WO2022260138A1

WO2022260138A1 - Production method for aqueous fluorine-containing elastomer dispersion, fluorine-containing elastomer, and composition

Info

Publication number: WO2022260138A1
Application number: PCT/JP2022/023336
Authority: WO
Inventors: 利奈玉井; 達也森川; 颯太湯浅; 光平竹村; 正樹入江
Original assignee: ダイキン工業株式会社
Priority date: 2021-06-11
Filing date: 2022-06-09
Publication date: 2022-12-15
Also published as: JPWO2022260138A1

Abstract

The present invention provides a production method for an aqueous fluorine-containing elastomer dispersion in which an aqueous dispersion of a fluorine-containing elastomer that has a methylene group in the main chain is produced by polymerizing fluorine-containing monomers in the presence of: a fluorine-containing allyl ether (1) represented by general formula (1) CX¹¹ ₂=CY¹¹(-CZ¹¹ ₂-O-Rf¹¹-Y¹²); a fluorine-containing vinyl ether (2) represented by general formula (2) CX²¹ ₂=CY²¹(-O-Rf²¹-Y²²); and an aqueous medium.

Description

Method for producing fluorine-containing elastomer aqueous dispersion, fluorine-containing elastomer and composition

The present disclosure relates to a method for producing a fluorine-containing elastomer aqueous dispersion, a fluorine-containing elastomer, and a composition.

In Patent Document 1, in producing a fluorine-containing elastomer by copolymerizing at least one of each of a fluoromonomer and a comonomer containing or not containing fluorine by the action of a polymerization initiation source, the general formula CF ₂ =CFO (CF ₂ ) A compound represented by _n OOM (where n is an integer of 1 to 7 and M is NH ₄ or an alkali metal) is present in the total monomer mixture at 0.5 to 10 mol% and the polymerization reaction is substantially A method for producing a fluorine-containing elastomer is described, which is characterized in that it is carried out in an aqueous medium maintained at a liquid pH of 5 to 10 in the absence of a surfactant.

In Patent Document 2, a fluorine-containing monomer is represented by the general formula CF2 ₌ CF[OCF2CF ₍ _CF3 )] _bO (CF2) _aO [CF ₍ _CF3 ) _CF2O ] _cCF ( _CF3 ) COOM [I]
(Here, M is sodium or potassium, a is an integer of 1 to 6, and b+c is an integer of 0 to 6). The method for producing a fluorine-containing elastomer according to claim 1 is described, wherein the copolymerization reaction is carried out in the presence of an acid alkali metal salt.

Patent Document 3 discloses a method for producing a partially fluorinated polymer dispersion, wherein one or more fluorinated monomers are polymerized by aqueous emulsion polymerization in the presence of a polymerizable fluorinated emulsifier to obtain partially fluorinated forming a fluorinated polymer, wherein the polymerizable fluorinated emulsifier has the formula:
X ₂ C═CX(CF ₂ ) _m (CH ₂ ) _n [O—(CX ₂ ) _p ] _q —[O—(CX ₂ ) _r ] _s —[O—(CX ₂ —CX ₂ )] _t — [(O) _w- (CX2) _u ] _v- [ _CH2 ] _z _- Y
(wherein X is independently selected from H, F, or _CF3 ; Y is COOM or _SO3M ; M is H, an alkali metal, or _NH4 ; m is 0-5, n is 0-5, p is at least 1, q is 0-5, r is 0-5, s is 0-5, t is 0-5, u is 0-5, v is 0-5, w is 0 or 1, z is 0-5; m, n, q , s, t, u, v, and z is at least 1, and the polymerizable fluorinated emulsifier (a) comprises at least one fluorine atom and (b) A method is described in which less than 1% by weight, based on the total weight of monomers used, said partially fluorinated polymer comprises less than 50 mol% vinylidene fluoride.

Japanese Patent Publication No. 61-33848 JP 2015-131894 A Japanese Patent Publication No. 2015-537106

An object of the present disclosure is to provide a method for producing an aqueous fluoroelastomer dispersion that can generate a sufficient number of fluoroelastomer particles and greatly suppress adhesion of the fluoroelastomer to a polymerization tank. aim.

According to the present disclosure, in the presence of a fluorinated allyl ether (1) represented by the general formula (1), a fluorinated vinyl ether (2) represented by the general formula (2) and an aqueous medium, a fluorinated monomer A method for producing an aqueous dispersion of a fluoroelastomer containing a methylene group in its main chain is provided by polymerizing a fluoroelastomer.
CX ¹¹ ₂ =CY ¹¹ (-CZ ¹¹ ₂ -O-Rf ¹¹ -Y ¹² ) (1)
(Wherein, X ¹¹ is the same or different and is -H or -F, Y ¹¹ is -H, -F, an alkyl group or a fluorine-containing alkyl group, Z ¹¹ is the same or different and - H, —F, alkyl group or fluorine-containing alkyl group Rf ¹¹ is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond Y ¹² is a hydrophilic group.)
CX ²¹ ₂ = CY ²¹ (-O-Rf ²¹ -Y ²² ) (2)
(Wherein, X ²¹ is the same or different and is -H or -F, Y ²¹ is -H, -F, alkyl group or fluorine-containing alkyl group, Rf ²¹ is C 1-40 A fluorine alkylene group or a fluorine-containing alkylene group having an ether bond with 2 to 100 carbon atoms, and Y ²² is a hydrophilic group.)

In the production method of the present disclosure, Y ¹² is —NH ₂ , —P(O)(OM) ₂ , —OP(O)(OM) ₂ , —SO ₃ M, —OSO ₃ M, —COOM, —B (OM) ₂ or —OB(OM) ₂ ₍ wherein M is H, a metal atom, NR ⁷⁴ , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, R ⁷ is H or an organic group, which may be the same or different, any two of which may be combined to form a ring.) is preferably
In the production method of the present disclosure, the production method according to claim 1 or 2, wherein all X ¹¹ are -H, is preferred.
In the production method of the present disclosure, the amount of the fluorine-containing allyl ether (1) is preferably 3-5000 mass ppm with respect to the aqueous medium.
In the production method of the present disclosure, Y ²² is —NH ₂ , —P(O)(OM) ₂ , —OP(O)(OM) ₂ , —SO ₃ M, —OSO ₃ M, —COOM, —B (OM) ₂ or —OB(OM) ₂ ₍ wherein M is H, a metal atom, NR ⁷⁴ , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium, R ⁷ is H or an organic group, which may be the same or different, any two of which may be combined to form a ring.) is preferably
In the production method of the present disclosure, the amount of the fluorine-containing vinyl ether (2) is preferably 3-5000 mass ppm with respect to the aqueous medium.
In the production method of the present disclosure, it is preferable to further polymerize the fluorine-containing monomer in the presence of a chain transfer agent.
In the production method of the present disclosure, it is preferable to polymerize the fluorine-containing monomer at 10 to 120°C.
In the production method of the present disclosure, it is preferable to polymerize the fluorine-containing monomer at 0.5 to 10 MPaG.
In the production method of the present disclosure, the fluorine-containing elastomer preferably contains vinylidene fluoride units.
In the production method of the present disclosure, the fluorine-containing elastomer preferably contains vinylidene fluoride units in an amount of 50 mol % or more with respect to all monomer units.
In the production method of the present disclosure, the Mooney viscosity (ML1+10 (100° C.)) of the fluorine-containing elastomer is preferably 10-130.

Further, according to the present disclosure, the main chain contains a methylene group, and the monomer unit (1) based on the fluorine-containing allyl ether (1) represented by the general formula (1) and the general formula (2) A fluorine-containing elastomer containing monomer units (2) based on the fluorine-containing vinyl ether (2) represented is provided.
CX ¹¹ ₂ =CY ¹¹ (-CZ ¹¹ ₂ -O-Rf ¹¹ -Y ¹² ) (1)
(Wherein, X ¹¹ is the same or different and is -H or -F, Y ¹¹ is -H, -F, an alkyl group or a fluorine-containing alkyl group, Z ¹¹ is the same or different and - H, —F, alkyl group or fluorine-containing alkyl group Rf ¹¹ is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond Y ¹² is a hydrophilic group.)
CX ²¹ ₂ = CY ²¹ (-O-Rf ²¹ -Y ²² ) (2)
(Wherein, X ²¹ is the same or different and is -H or -F, Y ²¹ is -H, -F, alkyl group or fluorine-containing alkyl group, Rf ²¹ is C 1-40 A fluorine alkylene group or a fluorine-containing alkylene group having an ether bond with 2 to 100 carbon atoms, and Y ²² is a hydrophilic group.)

The fluorine-containing elastomer of the present disclosure preferably contains vinylidene fluoride units.

Further, according to the present disclosure, there is provided a fluoroelastomer aqueous dispersion containing the above fluoroelastomer and an aqueous medium.

According to the present disclosure, there is provided a method for producing a fluoroelastomer aqueous dispersion that can generate a sufficient number of fluoroelastomer particles and greatly suppress adhesion of the fluoroelastomer to a polymerization tank. be able to.

Before describing specific embodiments of the present disclosure, some terms used in the present disclosure will be defined or explained.

In the present disclosure, the fluorine-containing elastomer is an amorphous fluoropolymer. “Amorphous” means a melting peak (ΔH ) is 4.5 J/g or less. Fluorine-containing elastomers exhibit elastomeric properties by cross-linking. By elastomeric properties is meant the property of being able to stretch a polymer and retain its original length when the force required to stretch the polymer is no longer applied.

