WO2015125726A1 - パーフルオロエラストマー水性分散液の製造方法及びパーフルオロエラストマーの製造方法 - Google Patents
パーフルオロエラストマー水性分散液の製造方法及びパーフルオロエラストマーの製造方法 Download PDFInfo
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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
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1408—Monomers containing halogen
Definitions
- the present invention relates to a method for producing an aqueous perfluoroelastomer dispersion and a method for producing a perfluoroelastomer.
- a method for producing an aqueous dispersion of a non-perfluoroelastomer or a fluororesin by emulsion polymerization using perfluorohexanoic acid (C 5 F 11 COOH) or a salt thereof is known.
- Patent Document 1 discloses that a fluorine-containing material other than vinylidene fluoride and vinylidene fluoride in the presence of an emulsifier represented by C 5 F 11 COOM (wherein M represents H, NH 4 or an alkali metal).
- An emulsifier represented by C 5 F 11 COOM wherein M represents H, NH 4 or an alkali metal.
- Patent Document 2 describes that a tetrafluoroethylene / propylene copolymer latex was produced by emulsion polymerization using CF 3 (CF 2 ) 4 COO ⁇ (NH 4 ) + as an emulsifier (Reference Example 5). ).
- Patent Document 3 discloses that in emulsion polymerization of a fluorinated monomer using a polymerization catalyst in an aqueous medium containing a fluorinated carboxylic acid compound, the pH of the aqueous medium during polymerization is 4 or less. A method for producing a fluoropolymer is described. In Examples, it is described that tetrafluoroethylene was emulsion-polymerized in the presence of C 5 F 11 COOH to prepare an aqueous emulsion of polytetrafluoroethylene.
- an aqueous dispersion of perfluoroelastomer is represented by the following general formula (1): X- (CF 2 ) m1 -Y (1) (Wherein X represents H or F, m1 represents an integer of 3 to 6, Y represents —SO 3 M, —SO 4 M, —SO 3 R, —SO 4 R, —COOM, —PO 3 A fluorine-containing surfactant represented by M 2 , —PO 4 M 2 (M represents H, NH 4 or an alkali metal, and R represents an alkyl group having 1 to 12 carbon atoms). The manufacturing method is not known.
- An object of the present invention is to provide a method for producing an aqueous perfluoroelastomer dispersion and a perfluoroelastomer capable of realizing a sufficient number of particles and polymerization rate using the fluorine-containing surfactant represented by the general formula (1). It is in providing the manufacturing method of.
- the present inventors In the production of an aqueous perfluoroelastomer dispersion, the present inventors have conventionally carried out emulsion polymerization of a perfluoromonomer in the presence of a specific concentration of the fluorine-containing surfactant represented by the general formula (1).
- the present invention has found that a sufficient number of particles and polymerization rate can be realized without using a fluorine-containing surfactant (for example, perfluorooctanoic acid or a salt thereof) that has been used in the production of an aqueous perfluoroelastomer dispersion. It came to complete.
- perfluoromonomer is emulsion-polymerized in an aqueous medium in the presence of 2 parts by mass or more of the fluorine-containing surfactant represented by the following general formula (1) with respect to 100 parts by mass of the aqueous medium.
- a method for producing an aqueous perfluoroelastomer dispersion comprising a step of obtaining an aqueous dispersion containing perfluoroelastomer particles.
- X- (CF 2 ) m1 -Y (1)
- X represents H or F
- m1 represents an integer of 3 to 6
- Y represents —SO 3 M, —SO 4 M, —SO 3 R, —SO 4 R, —COOM, —PO 3 M 2 , —PO 4 M 2
- M represents H, NH 4 or an alkali metal, and R represents an alkyl group having 1 to 12 carbon atoms.
- the perfluoroelastomer constituting the perfluoroelastomer particles includes tetrafluoroethylene / fluoromonomer copolymer represented by the following general formula (3) and tetrafluoroethylene / fluoro represented by the following general formula (3). It is preferably at least one selected from the group consisting of a monomer / monomer copolymer that provides a crosslinking site.
- CF 2 CF (O (CF 2) n31) m31 (OCF 2) x31 (OCF 2 CF (CF 3)) y31 ORf 31
- n31 represents an integer of 1 to 6
- m31 represents an integer of 0 to 4
- x31 represents an integer of 0 to 6
- y31 represents an integer of 0 to 4
- Rf 31 represents 1 carbon number.
- the perfluoroelastomer constituting the perfluoroelastomer particles is TFE / fluoromonomer copolymer represented by the following general formula (8), (10) or (11) and TFE / the following general formula (8), (10 ) Or (11) is more preferably at least one selected from the group consisting of a fluoromonomer / monomer copolymer that provides a crosslinking site.
- Formula (8): CF 2 CF-ORf 81 (Wherein Rf 81 represents a perfluoroalkyl group having 1 to 8 carbon atoms.)
- Formula (10): CF 2 CFOCF 2 ORf 101 (Wherein Rf 101 is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, or 2 to 6 carbon atoms containing 1 to 3 oxygen atoms.
- CF 2 CFO (CF 2 CF (Y 11) O) m (CF 2) n F (Wherein Y 11 represents a fluorine atom or a trifluoromethyl group.
- M is an integer of 1 to 4.
- n is an integer of 1 to 4.
- the aqueous dispersion containing the perfluoroelastomer particles preferably has a perfluoroelastomer particle number of 5 ⁇ 10 14 particles / cc or more.
- This invention is also a manufacturing method of the perfluoroelastomer characterized by including the process of obtaining a perfluoroelastomer by removing an aqueous medium from the aqueous dispersion liquid containing the perfluoroelastomer particle obtained by the said manufacturing method.
- a sufficient number of particles and polymerization rate can be realized without using a conventional fluorine-containing surfactant such as perfluorooctanoic acid or a salt thereof. it can.
- perfluoromonomer is emulsion-polymerized in an aqueous medium in the presence of 2 parts by mass or more of a specific fluorine-containing surfactant with respect to 100 parts by mass of the aqueous medium. And obtaining an aqueous dispersion containing perfluoroelastomer particles.
- the fluorine-containing surfactant used in the above step is represented by the following general formula (1): X- (CF 2 ) m1 -Y (1) (Wherein X represents H or F, m1 represents an integer of 3 to 6, Y represents —SO 3 M, —SO 4 M, —SO 3 R, —SO 4 R, —COOM, —PO 3 M 2 , —PO 4 M 2 (M represents H, NH 4 or an alkali metal, R represents an alkyl group having 1 to 12 carbon atoms)) .
- Y is preferably —COOM.
- M in the general formula (1) is preferably NH 4 or H, more preferably NH 4 in terms of easy removal from the resulting perfluoroelastomer.
- m1 is preferably an integer of 3 to 5.
- fluorine-containing surfactant examples include the following general formula (1-1): C 5 F 11 COOM (1-1) (Wherein, M represents H, NH 4 or an alkali metal), that is, perfluorohexanoic acid or a salt thereof is preferable. M is preferably NH 4 or H, more preferably NH 4 in terms of easy removal from the resulting perfluoroelastomer.
- the fluorine-containing surfactant represented by the general formula (1) (hereinafter also referred to as fluorine-containing surfactant (1)) is removed from the perfluoroelastomer as compared with other fluorine-containing surfactants.
- fluorine-containing surfactant (1) has the advantage of being easy.
- the fluoroelastomer is obtained in the form of agglomerates, the fluorosurfactant is taken into the mass. Therefore, when removing the fluorine-containing surfactant from the fluoroelastomer, it is difficult to remove the fluorine-containing surfactant by washing.
- the fluorine-containing surfactant is generally removed by heating, particularly drying by heating under vacuum.
- the fluorine-containing surfactant (1) can be easily removed from the perfluoroelastomer by heating as compared with perfluorooctanoic acid or a salt thereof conventionally used for the production of aqueous dispersions of perfluoroelastomer. It has been found that it can be removed. The inventors have found for the first time that the fluorinated surfactant (1) is easily removed by heating compared to other fluorinated surfactants.
- the fluorine-containing surfactant (1) 2 parts by mass or more of the fluorine-containing surfactant (1) is used with respect to 100 parts by mass of the aqueous medium.
- a fluorine-containing surfactant (1) at a concentration within the above range, a sufficient number of particles and polymerization rate can be obtained without using a conventional fluorine-containing surfactant such as perfluorooctanoic acid or a salt thereof. Can be realized.
- the viscosity of the obtained perfluoroelastomer can also be made high.
- the lower limit of the amount of the fluorine-containing surfactant (1) used in the emulsion polymerization is preferably 4 parts by mass, more preferably 6 parts by mass, and still more preferably 9 parts by mass with respect to 100 parts by mass of the aqueous medium.
- the upper limit is not particularly limited, but if the amount used is too large, an effect commensurate with the amount used cannot be obtained and it is economically disadvantageous. Part is more preferable, 50 parts by mass is further preferable, and 25 parts by mass is particularly preferable.
- an aqueous dispersion containing perfluoroelastomer particles is produced by emulsion polymerization of a perfluoromonomer.
- the perfluoromonomer is a monomer that does not contain a carbon atom-hydrogen atom bond in the molecule.
- the perfluoromonomer may be a monomer in which some of the fluorine atoms bonded to the carbon atom are substituted with a chlorine atom in addition to the carbon atom and the fluorine atom. And those having a sulfur atom.
- the perfluoromonomer is preferably a monomer in which all hydrogen atoms are substituted with fluorine atoms. As said perfluoro monomer, what has an oxygen atom is also preferable.
- perfluoromonomer a monomer consisting only of carbon atoms and fluorine atoms and / or a monomer consisting only of carbon atoms, fluorine atoms and oxygen atoms are particularly preferred.
- the perfluoromonomer does not include a monomer that provides a crosslinking site.
- the perfluoroelastomer is a fluoropolymer having a perfluoromonomer unit content of 90 mol% or more based on the total polymerization units, having a glass transition temperature of 20 ° C. or less, and 4.5 J / g. It is a fluoropolymer having the following melting peak ( ⁇ H) size or having no melting peak, and is a polymer having a fluorine atom concentration of 71% by mass or more contained in the fluoropolymer.
- ⁇ H melting peak
- the concentration of fluorine atoms contained in the fluoropolymer is obtained by calculating the concentration (% by mass) of fluorine atoms contained in the fluoropolymer from the type and content of each monomer constituting the fluoropolymer. .
- CF 2 CF (O (CF 2) n31) m31 (OCF 2) x31 (OCF 2 CF (CF 3)) y31 ORf 31 (In the formula, n31 represents an integer of 1 to 6, m31 represents an integer of 0 to 4, x31 represents an integer of 0 to 6, y31 represents an integer of 0 to 4, and Rf 31 represents 1 carbon number.
- CF 2 CFO (CF 2 CF (Y 11) O) m (CF 2) n F (Wherein Y 11 represents a fluorine atom or a trifluoromethyl group, m is an integer of 1 to 4, and n is an integer of 1 to 4). More preferably, it is at least one kind.
- the fluoromonomer represented by the general formula (8) includes at least one selected from the group consisting of perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether), and perfluoro (propyl vinyl ether). Perfluoro (methyl vinyl ether) is preferable.
- CF 2 CFOCF 2 CF (CF 3 ) O (CF 2 ) 3 F
- CF 2 CFO (CF 2 CF (CF 3 ) O) 2 (CF 2 ) 3 F
- CF 2 ⁇ CFO (CF 2 CF (CF 3 ) O) 3 (CF 2 ) 2 F are preferably at least one selected from the group consisting of F.
- the perfluoroelastomer particles can also be produced by polymerizing a perfluoromonomer and a monomer that gives a crosslinking site.
- the monomer that gives a crosslinking site is a monomer having a crosslinkable group that gives the fluoropolymer a crosslinking site for forming a crosslink with a curing agent (cure site monomer).
- CX 3 2 CX 3 -R f 121 CHR 121 X 4
- X 3 is a hydrogen atom, a fluorine atom or CH 3
- R f 121 is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro (poly) oxyalkylene group
- R 121 Is a hydrogen atom or CH 3
- X 4 is an iodine atom or a bromine atom
- CX 3 2 CX 3 -Rf 131 X 4
- X 3 is a hydrogen atom, a fluorine atom or CH 3
- Rf 131 is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or
- m is an integer of 0 to 5
- n is an integer of 1 to 3
- X 6 is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or —CH 2 OH.
- X 3 is preferably a fluorine atom.
- R f 121 and R f 131 are preferably perfluoroalkylene groups having 1 to 5 carbon atoms.
- R 121 is preferably a hydrogen atom.
- aqueous dispersion containing perfluoroelastomer particles can be produced by emulsion polymerization of only the perfluoromonomer or only the perfluoromonomer and the monomer that gives a crosslinking site.
- a fluoromonomer copolymer represented by TFE / general formula (3) and a fluoromonomer / crosslinking site represented by TFE / general formula (3) are used. At least one selected from the group consisting of monomer copolymers to be provided is preferred.
- a perfluoroelastomer containing TFE for example, a fluoromonomer copolymer represented by TFE / general formula (8), (10) or (11) and TFE / general More preferred is at least one selected from the group consisting of a fluoromonomer represented by the formula (8), (10) or (11) / a monomer copolymer which gives a crosslinking site.
- the composition is preferably 45 to 90/10 to 55 (mol%), more preferably 55 to 80/20 to 45, and still more preferably 55 to 70/30 to 45.
