroxide (iii) preferably generates a peroxy radical easily in the presence of heat or a redox system.
  • a peroxy radical easily in the presence of heat or a redox system.
  • the content of the peroxide (iii) is preferably 0.5 parts by mass or more and 100 parts by mass or more with respect to 100 parts by mass of the fluorine-containing elastomer (i) from the viewpoint that a sufficient vulcanization rate can be obtained. More preferred. Moreover, 10.0 mass parts or less are preferable with respect to 100 mass parts of fluorine-containing elastomer (i) from the point that sufficient characteristic is acquired, and, as for content of peroxide (iii), 5.0 mass parts or less are preferable. More preferred.
  • peroxide vulcanizing composition of the present invention it is possible to add usual additives, for example, fillers, processing aids, plasticizers, colorants, etc., which are blended into the vulcanizable elastomer composition as necessary. it can. Further, one or more conventional vulcanizing agents and vulcanization accelerators different from those described above may be blended. Moreover, you may mix and use another type of elastomer in the range which does not impair the effect of this invention.
  • the peroxide vulcanizing composition of the present invention may contain a general filler.
  • Common fillers include organic fillers made of engineering plastics such as polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyoxybenzoate, polytetrafluoroethylene powder; aluminum oxide, silicon oxide, yttrium oxide, titanium oxide, etc.
  • Metal oxide fillers; metal carbide fillers such as silicon carbide and aluminum carbide; metal nitride fillers such as silicon nitride and aluminum nitride; such as aluminum fluoride, carbon fluoride, barium sulfate, carbon black, silica, clay and talc Examples include inorganic fillers.
  • layered minerals represented by montmorillonite are useful for improving low fuel permeability.
  • the inorganic filler and organic filler may be used alone or in combination of two or more.
  • the peroxide vulcanizing composition of the present invention can be prepared by mixing the above-described components using a normal rubber processing machine such as an open roll, a Banbury mixer, a kneader or the like. In addition, it can be prepared by a method using a closed mixer or a method of co-coagulation from emulsion mixing.
  • the vulcanization conditions in the present invention are not particularly limited, and can be performed under the vulcanization conditions of a normal fluorine-containing elastomer composition.
  • the vulcanizing composition is placed in a mold and kept under pressure at 120 to 250 ° C. (preferably 180 to 220 ° C.) for 1 to 120 minutes to perform press vulcanization, followed by 160 to 300
  • a vulcanized product is obtained.
  • 0 ° C. preferably 180 to 250 ° C., more preferably 180 to 200 ° C.
  • a vulcanized product is obtained.
  • Can do preferably 180 to 250 ° C., more preferably 180 to 200 ° C.
  • the present invention also relates to an automobile part that comes into contact with fuel molded using the above-described peroxide vulcanizing composition.
  • automotive parts that come into contact with fuel include, for example, gaskets such as tank gaskets and air intake manifold gaskets, O-rings such as fuel pipe connector O-rings and injector O-rings, fuel pump diaphragms, etc.
  • gaskets such as tank gaskets and air intake manifold gaskets
  • O-rings such as fuel pipe connector O-rings and injector O-rings
  • fuel pump diaphragms etc.
  • the present invention is not limited to these, such as packings and seal materials used for fuel system parts.
  • Tb tensile breaking strength