In the present disclosure, a perfluoromonomer is a monomer that does not contain a carbon atom-hydrogen atom bond in its molecule. The perfluoromonomer may be a monomer in which some of the fluorine atoms bonded to the carbon atoms are substituted with chlorine atoms in addition to carbon atoms and fluorine atoms, and in addition to carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, boron atoms or silicon atoms. The above perfluoromonomer is preferably a monomer in which all hydrogen atoms are substituted with fluorine atoms. The above perfluoromonomers do not include monomers that provide crosslinkable groups.

A monomer that provides a cross-linking site is a monomer (cure site monomer) that provides the fluoropolymer with a cross-linking site for forming cross-links with a curing agent. A monomer that provides a cross-linking site includes a monomer that provides a cross-linkable group.

In the present disclosure, the content of each monomer unit constituting the fluorine-containing elastomer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.

In this disclosure, "organic group" means a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound.
Examples of such "organic groups" are
an alkyl group optionally having one or more substituents,
an alkenyl group optionally having one or more substituents,
an alkynyl group optionally having one or more substituents,
a cycloalkyl group optionally having one or more substituents,
a cycloalkenyl group optionally having one or more substituents,
a cycloalkadienyl group optionally having one or more substituents,
an aryl group optionally having one or more substituents,
an aralkyl group optionally having one or more substituents,
a non-aromatic heterocyclic group optionally having one or more substituents,
a heteroaryl group optionally having one or more substituents,
cyano group,
formyl group,
RaO-,
RaCO-,
_RaSO2- ,
RaCOO-,
RaNRaCO-,
RaCONRa-,
RaOCO-,
RaOSO ₂ -, and
_RaNRbSO2-
(In these formulas, Ra is independently
an alkyl group optionally having one or more substituents,
an alkenyl group optionally having one or more substituents,
an alkynyl group optionally having one or more substituents,
a cycloalkyl group optionally having one or more substituents,
a cycloalkenyl group optionally having one or more substituents,
a cycloalkadienyl group optionally having one or more substituents,
an aryl group optionally having one or more substituents,
an aralkyl group optionally having one or more substituents,
a non-aromatic heterocyclic group optionally having one or more substituents, or
a heteroaryl group optionally having one or more substituents,
Rb is independently H or an alkyl group optionally having one or more substituents)
encompasses
As the organic group, an alkyl group optionally having one or more substituents is preferable.

In addition, in the present disclosure, "substituent" means a substitutable group. Examples of the "substituent" include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, an aliphatic oxycarbonyl group , aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, aromatic sulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, aromatic sulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aromatic sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, aromatic amino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aromatic oxycarbonylamino group, heterocyclic oxycarbonylamino group, aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic thio group, aromatic thio group, hydroxy group, cyano group, sulfo group, carboxy group, aliphatic oxyamino group, aromatic oxy includes amino group, carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl group, and diaromatic oxyphosphinyl group .

The above aliphatic group may be saturated or unsaturated, and may be a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group. , an acylamino group, a carbamoylamino group, and the like. Examples of the aliphatic group include alkyl groups having a total carbon number of 1 to 8, preferably 1 to 4, such as methyl, ethyl, vinyl, cyclohexyl and carbamoylmethyl groups.

The aromatic group includes, for example, a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, and the like. You may have The aromatic group includes an aryl group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms in total, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group and a 4-methanesulfonylphenyl group. etc.

The heterocyclic group has a halogen atom, a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, and the like. may Examples of the heterocyclic group include 5- to 6-membered heterocyclic rings having a total carbon number of 2 to 12, preferably 2 to 10, such as 2-tetrahydrofuryl group and 2-pyrimidyl group.

The acyl group includes an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a hydroxy group, a halogen atom, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, and an amino group. , an aliphatic amino group, an acylamino group, a carbamoylamino group, and the like. The acyl group includes acyl groups having 2 to 8, preferably 2 to 4 carbon atoms in total, such as acetyl, propanoyl, benzoyl and 3-pyridinecarbonyl groups.

The acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group, and the like, and has, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, and the like. may be Examples of the acylamino group include acylamino groups having a total number of carbon atoms of 2 to 12, preferably 2 to 8, and alkylcarbonylamino groups having a total number of carbon atoms of 2 to 8, such as acetylamino, benzoylamino and 2-pyridinecarbonylamino. groups, propanoylamino groups, and the like.

The aliphatic oxycarbonyl group may be saturated or unsaturated, and may be a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic It may have an amino group, an acylamino group, a carbamoylamino group, or the like. Examples of the aliphatic oxycarbonyl group include alkoxycarbonyl groups having 2 to 8, preferably 2 to 4 carbon atoms in total, such as methoxycarbonyl, ethoxycarbonyl and (t)-butoxycarbonyl groups.

The carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, and the like. Examples of the carbamoyl group include an unsubstituted carbamoyl group, an alkylcarbamoyl group having a total of 2 to 9 carbon atoms, preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having a total of 2 to 5 carbon atoms, such as an N-methylcarbamoyl group, N,N-dimethylcarbamoyl group, N-phenylcarbamoyl group and the like.

The aliphatic sulfonyl group may be saturated or unsaturated, and may be a hydroxy group, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group. , an aliphatic amino group, an acylamino group, a carbamoylamino group, and the like. Examples of the aliphatic sulfonyl groups include alkylsulfonyl groups having 1 to 6 total carbon atoms, preferably 1 to 4 total carbon atoms, such as methanesulfonyl groups.

The aromatic sulfonyl group includes a hydroxy group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, and the like. You may have Examples of the aromatic sulfonyl group include arylsulfonyl groups having 6 to 10 carbon atoms in total, such as benzenesulfonyl groups.

The above amino group may have an aliphatic group, an aromatic group, a heterocyclic group, or the like.

The acylamino group may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, and the like. The acylamino group includes acylamino groups having 2 to 12 total carbon atoms, preferably 2 to 8 carbon atoms, more preferably alkylcarbonylamino groups having 2 to 8 total carbon atoms, such as acetylamino and benzoylamino. group, 2-pyridinecarbonylamino group, propanoylamino group and the like.

The aliphatic sulfonamide group, aromatic sulfonamide group, and heterocyclic sulfonamide group may be, for example, a methanesulfonamide group, a benzenesulfonamide group, a 2-pyridinesulfonamide group, and the like.

The above sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, and the like. Examples of the sulfamoyl group include a sulfamoyl group, an alkylsulfamoyl group having a total number of carbon atoms of 1 to 9, a dialkylsulfamoyl group having a total number of carbon atoms of 2 to 10, and an arylsulfamoyl group having a total number of carbon atoms of 7 to 13. , a heterocyclic sulfamoyl group having a total of 2 to 12 carbon atoms, more preferably a sulfamoyl group, an alkylsulfamoyl group having a total of 1 to 7 carbon atoms, a dialkylsulfamoyl group having a total of 3 to 6 carbon atoms, a total carbon arylsulfamoyl group having 6 to 11 atoms, heterocyclic sulfamoyl group having 2 to 10 total carbon atoms, such as sulfamoyl group, methylsulfamoyl group, N,N-dimethylsulfamoyl group, phenylsulfamoyl group; group, 4-pyridinesulfamoyl group, and the like.

The aliphatic oxy group may be saturated or unsaturated, and may have a methoxy group, ethoxy group, i-propyloxy group, cyclohexyloxy group, methoxyethoxy group, and the like. Examples of the aliphatic oxy group include alkoxy groups having a total carbon number of 1 to 8, preferably 1 to 6, such as methoxy, ethoxy, i-propyloxy, cyclohexyloxy and methoxyethoxy.

The above aromatic amino group and heterocyclic amino group are an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic group condensed with the aryl group, an aliphatic oxycarbonyl group, preferably the total number of carbon atoms 1 to 4 aliphatic groups, 1 to 4 total carbon atom aliphatic oxy groups, halogen atoms, 1 to 4 total carbon atom carbamoyl groups, nitro groups, 2 to 4 total carbon atom aliphatic oxycarbonyls You may have a group.

The aliphatic thio group may be saturated or unsaturated, and an alkylthio group having 1 to 8 total carbon atoms, more preferably 1 to 6 total carbon atoms, such as a methylthio group and an ethylthio group. , carbamoylmethylthio group, t-butylthio group and the like.

The carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group, and the like. Examples of the carbamoylamino group include a carbamoylamino group, an alkylcarbamoylamino group having 2 to 9 total carbon atoms, a dialkylcarbamoylamino group having 3 to 10 total carbon atoms, an arylcarbamoylamino group having 7 to 13 total carbon atoms, heterocyclic carbamoylamino group having 3 to 12 total carbon atoms, preferably carbamoylamino group, alkylcarbamoylamino group having 2 to 7 total carbon atoms, dialkylcarbamoylamino group having 3 to 6 total carbon atoms, 7-11 arylcarbamoylamino groups, heterocyclic carbamoylamino groups having 3-10 total carbon atoms, such as carbamoylamino, methylcarbamoylamino, N,N-dimethylcarbamoylamino, phenylcarbamoylamino, 4- and a pyridinecarbamoylamino group.

In this disclosure, ranges represented by endpoints include all numbers subsumed within that range (eg, 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9 .98, etc.).

In this disclosure, reference to "at least 1" includes all numbers greater than or equal to 1 (eg, at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.) .

Specific embodiments of the present disclosure will be described in detail below, but the present disclosure is not limited to the following embodiments.

The production method of the present disclosure is a method for producing an aqueous dispersion of a fluorine-containing elastomer containing a methylene group in the main chain, wherein the general formula (1): CX ¹¹ ₂ =CY ¹¹ ( -CZ ¹¹ ₂ -O-Rf ¹¹ -Y ¹¹ ), general formula (2): CX ²¹ ₂ =CY ²¹ (-O-Rf ²¹ -Y ²¹ ) A fluorine-containing monomer is polymerized in the presence of a fluorine-containing vinyl ether (2) and an aqueous medium.