- a monomer copolymer giving a TFE / PMVE / crosslinking site it is preferably 45 to 89.9 / 10 to 54.9 / 0.01 to 4 (mol%), more preferably 55 to 79. 9/20 to 44.9 / 0.1 to 3.5, and more preferably 55 to 69.8 / 30 to 44.8 / 0.2 to 3.
- a fluoromonomer copolymer represented by the general formula (8), (10) or (11) having 4 to 12 carbon atoms preferably 50 to 90/10 to 50 (mol%). More preferably, it is 60 to 88/12 to 40, and still more preferably 65 to 85/15 to 35.
- the composition is out of the range, the properties as a rubber elastic body are lost, and the properties tend to be similar to those of a resin.
- perfluoroelastomer examples include TFE / fluoromonomer copolymer represented by the general formula (11), TFE / fluoromonomer represented by the general formula (11) / monomer copolymer that provides a crosslinking site, TFE / general It is at least one selected from the group consisting of a fluoromonomer copolymer represented by formula (8) and a fluoromonomer represented by TFE / general formula (8) / a monomer copolymer that provides a crosslinking site. More preferably.
- perfluoroelastomer examples include perfluoroelastomers described in International Publication No. 97/24381 pamphlet, Japanese Patent Publication No. 61-57324, Japanese Patent Publication No. 4-81608, Japanese Patent Publication No. 5-13961, and the like. be able to.
- the monomer unit composition of the perfluoroelastomer can be measured by appropriately combining NMR, IR, UV, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.
- the aqueous medium used in the emulsion polymerization means a reaction medium for performing polymerization and means a liquid containing water.
- the aqueous medium is not particularly limited as long as it contains water, and water and, for example, a fluorine-free organic solvent such as alcohol, ether, and ketone, and / or a fluorine-containing organic solvent having a boiling point of 200 ° C. or lower. May be included.
- the emulsion polymerization is usually performed in the presence of a polymerization initiator.
- a polymerization initiator an oil-soluble radical polymerization initiator or a water-soluble radical initiator 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-butylperoxydicarbonate, t-butylperoxy Peroxyesters such as isobutyrate and t-butyl peroxypivalate, dialkyl peroxides such as di-t-butyl peroxide, and di ( ⁇ -hydro-dodecafluoroheptanoyl) peroxide, di ( ⁇ -hydro-tetradecafluoroheptanoyl) peroxide, di ( ⁇ -hydro-hexadecafluorononanoyl) peroxide, di (perfluorobutyryl) peroxide, di (perfluorovaleryl) peroxide, di (Perfluorohexanoyl) pero Side, di (perfluoroheptanoyl) peroxide, di (perfluor
- the water-soluble radical polymerization initiator may be a known water-soluble peroxide, for example, ammonium salts such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, percarbonate, potassium salts, sodium salts. , T-butyl permaleate, t-butyl hydroperoxide and the like.
- a reducing agent such as sulfites and sulfites may also be included, and the amount used may be 0.1 to 20 times that of the peroxide.
- a redox initiator that combines an oxidizing agent and a reducing agent as the polymerization initiator.
- the oxidizing agent is preferably a persulfate
- the reducing agent is preferably a sulfite.
- the persulfate include ammonium persulfate and potassium persulfate.
- the sulfite include sodium sulfite and ammonium sulfite.
- a copper salt or an iron salt to the combination of redox initiators.
- the copper salt include copper (II) sulfate
- examples of the iron salt include iron (II) sulfate.
- the addition amount of the polymerization initiator is not particularly limited, but an amount that does not significantly reduce the polymerization rate (for example, several ppm to water concentration) or more is collectively or sequentially or continuously in the initial stage of polymerization. Can be added.
- the upper limit is a range in which the polymerization reaction heat can be removed from the surface of the production apparatus.
- the above emulsion polymerization may be performed in the presence of a chain transfer agent.
- chain transfer agent include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, dimethyl succinate, isopentane, methane, ethane, propane, isopropanol, acetone, various mercaptans, Examples thereof include carbon tetrachloride and cyclohexane.
- a bromine compound or iodine compound may be used as the chain transfer agent.
- Examples of the polymerization method performed using a bromine compound or an iodine compound include a method of polymerizing a fluoromonomer in an aqueous medium in the presence of a bromine compound or an iodine compound in a substantially oxygen-free state ( Iodine transfer polymerization method).
- bromine compounds or iodine compounds to be used include, for example, the general formula: R 2 I x Br y (Wherein x and y are each an integer of 0 to 2 and satisfy 1 ⁇ x + y ⁇ 2, and R 2 is a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or chlorofluoro A hydrocarbon group, or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom).
- a bromine compound or an iodine compound iodine or bromine is introduced into the polymer and functions as a crosslinking point.
- iodine compound examples include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5- Diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane , diiodomethane, 1,2-diiodoethane, 1,3-diiodo -n- propane, CF 2 Br 2, BrCF 2 CF 2 Br, CF 3 CFBrCF 2 Br, CFClBr 2, BrCF 2 CFClBr, CFBrC
- 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are used from the viewpoint of polymerization reactivity, crosslinking reactivity, availability, and the like. Is preferred.
- the amount of the chain transfer agent used is usually 1 to 100000 ppm with respect to the total amount of monomers supplied, a preferred lower limit is 10 ppm, and a preferred upper limit is 50000 ppm.
- the polymerization temperature, polymerization pressure, and polymerization time vary depending on the type of solvent and polymerization initiator, but may be -15 to 150 ° C., atmospheric pressure to 6.5 MPa, and 1 to 96 hours.
- the polymerization temperature is preferably 15 to 95 ° C.
- the polymerization temperature is preferably 0 to 100 ° C, more preferably 10 to 95 ° C.
- the emulsion polymerization is preferably performed at 0.1 to 3.9 MPaG, more preferably at 0.6 MPaG or more, and more preferably at 3.0 MPaG or less.
- an aqueous medium, a fluorine-containing surfactant (1) and a monomer are charged into a polymerization reactor, the contents of the reactor are stirred, and the reactor is maintained at a predetermined polymerization temperature. Then, a polymerization initiator is added and the polymerization reaction is started.
- an aqueous medium and a fluorine-containing surfactant (1) are charged into a polymerization reactor, stirred and maintained at a predetermined polymerization temperature, then a monomer is charged, and then a polymerization initiator is added to start a polymerization reaction. May be performed.
- additives or the like may be charged into the reactor as necessary.
- a monomer, a polymerization initiator, a chain transfer agent, or the like may be additionally added depending on the purpose.
- the emulsion polymerization in the production method of the present invention is represented by the following general formula (2).
- X represents H or F, m2 represents an integer of 7 or more, and Y represents —SO 3 M, —SO 4 M, —SO 3 R, —SO 4 R, —COOM, —PO 3 M 2 , —PO 4 M 2 (M represents H, NH 4 or an alkali metal, and R represents an alkyl group having 1 to 12 carbon atoms)) in the absence of a fluorine-containing compound represented by Preferably it is done.
- the production method of the present invention a sufficient number of particles and polymerization rate can be realized without using such a conventional fluorine-containing surfactant. Furthermore, the emulsion polymerization is preferably performed in the absence of a fluorinated surfactant other than the fluorinated surfactant (1).
- the emulsion polymerization is preferably radical polymerization.
- an aqueous dispersion containing perfluoroelastomer particles can be produced.
- the aqueous dispersion containing the perfluoroelastomer particles preferably has a perfluoroelastomer particle number of 5 ⁇ 10 14 particles / cc or more.
- the number of particles can be adjusted by adjusting the amount of the fluorine-containing surfactant (1) used, the stirring speed, the amount of monomer added, and the like.
- the lower limit of the number of particles is more preferably 1 ⁇ 10 15 particles / cc, and further preferably 7 ⁇ 10 15 particles / cc.
- an upper limit is not specifically limited, It is preferable that it is 5 * 10 ⁇ 17 > piece / cc.
- the method for measuring the number of particles is as described as a measuring method in Examples described later.
- the perfluoroelastomer particles preferably have a volume average particle diameter of 0.1 to 100 nm.
- the volume average particle diameter of the perfluoroelastomer particles is more preferably 0.5 nm or more, further preferably 1.0 nm or more, more preferably 70 nm or less, and further preferably 50 nm or less. , 30 nm or less is particularly preferable.
- the measuring method of the volume average particle diameter is as described as a measuring method in Examples described later.
- the aqueous dispersion containing the perfluoroelastomer particles preferably has a solid content concentration of 1% by mass or more, more preferably 10% by mass or more, and still more preferably 18% by mass or more.
- the solid content concentration is high in this way, if the particle diameter of the perfluoroelastomer particles is the same, the number of particles per unit aqueous medium amount increases and the polymerization rate increases. As a result, the productivity of synthesis of perfluoroelastomer particles is improved.
- an upper limit is not specifically limited, It is preferable that it is 30 mass%.
- the measurement method of the solid content concentration is as described as a measurement method in Examples described later.
- the aqueous dispersion containing the perfluoroelastomer particles may be subjected to multistage polymerization. That is, in the presence of the perfluoroelastomer particles and the polymerization initiator, the fluoromonomer may be further polymerized in an aqueous medium.
- the perfluoroelastomer has a glass transition temperature of preferably ⁇ 70 ° C. or higher, more preferably ⁇ 50 ° C. or higher, and further preferably ⁇ 30 ° C. or higher, from the viewpoint of excellent compression set at high temperatures. preferable. Further, from the viewpoint of good cold resistance, it is preferably 5 ° C. or lower, more preferably 0 ° C. or lower, and further preferably ⁇ 3 ° C. or lower.
- the glass transition temperature can be determined as follows. Using a differential scanning calorimeter (manufactured by METTLER TOLEDO, DSC822e), a DSC curve is obtained by heating 10 mg of the sample at 10 ° C./min, and the peak top temperature of the differential curve defined in JIS K6240 is the glass transition. Let it be temperature.
- the perfluoroelastomer preferably has a Mooney viscosity ML (1 + 10) at 100 ° C. of 10 or more, more preferably 20 or more, and still more preferably 30 or more from the viewpoint of good heat resistance. Further, in terms of good workability, it is preferably 120 or less, more preferably 100 or less, and still more preferably 80 or less.
- the perfluoroelastomer preferably has a Mooney viscosity ML (1 + 20) at 170 ° C. of 30 or more, more preferably 40 or more, and still more preferably 50 or more from the viewpoint of good heat resistance. Further, in terms of good workability, it is preferably 150 or less, more preferably 120 or less, and even more preferably 110 or less.
- the Mooney viscosity can be measured according to JIS K6300 at 100 ° C. or 170 ° C. using a Mooney viscometer MV2000E type manufactured by ALPHA TECHNOLOGIES.
- the perfluoroelastomer can be peroxide-crosslinked and has excellent mechanical properties. It is preferable that the iodine content in the obtained perfluoroelastomer is 0.02 to 5.0% by mass in that a crosslinked elastic body is obtained.
- the iodine content is more preferably 0.05 to 3.0% by mass, and further preferably 0.1 to 2.0% by mass.
- the present invention includes a step of obtaining a perfluoroelastomer by removing an aqueous medium from an aqueous dispersion containing perfluoroelastomer particles obtained by the above method for producing an aqueous perfluoroelastomer dispersion. It is also a method for producing an elastomer.
- Examples of the method for removing the aqueous medium from the aqueous dispersion containing perfluoroelastomer particles include (i) a method of heating, evacuating or both of the aqueous dispersion, and (ii) the aqueous dispersion. And a method of heating, evacuating or both of the coagulated product after obtaining the coagulated product.
- the aqueous dispersion obtained by the above method for producing an aqueous perfluoroelastomer dispersion contains a fluorine-containing surfactant (1).
- fluorine-containing surfactant (1) is easier to remove by heating or vacuuming than conventional fluorine-containing surfactants such as perfluorooctanoic acid or a salt thereof, in the method for producing the perfluoroelastomer of the present invention, Can sufficiently remove the fluorine-containing surfactant (1) simultaneously with the removal of the aqueous medium.
- the heating in the method (i) is performed at 50 to 200 ° C. for 2 to 100 hours in order to remove the aqueous medium and the fluorine-containing surfactant (1) without deteriorating the perfluoroelastomer itself. It is preferable.
- the evacuation in the method (i) is preferably performed by placing the aqueous dispersion under vacuum for 2 to 100 hours. In the method (i), heating is preferably performed, and both heating and evacuation are performed in order to more reliably remove the aqueous medium and the fluorine-containing surfactant (1) (for example, the heating described above). Is more preferably performed under vacuum).
- the coagulation in the above method (ii) is carried out by adding an inorganic salt or inorganic acid such as aluminum sulfate to the aqueous dispersion, applying mechanical shearing force to the aqueous dispersion, or freezing the aqueous dispersion. It can be carried out.
- the heating in the method (ii) is performed at 50 to 200 ° C. for 2 to 100 hours in order to remove the aqueous medium and the fluorine-containing surfactant (1) without deteriorating the perfluoroelastomer itself. It is preferable.
- the evacuation in the method (ii) is preferably performed by placing the coagulated material under vacuum for 2 to 100 hours. In the method (ii), heating is preferably performed, and both heating and evacuation are performed in order to more reliably remove the aqueous medium and the fluorine-containing surfactant (1) (for example, the heating described above). Is more preferably performed under vacuum).
- the coagulated product obtained by coagulating the aqueous dispersion may be washed as necessary.
- a conventional method may be adopted for the washing.
- the method (ii) is preferable in that the following effects can be obtained.
