US 12,473,386 B2
Fluorine-containing elastomer, crosslinkable composition and molded article
Takahiro Furutani, Osaka (JP); Akihiro Gotou, Osaka (JP); and Masaki Irie, Osaka (JP)
Assigned to DAIKIN INDUSTRIES, LTD., Osaka (JP)
Appl. No. 17/285,540
Filed by DAIKIN INDUSTRIES, LTD., Osaka (JP)
PCT Filed Oct. 18, 2019, PCT No. PCT/JP2019/041095
§ 371(c)(1), (2) Date Apr. 15, 2021,
PCT Pub. No. WO2020/080523, PCT Pub. Date Apr. 23, 2020.
Claims priority of application No. 2018-196485 (JP), filed on Oct. 18, 2018.
Prior Publication US 2021/0380739 A1, Dec. 9, 2021
Int. Cl. C08F 214/22 (2006.01); C08K 5/00 (2006.01)
CPC C08F 214/222 (2013.01) [C08K 5/0025 (2013.01)] 6 Claims
 
1. A crosslinkable composition consisting of
a fluorine-containing elastomer,
a cross-linking agent, and
optionally at least one selected from the group consisting of a crosslinking aid, a crosslinking accelerator, a filler, a plasticizer, a processing aid, an acid acceptor, a mold release agent, a pigment, a flame retarder, a lubricant, a light stabilizer, a weathering stabilizer, an antistatic agent, an ultraviolet absorbing agent, an antioxidant, a foaming agent, a perfume, an oil, a softener, a solvent and a polymer different from the fluorine-containing elastomer,
wherein the fluorine-containing elastomer consists of:
a vinylidene fluoride unit,
at least one unsaturated ether unit selected from the group consisting of a unit based on a monomer (1) represented by the general formula (1) and a unit based on a monomer (2) represented by the general formula (2), and
optionally at least one selected from the group consisting of tetrafluoroethylene unit, hexafluoropropylene unit, perfluoro(methyl vinyl ether) unit, perfluoro(ethyl vinyl ether) unit, perfluoro(propyl vinyl ether) unit, chlorotrifluoroethylene unit, trifluoroethylene unit, hexafluoroisobutene unit, vinyl fluoride unit, ethylene unit, propylene unit, alkyl vinyl ether unit, a unit based on a fluorine-containing monomer represented by the general formula (11), a unit based on an iodine- or bromine-containing monomer represented by the general formula (12), a unit based on an iodine- or bromine-containing monomer represented by the general formula (13), a unit based on a monomer represented by the general formula (14), a unit based on a monomer represented by the general formula (15) and a unit based on a monomer represented by the general formula (16),
the polymer different from the fluorine-containing elastomer consists of at least one selected from the group consisting of a nitrile rubber, an acrylic rubber, an epichlorohydrin rubber, a fluorosilicone rubber, a silicone rubber and a fluorine-containing thermoplastic elastomer,
a molar ratio of the vinylidene fluoride unit to the unsaturated ether unit (vinylidene fluoride unit/unsaturated ether unit) is 95/5 to 20/80,
a glass transition temperature of the fluorine-containing elastomer is 20° C. or lower, and
the cross-linking agent is an organic peroxide,
CH2═CFCF2—O—Rf1  the general formula (1):
wherein Rf1 is a partially fluorinated alkyl group where a part of hydrogen atoms bonded to a carbon atom is substituted by a fluorine atom or a perfluorinated alkyl group where all hydrogen atoms bonded to a carbon atom are substituted by fluorine atoms, and the partially fluorinated alkyl group and the perfluorinated alkyl group are linear or branched chain, have 1 to 20 carbon atoms, and optionally contain an oxygen atom between carbon-carbon atoms when the partially fluorinated alkyl group or the perfluorinated alkyl group has 2 or more carbon atoms;
CH2═CF—O—Rf2  the general formula (2):
wherein Rf2 is a fluorinated alkyl group containing no substituent other than a fluorine atom;
CHX11—CX12Rf  the general formula (11):
wherein one of X11 and X12 is H, the other is F, and Rf is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms;
CX132═CX13—Rf11CHR11X14  the general formula (12):
wherein each X13 is the same or different and is H, F or —CH3, Rf11 is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro(poly)oxyalkylene group, R11 is H or —CH3, and X14 is I or Br;
CX152═CX15—Rf12X16  the general formula (13):
wherein each X15 is the same or different and is H, F or —CH3, Rf12 is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro(poly)oxyalkylene group, and X16 is I or Br;
CF2═CFO(CF2CF(CF3)O)m(CF2)n—X17  the general formula (14):
wherein m is an integer of 0 to 5, n is an integer of 1 to 3, and X17 is a cyano group, a carboxyl group, an alkoxycarbonyl group, I or Br;
CH2═CFCF2O(CF(CF3)CF2O)m(CF(CF3))n—X18  the general formula (15):
wherein m is an integer of 0 to 5, n is an integer of 1 to 3, and X18 is a cyano group, a carboxyl group, an alkoxycarbonyl group, I, Br or —CH2OH; and
CR12R13═CR14—Z—CR15═CR16CR17  the general formula (16):
wherein R12 to R17 are the same or different and are each H or an alkyl group having 1 to 5 carbon atoms; and
Z is an alkylene group having 1 to 18 carbon atoms and being linear or branched chain and optionally having an oxygen atom, a cycloalkylene group having 3 to 18 carbon atoms and being linear or branched chain and optionally having an oxygen atom, at least partially fluorinated alkylene or oxyalkylene group having 1 to 10 carbon atoms and being linear or branched chain and optionally having an oxygen atom, or a (per)fluoropolyoxyalkylene group represented by
-(Q)p-CF2O—(CF2CF2O)m(CF2O)n—CF2-(Q)p-
wherein Q is an alkylene or oxyalkylene group, p is 0 or 1, m is 0.2 to 5, and n is 0.2 to 5, and having a molecular weight of 500 to 10,000.