By using two types of compounds having different structures, the fluorine-containing allyl ether (1) and the fluorine-containing vinyl ether (2), it is possible to generate a sufficient number of fluorine-containing elastomer particles for the smooth progress of the polymerization reaction. At the same time, adhesion of the fluorine-containing elastomer to the polymerization tank can be greatly suppressed. Although the reason for this is not clear, the two types of compounds having different structures have different reactivities with fluorine-containing monomers. In the subsequent polymerization reaction, mainly the fluorine-containing vinyl ether (2) reacts with the fluorine-containing monomer to have a hydrophilic group. It is presumed that this is for the purpose of forming fluorine-containing elastomer particles with high stability.

Fluorine-containing allyl ether (1) is represented by general formula (1).
CX ¹¹ ₂ =CY ¹¹ (-CZ ¹¹ ₂ -O-Rf ¹¹ -Y ¹² ) (1)
(Wherein, X ¹¹ is the same or different and is -H or -F, Y ¹¹ is -H, -F, an alkyl group or a fluorine-containing alkyl group, Z ¹¹ is the same or different and - H, —F, alkyl group or fluorine-containing alkyl group Rf ¹¹ is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond Y ¹² is a hydrophilic group.)

In general formula (1), X ¹¹ is -H or -F. Both of X ¹¹ may be -F, or at least one may be -H. For example, one may be -F and the other may be -H, or both may be -H. All of X ¹¹ are preferably —H, since more fluorine-containing elastomer particles can be generated and adhesion of the fluorine-containing elastomer to the polymerization tank can be further suppressed.

In general formula (1), Y ¹¹ is —H, —F, an alkyl group or a fluorine-containing alkyl group. The alkyl group is an alkyl group containing no fluorine atoms and may have 1 or more carbon atoms. The number of carbon atoms in the alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. The fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and may have 1 or more carbon atoms. The number of carbon atoms in the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. Y ¹¹ is preferably -H, -F or -CF ₃ , more preferably -F.

In general formula (1), Z ¹¹ are the same or different and are —H, —F, an alkyl group or a fluoroalkyl group. The alkyl group is an alkyl group containing no fluorine atoms and may have 1 or more carbon atoms. The number of carbon atoms in the alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. The fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and may have 1 or more carbon atoms. The number of carbon atoms in the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. Z ¹¹ is preferably -H, -F or -CF ₃ , more preferably -F.

In general formula (1), at least one of X ¹¹ , Y ¹¹ and Z ¹¹ preferably contains a fluorine atom. For example, X ¹¹ can be -H and Y ¹¹ and Z ¹¹ can be -F.

In general formula (1), Rf ¹¹ is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond. A fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group containing an ether bond between carbon atoms without a structure terminating with an oxygen atom. The number of carbon atoms in the fluorine-containing alkylene group is preferably 2 or more. The number of carbon atoms in the fluorine-containing alkylene group is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. The fluorine-containing alkylene group includes -CF ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CF _{2 CH 2 -, -CF 2 CF 2} _{CH 2} _- _, _-CF (CF ₃ )- , -CF(CF ₃ )CF ₂ -, -CF(CF ₃ )CH ₂ - and the like. The fluorine-containing alkylene group is preferably a perfluoroalkylene group.

The number of carbon atoms in the fluorine-containing alkylene group having an ether bond is preferably 3 or more. Moreover, the carbon number of the fluorine-containing alkylene group having an ether bond is preferably 60 or less, more preferably 30 or less, and even more preferably 12 or less.

Examples of the fluorine-containing alkylene group having an ether bond include the following formula:
-(CFZ ¹² CF ₂ O) _p1 -(CF ₂ O) _q1 - ⁽ CZ 132 CF ₂ CF ₂ O) _r1 -CZ ¹⁴ Z ¹⁵ -(CF ₂ ) _s1 - _{(CH 2} ₎ _t1 -
(Wherein, Z ¹² is F or CF ₃ ; Z ¹³ and Z ¹⁴ are each H or F; Z ¹⁵ is H, F or CF ₃ ; p1+q1+r1 is an integer of 1 to 10; s1 is 0 or 1; It is also preferably a divalent group represented by an integer of up to 5).

Specific examples of the fluorine-containing alkylene group having an ether bond include -CF(CF ₃ )CF ₂ -O-CF(CF ₃ )-, -(CF(CF ₃ )CF ₂ -O) _n -CF(CF ₃ )-(wherein n is an integer of 1 to 10), -CF(CF ₃ )CF ₂ -O-CF(CF ₃ )CH ₂ -, -(CF(CF ₃ )CF ₂ -O) _n -CF (CF ₃ )CH ₂ — (wherein n is an integer of 1 to 10), —CH ₂ CF ₂ CF ₂ O—CH ₂ CF ₂ CH ₂ —, —CF ₂ CF ₂ CF ₂ O—CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ O--CF ₂ CF ₂ CH ₂ -, -CF ₂ CF ₂ O--CF ₂ -, -CF ₂ CF ₂ O--CF ₂ CH ₂ - and the like. The fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

Y12 in general formula ( ¹ ) is a hydrophilic group. Examples of hydrophilic groups include -NH ₂ , -P(O)(OM) ₂ , -OP(O)(OM) ₂ , -SO ₃ M, -OSO ₃ M, -COOM, -B(OM) ₂ , —OB(OM) ₂ (in each formula, M is H, a metal atom, NR ⁷⁴ , imidazolium optionally having substituent ₍ s), pyridinium optionally having substituent(s) or substituent Phosphonium which may be present, R ⁷ is H or an organic group, which may be the same or different, any two of which may be bonded to each other to form a ring) is preferred. The hydrophilic group is preferably an anionic group such as -P(O)(OM) ₂ , -OP(O)(OM) ₂ , -SO ₃ M, -OSO ₃ M, -COOM, -B(OM). ₂ , -OB(OM) ₂ are more preferred. An alkyl group is preferred as the organic group for ^R7 . R ⁷ is preferably H or a C _1-10 organic group, more preferably H or a C _1-4 organic group, still more preferably H or a C _1-4 alkyl group, most preferably H. The metal atom includes a monovalent or divalent metal atom, preferably an alkali metal (group 1) or an alkaline earth metal (group 2), more preferably Na, K or Li.

In the general formula (1), as Y ¹² , —COOM, —SO ₃ can generate more fluorine-containing elastomer particles and can further suppress adhesion of the fluorine-containing elastomer to the polymerization tank. M or —OSO ₃ M (M is H, a metal atom, NR ⁷⁴ , imidazolium optionally having substituent ₍ s), pyridinium optionally having substituent(s) or good phosphonium, R ⁷ is H or an organic group, which may be the same or different, any two of which may be linked together to form a ring) is preferred.

An alkyl group is preferable as the organic group for ^R7 . R ⁷ is preferably H or a C _1-10 organic group, more preferably H or a C _1-4 organic group, and even more preferably H or a C _1-4 alkyl group. Examples of metal atoms include alkali metals (group 1) and alkaline earth metals (group 2), with Na, K or Li being preferred. M is preferably —H, a metal atom or —NR ⁷⁴ , more preferably —H, an alkali metal (group ₁ ), an alkaline earth metal (group ₂ ) or —NR ⁷⁴ , and —H, —Na, -K, -Li or -NH ₄ is more preferred, -Na, -K or -NH ₄ is even more preferred, -Na or -NH ₄ is particularly preferred, and -NH ₄ is most preferred. Y ¹² is preferably -COOM or -SO ₃ M, more preferably -COOM.

The fluorine-containing allyl ether (1) is preferably a compound (1a) represented by general formula (1a).
CH ₂ ═CF(—CF ₂ —O—Rf ¹¹ —Y ¹² ) (1a)
(In the formula, Rf ¹¹ and Y ¹² are the same as above.)

Specific examples of the compound (1a) include the following formula: CH ₂ =CFCF ₂ O--(CFZ ¹² CF ₂ O) _p1 --(CF ₂ O) _q1 --(CZ ¹³ ₂ CF ₂ CF ₂ O) _r1 --CZ ¹⁴ Z ^15- ( _CF2 ) _s1- ( _CH2 ) _t1 - ^Y12
(Wherein, Z ¹² is F or CF ₃ ; Z ¹³ and Z ¹⁴ are each H or F; Z ¹⁵ is H, F or CF ₃ ; p1+q1+r1 is an integer of 0 to 10; s1 is 0 or 1; and Y ¹² is the same as above, provided that when Z ¹⁴ and Z ¹⁵ are both H, p1+q1+r1+s1 is not 0).

As compound (1a), more specifically,
_CH2 = _CFCF2OCF ( _CF3 ) ^-Y12
_CH2 = _CFCF2OCF ( _CF3 ) _CF2OCF ( _CF3 ) ^-Y12
_CH2 =CFCF2O-[CF( _CF3 ) _CF2O ] ₂ _- CF( _CF3 ) ^-Y12
_CH2 = ^CFCF2OCF ( _CF3 ) _CH2 _- Y12
_CH2 = ^CFCF2OCF ( _CF3 ) _CF2OCF ( _CF3 ) _CH2 _- Y12
_CH2 =CFCF2O-[CF( _CF3 ) ^CF2O ] ₂ _- CF( _CF3 ) _CH2 _- Y12
_CH2 ₌ _CFCF2OCH2CF2 _- ^Y12
_CH2 ₌ _CFCF2O- [ _CH2CF2CF2O ] ₂ _- _CH2CF2 _- ^Y12
_CH2 ₌ _{CFCF2OCF2CH2CF2} _- ^Y12 _{_}
_CH2 ₌ _CFCF2O ₍ _CH2CF2CF2O ⁾ _CH2CF2CH2 _- _Y12
_CH2 ₌ _CFCF2OCF2CF2 _- ^Y12
_CH2 ₌ _CFCF2O ₍ _CF2CF2CF2O ) _CF2CH2 _- ^Y12
_CH2 ₌ _{CFCF2OCF2CF2CH2} _- ^Y12 _{_}
_CH2 ₌ _CFCF2O ₍ _CF2CF2CF2O ⁾ _CF2CF2CH2 _- _Y12
_CH2 = _CFCF2OCF2 _- ^Y12
_CH2 = _CFCF2O ₍ _CF2CF2O )CF2 _- ^Y12
_CH2 ₌ _CFCF2OCF2CH2 _- ^Y12
_CH2 ₌ _CFCF2O ₍ _CF2CF2O ) ^CF2CH2 _- Y12
etc.