- the aqueous dispersion containing the perfluoroelastomer particles is coagulated, a massive coagulated product is obtained. Since the fluorine-containing surfactant used in the emulsion polymerization is taken into the coagulated product, the fluorine-containing surfactant cannot be sufficiently removed only by washing. For this reason, it is necessary to remove the fluorine-containing surfactant by heating and / or evacuation.
- the fluorine-containing surfactant contained in the aqueous dispersion obtained by the above method for producing an aqueous dispersion of perfluoroelastomer is a fluorine-containing surfactant (1)
- conventional fluorine-containing surfactants such as perfluorooctanoic acid or a salt thereof are used. Removal by heating and / or evacuation is easier than when a fluorosurfactant is used.
- the fluorine-containing surfactant (1) can be more easily removed by heat drying under vacuum.
- a perfluoroelastomer can be produced by the above method.
- Examples of the form of perfluoroelastomer include crumb and sheet.
- aqueous perfluoroelastomer dispersion and perfluoroelastomer obtained by the production method of the present invention have excellent physical properties that are not inferior to conventional perfluoroelastomer aqueous dispersions and perfluoroelastomers. It can be used in the same manner as known perfluoroelastomer aqueous dispersions and perfluoroelastomers and can be used in the same applications.
- a perfluoroelastomer comprising polymerized units based on perfluoro (alkyl vinyl ether) (PAVE), wherein the content of polymerized units based on PAVE is 42.0 to 55.0 mol% based on the total polymerized units, 170 Perfluoroelastomers having a Mooney viscosity ML (1 + 20) at 30 ° C. of 30 to 120 are also useful.
- the perfluoroelastomer is a novel perfluoroelastomer. According to the manufacturing method described above, such a perfluoroelastomer can be easily manufactured.
- the perfluoroelastomer is excellent in low-temperature resistance because the content of polymerized units based on PAVE is 42.0 to 55.0 mol% with respect to all polymerized units.
- the lower limit of the content of polymerized units based on PAVE is preferably 42.5 mol%, more preferably 43.0 mol%, more preferably 43.5 mol%, based on all polymerized units. Further preferred.
- the upper limit is preferably 54.0 mol%, more preferably 53.0 mol%, still more preferably 52.0 mol%, based on all polymerized units.
- CF 2 CF-ORf 81
- Rf 81 represents a perfluoroalkyl group having 1 to 8 carbon atoms), and is preferably perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether), and perfluoroalkyl group. At least one selected from the group consisting of fluoro (propyl vinyl ether) is more preferable, and perfluoro (methyl vinyl ether) is more preferable.
- the perfluoroelastomer preferably includes polymerized units based on tetrafluoroethylene (TFE).
- TFE tetrafluoroethylene
- the content of polymerized units based on TFE is preferably 45.0 to 58.0 mol% with respect to the total polymerized units.
- the lower limit of the content of polymerized units based on TFE is more preferably 46.0 mol%, even more preferably 47.0 mol%, and 48.0 mol% with respect to all polymerized units. Is particularly preferred.
- the upper limit is more preferably 57.5 mol%, more preferably 57.0 mol%, and particularly preferably 56.5 mol%, based on all polymerized units.
- the lower limit of the content of polymerized units based on TFE may be 44.99 mol%, 44.9 mol%, or 44.8 mol% based on all polymerized units.
- the upper limit of the content of polymerized units based on TFE may be 57.9 mol%, 57.9 mol%, or 57.8 mol% with respect to all polymerized units. .
- the perfluoroelastomer may further include a polymer unit based on a perfluoro monomer other than TFE and PAVE and a polymer unit based on a monomer that provides a crosslinking site.
- perfluoromonomer other than TFE and PAVE examples include those other than TFE and PAVE among the above-mentioned perfluoromonomers.
- Examples of the monomer that gives a crosslinking site include those described above.
- the content of the polymerized units based on the monomer that gives a crosslinking site may be 10 mol% or less, preferably 0.01 to 4.00 mol%, based on the total polymerized units.
- the lower limit is more preferably 0.1 mol%, still more preferably 0.2 mol%.
- the upper limit is more preferably 3.5 mol%, further preferably 3 mol%.
- the perfluoroelastomer preferably has a cyano group.
- the cyano group can be introduced, for example, by copolymerization of the monomer having the cyano group.
- the perfluoroelastomer is excellent in vulcanizability, tensile strength and compression set resistance of the resulting vulcanizate because the Mooney viscosity ML (1 + 20) at 170 ° C. is 30 to 120.
- the lower limit of Mooney viscosity ML (1 + 20) at 170 ° C. is preferably 35, more preferably 40, and still more preferably 45.
- the upper limit is preferably 115, more preferably 110, and still more preferably 105.
- the aqueous perfluoroelastomer dispersion obtained by the method for producing an aqueous perfluoroelastomer dispersion of the present invention, the perfluoroelastomer obtained by the method for producing a perfluoroelastomer of the present invention, and the above-mentioned novel perfluoroelastomer are:
- the perfluoroelastomer composition can be constituted with necessary components. Such perfluoroelastomer compositions are also useful.
- the perfluoroelastomer composition preferably contains a perfluoroelastomer and a crosslinking agent, and may further contain water and / or an organic solvent depending on the application.
- a perfluoroelastomer composition may be obtained by adding necessary components to the aqueous perfluoroelastomer dispersion, or a perfluoroelastomer composition may be obtained by adding necessary components to the perfluoroelastomer.
- the perfluoroelastomer composition can be applied to various uses as a molded article by crosslinking and molding. Such molded articles are also useful.
- the molded article can be produced by molding the perfluoroelastomer composition and crosslinking the resulting molded article, or can be produced by simultaneously molding and crosslinking.
- the molding method is not particularly limited, and examples thereof include compression molding, extrusion molding, transfer molding, and injection molding.
- the molded article can also be obtained as a coating film by coating and crosslinking the perfluoroelastomer composition.
- fields in which the molded products are used include, for example, semiconductor-related fields, automotive fields, aircraft fields, space / rocket fields, ship fields, chemical fields such as chemical plants, pharmaceutical fields such as pharmaceuticals, photographic fields such as developing machines, Printing field such as printing machinery, painting field such as coating equipment, analysis equipment, analysis / physical machinery field such as instruments, food equipment field including food plant equipment and household goods, beverage food production equipment field, pharmaceutical production equipment field, medical treatment Parts field, chemical transport equipment field, nuclear power plant equipment field, steel field such as iron plate processing equipment, general industrial field, electrical field, fuel cell field, electronic component field, optical equipment part field, space equipment part field, petroleum Examples include chemical plant equipment field, oil and gas energy resource exploration equipment parts field, oil refining field, oil transportation equipment parts field, etc.
- Examples of usage of the molded product include rings, packing, gaskets, diaphragms, oil seals, bearing seals, lip seals, plunger seals, door seals, lip and face seals, gas delivery plate seals, wafer support seals, and barrel seals.
- Such as various sealing materials and packing As a sealing material, it can be used for applications requiring heat resistance, solvent resistance, chemical resistance, and non-adhesiveness.
- the cross-sectional shapes of the ring, packing, and seal may be various shapes.
- the ring, the packing, and the seal may have a square shape, an O shape, a ferrule shape, a D shape, Different shapes such as an L shape, a T shape, a V shape, an X shape, and a Y shape may be used.
- semiconductor manufacturing apparatus liquid crystal panel manufacturing apparatus, plasma panel manufacturing apparatus, plasma display panel manufacturing apparatus, plasma address liquid crystal panel manufacturing apparatus, organic EL panel manufacturing apparatus, field emission display panel manufacturing apparatus, solar It can be used for a battery substrate manufacturing apparatus, a semiconductor transfer apparatus, and the like.
- examples of such an apparatus include a gas control apparatus such as a CVD apparatus and a semiconductor gas control apparatus, a dry etching apparatus, a wet etching apparatus, a plasma etching apparatus, a reactive ion etching apparatus, a reactive ion beam etching apparatus, and a sputter etching.
- Apparatus ion beam etching apparatus, oxidation diffusion apparatus, sputtering apparatus, ashing apparatus, plasma ashing apparatus, cleaning apparatus, ion implantation apparatus, plasma CVD apparatus, exhaust apparatus, exposure apparatus, polishing apparatus, film forming apparatus, dry etching cleaning apparatus, UV / O 3 cleaning device, ion beam cleaning device, laser beam cleaning device, plasma cleaning device, gas etching cleaning device, extraction cleaning device, Soxhlet extraction cleaning device, high temperature high pressure extraction cleaning device, microwave extraction cleaning device, supercritical extraction Cleaning equipment Equipment, cleaning equipment using hydrofluoric acid, hydrochloric acid, sulfuric acid, ozone water, stepper, coater / developer, CMP equipment, excimer laser exposure machine, chemical piping, gas piping, NF 3 plasma treatment, O 2 plasma treatment, fluorine plasma treatment Equipment for plasma processing such as heat treatment film forming equipment, wafer transfer equipment, wafer cleaning equipment, silicon wafer cleaning equipment, silicon wafer processing equipment, equipment used in LP-CVD processes, equipment used in lamp
- Specific usage forms in the field of semiconductors include, for example, various sealing materials such as gate valves, quartz windows, chambers, chamber lits, gates, bell jars, couplings, pump O-rings and gaskets; resist developers and stripping Various sealing materials such as O-rings for liquid, hoses and tubes; resist developer tank, stripper tank, wafer cleaning liquid tank, wet etching tank lining and coating; pump diaphragm; wafer transfer roll; wafer cleaning liquid Hose tube; Clean equipment sealant such as sealant for clean equipment such as clean room; Sealing material for storage for storing devices such as semiconductor manufacturing equipment and wafers; Diaphragm for transferring chemicals used in semiconductor manufacturing processes Can be mentioned.
- various sealing materials such as gate valves, quartz windows, chambers, chamber lits, gates, bell jars, couplings, pump O-rings and gaskets
- resist developers and stripping Various sealing materials such as O-rings for liquid, hoses and tubes; resist developer tank, stripper tank, wafer cleaning liquid tank
- the engine body In the automotive field, the engine body, main motion system, valve system, lubrication / cooling system, fuel system, intake / exhaust system, drive system transmission system, chassis steering system, brake system, basic electrical components, control It can be used for electrical components such as system electrical components and equipment electrical components.
- the automobile field includes a motorcycle.
- the molded product can be used for various sealing materials that are required to have heat resistance, oil resistance, fuel oil resistance, engine cooling antifreeze resistance, and steam resistance.
- Non-contact type or contact type packings such as seals such as gaskets, shaft seals, valve stem seals, self seal packings, piston rings, split ring type packings, mechanical seals, oil seals, etc. Examples include bellows, diaphragms, hoses, tubes, electric wires, cushioning materials, vibration-proof materials, and various sealing materials used in belt AT devices.
- Specific usage forms in the above fuel system include fuel injectors, cold start injectors, fuel line quick connectors, sender flange quick connectors, fuel pumps, fuel tank quick connectors, gasoline mixing pumps, gasoline pumps, fuel O-rings used in tube bodies, fuel tube connectors, injectors, etc .; expiratory manifolds, fuel filters, pressure regulators, canisters, fuel tank caps, fuel pumps, fuel tanks, fuel tank sender units, fuel Used in injection devices, high-pressure fuel pumps, fuel line connector systems, pump timing control valves, suction control valves, solenoid subassemblies, fuel cut valves, etc.
- Seal canister, purge, solenoid, valve seal, onboard, refueling, vapor, recovery (ORVR) valve seal, oil seal for fuel pump, fuel sender seal, fuel tank rollover valve seal, filler seal, Injector seal, filler cap seal, filler cap valve seal; fuel hose, fuel supply hose, fuel return hose, vapor (evaporation) hose, vent (breather) hose, filler hose, filler neck hose, hose in fuel tank (in Tank hoses), carburetor control hoses, fuel inlet hoses, fuel breather hoses and other hoses; gas filters used in fuel filters, fuel line connector systems, etc.
- Flange gaskets used for fuel tanks, carburetors, etc . Line materials such as steam recovery lines, fuel feed lines, vapor / ORVR lines; canisters, ORVR, fuel pumps, fuel tank pressure sensors, gasoline pumps, carburetor sensors, combined air control Diaphragms used in equipment (CAC), pulsation dampers, canisters, auto cocks, etc., pressure regulator diaphragms for fuel injection devices; valves for fuel pumps, carburetor needle valves, rollover check valves, check valves; Breather), tubes used in fuel tanks; tank packings for fuel tanks, packings for accelerating pump pistons for carburetors; fuel sender anti-vibration parts for fuel tanks O-ring and diaphragm to control fuel pressure; accelerator pump cup; in-tank fuel pump mount; fuel injector injector cushion ring; injector seal ring; carburetor needle valve core valve; carburetor acceleration pump Examples include a piston; a valve seat of a composite air control device (CAC); a fuel
- Specific usage forms in the brake system include: a diaphragm used for a master back, a hydraulic brake hose air brake, a brake chamber of an air brake; a hose used for a brake hose, a brake oil hose, a vacuum brake hose, etc .; an oil seal Various sealing materials such as O-rings, packings, brake piston seals, atmospheric valves and vacuum valves for master backs, check valves for brake valves, piston cups (rubber cups) for master cylinders, brake cups, hydraulic brakes Master cylinders and vacuum boosters, hydraulic brake wheel cylinder boots, anti-lock brake system (ABS) O-rings and grommets.