  • Eb tensile breaking elongation
  • ⁇ Fuel permeability> Each composition is subjected to primary press vulcanization and secondary oven vulcanization under standard vulcanization conditions to form a sheet having a thickness of 0.5 mm, and fuel permeation at 40 ° C. using CE20 by the cup method in accordance with ASTM E96. Measure the coefficient. The smaller the fuel permeability coefficient, the better the fuel permeability.
  • Tg Glass transition temperature
  • VdF / TFE / PMVE 68/12/20 mol%
  • the glass transition temperature measured by DSC was ⁇ 31 ° C.
  • Reference Example 2 (polymerization of VdF / TFE / PMVE copolymer)
  • the glass transition temperature measured by DSC was ⁇ 25 ° C.
  • Example 1 Block copolymer of VdF / TFE / PMVE and TFE / PMVE
  • a stainless steel autoclave with an internal volume of 3 liters having no ignition source was charged with 1390 g of the disversion obtained in Reference Example 1 and 210 g of pure water, and 1.8 g of C 7 F 15 COONH 4 as an emulsifier.
  • APS ammonium persulfate
  • APS was added every 3 hours, and 2.8g was added by the completion
  • the obtained dispersion was coagulated with aluminum sulfate, washed thoroughly with pure water, and then dried with hot air at 80 ° C. for 8 hours and 120 ° C. for 12 hours to obtain 433 g of polymer.
  • the content of the TFE / PMVE segment in the obtained polymer calculated from the obtained amount was 15% by mass in the polymer.
  • Table 1 shows the Mooney viscosity, fluorine content, and glass transition temperature at 100 ° C. of the obtained polymer (block copolymer).
  • Example 2 Block copolymer of VdF / TFE / PMVE and TFE / PMVE Polymerization was carried out in the same manner as in Example 1 except that the dispersion used was replaced with that obtained in Reference Example 2 and that the charge was changed to 1590 g and the charge of pure water was eliminated.
  • Table 1 shows the Mooney viscosity, fluorine content, and glass transition temperature at 100 ° C. of the obtained polymer (block copolymer).
  • the rubbery fluorine-containing copolymer was kneaded in the same manner as in Example 1, vulcanized, and the physical properties were examined. The results are as shown in Table 1, and a molded article excellent in cold resistance, low fuel permeability and flexibility was obtained.
  • Example 3 Block copolymer of VdF / TFE / PMVE and VdF / TFE / HFP
  • a stainless steel autoclave with an internal volume of 3 liters was charged with 1390 g of the disversion obtained in Reference Example 1 and 210 g of pure water and 1.8 g of C 7 F 15 COONH 4 as an emulsifier, and the system was thoroughly replaced with nitrogen gas.
  • 2 ml of a 6 mg / ml aqueous solution of ammonium persulfate (APS) was injected under nitrogen pressure to initiate the reaction.
  • APS ammonium persulfate
  • the obtained dispersion was coagulated with aluminum sulfate, washed thoroughly with pure water, and then dried with hot air at 80 ° C. for 8 hours and 120 ° C. for 12 hours to obtain 397 g of polymer.
  • the content of the VdF / TFE / HFP segment in the obtained polymer calculated from the obtained amount was 15% by mass in the polymer.
  • the fluorine content of the VdF / TFE / HFP segment was 73% by mass.
  • Table 1 shows the Mooney viscosity, fluorine content, and glass transition temperature at 100 ° C. of the obtained polymer (block copolymer).
  • Comparative Example 1 Using the VdF / TFE / PMVE copolymer obtained in Reference Example 1, a molded product was prepared in the same manner as in Example 1, and the characteristics were examined. The results are shown in Table 1. As shown in Table 1, it can be seen that the fuel permeability is large.