As the compound (1a), among others, CH ₂ =CFCF ₂ OCF(CF ₃ )-Y ¹²
_CH2 = _CFCF2OCF ( _CF3 ) _CF2OCF ( _CF3 ) ^-Y12
_CH2 =CFCF2O-[CF( _CF3 ) _CF2O ] ₂ _- CF( _CF3 ) ^-Y12
_CH2 = ^CFCF2OCF ( _CF3 ) _CH2 _- Y12
_CH2 = ^CFCF2OCF ( _CF3 ) _CF2OCF ( _CF3 ) _CH2 _- Y12
_CH2 =CFCF2O-[CF( _CF3 ) ^CF2O ] ₂ _- CF( _CF3 ) _CH2 _- Y12
is preferred.

Compound (1a) is preferably a compound having —COOM as Y ¹² in formula (1a), especially CH ₂ ═CFCF ₂ OCF(CF ₃ )COOM and CH ₂ ═CFCF ₂ OCF(CF ₃ )CF ₂ At least one selected from the group consisting of OCF(CF ₃ )COOM (wherein M is as defined above) is preferred.

The fluorine-containing allyl ether (1) is preferably a compound (1b) represented by general formula (1b).
CX ¹² ₂ =CFCF ₂ -O-(CF(CF ₃ )CF ₂ O) _n5 -CF(CF ₃ )-Y ¹² (1b)
(In the formula, each X ¹² is the same and represents F or H. n5 represents 0 or an integer of 1 to 10, and Y ¹² is the same as defined above.)

In general formula (1b), n5 is preferably an integer of 0 or 1 to 5, more preferably 0, 1 or 2, from the viewpoint of the stability of the resulting aqueous dispersion. It is even more preferable to have Y ¹² is preferably -COOM in terms of obtaining appropriate water solubility and stability of the aqueous dispersion, and M is less likely to remain as an impurity and improves the heat resistance of the obtained molded product. , H or _NH4 .

Examples of the compound (1b) include _CH2 =CFCF2OCF( _CF3 )COOM, _CH2 ₌ _CFCF2OCF ( _CF3 ) _CF2OCF ( _CF3 )COOM (wherein M is the same as defined above). ).

Further, examples of the fluorine-containing allyl ether (1) include the compound (1c) represented by the general formula (1c).
CF ₂ =CFCF ₂ -O-Rf ¹¹ -Y ¹² (1c)
(Wherein, Rf ¹¹ and Y ¹² are the same as above)

As compound (1c), more specifically,
_CF2 ₌ _{CFCF2OCF2CF2CF2} _- ^Y12 _{_}
CF ₂ = CFCF ₂ OCFCF(CF ₃ )-Y ¹²
_CF2 ₌ _{CFCF2OCF2CF2CF2CH2} _- ^Y12 _{_} _{_}
CF2= _CFCF2OCF2CF ₍ _CF3 ) _CH2 _- ^Y12
etc.

As the fluorine-containing allyl ether (1), the compound (1a) represented by the general formula (1a) is preferable, and _CH2 =CFCF2OCF( _CF3 )COOM and _CH2 ₌ _CFCF2OCF ( _CF3 ) _CF2 At least one selected from the group consisting of OCF(CF ₃ )COOM (wherein M is as defined above) is more preferred.

In the polymerization of the fluorine-containing monomer, the amount of the fluorine-containing allyl ether (1) is preferably 3 to 5000 ppm by mass, more preferably 5 ppm by mass or more, and still more preferably 10 mass ppm or more, particularly preferably 20 mass ppm or more, most preferably 30 mass ppm or more, more preferably 1000 mass ppm or less, still more preferably 500 mass ppm or less, especially It is preferably 200 mass ppm or less, most preferably 100 mass ppm or less.

It is also preferable to adjust the amount of the fluorine-containing allyl ether (1) depending on the type of polymerization initiator used for polymerization and the polymerization temperature.
When a non-redox polymerization initiator is used as the polymerization initiator and the polymerization is carried out at 40 to 70° C., the amount of the fluorine-containing allyl ether (1) is preferably 3 to 300 mass ppm, preferably 3 to 150 mass ppm, relative to the aqueous medium. Weight ppm is more preferred, 5 to 100 weight ppm is more preferred, and 8 to 80 weight ppm is most preferred.
When a non-redox polymerization initiator is used as the polymerization initiator and the polymerization is carried out at more than 70° C. and 98° C. or less, the amount of the fluorine-containing allyl ether (1) is preferably 3 to 500 ppm by mass with respect to the aqueous medium. ~200 ppm by weight is more preferred, 5 to 120 ppm by weight is more preferred, and 20 to 110 ppm by weight is most preferred.
When a redox polymerization initiator is used as the polymerization initiator and the polymerization is carried out at 10° C. or more and less than 40° C., the amount of the fluorine-containing allyl ether (1) is preferably 3 to 300 ppm by mass with respect to the aqueous medium, and 3 to 300 ppm by mass. 100 mass ppm is more preferred, 5 to 80 mass ppm is more preferred, and 10 to 70 mass ppm is most preferred.
When a redox polymerization initiator is used as the polymerization initiator and the polymerization is carried out at 40 to 70° C., the amount of the fluorine-containing allyl ether (1) is preferably 3 to 500 mass ppm, more preferably 5 to 300 mass ppm, relative to the aqueous medium. ppm is more preferred, 10 to 200 ppm by weight is more preferred, and 15 to 150 ppm by weight is most preferred.
When a redox polymerization initiator is used as the polymerization initiator and the polymerization is carried out at a temperature higher than 70° C. and 98° C. or lower, the amount of the fluorine-containing allyl ether (1) is preferably 5 to 500 ppm by mass with respect to the aqueous medium, and 8 to 500 ppm by mass. 300 ppm by mass is more preferred, 15 to 200 ppm by mass is more preferred, and 20 to 150 ppm by mass is most preferred.
When the amount of the fluorine-containing allyl ether (1) is within the above range, the adhesion rate can be further reduced and the polymerization time can be shortened.

The fluorine-containing allyl ether (1) is preferably added before starting the polymerization reaction by adding the polymerization initiator. Moreover, it is preferable to add only before starting the polymerization reaction and not to add it after starting the polymerization.

The fluorine-containing vinyl ether (2) is represented by general formula (2).
CX ²¹ ₂ = CY ²¹ (-O-Rf ²¹ -Y ²² ) (2)
(Wherein, X ²¹ is the same or different and is -H or -F, Y ²¹ is -H, -F, alkyl group or fluorine-containing alkyl group, Rf ²¹ is C 1-40 A fluorine alkylene group or a fluorine-containing alkylene group having an ether bond with 2 to 100 carbon atoms, and Y ²² is a hydrophilic group.)

In general formula (2), X ²¹ is -H or -F. Both of X ²¹ may be -F, or at least one may be -H. For example, one may be -F and the other may be -H, or both may be -H. All of X ²¹ are preferably -F, since more fluorine-containing elastomer particles can be generated and adhesion of the fluorine-containing elastomer to the polymerization tank can be further suppressed.

In general formula (2), Y ²¹ is —H, —F, an alkyl group or a fluorine-containing alkyl group. The alkyl group is an alkyl group containing no fluorine atoms and may have 1 or more carbon atoms. The number of carbon atoms in the alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. The fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and may have 1 or more carbon atoms. The number of carbon atoms in the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. Y ²¹ is preferably -H, -F or -CF ₃ , more preferably -F.

In general formula (2), at least one of X ²¹ and Y ²¹ preferably contains a fluorine atom. For example, X ²¹ can be -H and Y ²¹ and Z can be -F.

In general formula (2), Rf ²¹ is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and having an ether bond. A fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group containing an ether bond between carbon atoms without a structure terminating with an oxygen atom. The number of carbon atoms in the fluorine-containing alkylene group is preferably 2 or more. The number of carbon atoms in the fluorine-containing alkylene group is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. The fluorine-containing alkylene group includes -CF ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CF _{2 CH 2 -, -CF 2 CF 2} _{CH 2} _- _, _-CF (CF ₃ )-, -CF(CF ₃ )CF ₂ -, -CF ₂ CF(CF ₃ )-, -CF(CF ₃ )CH ₂ - and the like. The fluorine-containing alkylene group is preferably a perfluoroalkylene group.

Y22 in general formula ⁽ 2) is a hydrophilic group. Examples of hydrophilic groups include -NH ₂ , -P(O)(OM) ₂ , -OP(O)(OM) ₂ , -SO ₃ M, -OSO ₃ M, -COOM, -B(OM) ₂ , —OB(OM) ₂ (in each formula, M is H, a metal atom, NR ⁷⁴ , imidazolium optionally having substituent ₍ s), pyridinium optionally having substituent(s) or substituent Phosphonium which may be present, R ⁷ is H or an organic group, which may be the same or different, any two of which may combine with each other to form a ring). The hydrophilic group is preferably an anionic group such as -P(O)(OM) ₂ , -OP(O)(OM) ₂ , -SO ₃ M, -OSO ₃ M, -COOM, -B(OM). ₂ , -OB(OM) ₂ are more preferred. An alkyl group is preferable as the organic group for ^R7 . R ⁷ is preferably H or a C _1-10 organic group, more preferably H or a C _1-4 organic group, still more preferably H or a C _1-4 alkyl group, and most preferably H. When two M's are included in each formula, the two M's may be the same or different. The metal atom includes a monovalent or divalent metal atom, preferably an alkali metal (group 1) or an alkaline earth metal (group 2), more preferably Na, K or Li.