- sealing materials such as O-rings, packings, brake piston seals, atmospheric valves and vacuum valves for master backs, check valves for brake valves, piston cups (rubber cups) for master cylinders, brake cups, hydraulic brakes Master cylinders and vacuum boosters, hydraulic brake wheel cylinder boots, anti-lock brake system (ABS) O-rings
- Specific usage forms in the basic electrical component include an insulator and sheath of an electric wire (harness), a tube of a harness exterior component, a grommet for a connector, and the like.
- Specific usage forms in the control system electrical component include coating materials for various sensor wires.
- Specific use forms for the above-mentioned electrical components include car air conditioner O-rings, packing, cooler hoses, high pressure air conditioner hoses, air conditioner hoses, gaskets for electronic throttle units, plug plugs for direct ignition, distributor diaphragms, etc. Is mentioned. It can also be used for bonding electrical components.
- Specific usage forms in the intake / exhaust system include packing used for intake manifolds, exhaust manifolds, etc., throttle body packing of throttles; EGR (exhaust gas recirculation), pressure control (BPT), wastegate, turbo waist Diaphragms used for gates, actuators, variable turbine geometry (VTG) turbo actuators, exhaust purification valves, etc .; EGR (exhaust recirculation) control hoses, emission control hoses, turbocharger turbo oil hoses (supply), turbo Oil hose (return), turbo air hose, intercooler hose, turbocharger hose, hose connected to compressor of turbo engine equipped with intercooler, exhaust Hose such as air hose, air intake hose, turbo hose, DPF (diesel particulate collection filter) sensor hose; air duct or turbo air duct; intake manifold gasket; EGR sealing material, AB valve afterburn prevention valve seat, (turbocharger etc.
- the seal member used for groove parts such as a turbine shaft seal,
- seals used for steam recovery canisters, catalytic converters, exhaust gas sensors, oxygen sensors, etc., and steam recovery and steam canister solenoid armature seals; used as intake manifold gaskets, etc. Can do.
- it can be used as an O-ring seal for a direct injection injector, a rotary pump seal, a control diaphragm, a fuel hose, an EGR, a priming pump, a boost compensator diaphragm, and the like. It can also be used for O-rings, seal materials, hoses, tubes, diaphragms used in urea SCR systems, urea water tank bodies of urea SCR systems, and seal materials for urea water tanks.
- Transmissions include AT (automatic transmission), MT (manual transmission), CVT (continuously variable transmission), DCT (dual clutch transmission), and the like.
- oil seals, gaskets, O-rings and packings for manual or automatic transmissions oil seals, gaskets, O-rings and packings for continuously variable transmissions (belt type or toroidal type), ATF linear solenoids Packing, oil hose for manual transmission, ATF hose for automatic transmission, CVTF hose for continuous transmission (belt type or toroidal type), and the like.
- Specific usage forms in the steering system include a power steering oil hose and a high pressure power steering hose.
- cylinder head gaskets For example, cylinder head gaskets, cylinder head cover gaskets, oil pan packings, gaskets such as general gaskets, seals such as O-rings, packings, timing belt cover gaskets, control hoses, etc.
- gaskets such as general gaskets
- seals such as O-rings, packings, timing belt cover gaskets, control hoses, etc.
- hoses engine mount anti-vibration rubber, control valve diaphragms, camshaft oil seals and the like.
- a shaft seal such as a crankshaft seal and a camshaft seal
- a valve system of an automobile engine it can be used for a valve stem oil seal of an engine valve, a valve seat of a butterfly valve, and the like.
- engine oil cooler hoses In automotive engine lubrication and cooling systems, engine oil cooler hoses, oil return hoses, seal gaskets, water hoses around radiators, radiator seals, radiator gaskets, radiator O-rings, vacuum pumps, etc.
- a vacuum pump oil hose In addition to a vacuum pump oil hose, etc., it can be used for a radiator hose, a radiator tank, an oil pressure diaphragm, a fan coupling seal, and the like.
- specific examples of use in the automotive field include engine head gaskets, oil pan gaskets, manifold packings, oxygen sensor seals, oxygen sensor bushings, nitrogen oxide (NOx) sensor seals, and nitrogen oxide (NOx).
- Sensor bushing sulfur oxide sensor seal, temperature sensor seal, temperature sensor bush, diesel particle filter sensor seal, diesel particle filter sensor bush, injector O-ring, injector packing, fuel pump O-ring and diaphragm, gearbox Seal, power piston seal, cylinder liner seal, valve stem seal, static valve stem seal, dynamic valve stem seal, automatic Speed pump front pump seal, rear axle pinion seal, universal joint gasket, speedometer pinion seal, foot brake piston cup, torque transmission device O-ring and oil seal, exhaust gas recombustion device seal and bearing seal, Recombustion device hose, carburetor sensor diaphragm, anti-vibration rubber (engine mount, exhaust, muffler hanger, suspension bush, center bearing, strut bumper rubber, etc.), suspension anti-vibration rubber (strut mount, bush,
- the fuel system and the lubricating oil system can be used.
- various types of sealing parts for aircraft various types of aircraft parts for aircraft engine oil, jet engine valve stem seals, gaskets and O-rings, rotating shaft seals, hydraulic equipment gaskets, firewall seals, etc. They can be used as fuel supply hoses, gaskets, O-rings, aircraft cables, oil seals, shaft seals, and the like.
- lip seals for diaphragms, jet engines, missiles, diaphragms, O-rings, O-rings for gas turbine engine oils, anti-vibration stand pads for missile ground control, etc. Can be used.
- O-rings for mechanical seals, O-rings for compressor sealing; high-temperature vacuum dryers, gas chromatography and pH Packing used for the tube connection of a heater, glass cooler packing for sulfuric acid production equipment; Diaphragms used for diaphragm pumps, analytical instruments and physics and chemistry instruments; Gaskets used for analytical instruments and instruments; Analytical instruments and instruments Ferrules used in the field; valve seats; U cups; linings used in chemical equipment, gasoline tanks, wind tunnels, etc., corrosion resistant linings in anodized processing tanks; coating of masking jigs for plating; valves for analytical instruments and physics and chemistry instruments Parts; Expansion joints of flue gas desulfurization plants; Acid-resistant hoses for concentrated sulfuric acid, chlorine gas transfer hoses, oil-resistant hoses, rainwater drain hoses for benzene and toluene storage tanks; chemical-resistant tubes used for analytical instruments and physics and chemistry instruments Medical tube; Trickle resistant for textile dyeing Use roll
- the photographic field such as the developing machine, the printing field such as a printing machine, and the coating field such as a coating facility, it can be used as a roll, a belt, a seal, a valve part, etc. of a dry copying machine.
- Specific usage forms in the photographic field, printing field, and painting field include a surface layer of a transfer roll of a copying machine, a cleaning blade of a copying machine, a belt of a copying machine; for OA equipment such as a copying machine, a printer, and a facsimile machine.
- Rolls for example, fixing rolls, pressure rolls, pressure rolls, etc.
- belts rolls for PPC copiers, roll blades, belts; rolls for film developing machines and X-ray film developing machines; printing rolls for printing machines , Scrapers, tubes, valve parts, belts; printer ink tubes, rolls, belts; coating, painting equipment coating rolls, scrapers, tubes, valve parts; development rolls, gravure rolls, guide rolls, magnetic tape production coating lines Guide rolls, gravure rolls and coating rolls for magnetic tape production coating lines And the like.
- packing, a gasket, a tube, a diaphragm, a hose, a joint sleeve etc. which are used for products, such as alcoholic beverages and soft drinks, a filling device, a food sterilizer, a brewing device, a water heater, various automatic food vending machines, etc. are also mentioned.
- the nuclear plant equipment field it can be used as a check valve, a pressure reducing valve, a seal of a uranium hexafluoride concentrator, etc. around the reactor.
- Specific usage forms in the general industrial field include: sealing materials for hydraulic equipment such as machine tools, construction machines, hydraulic machines; seals and bearing seals for hydraulic and lubrication machines; sealing materials used for mandrels, etc .; dry cleaning equipment Seals used for windows, etc .; cyclotron seals, (vacuum) valve seals, proton accelerator seals, automatic packaging machine seals, pump diaphragms and snakes for sulfur dioxide and chlorine gas analyzers (pollution measuring instruments) in the air Pump lining, printing press rolls and belts, transport belts (conveyor belts), pickling squeezing rolls such as iron plates, robot cables, solvent squeezing rolls such as aluminum rolling lines, coupler O-rings, acid-resistant cushioning materials , Dust seals and lip rubber on sliding parts of cutting machines, garbage incinerators Basket, friction materials, surface modifier metal or rubber, dressings and the like.
- gaskets and sealants for equipment used in the papermaking process sealants for clean room filter units, sealants for construction, protective coatings for concrete and cement, glass cloth impregnated materials, polyolefin processing aids, polyethylene molding It can also be used as a property improving additive, a fuel container such as a small generator or lawn mower, a pre-coated metal obtained by subjecting a metal plate to a primer treatment, and the like. In addition, it can be impregnated into a woven fabric and baked to be used as a sheet and a belt.
- Specific usage forms in the steel field include iron plate processing rolls for iron plate processing equipment.
- Specific usage forms in the electrical field include: Shinkansen insulating oil caps, liquid-sealed transformer benching seals, transformer seals, oil well cable jackets, electric furnace oven oven seals, microwave oven window frames, etc. Used for sealing, sealing materials used when bonding CRT wedges and necks, halogen lamp sealing materials, electrical component fixing agents, sheathing heater end treatment sealing materials, electrical equipment lead wire terminals The sealing material etc. which are used are mentioned. Also used for coating materials such as oil and heat resistant wires, high heat resistant wires, chemical resistant wires, high insulating wires, high voltage transmission lines, cables, wires used in geothermal power generation equipment, wires used around automobile engines, etc. You can also. It can also be used for oil seals and shaft seals for vehicle cables.
- electrical insulating materials for example, insulating spacers for various electrical equipment, insulating tapes used for cable joints and end portions, materials used for heat-shrinkable tubes, etc.
- electronic equipment materials for example, lead wire materials for motors, wire materials around high-temperature furnaces.
- sealing layer and protective film (back sheet) of a solar cell can be used also for the sealing layer and protective film (back sheet) of a solar cell.
- sealing materials between electrodes, electrode-separators, piping seals, packings, separators for hydrogen, oxygen, produced water, etc. in polymer electrolyte fuel cells, phosphate fuel cells, etc. Etc. can be used.
- buffer rubber (crash stopper) for hard disk drives binder for electrode active materials for nickel hydride secondary batteries, binder for active materials for lithium ion batteries, polymer electrolyte for lithium secondary batteries, binder for positive electrodes for alkaline storage batteries, EL element (electroluminescent element) binder, capacitor electrode active material binder, sealant, sealing agent, optical fiber quartz coating, optical fiber coating film and sheets, electronic parts, circuit board potting And coating and adhesive seals, electronic component fixing agents, epoxy and other sealant modifiers, printed circuit board coating agents, epoxy and other printed wiring board prepreg resin modifiers, light bulbs and other anti-scattering materials, computer gaskets , Large computer cooling hose, secondary battery, Packing such as gaskets and O- ring for a lithium secondary battery, a sealing layer covering one or both sides of the
- energy resource search and mining equipment parts such as oil and gas
- it is used as various sealing materials used in the mining of oil and natural gas, boots for electrical connectors used in oil wells, and the like.
- Specific uses in the energy resource search and mining equipment parts field include drill bit seals, pressure adjustment diaphragms, horizontal drilling motor (stator) seals, stator bearing (shaft) seals, and blowout prevention devices (BOP).
- Sealing material sealing material used for rotation blowout prevention device (pipe wiper), sealing material used for MWD (real-time excavation information detection system), gas-liquid connector, logging used for logging equipment (logging equipment) Tool seals (for example, O-rings, seals, packings, gas-liquid connectors, boots, etc.), inflatable packers and completion packers, packer seals used in them, seals and packings used in cementing devices, perforators (perforators) ) Seal, packing used for mud pump, packing, motor lining, underground detector cover, U cup, composition seating cup, rotating seal, laminated elastomeric bearing, flow control seal, sand control seal, safety valve Seals, hydraulic fracturing equipment (fracturing equipment) seals, linear packer and linear hanger seals and packing, wellhead seals and packing, chalk and valve seals and packing, and LWD (logging during drilling) seals And diaphragms used in petroleum exploration and oil drilling applications (for example, diaphragms for supplying lubricating oil such as
- joint seals for kitchens, bathrooms, toilets, etc . outdoor tent pulling cloth; seals for printing materials; rubber heat hoses for gas heat pumps, refractory rubber hoses; agricultural films, linings, weatherproof covers; It can also be used for tanks such as laminated steel plates used in the above.
- metal such as aluminum
- metal rubber parts combined with metals such as piston seals, diaphragms, and metal gaskets combined with metals. It can also be used for rubber parts, brake shoes, brake pads, etc. in bicycles.
- a belt is mentioned as one of the forms of the said molded article. Such a belt is also useful. The following are illustrated as said belt.
- Power transmission belts including flat belts, V-belts, V-ribbed belts, toothed belts, etc.
- conveyor belts conveyor belts
- the belt may have a single layer structure or a multilayer structure.
- the belt may be composed of a layer obtained by crosslinking the crosslinkable composition and a layer made of another material.
- the layer made of another material include a layer made of another rubber, a layer made of a thermoplastic resin, various fiber reinforcing layers, a canvas, a metal foil layer, and the like.
- the molded article can also be used for industrial vibration-proof pads, vibration-proof mats, railway slab mats, pads, automobile vibration-proof rubbers, and the like.
- Anti-vibration rubbers for automobiles include anti-vibration rubbers for engine mount, motor mount, member mount, strut mount, bush, damper, muffler hanger, center bearing and the like.