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Abstract

L'invention porte sur un élastomère fluoré qui, tout en conservant la résistance au froid possédée par les caoutchoucs fluorés résistants au froid, présente une dureté faible et une très faible perméabilité au carburant. L'invention porte également sur une composition destinée à la vulcanisation par peroxyde et sur un composant d'automobile dans un système de carburant fabriqué par moulage la composition. L'élastomère fluoré est un élastomère fluoré vulcanisable par peroxyde. L'élastomère fluoré contient un atome d'iode et est un copolymère séquencé constitué d'un segment d'élastomère fluoré (A) présentant soit (1) un rapport de composition de copolymère de fluorure de vinylidène/oxyde de perfluoroalkyle et de vinyle de 50 à 85/15 à 50 % en mole soit (2) un rapport de composition de copolymère de fluorure de vinylidène/tétrafluoroéthylène/oxyde de perfluoroalkyle et de vinyle de 45 à 85/1 à 30/15 à 30 % en mole et d'un segment d'élastomère fluoré (B) pratiquement incompatible avec le segment d'élastomère fluoré (A).
PCT/JP2009/056084 2008-03-28 2009-03-26 Copolymère séquencé à faible perméabilité au carburant Ceased WO2009119723A1 (fr)

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JP2014515998A (ja) * 2011-05-27 2014-07-07 スリーエム イノベイティブ プロパティズ カンパニー ポリアミド及びフルオロエラストマーを含む複合材料
WO2017011379A1 (fr) * 2015-07-13 2017-01-19 3M Innovative Properties Company Copolymères séquencés fluorés
WO2018050688A1 (fr) * 2016-09-16 2018-03-22 Solvay Specialty Polymers Italy S.P.A. Élastomère thermoplastique fluoré
WO2018136331A1 (fr) * 2017-01-18 2018-07-26 3M Innovative Properties Company Copolymères séquencés fluorés
US11267922B2 (en) 2017-01-18 2022-03-08 3M Innovative Properties Company Fluorinated block copolymers derived from nitrile cure-site monomers
EP4212558A4 (fr) * 2020-09-09 2024-03-13 Zhonghao Chenguang Research Institute of Chemical Industry Co., Ltd. Caoutchouc fluoré à base d'éther perfluoré et procédé de préparation s'y rapportant et son utilisation
WO2025033328A1 (fr) * 2023-08-08 2025-02-13 Ａｇｃ株式会社 Procédé de fabrication de polymère fluoré, dispersion aqueuse, particules, et composition
JP7804869B2 (ja) 2023-08-08 2026-01-23 Ａｇｃ株式会社 含フッ素重合体の製造方法、水性分散液、粒子、及び組成物

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JPS533495A (en) * 1976-06-30 1978-01-13 Daikin Ind Ltd Preparation of fluorine-containing polymer having plurality of chain segments
JPS5933313A (ja) * 1982-08-16 1984-02-23 Daikin Ind Ltd 含フツ素セグメント化ポリマ−およびその製法
JPH0215873Y2 (fr) * 1984-09-04 1990-04-27
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014515998A (ja) * 2011-05-27 2014-07-07 スリーエム イノベイティブ プロパティズ カンパニー ポリアミド及びフルオロエラストマーを含む複合材料
US10590224B2 (en) 2015-07-13 2020-03-17 3M Innovative Properties Company Fluorinated block copolymers
CN107849200B (zh) * 2015-07-13 2020-07-28 3M创新有限公司 氟化嵌段共聚物
CN107849200A (zh) * 2015-07-13 2018-03-27 3M创新有限公司 氟化嵌段共聚物
US20180194888A1 (en) * 2015-07-13 2018-07-12 3M Innovative Properties Company Fluorinated block copolymers
JP2018520248A (ja) * 2015-07-13 2018-07-26 スリーエム イノベイティブ プロパティズ カンパニー フッ素化ブロックコポリマー
WO2017011379A1 (fr) * 2015-07-13 2017-01-19 3M Innovative Properties Company Copolymères séquencés fluorés
WO2018050688A1 (fr) * 2016-09-16 2018-03-22 Solvay Specialty Polymers Italy S.P.A. Élastomère thermoplastique fluoré
CN110191919B (zh) * 2017-01-18 2022-01-18 3M创新有限公司 氟化嵌段共聚物
CN110191919A (zh) * 2017-01-18 2019-08-30 3M创新有限公司 氟化嵌段共聚物
WO2018136331A1 (fr) * 2017-01-18 2018-07-26 3M Innovative Properties Company Copolymères séquencés fluorés
US11261280B2 (en) 2017-01-18 2022-03-01 3M Innovative Properties Company Fluorinated block copolymers
US11267922B2 (en) 2017-01-18 2022-03-08 3M Innovative Properties Company Fluorinated block copolymers derived from nitrile cure-site monomers
EP4212558A4 (fr) * 2020-09-09 2024-03-13 Zhonghao Chenguang Research Institute of Chemical Industry Co., Ltd. Caoutchouc fluoré à base d'éther perfluoré et procédé de préparation s'y rapportant et son utilisation
WO2025033328A1 (fr) * 2023-08-08 2025-02-13 Ａｇｃ株式会社 Procédé de fabrication de polymère fluoré, dispersion aqueuse, particules, et composition
JPWO2025033328A1 (fr) * 2023-08-08 2025-02-13
JP7804869B2 (ja) 2023-08-08 2026-01-23 Ａｇｃ株式会社 含フッ素重合体の製造方法、水性分散液、粒子、及び組成物

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