In the above general formula (2), Y ²² can generate more fluorine-containing elastomer particles and can further suppress adhesion of the fluorine-containing elastomer to the polymerization tank. ₃ M or —OSO ₃ M ₍ M is H, a metal atom, NR ⁷⁴ , imidazolium optionally having substituents, pyridinium optionally having substituents, or phosphonium, R ⁷ is H or an organic group, which may be the same or different, any two of which may be combined with each other to form a ring) is preferred.

An alkyl group is preferable as the organic group for ^R7 . R ⁷ is preferably H or a C _1-10 organic group, more preferably H or a C _1-4 organic group, and even more preferably H or a C _1-4 alkyl group. Examples of the metal atom include alkali metals (group 1) and alkaline earth metals (group 2), and Na, K, and Li are preferable. The above M is preferably -H, a metal atom or -NR ⁷ ₄ , more preferably -H, an alkali metal (group 1), an alkaline earth metal (group 2) or -NR ⁷ ₄ , -H, -Na , -K, -Li or -NH ₄ are more preferred, -Na, -K or -NH ₄ are even more preferred, -Na or -NH ₄ are particularly preferred, and -NH ₄ is most preferred. The above Y ²² is preferably -COOM or -SO ₃ M.

The compound represented by general formula (2) is preferably at least one selected from the group consisting of compounds represented by general formulas (2a) to (2f).
CF ₂ =CF-O-(CF ₂ ) _n1 -Y ²² (2a)
(Wherein, n1 represents an integer of 1 to 10, and Y ²² is the same as defined above)
CF ₂ =CF-O-(CF ₂ C(CF ₃ )F) _n2 -Y ²² (2b)
(Wherein, n2 represents an integer of 1 to 5, and Y ²² is the same as defined above.)
CF ₂ =CF-O-(CFX ²² ) _n3 -Y ²² (2c)
(Wherein, X ²² represents F or CF ₃ , n3 represents an integer of 1 to 10, and Y ²² is the same as defined above.)
CF2=CF _- O-( _CF2CFX22O ) ^n4- ⁽ _CF2 ) _n6 -Y22 ( _2d )
(In the formula, n4 represents an integer of 1 to 10, n6 represents an integer of 1 to 3, and Y ²² and X ²² are the same as defined above.)
CF2 ₌ CF _- O- ₍ ^CF2CF2CFX22O ) _n5 _- _CF2CF2CF2 _- Y22 ⁽ 2e)
(In the formula, n5 represents an integer of 0 to 10, and Y ²² and X ²² are the same as defined above.)
CF ₂ =CF-O(-CF ₂ ) _n6 -O-CF ₂ -Y ²² (2f)
(In the formula, n6 represents an integer of 1 to 6, and Y ²² is the same as defined above.)

In general formula (2a), n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less. Y ²² is preferably —COOM or —SO ₃ M in terms of obtaining appropriate water solubility and stability of the aqueous dispersion, and M is easy to synthesize the fluorine-containing vinyl ether (2). Therefore, it is preferably Na, H, or _NH4 , and M is preferably H or _NH4 , since it hardly remains as an impurity and improves the heat resistance of the obtained molded product.

Examples of compounds represented by the general formula (2a) include CF ₂ =CF-O-CF ₂ COOM, CF ₂ =CF (OCF ₂ CF ₂ COOM), CF ₂ =CF (OCF ₂ CF ₂ CF ₂ COOM ), CF2 ₌ CF ₍ _OCF2CF2SO3M ), CF2 ₌ CF ₍ _OCF2SO3M ) _, _CF2 ₌ CF ₍ _{OCF2CF2CF2SO3M} ) ₍ where M is the above Same as the definition.).

In the general formula (2b), n2 is preferably an integer of 3 or less from the viewpoint of the stability of the resulting aqueous dispersion, and Y ²² provides appropriate water solubility and stability of the aqueous dispersion. In that respect, it is preferably -COOM or -SO ₃ M, M is preferably Na or H or NH ₄ because the synthesis of the fluorine-containing vinyl ether (2) is easy, and M is an impurity H or NH ₄ is preferable in that it is less likely to remain as a residue and the heat resistance of the resulting molded product is improved.

In general formula (2c), n3 is preferably an integer of 5 or less in terms of water solubility, and Y ²² is -COOM or - in terms of obtaining appropriate water solubility and stability of the aqueous dispersion. SO ₃ M is preferable, and M is preferably Na, H, or NH ₄ in terms of improving dispersion stability.

In the general formula (2d), X ²² is preferably —CF ₃ from the viewpoint of stability of the aqueous dispersion, n4 is preferably an integer of 5 or less from the viewpoint of water solubility, and Y ²² is preferably —COOM or —SO ₃ M, and M is preferably Na or H or NH ₄ in terms of obtaining appropriate water solubility and stability of the aqueous dispersion.

As the compound represented by the general formula (2d), for example, CF2 ₌ CFOCF2CF ₍ _CF3 ) _OCF2CF2COOM , CF2 ₌ _CFOCF2CF ₍ _CF3 ) _OCF2COOM , CF2 ₌ _CFOCF2 CF ₍ _CF3 ) _{OCF2CF2CF2COOM} , CF2 ₌ _CFOCF2CF ₍ _CF3 ) _OCF2SO3M , CF2 ₌ _CFOCF2CF ₍ _CF3 ) _OCF2CF2SO3M _, _CF2 ₌ _CFOCF2CF ₍ _CF3 ) _{OCF2CF2CF2SO3M} ₍ wherein M represents H _, _NH4 or an alkali metal).

In the general formula (2e), n5 is preferably an integer of 5 or less in terms of water solubility, and Y ²² is -COOM or -SO in terms of obtaining moderate water solubility and stability of the aqueous dispersion. ₃ M, preferably M is Na or H or NH ₄ .

Examples of compounds represented by general _formula (2e) include CF2 ₌ _{CFOCF2CF2CF2COOM} ₍ wherein M represents H, _NH4 or an alkali metal).

Examples of the compound represented by the general _formula ₍ 2f) include CF2 ₌ _{CFOCF2CF2CF2OCF2COOM} ₍ wherein M represents H, _NH4 or an alkali metal).

The fluorine-containing vinyl ether (2) is preferably at least one selected from the group consisting of compounds represented by the general formula (2a) and compounds represented by the general formula (2d), and CF ₂ =CF(OCF ₂ _CF2COOM ), CF2 ₌ CF ₍ _OCF2CF2SO3M ), CF2 ₌ _CFOCF2CF ₍ _CF3 ) _OCF2CF2COOM and _CF2 ₌ _CFOCF2CF ₍ _CF3 ) _OCF2CF2SO At least one selected from the group consisting of ₃ M (wherein M is the same as defined above) is preferred.

In the polymerization of the fluorine-containing monomer, the amount of the fluorine-containing vinyl ether (2) is preferably 3 to 5000 mass ppm, more preferably 5 mass ppm or more, and still more preferably 10 mass ppm, relative to the aqueous medium. mass ppm or more, particularly preferably 20 mass ppm or more, most preferably 30 mass ppm or more, more preferably 1000 mass ppm or less, still more preferably 500 mass ppm or less, and particularly preferably is 200 mass ppm or less, most preferably 100 mass ppm or less.

It is also preferable to adjust the amount of the fluorine-containing vinyl ether (2) depending on the type of polymerization initiator used for polymerization and the polymerization temperature.
When a non-redox polymerization initiator is used as the polymerization initiator and polymerization is carried out at 40 to 70° C., the amount of the fluorine-containing vinyl ether (2) is preferably 3 to 300 mass ppm, more preferably 3 to 150 mass ppm, relative to the aqueous medium. ppm is more preferred, 5 to 100 ppm by weight is more preferred, and 8 to 80 ppm by weight is most preferred.
When a non-redox polymerization initiator is used as the polymerization initiator and the polymerization is carried out at a temperature higher than 70° C. and 98° C. or lower, the amount of the fluorine-containing vinyl ether (2) is preferably 3 to 500 ppm by mass relative to the aqueous medium, and 3 to 500 ppm by mass. 200 mass ppm is more preferred, 5 to 120 mass ppm is more preferred, and 20 to 110 mass ppm is most preferred.
When a redox polymerization initiator is used as the polymerization initiator and the polymerization is carried out at 10° C. or more and less than 40° C., the amount of the fluorine-containing vinyl ether (2) is preferably 3 to 300 mass ppm, more preferably 3 to 100 mass ppm, relative to the aqueous medium. Weight ppm is more preferred, 5 to 80 weight ppm is more preferred, and 10 to 70 weight ppm is most preferred.
When a redox polymerization initiator is used as the polymerization initiator and polymerization is carried out at 40 to 70° C., the amount of the fluorine-containing vinyl ether (2) is preferably 3 to 500 ppm by mass, more preferably 5 to 300 ppm by mass, relative to the aqueous medium. is more preferred, 10 to 200 ppm by mass is more preferred, and 15 to 150 ppm by mass is most preferred.
When a redox polymerization initiator is used as the polymerization initiator and the polymerization is carried out at a temperature higher than 70°C and not higher than 98°C, the amount of the fluorine-containing vinyl ether (2) is preferably 5 to 500 mass ppm, more preferably 8 to 300 mass ppm, relative to the aqueous medium. Weight ppm is more preferred, 15 to 200 weight ppm is more preferred, and 20 to 150 weight ppm is most preferred.
When the amount of the fluorine-containing vinyl ether (2) is within the above range, the adhesion rate can be further reduced and the polymerization time can be shortened.