- joint members such as flexible joints and expansion joints, boots, grommets, and the like. If it is a ship field, a marine pump etc. will be mentioned, for example.
- a joint member is a joint used in piping and piping equipment. It prevents vibration and noise from the piping system, absorbs expansion and contraction due to temperature changes and pressure changes, absorbs dimensional changes, earthquakes, and subsidence. It is used for applications such as mitigation and prevention of influences.
- Flexible joints and expansion joints are preferably used as complex shaped bodies for shipbuilding piping, mechanical piping such as pumps and compressors, chemical plant piping, electrical piping, civil engineering / water supply piping, automobiles, etc. it can.
- Boots include, for example, constant velocity joint boots, dust covers, rack and pinion steering boots, pin boots, piston boots and other automobile boots, agricultural machine boots, industrial vehicle boots, building machine boots, hydraulic machine boots, empty It can be preferably used as a compact shaped article such as various industrial boots such as pressure machine boots, centralized lubricator boots, liquid transfer boots, fire fighting boots and various liquefied gas transfer boots.
- the molded article can also be used for filter press diaphragms, blower diaphragms, water supply diaphragms, liquid storage tank diaphragms, pressure switch diaphragms, accumulator diaphragms, suspensions and other air spring diaphragms.
- an anti-slip agent for obtaining a molded product or a coating film which is difficult to slip in an environment wet with water such as rain, snow, ice or sweat can be obtained.
- the molded product is also used as a cushion material for hot press molding when manufacturing decorative plywood, printed circuit boards, electrical insulating boards, rigid polyvinyl chloride laminates, etc. made of melamine resin, phenol resin, epoxy resin, etc. be able to.
- the molded article can also contribute to impermeability of various supports such as weapon-related sealing gaskets and protective clothing against contact with invasive chemical agents.
- Lubricating oils engine oil, mission oil, gear oil, etc.
- amine additives especially amine additives used as antioxidants and detergent dispersants
- Tubes, hoses, various rubber rolls, coatings, belts, valve discs Etc. can also be used. It can also be used as a laminating material and a lining material.
- a vulcanized film may be formed on the molded product.
- non-adhesive oil-resistant rolls for copiers, weather strips for weathering and anti-icing, infusion rubber stoppers, vial rubber stoppers, mold release agents, non-adhesive light transport belts, anti-adhesion coatings on automobile engine mount play gaskets examples thereof include coating of synthetic fibers, bolt members having a thin coating layer for packing, or joints.
- the parts use of the motorcycle of the same structure is also included.
- the fuel for the automobile include light oil, gasoline, diesel engine fuel (including biodiesel fuel), and the like.
- the perfluoroelastomer composition can be used for various uses in various industrial fields, in addition to being applied to molded products.
- the above-mentioned perfluoroelastomer composition is a surface modifying material such as metal, rubber, plastic, glass, etc .; metal gasket, oil seal, etc., sealing material and coating that require heat resistance, chemical resistance, oil resistance, and non-adhesiveness Materials: Non-adhesive coating materials such as rolls for OA equipment, belts for OA equipment, or bleed barriers; Can be used for impregnation on woven fabric sheets and belts, coating by baking, and the like.
- the above-mentioned perfluoroelastomer composition can be used as a sealing material, lining, or sealant with a complicated shape by a normal usage by making it high viscosity and high concentration, and it is a thin film film of several microns by making it low viscosity. It can be used to form pre-coated metal, O-rings, diaphragms, and reed valves. Furthermore, it can also be used for coating woven fabrics and paper sheet transport rolls or belts, printing belts, chemical-resistant tubes, chemical stoppers, fuel hoses, and the like.
- Article base materials to be coated with the perfluoroelastomer composition include metals such as iron, stainless steel, copper, aluminum and brass; glass products such as glass plates, woven fabrics and nonwoven fabrics of glass fibers; polypropylene, polyoxymethylene Molded articles and coatings of general-purpose and heat-resistant resins such as polyimide, polyamideimide, polysulfone, polyethersulfone, polyetheretherketone; general-purpose rubber such as SBR, butyl rubber, NBR, EPDM, and silicone rubber, fluorine rubber, etc. And heat-resistant rubber moldings and coatings; natural and synthetic woven and non-woven fabrics; and the like.
- metals such as iron, stainless steel, copper, aluminum and brass
- glass products such as glass plates, woven fabrics and nonwoven fabrics of glass fibers
- polypropylene, polyoxymethylene Molded articles and coatings of general-purpose and heat-resistant resins such as polyimide, polyamideimide, polysulfone, polyethersulfone, poly
- the coating formed from the perfluoroelastomer composition can be used in fields where heat resistance, solvent resistance, lubricity, and non-adhesiveness are required, and specific applications include copying machines, printers, facsimiles, etc.
- Rolls for example, fixing rolls, pressure rolls
- conveyor belts for OA equipment; sheets and belts; O-rings, diaphragms, chemical resistant tubes, fuel hoses, valve seals, chemical plant gaskets, engine gaskets, etc. It is done.
- the perfluoroelastomer composition can also be dissolved in a solvent and used as a paint or an adhesive. Moreover, it can be used as a coating material as an emulsified dispersion (latex).
- the above composition is a surface treatment agent for structures composed of various materials, sealing materials for pipes and the like, linings, metals, ceramics, glass, stones, concrete, plastics, rubber, wood, paper, fibers, and other inorganic and organic substrates. Used as etc.
- the said composition can be apply
- the perfluoroelastomer composition may be used as a coating composition for casting films or dipping substrates such as fabrics, plastics, metals, or elastomers.
- the perfluoroelastomer composition is in the form of latex in the form of coated fabric, protective gloves, impregnated fiber, O-ring coating, fuel system quick connection O-ring coating, fuel system seal coating, fuel tank rollover valve
- To produce diaphragm coatings, fuel tank pressure sensor diaphragm coatings, oil filter and fuel filter seal coatings, fuel tank sender seals and sender head fitting seal coatings, copier fuser roll coatings, and polymer coating compositions May be used. They are useful for coating silicone rubber, nitrile rubber, and other elastomers.
- the base elastomer For the purpose of increasing both the permeation resistance and chemical resistance of the base elastomer as well as its thermal stability, they are also useful for coating parts made from such elastomers.
- Other applications include coatings for heat exchangers, expansion joints, bats, tanks, fans, flue ducts and other conduits, and storage structures such as concrete storage structures.
- the composition may be applied to the exposed cross section of the multilayer part structure, for example in a hose structure and a method of manufacturing a diaphragm. Sealing members at joints and joints often consist of a hard material, and the perfluoroelastomer composition has an improved frictional interface, increased dimensional tightening with reduced trace leakage along the sealing surface. Provide a fit.
- the latex enhances seal durability in various automotive system applications.
- compositions can also be used in the manufacture of power steering systems, fuel systems, air conditioning systems, and any joint where hoses and tubes are connected to other parts.
- a further utility of the composition is in repairing manufacturing defects (and damage due to use) in multilayer rubber structures such as three-layer fuel hoses.
- the composition is also useful for the application of thin steel sheets that can be formed or embossed before or after the coating is applied. For example, multiple layers of coated steel can be assembled to create a gasket between two rigid metal members. The sealing effect is obtained by applying the perfluoroelastomer composition between the layers. This process reduces the bolting force and strain of the assembled parts, while engine head gaskets and exhaust manifold gaskets for the purpose of providing good fuel savings and low emissions due to low cracks, deflection, and hole strain. Can be used to manufacture.
- the above-mentioned perfluoroelastomer composition includes, in addition, a coating agent; a base material-integrated gasket formed by dispenser molding on a base material containing an inorganic material such as metal or ceramic; packing; a base material containing an inorganic material such as metal or ceramic It can also be used as a multi-layered product formed by coating on.
- the number of polymer particles (the number of perfluoroelastomer particles) is per 1 cc of water
- the specific gravity is the measured value of the specific gravity of the synthesized perfluoroelastomer.
- Polymerization rate ⁇ weight of aqueous dispersion ⁇ solid concentration / 100 ⁇ / ⁇ (the amount of pure water used for polymerization + the amount of water contained in the fluorine-containing surfactant aqueous solution used for polymerization) ⁇ polymerization time ⁇
- the unit of each amount in the formula is as follows.
- Amount of pure water used for polymerization kg
- volume average particle diameter Measured by dynamic light scattering method.
- the aqueous dispersion obtained by polymerization was diluted 10-fold with pure water to prepare an aqueous dispersion for particle diameter measurement, and ELSZ-1000S (manufactured by Otsuka Electronics Co., Ltd.) was used at 25 ° C. for a total of 70 times.
- Measured at Solvent The refractive index of water was 1.3328, and the viscosity of the solvent was 0.8878. The average value of the volume distribution was taken as the particle size.
- Glass transition temperature of perfluoroelastomer The glass transition temperature is obtained by using a differential scanning calorimeter (manufactured by METTLER TOLEDO, DSC822e) to obtain a DSC curve by heating 10 mg of the sample at 10 ° C./min. The peak of the differential curve defined in JIS K6240 The top temperature was taken as the glass transition temperature.
- Solid content concentration 1 g of the aqueous dispersion was dried in an air dryer at 150 ° C. for 12 hours, and the value of the ratio of the mass of the heating residue to the mass of the aqueous dispersion (1 g) was used as a percentage.
- Mooney viscosity The Mooney viscosity was measured according to JIS K6300 using a Mooney viscometer MV2000E type manufactured by ALPHA TECHNOLOGIES.
- Example 1 (F (CF 2 ) 5 COONH 4 5 parts by mass with respect to 100 parts by mass of water) (polymerization)
- a stainless steel autoclave (max) having an internal volume of 6 liters having no ignition source was prepared by mixing 2221 g of pure water, 234 g of a 50 mass% aqueous solution of F (CF 2 ) 5 COONH 4 and 0.21 g of ammonium carbonate.
- a blend-type stirring blade and a baffle plate are included), the system is thoroughly replaced with nitrogen gas, degassed, and heated to 52 ° C. while stirring at 400 rpm.
- 0.92 g of CF 2 CFOCF 2 CF (CF 3 ) OCF 2 CF 2 CN (CNVE) was injected with nitrogen, and then 12.3 g of ammonium persulfate (APS) was dissolved in 30 g of water and injected with nitrogen. The reaction was started.
- the pressure in the tank decreased.
- 7 g of TFE and 8 g of PMVE were introduced into the autoclave and the pressure was increased.
- the pressure in the tank decreases, so TFE and PMVE are injected at a ratio of 60/40 mol%, and the pressure is increased and decreased repeatedly between 0.662 MPa ⁇ G and 0.76 MPa ⁇ G.
- 326 g of TFE and 361 g of PMVE were press-fitted including the above-mentioned TFE 7 g and PMVE 8 g.
- CNVE was added 17 times, 0.90 g in the middle, and was pressed into the polymerization tank together with 2 g of water. CNVE was added during the x-th time (1 ⁇ x ⁇ 17) when the amount of TFE charged exceeded ⁇ (326/18) ⁇ x ⁇ g.
- the polymerization rate was calculated by the above formula and found to be 21.6 g / (time ⁇ kg).
- the volume average particle diameter of the perfluoroelastomer particles in the aqueous dispersion was 67.4 nm.
- the number of perfluoroelastomer particles in the aqueous dispersion was calculated according to the above formula, it was 8.5 ⁇ 10 14 particles / cc.
- the specific gravity of the polymer was 2.038.
- Example 2 (F (CF 2 ) 5 COONH 4 10 parts by mass with respect to 100 parts by mass of water) Polymerization was conducted in the same manner as in Example 1 except that the amount of pure water initially charged was changed to 2104 g, and the amount of 50 mass% aqueous solution of F (CF 2 ) 5 COONH 4 was changed to 468 g. 3389 g of a 21.2% by weight aqueous dispersion was obtained. The polymerization time was 7.10 hours. After the aqueous dispersion was taken out, there was no adhering polymer in the tank such as the stirring blade, the inner wall of the tank and the baffle plate of the autoclave.
- the polymerization rate is 43.2 g / (time ⁇ kg), the volume average particle diameter of perfluoroelastomer particles in the aqueous dispersion is 23.8 nm, and the number of perfluoroelastomer particles in the aqueous dispersion is 1.9 ⁇ 10 16 / Cc.
- the specific gravity of the polymer was 2.038.
- Example 3 (F (CF 2 ) 5 COONH 4 20 parts by mass with respect to 100 parts by mass of water) Polymerization was conducted in the same manner as in Example 1 except that the amount of pure water charged first was 1871 g and the amount of 50 mass% aqueous solution of F (CF 2 ) 5 COONH 4 was changed to 935 g, respectively. 3651 g of a 20.63% by weight aqueous dispersion was obtained. The polymerization time was 5.93 hours. After the aqueous dispersion was taken out, there was no adhering polymer in the tank such as the stirring blade, the inner wall of the tank and the baffle plate of the autoclave.
- Example 2 The obtained aqueous dispersion was post-treated in the same manner as in Example 1 to obtain a white polymer.
- the obtained polymer was analyzed in the same manner as in Example 1, the following results were obtained.
- the DTA measurement from room temperature to 600 ° C. and the DSC measurement from ⁇ 50 ° C. to 100 ° C., no melting peak was observed.
- the polymerization rate is 54.3 g / (time ⁇ kg)
- the volume average particle diameter of the perfluoroelastomer particles in the aqueous dispersion is 19.3 nm
- the number of perfluoroelastomer particles in the aqueous dispersion is 3.4 ⁇ 10 16 / Cc.
