Fluorine-containing elastomer, crosslinkable composition and molded article

Patent metadata

Field	Value
Publication number	US-12473386-B2
Application number	US-201917285540-A
Country	US
Kind code	B2
Filing date	Oct 18, 2019
Priority date	Oct 18, 2018
Publication date	Nov 18, 2025
Grant date	Nov 18, 2025

Abstract

A fluorine-containing elastomer including a vinylidene fluoride unit and an unsaturated ether unit selected from a unit based on a monomer (1) represented by the general formula (1): CH 2 ═CFCF 2 —O—Rf 1 and a unit based on a monomer (2) represented by the general formula (2): CH 2 ═CF—O—Rf 2 , and having a glass transition temperature of 20° C. or lower, a crosslinkable composition including the fluorine-containing elastomer, and a molded article obtained from the fluorine-containing elastomer or the crosslinkable composition.

First claim

The invention claimed is:

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,
CH 2 ═CFCF 2 —O—Rf 1   the general formula (1):

wherein Rf 1 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;
CH 2 ═CF—O—Rf 2   the general formula (2):

wherein Rf 2 is a fluorinated alkyl group containing no substituent other than a fluorine atom;
CHX 11 —CX 12 Rf  the general formula (11):

wherein one of X 11 and X 12 is H, the other is F, and Rf is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms;
CX 13 2 ═CX 13 —Rf 11 CHR 11 X 14   the general formula (12):

wherein each X 13 is the same or different and is H, F or —CH 3 , Rf 11 is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro(poly)oxyalkylene group, R 11 is H or —CH 3 , and X 14 is I or Br;
CX 15 2 ═CX 15 —Rf 12 X 16   the general formula (13):

wherein each X 15 is the same or different and is H, F or —CH 3 , Rf 12 is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro(poly)oxyalkylene group, and X 16 is I or Br;
CF 2 ═CFO(CF 2 CF(CF 3 )O) m (CF 2 ) n —X 17   the general formula (14):

wherein m is an integer of 0 to 5, n is an integer of 1 to 3, and X 17 is a cyano group, a carboxyl group, an alkoxycarbonyl group, I or Br;
CH 2 ═CFCF 2 O(CF(CF 3 )CF 2 O) m (CF(CF 3 )) n —X 18   the general formula (15):

wherein m is an integer of 0 to 5, n is an integer of 1 to 3, and X 18 is a cyano group, a carboxyl group, an alkoxycarbonyl group, I, Br or —CH 2 OH; and
CR 12 R 13 ═CR 14 —Z—CR 15 ═CR 16 CR 17   the general formula (16):

wherein R 12 to R 17 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 -CF 2 O—(CF 2 CF 2 O) m (CF 2 O) n —CF 2 -(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.

2 . The crosslinkable composition according to claim 1 , wherein the at least one unsaturated ether unit is the unit based on the monomer (1).

3 . The crosslinkable composition according to claim 1 , wherein Rf 1 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 and have 1 to 14 carbon atoms, or 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 2 to 20 carbon atoms, and contain an oxygen atom between carbon-carbon atoms.

4 . The crosslinkable composition according to claim 1 , wherein Rf 1 is a group represented by
—(Rf 3 —O) n —Rf 4   the general formula (3):
wherein Rf 3 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 and have 1 to 4 carbon atoms, Rf 4 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, the partially fluorinated alkyl group and the perfluorinated alkyl group are linear or branched chain and have 1 to 4 carbon atoms, and n is an integer of 0 to 4.

5 . The crosslinkable composition according to claim 4 , wherein n in the general formula (3) is an integer of 1 to 4.

6 . A molded article obtained from the crosslinkable composition according to claim 1 .

Assignees

• Daikin Ind Ltd

Inventors

• Furutani Takahiro
• Gotou Akihiro
• Irie Masaki

Classifications

• C08K5/0025

  Crosslinking or vulcanising agents; including accelerators · CPC title

• C08F216/1425

  Monomers containing side chains of polyether groups · CPC title

• C08K5/14

  Peroxides · CPC title

• C08K5/34924

  containing cyanurate groups; Tautomers thereof · CPC title

• C08F214/222 Primary

  with fluorinated vinyl ethers · CPC title