The fluorine-containing vinyl ether (2) is preferably added before starting the polymerization reaction by adding the polymerization initiator. Moreover, it is preferable to add only before starting the polymerization reaction and not to add it after starting the polymerization.

The mass ratio ((1)/(2)) between the amount of the fluorine-containing allyl ether (1) and the amount of the fluorine-containing vinyl ether (2) used in the polymerization of the fluorine-containing monomer is preferably from 1/99. 99/1, more preferably 20/80 to 80/20, still more preferably 20/80 to 60/40. By setting the mass ratio ((1)/(2)) within the above range, more fluorine-containing elastomer particles can be generated, and adhesion of the fluorine-containing elastomer to the polymerization vessel can be further suppressed. can.

The production method of the present disclosure can efficiently produce a fluorine-containing elastomer when at least the fluorine-containing allyl ether (1) and the fluorine-containing vinyl ether (2) are used in combination. In addition, in the production method of the present disclosure, two or more fluorine-containing allyl ethers (1) may be used simultaneously, two or more fluorine-containing vinyl ethers (2) may be used simultaneously, and those having volatility or Other compounds having surface activity may be used at the same time as long as they may remain in the molded article containing the fluorine-containing elastomer.

In one embodiment of the production method of the present disclosure, a fluorine-containing monomer is polymerized in the presence of a non-fluorine-containing surfactant (hydrocarbon-based surfactant). In one embodiment of the production method of the present disclosure, the fluorine-containing monomer is polymerized in the absence of a non-fluorine-containing surfactant (hydrocarbon-based surfactant). According to the production method of the present disclosure, a sufficient number of fluorine-containing elastomer particles can be generated even when a fluorine-containing monomer is polymerized in the absence of a non-fluorine-containing surfactant. , the adhesion of the fluorine-containing elastomer to the polymerization tank can be greatly suppressed.

In one embodiment of the production method of the present disclosure, a fluorine-containing monomer is polymerized in the absence of a fluorine-containing surfactant (excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)). do. According to the production method of the present disclosure, a sufficient number of fluorine-containing elastomer particles can be generated even when a fluorine-containing monomer is polymerized in the absence of a fluorine-containing surfactant, Adhesion of the fluorine-containing elastomer to the polymerization tank can be greatly suppressed.

Examples of the fluorine-containing surfactant include anionic fluorine-containing surfactants. The anionic fluorine-containing surfactant may be, for example, a surfactant containing a fluorine atom having a total carbon number of 20 or less in the portion excluding the anionic group.

The fluorine-containing surfactant may also be a fluorine-containing surfactant having an anionic moiety with a molecular weight of 1000 or less, preferably 800 or less. The "anionic portion" means the portion of the fluorine-containing surfactant excluding the cation. For example, in the case of F(CF ₂ ) _n1 COOM represented by formula (I) described later, it is the portion of “F(CF ₂ ) _n1 COO”.

The fluorine-containing surfactant also includes a fluorine-containing surfactant having a LogPOW of 3.5 or less. The above LogPOW is the partition coefficient between 1-octanol and water, and LogP [wherein P is the octanol/water (1:1) mixture containing the fluorine-containing surfactant during phase separation. represents the concentration ratio of the fluorine-containing surfactant/the concentration of the fluorine-containing surfactant in water].

The above LogPOW is a column; TOSOH ODS-120T column (φ4.6 mm × 250 mm, manufactured by Tosoh Corporation), eluent; acetonitrile/0.6 mass% HClO ₄ water = 1/1 (vol/vol%), flow rate; HPLC for standard substances (heptanoic acid, octanoic acid, nonanoic acid and decanoic acid) with known octanol/water partition coefficients under the conditions of 0 ml/min, sample volume: 300 μL, column temperature: 40° C., detection light: UV 210 nm. to create a calibration curve between each elution time and a known octanol/water partition coefficient, and based on this calibration curve, calculate from the HPLC elution time of the sample solution.

Specific examples of the fluorine-containing surfactant include US Patent Application Publication No. 2007/0015864, US Patent Application Publication No. 2007/0015865, US Patent Application Publication No. 2007/0015866, and US Patent US2007/0276103, US2007/0117914, US2007/142541, US2008/0015319, US3250808 Specification, US Patent No. 3271341, JP 2003-119204, WO 2005/042593, WO 2008/060461, WO 2007/046377, JP 2007-119526 Publication, International Publication No. 2007/046482, International Publication No. 2007/046345, US Patent Application Publication No. 2014/0228531, International Publication No. 2013/189824, International Publication No. 2013/189826, etc. mentioned.

As the anionic fluorine-containing surfactant, the following general formula (N ⁰ ):
X ⁿ⁰ −Rf ⁿ⁰ −Y ⁰ (N ⁰ )
(In the formula, X ⁿ⁰ is H, Cl or and F. Rf ⁿ⁰ has 3 to 20 carbon atoms and is chain, branched or cyclic, and some or all of H is replaced by F is an alkylene group, the alkylene group may contain one or more ether bonds, and some H may be substituted with Cl. Y ⁰ is an anionic group.) The compound represented by mentioned.

The anionic group of Y ⁰ may be -COOM, -SO ₂ M, or -SO ₃ M, and may be -COOM or -SO ₃ M.
M is H, a metal atom, NR ⁷⁴ , _optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium ^; is H or an organic group.
Examples of the metal atom include alkali metals (group 1) and alkaline earth metals (group 2), such as Na, K, and Li.
R ⁷ may be H or a C _1-10 organic group, may be H or a C _1-4 organic group, or may be H or a C _1-4 alkyl group.
M may be H, a metal atom or NR ⁷ ₄ , may be H, an alkali metal (group 1), an alkaline earth metal (group 2) or NR ⁷ ₄ , H, Na, K, Li or _NH4 .
In Rf ⁿ⁰ , 50% or more of H may be substituted with fluorine.

As the compound represented by the general formula (N ⁰ ), the following general formula (N ¹ ):
X ⁿ⁰ −(CF ₂ ) _m1 −Y ⁰ (N ¹ )
(Wherein, X ⁿ⁰ are H, Cl and F, m1 is an integer of 3 to 15, and Y ⁰ is as defined above.) The compound represented by the following general formula (N ² ):
Rf ⁿ¹ —O—(CF(CF ₃ )CF ₂ O) _m2 CFX ⁿ¹ —Y ⁰ (N ² )
(wherein Rf ⁿ¹ is a perfluoroalkyl group having 1 to 5 carbon atoms, m2 is an integer of 0 to 3, X ⁿ¹ is F or CF ₃ , and Y ⁰ is the above-defined is a compound represented by the following general formula (N ³ ):
^Rfn2 ( _CH2 ) _m3- ( ^Rfn3 ) _q ^- ^Y0 (N3)
(wherein Rf ⁿ² is a partially or fully fluorinated alkyl group that may contain an ether bond of 1 to 13 carbon atoms, m3 is an integer of 1 to 3, and Rf ⁿ³ is a linear or a branched perfluoroalkylene group having 1 to 3 carbon atoms, q is 0 or 1, and Y ⁰ is as defined above.), the following general formula (N ⁴ ):
Rf ⁿ⁴ —O—(CY ⁿ¹ Y ⁿ² ) _p CF ₂ —Y ⁰ (N ⁴ )
(Wherein, Rf ⁿ⁴ is a linear or branched partially or fully fluorinated alkyl group that may contain an ether bond having 1 to 12 carbon atoms, and Y ⁿ¹ and Y ⁿ² are the same or different , H or F, p is 0 or 1, and Y ⁰ is as defined above), and the following general formula (N ⁵ ):

(Wherein, X ⁿ² , X ⁿ³ and X ⁿ⁴ may be the same or different, and may be H, F, or a linear or branched partial or complete chain containing an ether bond having 1 to 6 carbon atoms. is a fluorinated alkyl group, Rf ⁿ⁵ is a linear or branched partially or fully fluorinated alkylene group that may contain an ether bond of 1 to 3 carbon atoms, and L is a linking group; , Y ⁰ are as defined above, provided that the total number of carbon atoms of X ⁿ² , X ⁿ³ , X ⁿ⁴ and Rf ⁿ⁵ is 18 or less.

More specifically, the compound represented by the general formula (N ⁰ ) includes perfluorocarboxylic acid (I) represented by the following general formula (I), ω-H perm represented by the following general formula (II), Fluorocarboxylic acid (II), perfluoroethercarboxylic acid (III) represented by the following general formula (III), perfluoroalkylalkylenecarboxylic acid (IV) represented by the following general formula (IV), the following general formula ( V) represented by perfluoroalkoxyfluorocarboxylic acid (V), perfluoroalkylsulfonic acid (VI) represented by the following general formula (VI), ω-H perfluoro represented by the following general formula (VII) Sulfonic acid (VII), perfluoroalkylalkylene sulfonic acid (VIII) represented by general formula (VIII) below, alkylalkylene carboxylic acid (IX) represented by general formula (IX) below, general formula (X) below A fluorocarboxylic acid represented by (X), an alkoxyfluorosulfonic acid (XI) represented by the following general formula (XI), a compound (XII) represented by the following general formula (XII), the following general formula (XIII) Compound (XIII) represented by is mentioned.

The perfluorocarboxylic acid (I) has the following general formula (I)
F( _CF2 ) _n1COOM (I)
(Wherein, n1 is an integer of 3 to ₁₄ , M is H, a metal atom, NR ⁷⁴ , imidazolium optionally having substituents, pyridinium optionally having substituents or It is a phosphonium which may have a substituent, and R ⁷ is H or an organic group.).