- the specific gravity of the polymer was 2.038.
- the polymerization rate was 3.1 g / (time ⁇ kg).
- Comparative Example 2 (C 3 F 7 OCF (CF 3 ) CF 2 OCF (CF 3 ) COONH 4 5 parts by mass with respect to 100 parts by mass of water)
- the amount of pure water initially charged is 2338 g, and a 50 mass% aqueous solution of F (CF 2 ) 5 COONH 4 is used as a C. 3 F 7 OCF (CF 3 ) CF 2 OCF (CF 3 ) COONH 4 100% pure product.
- Polymerization was conducted in the same manner as in Example 1 except that the amount was changed to 9 g, to obtain 3257 g of an aqueous dispersion having a solid content concentration of 22.0% by mass.
- the polymerization time was 5.35 hours.
- Comparative Example 3 (C 3 F 7 OCF (CF 3 ) CF 2 OCF (CF 3 ) COONH 4 1 part by mass with respect to 100 parts by mass of water)
- the amount of pure water charged was 2338 g, and 50% by mass aqueous solution of F (CF 2 ) 5 COONH 4 was used as a C 3 F 7 OCF (CF 3 ) CF 2 OCF (CF 3 ) COONH 4 100% pure product.
- Polymerization was conducted in the same manner as in Example 1 except that the amount was changed to 4 g, to obtain 3128 g of an aqueous dispersion having a solid content concentration of 22.4% by mass.
- the polymerization time was 7.53 hours.
- the polymerization rate is 39.9 g / (time ⁇ kg)
- the volume average particle diameter of perfluoroelastomer particles in the aqueous dispersion is 27.0 nm
- the number of perfluoroelastomer particles in the aqueous dispersion is 1.38 ⁇ 10 16 / Cc.
- the specific gravity of the polymer was 2.038.
- the polymerization rate is 68.4 g / (time ⁇ kg)
- the volume average particle diameter of perfluoroelastomer particles in the aqueous dispersion is 17.0 nm
- the number of perfluoroelastomer particles in the aqueous dispersion is 5.4 ⁇ 10 16 / Cc.
- the specific gravity of the polymer was 2.038.
- the polymerization rate is 40.3 g / (time ⁇ kg), the volume average particle size of perfluoroelastomer particles in the aqueous dispersion is 26.8 nm, and the number of perfluoroelastomer particles in the aqueous dispersion is 1.40 ⁇ 10 16 / Cc.
- the specific gravity of the polymer was 2.038.
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Abstract
Description
X-(CF2)m1-Y (1)
(式中、XはH又はFを表し、m1は3~6の整数を表し、Yは-SO3M、-SO4M、-SO3R、-SO4R、-COOM、-PO3M2、-PO4M2(MはH、NH4又はアルカリ金属を表し、Rは炭素数1~12のアルキル基を表す。)を表す。)で表される含フッ素界面活性剤を使用して製造する方法は知られていない。
X-(CF2)m1-Y (1)
(式中、XはH又はFを表し、m1は3~6の整数を表し、Yは-SO3M、-SO4M、-SO3R、-SO4R、-COOM、-PO3M2、-PO4M2(MはH、NH4又はアルカリ金属を表し、Rは炭素数1~12のアルキル基を表す。)を表す。)
一般式(3):CF2=CF(O(CF2)n31)m31(OCF2)x31(OCF2CF(CF3))y31ORf31
(式中、n31は1~6の整数を表し、m31は0~4の整数を表し、x31は0~6の整数を表し、y31は0~4の整数を表し、Rf31は炭素数1~8の直鎖又は分岐状パーフルオロアルキル基、炭素数5~6の環式パーフルオロアルキル基、1~3個の酸素原子を含む炭素数2~6の直鎖又は分岐状パーフルオロオキシアルキル基である。)
一般式(8):CF2=CF-ORf81
(式中、Rf81は、炭素数1~8のパーフルオロアルキル基を表す。)
一般式(10):CF2=CFOCF2ORf101
(式中、Rf101は炭素数1~6の直鎖又は分岐状パーフルオロアルキル基、炭素数5~6の環式パーフルオロアルキル基、1~3個の酸素原子を含む炭素数2~6の直鎖又は分岐状パーフルオロオキシアルキル基である)
一般式(11):CF2=CFO(CF2CF(Y11)O)m(CF2)nF
(式中、Y11はフッ素原子又はトリフルオロメチル基を表す。mは1~4の整数である。nは1~4の整数である。)
X-(CF2)m1-Y (1)
(式中、XはH又はFを表し、m1は3~6の整数を表し、Yは-SO3M、-SO4M、-SO3R、-SO4R、-COOM、-PO3M2、-PO4M2(MはH、NH4又はアルカリ金属を表し、Rは炭素数1~12のアルキル基を表す。)を表す。)で表される含フッ素界面活性剤である。
C5F11COOM (1-1)
(式中、Mは、H、NH4又はアルカリ金属を表す。)で表される化合物、すなわち、パーフルオロヘキサン酸又はその塩が好ましい。上記Mは、得られるパーフルオロエラストマーからの除去が容易である点で、NH4又はHであることが好ましく、NH4であることが更に好ましい。
テトラフルオロエチレン〔TFE〕、
へキサフルオロプロピレン〔HFP〕、及び、
一般式(3):CF2=CF(O(CF2)n31)m31(OCF2)x31(OCF2CF(CF3))y31ORf31
(式中、n31は1~6の整数を表し、m31は0~4の整数を表し、x31は0~6の整数を表し、y31は0~4の整数を表し、Rf31は炭素数1~8の直鎖又は分岐状パーフルオロアルキル基、炭素数5~6の環式パーフルオロアルキル基、1~3個の酸素原子を含む炭素数2~6の直鎖又は分岐状パーフルオロオキシアルキル基である。)で表されるフルオロモノマー
からなる群より選択される少なくとも1種であることが好ましい。
テトラフルオロエチレン〔TFE〕、
へキサフルオロプロピレン〔HFP〕、
一般式(8):CF2=CF-ORf81
(式中、Rf81は、炭素数1~8のパーフルオロアルキル基を表す。)で表されるフルオロモノマー、
一般式(10):CF2=CFOCF2ORf101
(式中、Rf101は炭素数1~6の直鎖又は分岐状パーフルオロアルキル基、炭素数5~6の環式パーフルオロアルキル基、1~3個の酸素原子を含む炭素数2~6の直鎖又は分岐状パーフルオロオキシアルキル基である)で表されるフルオロモノマー、及び、
一般式(11):CF2=CFO(CF2CF(Y11)O)m(CF2)nF
(式中、Y11はフッ素原子又はトリフルオロメチル基を表す。mは1~4の整数である。nは1~4の整数である。)で表されるフルオロモノマー
からなる群より選択される少なくとも1種であることがより好ましい。
一般式(12):CX3 2=CX3-Rf 121CHR121X4
(式中、X3は、水素原子、フッ素原子又はCH3、Rf 121は、フルオロアルキレン基、パーフルオロアルキレン基、フルオロ(ポリ)オキシアルキレン基又はパーフルオロ(ポリ)オキシアルキレン基、R121は、水素原子又はCH3、X4は、ヨウ素原子又は臭素原子である)で表されるフルオロモノマー、
一般式(13):CX3 2=CX3-Rf131X4
(式中、X3は、水素原子、フッ素原子又はCH3、Rf131は、フルオロアルキレン基、パーフルオロアルキレン基、フルオロ(ポリ)オキシアルキレン基又はパーフルオロ(ポリ)オキシアルキレン基、X4は、ヨウ素原子又は臭素原子である)で表されるフルオロモノマー、
一般式(14):CF2=CFO(CF2CF(CF3)O)m(CF2)n-X5
(式中、mは0~5の整数、nは1~5の整数、X5は、シアノ基、カルボキシル基、アルコキシカルボニル基、ヨウ素原子、臭素原子、又は、-CH2Iである)で表されるフルオロモノマー、及び、
一般式(15):CH2=CFCF2O(CF(CF3)CF2O)m(CF(CF3))n-X6
(式中、mは0~5の整数、nは1~3の整数、X6は、シアノ基、カルボキシル基、アルコキシカルボニル基、ヨウ素原子、臭素原子、又は-CH2OHである)で表されるフルオロモノマー、及び、
一般式(16):CR162R163=CR164-Z-CR165=CR166R167
(式中、R162、R163、R164、R165、R166及びR167、は、同一又は異なって、水素原子又は炭素数1~5のアルキル基である。Zは、直鎖又は分岐状で酸素原子を有していてもよい、炭素数1~18のアルキレン基、炭素数3~18のシクロアルキレン基、少なくとも部分的にフッ素化している炭素数1~10のアルキレン基若しくはオキシアルキレン基、又は、
-(Q)p-CF2O-(CF2CF2O)m(CF2O)n-CF2-(Q)p-
(式中、Qはアルキレン基またはオキシアルキレン基である。pは0または1である。m/nが0.2~5である。)で表され、分子量が500~10000である(パー)フルオロポリオキシアルキレン基である。)で表されるモノマー
からなる群より選択される少なくとも1種であることが好ましい。
その組成は、TFE/PMVE共重合体の場合、好ましくは、45~90/10~55(モル%)であり、より好ましくは、55~80/20~45であり、更に好ましくは、55~70/30~45である。
TFE/PMVE/架橋部位を与えるモノマー共重合体の場合、好ましくは、45~89.9/10~54.9/0.01~4(モル%)であり、より好ましくは、55~79.9/20~44.9/0.1~3.5であり、更に好ましくは、55~69.8/30~44.8/0.2~3である。
TFE/炭素数が4~12の一般式(8)、(10)又は(11)で表されるフルオロモノマー共重合体の場合、好ましくは、50~90/10~50(モル%)であり、より好ましくは、60~88/12~40であり、更に好ましくは、65~85/15~35である。
TFE/炭素数が4~12の一般式(8)、(10)又は(11)で表されるフルオロモノマー/架橋部位を与えるモノマー共重合体の場合、好ましくは、50~89.9/10~49.9/0.01~4(モル%)であり、より好ましくは、60~87.9/12~39.9/0.1~3.5であり、更に好ましくは、65~84.8/15~34.8/0.2~3である。
これらの組成の範囲を外れると、ゴム弾性体としての性質が失われ、樹脂に近い性質となる傾向がある。
R2IxBry
(式中、x及びyはそれぞれ0~2の整数であり、かつ1≦x+y≦2を満たすものであり、R2は炭素数1~16の飽和若しくは不飽和のフルオロ炭化水素基又はクロロフルオロ炭化水素基、又は炭素数1~3の炭化水素基であり、酸素原子を含んでいてもよい)で表される化合物が挙げられる。臭素化合物又はヨウ素化合物を使用することによって、ヨウ素又は臭素が重合体に導入され、架橋点として機能する。
X-(CF2)m2-Y (2)
(式中、XはH又はFを表し、m2は7以上の整数を表し、Yは-SO3M、-SO4M、-SO3R、-SO4R、-COOM、-PO3M2、-PO4M2(MはH、NH4又はアルカリ金属を表し、Rは炭素数1~12のアルキル基を表す。)を表す。)で表される含フッ素化合物の非存在下に行うことが好ましい。本発明の製造方法によれば、このような従来の含フッ素界面活性剤を使用しなくても、充分な粒子数及び重合速度を実現することができる。更に、上記乳化重合は、含フッ素界面活性剤(1)以外の含フッ素界面活性剤の非存在下に行うことが好ましい。
CF2=CF-ORf81
(式中、Rf81は、炭素数1~8のパーフルオロアルキル基を表す。)で表されるものが好ましく、パーフルオロ(メチルビニルエーテル)(PMVE)、パーフルオロ(エチルビニルエーテル)、及び、パーフルオロ(プロピルビニルエーテル)からなる群より選択される少なくとも1種がより好ましく、パーフルオロ(メチルビニルエーテル)が更に好ましい。