The ω-H perfluorocarboxylic acid (II) has the following general formula (II)
H(CF2) _n2COOM ( _II )
(wherein n2 is an integer of 4 to 15, and M is as defined above).

The perfluoroether carboxylic acid (III) has the following general formula (III)
Rf ¹ -O-(CF(CF ₃ )CF ₂ O) _n3 CF(CF ₃ )COOM (III)
(Wherein, Rf ¹ is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is as defined above.) .

The perfluoroalkylalkylenecarboxylic acid (IV) has the following general formula (IV)
_{Rf2(CH2)n4Rf3COOM} ⁽ _IV ⁾
(In the formula, Rf ² is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ³ is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, n4 is 1 to 3 and M is defined above).

The alkoxyfluorocarboxylic acid (V) has the following general formula (V)
Rf4 ^- O ^- _CY1Y2CF2 ^- COOM (V)
(Wherein, Rf ⁴ is a linear or branched partially or fully fluorinated alkyl group that may contain an ether bond having 1 to 12 carbon atoms, and Y ¹ and Y ² are the same or different , H or F, where M is as defined above.

The perfluoroalkylsulfonic acid (VI) has the following general formula (VI)
F( _CF2)n5SO3M ₍ _VI )
(wherein n5 is an integer of 3 to 14, and M is as defined above).

The ω-H perfluorosulfonic acid (VII) has the following general formula (VII)
H( _CF2)n6SO3M ₍ _VII )
(wherein n6 is an integer of 4 to 14, and M is as defined above).

The perfluoroalkylalkylene sulfonic acid (VIII) has the following general formula (VIII)
^Rf5 ( _CH2 ) _n7SO3M ₍ VIII)
(Wherein, Rf ⁵ is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer of 1 to 3, and M is as defined above.) .

The alkylalkylenecarboxylic acid (IX) has the following general formula (IX)
^Rf6 ( _CH2 ) _n8COOM (IX)
(wherein Rf ⁶ is a linear or branched partially or fully fluorinated alkyl group which may contain an ether bond with 1 to 13 carbon atoms, n8 is an integer of 1 to 3, M is defined above.).

The fluorocarboxylic acid (X) has the following general formula (X)
Rf7 ^- O _- Rf8 ^- O-CF2-COOM(X)
(Wherein, Rf ⁷ is a linear or branched partially or fully fluorinated alkyl group that may contain an ether bond having 1 to 6 carbon atoms, and Rf ⁸ is a straight chain having 1 to 6 carbon atoms. A linear or branched, partially or fully fluorinated alkyl group, wherein M is as defined above.

The alkoxyfluorosulfonic acid (XI) has the following general formula (XI)
^Rf9 -O ^- _CY1Y2CF2 ^- _SO3M (XI)
(wherein Rf ⁹ is a linear or branched chained alkyl group which may contain an ether bond of 1 to 12 carbon atoms and which may contain chlorine and may be partially or fully fluorinated; Y ¹ and Y ² are the same or different and are H or F, and M is as defined above).

The above compound (XII) has the following general formula (XII):

In the formula, X ¹ , X ² and X ³ may be the same or different, and may contain H, F and an ether bond having 1 to 6 carbon atoms. is an alkyl group, Rf ¹⁰ is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a linking group, and Y ⁰ is an anionic group. ).

Y ⁰ can be -COOM, -SO ₂ M, or -SO ₃ M, and can be -SO ₃ M, or COOM, where M is as defined above.
Examples of L include a single bond, a partially fluorinated alkylene group which may contain an ether bond having 1 to 10 carbon atoms, and the like.

The compound (XIII) has the following general formula (XIII)
Rf ¹¹ —O—(CF ₂ CF(CF ₃ )O) _n9 (CF ₂ O) _n10 CF ₂ COOM (XIII)
(wherein Rf ¹¹ is a chlorine-containing fluoroalkyl group having 1 to 5 carbon atoms, n9 is an integer of 0 to 3, n10 is an integer of 0 to 3, and M is the above-defined It is represented by Compound (XIII) includes _CF2ClO ( _CF2CF ₍ _CF3 )O) _n9 ( _CF2O ) _n10CF2COONH4 ₍ a mixture with an average molecular weight of 750, where n9 and n10 are as defined above). There is.)

In one embodiment of the production method of the present disclosure, a fluorine-containing monomer is polymerized in the presence of a fluorine-containing surfactant (excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)). . In one embodiment of the production method of the present disclosure, a fluorine-containing monomer can be polymerized in the absence of a fluorine-containing compound represented by the general formula: X—(CF ₂ ) _m2 —Y. In one embodiment of the production method of the present disclosure, in the presence of a fluorine-containing surfactant (excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)), and the general formula: X-( The fluoromonomer can be polymerized in the absence of the fluorocompound represented by CF ₂ ) _m2 -Y.

As fluorine-containing surfactants (excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)) that can be present during polymerization, among fluorine-containing surfactants, general formula: X-(CF ₂ ) _m2 -Y (wherein X represents H or F, m2 represents an integer of 6 or more, 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). Fluorine-containing surfactants other than That is, in one embodiment of the production method of the present disclosure, a fluorine-containing surfactant (wherein the fluorine-containing allyl ether (1), the fluorine-containing vinyl ether (2) and the general formula: X—(CF ₂ ) _m2 —Y It is preferable to polymerize the fluorine-containing monomer in the presence of the fluorine-containing compound (excluding the fluorine-containing compound represented).

As the fluorine-containing surfactant that can be present during polymerization, among the fluorine-containing surfactants exemplified above as fluorine-containing surfactants that are not present during polymerization, the general formula: X-(CF ₂ ) _m2 -Y ( In the formula, X represents H or F, m2 represents an integer of 6 or more, 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). agents. Further, as fluorine-containing surfactants that can be present during polymerization, International Publication No. 2019/009248, International Publication No. 2007/120346, International Publication No. Examples include those described in Publication No. 2007/062059.

In the production method of the present disclosure, polymerization may be performed in the presence of a polymerization initiator.

In the production method of the present disclosure, the polymerization of the fluoromonomer is performed, for example, by charging a pressure-resistant polymerization tank equipped with a stirrer with the fluorinated allyl ether (1), the fluorinated vinyl ether (2), and an aqueous medium, and deoxidizing the reaction mixture. After that, a monomer is charged, the temperature is raised to a predetermined temperature, and a polymerization initiator is added to initiate the reaction. Since the pressure decreases as the reaction progresses, additional monomers are supplied continuously or intermittently so as to maintain the initial pressure, and the supply is stopped when a predetermined amount of monomers has been supplied. , purge the monomers in the reaction vessel and return the temperature to room temperature to complete the reaction.

　The polymerization initiator includes a radical polymerization initiator. The polymerization initiator is not particularly limited as long as it can generate radicals at the temperature at which the fluorine-containing monomer is polymerized, and oil-soluble polymerization initiators, water-soluble polymerization initiators, and the like can be used. , water-soluble polymerization initiators are preferred. Also, the polymerization initiator may be used in combination with a reducing agent or the like as a redox initiator.

The amount of the polymerization initiator when polymerizing the fluorine-containing monomer is appropriately determined according to the type of monomer, the molecular weight of the target fluorine-containing elastomer, and the reaction rate. The amount of the polymerization initiator is appropriately determined depending on the molecular weight of the target fluorine-containing elastomer and the polymerization reaction rate, but is preferably 0.00001 to 10% by mass with respect to 100% by mass of the total amount of monomers. More preferably, it is 0.0001 to 1% by mass.

As the polymerization initiator, an oil-soluble radical polymerization initiator, a water-soluble radical polymerization initiator, or an azo compound can be used.

Oil-soluble radical polymerization initiators may be known oil-soluble peroxides such as dialkylperoxycarbonates such as diisopropylperoxydicarbonate and disec-butylperoxydicarbonate; peroxy esters such as isobutyrate and t-butyl peroxypivalate; dialkyl peroxides such as di-t-butyl peroxide; (ω-hydro-tetradecafluorooctanoyl) peroxide, di(ω-hydro-hexadecafluorononanoyl) peroxide, di(perfluorobutyryl) peroxide, di(perfluorovaleryl) peroxide, di (perfluorohexanoyl) peroxide, di (perfluoroheptanoyl) peroxide, di (perfluorooctanoyl) peroxide, di (perfluorononanoyl) peroxide, di (ω-chloro-hexafluorobutyryl) Peroxide, di(ω-chloro-decafluorohexanoyl) peroxide, di(ω-chloro-tetradecafluorooctanoyl) peroxide, ω-hydro-dodecafluoroheptanoyl-ω-hydrohexadecafluorononanoyl- Peroxide, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydrododecafluoroheptanoyl-perfluorobutyryl-peroxide, di(dichloropentafluorobutanoyl) peroxide , di(trichlorooctafluorohexanoyl) peroxide, di(tetrachloroundecafluorooctanoyl) peroxide, di(pentachlorotetradecafluorodecanoyl) peroxide, di(undecachlorodotriacontafluorodocosanoyl) Typical examples include di[perfluoro(or fluorochloro)acyl]peroxides such as peroxides.

Azo compounds include azodicarboxylate, azodicarboxyldiamide, 2,2'-azobisisobutyronitrile, 2,2'-azobis 2,4-dimethylvaleronitrile, 2,2'-azobis ( 2-methylpropionamidine) dihydrochloride, 4,4′-azobis(4-cyanovaleric acid).