TFEに基づく重合単位の含有量の下限は、全重合単位に対して44.99モル%であってもよく、44.9モル%であってもよく、44.8モル%であってもよい。TFEに基づく重合単位の含有量の上限は、全重合単位に対して57.99モル%であってもよく、57.9モル%であってもよく、57.8モル%であってもよい。
上記成形品は、上記パーフルオロエラストマー組成物を成形し、得られた成形品を架橋することにより製造することもできるし、成形と架橋とを同時に行うことによって製造することもできる。成形方法は、特に限定されず、例えば、圧縮成形、押出し成形、トランスファー成形、射出成形等が挙げられる。上記成形品はまた、上記パーフルオロエラストマー組成物を塗装し、架橋することによって、塗膜として得ることもできる。
また、チューブ、ホース、ロール、各種ゴムロール、フレキシブルジョイント、ゴム板、コーティング、ベルト、ダンパー、バルブ、バルブシート、バルブの弁体、耐薬品用コーティング材料、ラミネート用材料、ライニング用材料等としても使用できる。
なお、上記リング、パッキン、シールの断面形状は、種々の形状のものであってよく、具体的には、例えば、四角、O字、へルール等の形状であってもよいし、D字、L字、T字、V字、X字、Y字等の異形状であってもよい。
上述のようなエンジン本体やその周辺装置では、耐熱性、耐油性、燃料油耐性、エンジン冷却用不凍液耐性、耐スチーム性が要求される各種シール材に上記成形品を用いることができ、そのようなシール材としては、例えば、ガスケット、シャフトシール、バルブステムシール等のシールや、セルフシールパッキン、ピストンリング、割リング形パッキン、メカニカルシール、オイルシール等の非接触型又は接触型のパッキン類、ベローズ、ダイアフラム、ホース、チューブの他、電線、緩衝材、防振材、ベルトAT装置に用いられる各種シール材等が挙げられる。
制御系電装部品における具体的な使用形態としては、各種センサー線の被覆材料等が挙げられる。
上記装備電装部品における具体的な使用形態としては、カーエアコンのO-リング、パッキンや、クーラーホース、高圧エアコンホース、エアコンホース、電子スロットルユニット用ガスケット、ダイレクトイグニッション用プラグブーツ、ディストリビューター用ダイアフラム等が挙げられる。また、電装部品の接着にも用いることができる。
また、ディーゼルエンジンに関する部品において、直噴インジェクター用のO-リングシール、回転ポンプシール、制御ダイアフラム、燃料ホース、EGR,プライミングポンプ,ブーストコンペンセーターのダイアフラム等として用いることができる。また、尿素SCRシステムに用いられるO-リング、シール材、ホース、チューブ、ダイアフラムや、尿素SCRシステムの尿素水タンク本体、及び尿素水タンクのシール材等にも用いることができる。
ミッションオイルシールや、ATのミッションオイルホース、ATFホース、O-リング、パッキン類等も挙げられる。
なお、トランスミッションには、AT(オートマチック・トランスミッション)、MT(マニュアル・トランスミッション)、CVT(連続可変トランスミッション)、DCT(デュアル・クラッチ・トランスミッション)等がある。
また、手動又は自動変速機用のオイルシール、ガスケット、O-リング、パッキンや、無段変速機(ベルト式又はトロイダル式)用のオイルシール、ガスケット、O-リング、パッキンの他、ATFリニアソレノイド用パッキング、手動変速機用オイルホース、自動変速機用ATFホース、無断変速機(ベルト式又はトロイダル式)用CVTFホース等も挙げられる。
ステアリング系における具体的な使用形態としては、パワーステアリングオイルホースや高圧パワーステアリングホース等が挙げられる。
自動車エンジンの主運動系においては、クランクシャフトシール、カムシャフトシール等のシャフトシール等に用いることができる。
自動車エンジンの動弁系においては、エンジンバルブのバルブステムオイルシール、バタフライバルブのバルブシート等に用いることができる。
自動車エンジンの潤滑・冷却系においては、エンジンオイルクーラーのエンジンオイルクーラーホース、オイルリターンホース、シールガスケットや、ラジエータ周辺のウォーターホース、ラジエータのシール、ラジエータのガスケット、ラジエータのO-リング、バキュームポンプのバキュームポンプオイルホース等の他、ラジエーターホース、ラジエータータンク、オイルプレッシャー用ダイアフラム、ファンカップリングシール等に用いることができる。
上記航空機分野においては、例えば、航空機用各種シール部品、航空機用エンジンオイル用途の航空機用各種部品、ジェットエンジンバルブステムシールやガスケットやO-リング、ローテーティングシャフトシール、油圧機器のガスケット、防火壁シール、燃料供給用ホースやガスケットやO-リング、航空機用ケーブルやオイルシールやシャフトシール等として用いることが可能である。
また、船舶分野においては、例えば、スクリューのプロペラシャフト船尾シール、ディーゼルエンジンの吸排気用バルブステムシール、バタフライバルブのバルブシール、バタフライバルブのバルブシートや軸シール、バタフライ弁の軸シール、船尾管シール、燃料ホース、ガスケット、エンジン用のO-リング、船舶用ケーブル、船舶用オイルシール、船舶用シャフトシール等として使用することができる。
上記化学品分野及び薬品分野における具体的な使用形態としては、化学装置、化学薬品用ポンプや流量計、化学薬品用配管、熱交換器、農薬散布機、農薬移送ポンプ、ガス配管、燃料電池、分析機器や理化学機器(例えば、分析機器や計器類のカラム・フィッティング等)、排煙脱硫装置の収縮継ぎ手、硝酸プラント、発電所タービン等に用いられるシールや、医療用滅菌プロセスに用いられるシール、メッキ液用シール、製紙用ベルトのコロシール、風洞のジョイントシール;反応機、攪拌機等の化学装置、分析機器や計器類、ケミカルポンプ、ポンプハウジング、バルブ、回転計等に用いられるO-リングや、メカニカルシール用O-リング、コンプレッサーシーリング用のO-リング;高温真空乾燥機、ガスクロマトグラフィーやpHメーターのチューブ結合部等に用いられるパッキンや、硫酸製造装置のガラス冷却器パッキン;ダイアフラムポンプ、分析機器や理化学機器等に用いられるダイアフラム;分析機器、計器類に用いられるガスケット;分析機器や計器類に用いられるはめ輪(フェルール);バルブシート;Uカップ;化学装置、ガソリンタンク、風洞等に用いられるライニングや、アルマイト加工槽の耐食ライニング;メッキ用マスキング冶具のコーティング;分析機器や理化学機器の弁部品;排煙脱硫プラントのエキスパンジョンジョイント;濃硫酸等に対する耐酸ホース、塩素ガス移送ホース、耐油ホース、ベンゼンやトルエン貯槽の雨水ドレンホース;分析機器や理化学機器等に用いられる耐薬品性チューブや医療用チューブ;繊維染色用の耐トリクレン用ロールや染色用ロール;医薬品の薬栓;医療用のゴム栓;薬液ボトル、薬液タンク、バッグ、薬品容器;耐強酸、耐溶剤の手袋や長靴等の保護具等が挙げられる。
上記写真分野、印刷分野及び塗装分野における具体的な使用形態としては、複写機の転写ロールの表面層、複写機のクリーニングブレード、複写機のベルト;複写機、プリンター、ファクシミリ等のOA機器用のロール(例えば、定着ロール、圧着ロール、加圧ロール等が挙げられる。)、ベルト;PPC複写機のロール、ロールブレード、ベルト;フィルム現像機、X線フィルム現像機のロール;印刷機械の印刷ロール、スクレーパー、チューブ、弁部品、ベルト;プリンターのインキチューブ、ロール、ベルト;塗布、塗装設備の塗装ロール、スクレーパー、チューブ、弁部品;現像ロール、グラビアロール、ガイドロール、磁気テープ製造塗工ラインのガイドロール、磁気テープ製造塗工ラインのグラビアロール、コーティングロール等が挙げられる。
上記食品機器分野における具体的な使用形態としては、プレート式熱交換器のシール、自動販売機の電磁弁シール、ジャーポットのパッキン、サニタリーパイプパッキン、圧力鍋のパッキン、湯沸器シール、熱交換器用ガスケット、食品加工処理装置用のダイアフラムやパッキン、食品加工処理機用ゴム材料(例えば、熱交換器ガスケット、ダイアフラム、O-リング等の各種シール、配管、ホース、サニタリーパッキン、バルブパッキン、充填時にビン等の口と充填剤との間のジョイントとして使用される充填用パッキン)等が挙げられる。また、酒類、清涼飲料水等の製品、充填装置、食品殺菌装置、醸造装置、湯沸し器、各種自動食品販売機等に用いられるパッキン、ガスケット、チューブ、ダイアフラム、ホース、ジョイントスリーブ等も挙げられる。
上記エネルギー資源探索採掘機器部品分野における具体的な使用形態としては、ドリルビットシール、圧力調整ダイアフラム、水平掘削モーター(ステーター)のシール、ステーターベアリング(シャフト)シール、暴噴防止装置(BOP)に用いられるシール材、回転暴噴防止装置(パイプワイパー)に用いられるシール材、MWD(リアルタイム掘削情報探知システム)に用いられるシール材や気液コネクター、検層装置(ロギングエクイップメント)に用いられる検層ツールシール(例えば、O-リング、シール、パッキン、気液コネクター、ブーツ等)、膨張型パッカーやコンプリーションパッカー及びそれらに用いるパッカーシール、セメンチング装置に用いられるシールやパッキン、パーフォレーター(穿孔装置)に用いられるシール、マッドポンプに用いられるシールやパッキンやモーターライニング、地中聴検器カバー、Uカップ、コンポジションシーティングカップ、回転シール、ラミネートエラストメリックベアリング、流量制御のシール、砂量制御のシール、安全弁のシール、水圧破砕装置(フラクチャリングエクイップメント)のシール、リニアーパッカーやリニアーハンガーのシールやパッキン、ウェルヘッドのシールやパッキン、チョークやバルブのシールやパッキン、LWD(掘削中検層)用シール材、石油探索・石油掘削用途で用いられるダイアフラム(例えば、石油掘削ピット等の潤滑油供給用ダイアフラム)、ゲートバルブ、電子ブーツ、穿孔ガンのシールエレメント等が挙げられる。
また、自転車におけるゴム部品、ブレーキシュー、ブレーキパッド等にも用いることができる。
上記ベルトとしては、次のものが例示される。動力伝達ベルト(平ベルト、Vベルト、Vリブドベルト、歯付きベルト等を含む)、搬送用ベルト(コンベアベルト)として、農業用機械、工作機械、工業用機械等のエンジン周り等各種高温となる部位に使用される平ベルト;石炭、砕石、土砂、鉱石、木材チップ等のバラ物や粒状物を高温環境下で搬送するためのコンベアベルト;高炉等の製鉄所等で使用されるコンベアベルト;精密機器組立工場、食品工場等において、高温環境下に曝される用途におけるコンベアベルト;農業用機械、一般機器(例えば、OA機器、印刷機械、業務用乾燥機等)、自動車用等のVベルトやVリブドベルト;搬送ロボットの伝動ベルト;食品機械、工作機械の伝動ベルト等の歯付きベルト;自動車用、OA機器、医療用、印刷機械等で使用される歯付きベルト等が挙げられる。
特に、自動車用歯付きベルトとしては、タイミングベルトが代表的である。
多層構造である場合、上記ベルトは、上記架橋性組成物を架橋して得られる層及び他の材料からなる層からなるものであってもよい。
多層構造のベルトにおいて、他の材料からなる層としては、他のゴムからなる層や熱可塑性樹脂からなる層、各種繊維補強層、帆布、金属箔層等が挙げられる。
ジョイント部材とは、配管及び配管設備に用いられる継ぎ手のことであり、配管系統から発生する振動、騒音の防止、温度変化、圧力変化による伸縮や変位の吸収、寸法変動の吸収や地震、地盤沈下による影響の緩和、防止等の用途に用いられる。
フレキシブルジョイント、エキスパンションジョイントは、例えば、造船配管用、ポンプやコンプレッサー等の機械配管用、化学プラント配管用、電気配管用、土木・水道配管用、自動車用等の複雑形状成形体として好ましく用いることができる。
ブーツは、例えば、等速ジョイントブーツ、ダストカバー、ラックアンドピニオンステアリングブーツ、ピンブーツ、ピストンブーツ等の自動車用ブーツ、農業機械用ブーツ、産業車両用ブーツ、建築機械用ブーツ、油圧機械用ブーツ、空圧機械用ブーツ、集中潤滑機用ブーツ、液体移送用ブーツ、消防用ブーツ、各種液化ガス移送用ブーツ等の各種産業用ブーツ等の複雑形状成形体として好ましく用いることができる。
また、上記自動車関連における燃料としては、軽油、ガソリン、ディーゼルエンジン用燃料(バイオディーゼルフューエルを含む)等が挙げられる。
上記パーフルオロエラストマー組成物は、高粘度、高濃度にすることによって、通常の用法により複雑な形状のシール材、ライニング、シーラントとして用いることができ、低粘度にすることによって、数ミクロンの薄膜フィルムの形成に用いることができ、また中粘度にすることによりプレコートメタル、O-リング、ダイアフラム、リードバルブの塗布に用いることができる。
さらに、織布や紙葉の搬送ロール又はベルト、印刷用ベルト、耐薬品性チューブ、薬栓、ヒューエルホース等の塗布にも用いることができる。
上記パーフルオロエラストマー組成物から形成される被覆物は、耐熱性、耐溶剤性、潤滑性、非粘着性が要求される分野で使用でき、具体的な用途としては、複写機、プリンター、ファクシミリ等のOA機器用のロール(例えば、定着ロール、圧着ロール)及び搬送ベルト;シート及びベルト;O-リング、ダイアフラム、耐薬品性チューブ、燃料ホース、バルブシール、化学プラント用ガスケット、エンジンガスケット等が挙げられる。
上記組成物は、各種装置、配管等のシール材やライニング、金属、セラミックス、ガラス、石、コンクリート、プラスチック、ゴム、木材、紙、繊維等の無機及び有機基材からなる構造物の表面処理剤等として使用される。
上記組成物は、ディスペンサー方式塗装やスクリーン印刷塗装により基材等に塗布することができる。
特に、上記パーフルオロエラストマー組成物は、ラテックスの形態として、被覆ファブリック、保護手袋、含浸繊維、O-リング被覆、燃料系クイック連結O-リング用被覆、燃料系シール用被覆、燃料タンクロールオーバーバルブダイヤフラム用被覆、燃料タンク圧力センサーダイヤフラム用被覆、オイルフィルター及び燃料フィルターシール用被覆、燃料タンクセンダーシール及びセンダーヘッドフィッテングシール用被覆、複写機定着機構ロール用被覆、並びにポリマー塗料組成物を製造するために使用されてもよい。
それらはシリコーンラバー、ニトリルラバー、及び他のエラストマーの被覆に有用である。その熱安定性と同様に基材エラストマーの耐透過性及び耐薬品性の両方を高める目的のために、それらはそのようなエラストマーから製造される部品の被覆にも有用である。他の用途は、熱交換器、エキスパンジョンジョイント、バット、タンク、ファン、煙道ダクト及び他の管路、並びに収納構造体、例えばコンクリート収納構造体用の被覆を含む。上記組成物は、多層部品構造の露出した断面に、例えばホース構造及びダイアフラムの製造方法において塗布されてもよい。接続部及び結合部におけるシーリング部材は、硬質材料からしばしば成り、そして上記パーフルオロエラストマー組成物は、改良された摩擦性界面、シーリング面に沿って低減された微量の漏れを伴う高められた寸法締りばめを提供する。そのラテックスは、種々の自動車システム用途におけるシール耐久性を高める。
それらは、パワーステアリング系統、燃料系統、エアーコンディショニング系統、並びに、ホース及びチューブが別の部品に接続されるいかなる結合部の製造においても使用されることもできる。上記組成物の更なる有用性は、3層燃料ホースのような多層ラバー構造における、製造欠陥(及び使用に起因する損傷)の補修においてである。上記組成物は、塗料が塗布される前又は後に、形成され、又はエンボス加工され得る薄鋼板の塗布にも有用である。例えば、被覆された鋼の多数の層は組み立てられて、2つの剛性金属部材の間にガスケットを作ることもできる。シーリング効果は、その層の間に上記パーフルオロエラストマー組成物を塗布することにより得られる。このプロセスは、組み立てられた部品のボルト力及びひずみを低下させ、一方、低い亀裂、たわみ、及び穴ひずみにより良好な燃料節約及び低放出を提供する目的のために、エンジンヘッドガスケット及び排気マニフォールドガスケットを製造するために使用され得る。
下記式により算出した。
自動比重計DMA-220H(新光電子株式会社製)を用いて測定した。
下記式により算出した。
重合速度={水性分散液重量×固形分濃度/100}/{(重合に使用した純水量+重合に使用した含フッ素界面活性剤水溶液に含まれる水の量)×重合時間}
式中の各量の単位は、下記の通りである。
水性分散液重量 :g
固形分濃度 :質量%
重合に使用した純水量 :kg
重合に使用した含フッ素界面活性剤水溶液に含まれる水の量 :kg
重合時間 :時間
重合速度 :g/(時間×kg)
動的光散乱法により測定する。重合により得られた水性分散液を、純水で10倍希釈し、粒子径測定用の水性分散液を作成し、ELSZ-1000S(大塚電子株式会社製)を使用して25℃、積算70回にて測定した。溶媒:水の屈折率1.3328、溶媒の粘度は0.8878とした。体積分布の平均値を粒子径とした。
ガラス転移温度は、示差走査熱量計(メトラー・トレド社製、DSC822e)を用い、試料10mgを10℃/minで昇温することによりDSC曲線を得て、JIS K6240に規定される微分曲線のピークトップ温度をガラス転移温度とした。
水性分散液1gを、送風乾燥機中で150℃、12時間の条件で乾燥し、水性分散液の質量(1g)に対する、加熱残分の質量の割合を百分率で表した値を採用した。
19F-NMRによって測定した。なお、数値を四捨五入したため、各モノマー単位量の合計は必ずしも100モル%になっていない。
上記ムーニー粘度は、ALPHA TECHNOLOGIES社製 ムーニー粘度計MV2000E型を用いて、JIS K6300に従い測定した。
(重合)
純水2221g、F(CF2)5COONH4の50質量%水溶液234g、及び、炭酸アンモニウム0.21gを混合した水溶液を、着火源をもたない内容積6リットルのステンレススチール製オートクレーブ(マックスブレンドタイプの攪拌翼と邪魔板1枚が付属)に入れた後、系内を窒素ガスで充分に置換した後、脱気し、400rpmで撹拌しながら、52℃に昇温し、テトラフルオロエチレン(TFE)とパーフルオロ(メチルビニルエーテル)(PMVE)の混合ガス(TFE/PMVE=35/65モル%比)を、内圧が0.757MPa・Gになるように仕込んだ。ついで、CF2=CFOCF2CF(CF3)OCF2CF2CN(CNVE)を0.90g窒素で圧入した後、過硫酸アンモニウム(APS)12.3gを水30gに溶解し、窒素で圧入して反応を開始した。
得られた水性分散液900gに純水900gを加え、混合希釈した。この混合希釈液を3.5%塩酸水溶液7500gに滴下した。滴下は、塩酸水溶液を攪拌しながら行なった。塩酸水溶液中に、ポリマーが凝析されるので、凝析されたポリマーをろ別し、純水10000g中に移し、10分間攪拌しながら、洗浄した。10分後、再びポリマーをろ別し、純水10000g中に移し、10分間攪拌しながら洗浄した。この純水10000gでの洗浄操作を6回繰り返した後、ポリマーをろ別した。ろ別されたポリマーは、70℃で60時間、真空乾燥させた。白色のポリマーが得られた。
19F-NMR(固体NMR)分析の結果、乾燥後のポリマーのモノマー単位組成は、TFE/PMVE/CNVE=54.5/45.1/0.43モル%であった。170℃でのムーニー粘度は、ML(1+20)が59であった。
ガラス転移温度は、-3.4℃であった。
室温から600℃までのDTA測定と、-50℃から100℃までのDSC測定の結果、融解ピークは観察されなかった。
水性分散液中のパーフルオロエラストマー粒子の体積平均粒子径は67.4nmであった。
水性分散液中のパーフルオロエラストマー粒子数を上記式により算出したところ、8.5×1014個/ccであった。ポリマーの比重は2.038であった。
最初に仕込む純水の量を2104gに、F(CF2)5COONH4の50質量%水溶液の量を468gに、それぞれ変更したこと以外は、実施例1と同様に重合を行い、固形分濃度21.2質量%の水性分散液3389gを得た。重合時間は7.10時間であった。水性分散液を取り出した後のオートクレーブの攪拌翼、槽内壁、邪魔板等の槽内には付着ポリマーは全く無かった。
ポリマーのモノマー単位組成:TFE/PMVE/CNVE=54.7/44.8/0.45モル%
170℃でのムーニー粘度 ML(1+20):99.5
ガラス転移温度:-2.7℃
室温から600℃までのDTA測定と、-50℃から100℃までのDSC測定の結果、融解ピークは観察されなかった。
最初に仕込む純水の量を1871gに、F(CF2)5COONH4の50質量%水溶液の量を935gに、それぞれ変更したこと以外は、実施例1と同様に重合を行い、固形分濃度20.63質量%の水性分散液3651gを得た。重合時間は5.93時間であった。水性分散液を取り出した後のオートクレーブの攪拌翼、槽内壁、邪魔板等の槽内には付着ポリマーは全く無かった。
ポリマーのモノマー単位組成:TFE/PMVE/CNVE=55.0/44.6/0.40モル%
170℃でのムーニー粘度 ML(1+20):89.4
ガラス転移温度:-3.4℃
室温から600℃までのDTA測定と、-50℃から100℃までのDSC測定の結果、融解ピークは観察されなかった。
最初に仕込む純水の量を2315gに、F(CF2)5COONH4の50質量%水溶液の量を46.8gに、それぞれ変更したこと以外は、実施例1と同様に重合を進めたが、重合がほとんど進行せず、6時間18分(6.3時間)の重合時間で、TFEは12g、PMVEは13g仕込んだだけで、実施例1と同じ量のTFE、PMVE、CNVEを仕込むことができなかった。固形分濃度1.90質量%の水性分散液2421gを得た。水性分散液を取り出した後のオートクレーブの攪拌翼、槽内壁、邪魔板等の槽内には付着ポリマーは全く無かった。
重合速度は3.1g/(時間×kg)であった。
最初に仕込む純水の量を2338gに、F(CF2)5COONH4の50質量%水溶液をC3F7OCF(CF3)CF2OCF(CF3)COONH4 100%純品の116.9gに、それぞれ変更したこと以外は、実施例1と同様に重合を行い、固形分濃度22.0質量%の水性分散液3257gを得た。重合時間は5.35時間であった。水性分散液を取り出した後のオートクレーブの攪拌翼、槽内壁、邪魔板等の槽内には付着ポリマーは全く無かった。
重合速度は57.4g/(時間×kg)であった。
ポリマーのモノマー単位組成:TFE/PMVE/CNVE=57.1/42.5/0.42モル%
最初に仕込む純水の量を2338gに、F(CF2)5COONH4の50質量%水溶液をC3F7OCF(CF3)CF2OCF(CF3)COONH4 100%純品の23.4gに、それぞれ変更したこと以外は、実施例1と同様に重合を行い、固形分濃度22.4質量%の水性分散液3128gを得た。重合時間は7.53時間であった。水性分散液を取り出した後のオートクレーブの攪拌翼、槽内壁、邪魔板等の槽内には付着ポリマーがあり、それらを採取し、加熱により水分を除去すると、11.8gであった。
ポリマーのモノマー単位組成:TFE/PMVE/CNVE=56.0/43.7/0.38モル%
170℃でのムーニー粘度 ML(1+20):107.0
ガラス転移温度:-2.1℃
室温から600℃までのDTA測定と、-50℃から100℃までのDSC測定の結果、融解ピークは観察されなかった。
最初に仕込む純水の量を1870gに、F(CF2)5COONH4の50質量%水溶液をF(CF2)7COONH4の20質量%水溶液の584.5gに、それぞれ変更したこと以外は、実施例1と同様に重合を行い、固形分濃度22.2質量%の水性分散液3280gを得た。重合時間は4.55時間であった。水性分散液を取り出した後のオートクレーブの攪拌翼、槽内壁、邪魔板等の槽内には付着ポリマーは全く無かった。
ポリマーのモノマー単位組成:TFE/PMVE/CNVE=57.1/42.5/0.38モル%
最初に仕込む純水の量を2242.8gに、F(CF2)5COONH4の50質量%水溶液をF(CF2)7COONH4の20質量%水溶液の119gに、それぞれ変更したこと以外は、実施例1と同様に重合を行い、固形分濃度22.3質量%の水性分散液3130gを得た。重合時間は7.40時間であった。水性分散液を取り出した後のオートクレーブの攪拌翼、槽内壁、邪魔板等の槽内には付着ポリマーがあり、それらを採取し、加熱により水分を除去すると、9.8gであった。
ポリマーのモノマー単位組成:TFE/PMVE/CNVE=56.5/43.1/0.40モル%
170℃でのムーニー粘度 ML(1+20):102.5
Claims (5)
- 水性媒体100質量部に対して2質量部以上の下記一般式(1)で表される含フッ素界面活性剤の存在下に、パーフルオロモノマーを水性媒体中で乳化重合してパーフルオロエラストマー粒子を含む水性分散液を得る工程を含むことを特徴とするパーフルオロエラストマー水性分散液の製造方法。
X-(CF2)m1-Y (1)
(式中、XはH又はFを表し、m1は3~6の整数を表し、Yは-SO3M、-SO4M、-SO3R、-SO4R、-COOM、-PO3M2、-PO4M2(MはH、NH4又はアルカリ金属を表し、Rは炭素数1~12のアルキル基を表す。)を表す。) - パーフルオロエラストマー粒子を構成するパーフルオロエラストマーは、テトラフルオロエチレン/下記一般式(3)で表されるフルオロモノマー共重合体、及び、テトラフルオロエチレン/下記一般式(3)で表されるフルオロモノマー/架橋部位を与えるモノマー共重合体からなる群より選択される少なくとも1種である請求項1記載の製造方法。
一般式(3):CF2=CF(O(CF2)n31)m31(OCF2)x31(OCF2CF(CF3))y31ORf31
(式中、n31は1~6の整数を表し、m31は0~4の整数を表し、x31は0~6の整数を表し、y31は0~4の整数を表し、Rf31は炭素数1~8の直鎖又は分岐状パーフルオロアルキル基、炭素数5~6の環式パーフルオロアルキル基、1~3個の酸素原子を含む炭素数2~6の直鎖又は分岐状パーフルオロオキシアルキル基である。) - パーフルオロエラストマー粒子を構成するパーフルオロエラストマーは、テトラフルオロエチレン/下記一般式(8)、(10)又は(11)で表されるフルオロモノマー共重合体、及び、テトラフルオロエチレン/下記一般式(8)、(10)又は(11)で表されるフルオロモノマー/架橋部位を与えるモノマー共重合体からなる群より選択される少なくとも1種である請求項1又は2記載の製造方法。
一般式(8):CF2=CF-ORf81
(式中、Rf81は、炭素数1~8のパーフルオロアルキル基を表す。)
一般式(10):CF2=CFOCF2ORf101
(式中、Rf101は炭素数1~6の直鎖又は分岐状パーフルオロアルキル基、炭素数5~6の環式パーフルオロアルキル基、1~3個の酸素原子を含む炭素数2~6の直鎖又は分岐状パーフルオロオキシアルキル基である)
一般式(11):CF2=CFO(CF2CF(Y11)O)m(CF2)nF
(式中、Y11はフッ素原子又はトリフルオロメチル基を表す。mは1~4の整数である。nは1~4の整数である。) - パーフルオロエラストマー粒子を含む水性分散液は、パーフルオロエラストマー粒子の粒子数が5×1014個/cc以上である請求項1、2又は3記載の製造方法。
- 請求項1、2、3又は4記載の製造方法により得られたパーフルオロエラストマー粒子を含む水性分散液から水性媒体を除去することによりパーフルオロエラストマーを得る工程
を含むことを特徴とするパーフルオロエラストマーの製造方法。
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