The water-soluble radical polymerization initiator may be a known water-soluble peroxide, for example, persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, ammonium salts such as percarbonic acid, potassium salts, sodium salts , disuccinic acid peroxide, diglutaric acid peroxide, t-butyl permaleate, t-butyl hydroperoxide and the like. A reducing agent such as sulfites may also be included, and the amount used may be 0.1 to 20 times that of the peroxide.

As the water-soluble peroxide, a salt of persulfate is preferable because it is easy to adjust the amount of generated radicals, and potassium persulfate (K ₂ S ₂ O ₈ ), ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), preferably sodium _persulfate ₍ _Na2S2O8 ), most preferably ammonium persulfate.

When the polymerization temperature is 45°C or higher and the polymerization is carried out using a water-soluble peroxide, it is preferable to carry out the polymerization without using a reducing agent.

For example, when performing polymerization at a low temperature of 60°C or less, it is preferable to use a redox initiator that combines an oxidizing agent and a reducing agent as the polymerization initiator. That is, the polymerization is preferably carried out in the presence of a redox initiator.

Examples of oxidizing agents include persulfates, organic peroxides, potassium permanganate, manganese triacetate, cerium ammonium nitrate, and bromates. Examples of reducing agents include sulfites, bisulfites, bromates, diimine, oxalic acid, metal sulfinic acid salts, and the like. Persulfates include ammonium persulfate, potassium persulfate and sodium persulfate. Sulfites include sodium sulfite and ammonium sulfite. It is also preferred to add a copper salt, an iron salt to the redox initiator combination in order to increase the decomposition rate of the initiator. Copper salts include copper (II) sulfate, and iron salts include iron (II) sulfate. Moreover, when using a copper salt or an iron salt, it is particularly preferable to add a chelating agent. As the chelating agent, ethylenediaminetetraacetic acid disodium salt dihydrate is preferred.

Examples of redox initiators include potassium permanganate/oxalic acid, ammonium persulfate/bisulfite/iron(II) sulfate, ammonium persulfate/sulfite/iron(II) sulfate, ammonium persulfate/sulfite, ammonium persulfate/ Iron (II) sulfate, manganese triacetate/oxalic acid, cerium ammonium nitrate/oxalic acid, bromate/sulfite, bromate/bisulfite, ammonium persulfate/sodium hydroxymethanesulfinate dihydrate, etc. , ammonium persulfate/sodium hydroxymethanesulfinate dihydrate.

When using a redox initiator, either the oxidizing agent or the reducing agent may be charged in advance into the polymerization tank, and then the other may be added continuously or intermittently to initiate polymerization. For example, when ammonium persulfate/sodium hydroxymethanesulfinate dihydrate is used, it is preferable to charge ammonium persulfate into a polymerization tank and continuously add sodium hydroxymethanesulfinate dihydrate thereto.

The amount of persulfate used in the redox initiator is preferably 0.001 to 2.0% by mass, more preferably 0.01 to 1.5% by mass, and 0.01 to 2.0% by mass, based on the aqueous medium used for polymerization. 05 to 1.0% by weight is particularly preferred.

The amount of the reducing agent used is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and particularly preferably 5 to 20% by mass, relative to the aqueous medium used for polymerization.

In addition, the amount of the third component (the copper salt, iron salt, etc.) used is preferably 0.001 to 0.5% by mass, more preferably 0.005 to 0.4% by mass, relative to the aqueous medium used for polymerization. is more preferable, and 0.01 to 0.3% by mass is particularly preferable.

In the production method of the present disclosure, the fluorine-containing monomer may be polymerized in the presence of a chain transfer agent. Known chain transfer agents can be used, for example, hydrocarbons, esters, ethers, alcohols, ketones, halogen-containing compounds, carbonates and the like can be used. Among them, _isopentane , _diethyl _malonate and _ethyl acetate _are preferable from the viewpoint that the reaction rate is less likely to decrease. It is preferable from the viewpoint that the terminal of the polymer can be iodinated and it can be used as a reactive polymer.

As a chain transfer agent, it is particularly preferable to use a bromine compound or an iodine compound. Polymerization methods using a bromine compound or an iodine compound include, for example, iodine transfer polymerization and bromine transfer polymerization.

　Iodine compounds and bromine compounds are water-insoluble and difficult to emulsify. Therefore, emulsion polymerization was originally limited, and there was a tendency that a large amount of surfactant had to be used. According to the production method of the present disclosure, a fluorine-containing elastomer is obtained by polymerization using an iodine compound or a bromine compound, such as iodine transfer polymerization or bromine transfer polymerization, even in the absence of conventionally used surfactants. became possible.

Iodine transfer polymerization is radically active due to the low dissociation energy of the carbon-iodine bond, and the chain transfer reaction is involved in the process of the radical polymerization reaction. It's about how to Regarding the reaction conditions, known conditions can be used as appropriate, and are not particularly limited. The conditions described in Japanese Patent Application Laid-Open No. 53-3495 can be appropriately adopted. Similar polymerizations can be carried out using bromine compounds in place of iodine compounds, and in this disclosure such polymerizations are referred to as bromine transfer polymerizations.

Among these, iodine transfer polymerization is preferable from the viewpoint of polymerization reactivity and cross-linking reactivity.

Representative examples of bromine compounds or iodine compounds include, for example, the general formula:
R ⁸ I _x Br _y
(Wherein, x and y are each an integer of 0 to 2 and satisfy 1 ≤ x + y ≤ 2, and R ⁸ 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). By using a bromine compound or an iodine compound, iodine or bromine is introduced into the polymer and functions as a cross-linking point.

Bromine compounds and iodine compounds include, for example, 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodoperfluoropropane, 1,4-diiodoperfluorobutane, 1 ,5-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodine perfluorohexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo-n _- propane, _CF2Br2 , _BrCF2CF2Br , _CF3CFBrCF2Br , _CFClBr2 _, _BrCF2CFClBr , _CFBrClCFClBr , _BrCF2 CF ₂ CF ₂ Br, BrCF ₂ CFBrOCF ₃ , 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3- iodoperfluorobutane, 3-bromo-4-iodoperfluorobutene-1, 2-bromo-4-iodoperfluorobutene-1, monoiodomonobromo substitution of benzene, diiodomonobromo substitution, and (2 -iodoethyl) and (2-bromoethyl) substitutions, etc., and these compounds may be used alone or in combination with each other.
Among these, from the viewpoint of polymerization reactivity, cross-linking reactivity, availability, etc., compounds containing only iodine and not containing bromine are preferred, such as 1,4-diiodoperfluorobutane, 1,6-diiodine Perfluorohexane or 2-iodoperfluoropropane is preferably used.

The amount of chain transfer agent is preferably 0.2×10 ⁻³ to 2 mol %, more preferably 1.0×10 ⁻³ to 1 mol %, based on the total amount of monomers used in the polymerization. is.

"Aqueous medium" means a liquid containing water. The aqueous medium is not particularly limited as long as it contains water. For example, water and fluorine-free organic solvents such as alcohols, ethers and ketones, and/or fluorine-containing organic solvents having a boiling point of 40° C. or less. may include.

Phosphate, sodium hydroxide, potassium hydroxide, aqueous ammonia, etc. may be used as a pH adjuster in the polymerization of the fluorine-containing monomer.

The aqueous medium is preferably acidic. Adhesion of the fluorine-containing polymer to the polymerization tank is further suppressed by polymerizing the fluorine-containing monomer in the presence of the fluorine-containing allyl ether (1) and the fluorine-containing vinyl ether (2) using an acidic aqueous medium. can. The pH of the aqueous medium is preferably 7 or less, more preferably 6 or less, and preferably 3 or more.

In the production method of the present disclosure, the fluoromonomer may be polymerized in the presence or absence of the fluoromonomer polymerization seed particles.

The above-mentioned "fluorine-containing monomer polymerized seed particles" are obtained by polymerizing a fluorine-containing monomer in an aqueous medium, and include monomers and additives (e.g., polymerization Initiator, etc.) are present during the second polymerization in which the types and proportions of components such as initiators, reaction conditions, etc. are different. The fluoromonomer polymerized seed particles act as so-called seed particles during the polymerization of the fluoromonomer, and constitute the polymerization of the fluoromonomer in the presence of the seed particles, ie, the so-called seed polymerization. In the production method of the present disclosure, such seed polymerization may not be performed when polymerizing the fluorine-containing monomer.

In the production method of the present disclosure, the polymerization temperature for polymerizing the fluorine-containing monomer is preferably 10 to 120°C, more preferably 20 to 100°C. The polymerization temperature is preferably 15 to 60°C, more preferably 18 to 55°C, and even more preferably 20 to 50°C, from the viewpoints of stability of the aqueous dispersion and reduction of adhesion rate. The polymerization temperature is preferably 60 to 120° C., more preferably 60 to 100° C., more preferably 70 to 100° C., because the polymerization rate is high and a fluorine-containing elastomer that gives molded articles having excellent physical properties can be obtained. 90°C is more preferred.

In the production method of the present disclosure, the polymerization pressure for polymerizing the fluorine-containing monomer is preferably 0.5-10 MPaG, more preferably 1-7 MPaG.

In the production method of the present disclosure, the fluorine-containing monomer is polymerized in the presence of the fluorine-containing allyl ether (1), the fluorine-containing vinyl ether (2), and an aqueous medium, so that the polymer (fluorine-containing elastomer) is transferred to the polymerization tank. adhesion can be suppressed. The polymer adhesion rate to the polymerization tank is preferably 8% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, and most preferably 2% by mass or less.

The polymer adhesion rate is the ratio of the mass of the polymer deposit adhering to the polymerization tank after the polymerization to the total amount of the polymer (fluorine-containing elastomer) after the polymerization (adhesion rate to the polymerization tank). The polymer deposits include the polymer adhering to the inside of the polymerization vessel such as the inner wall of the polymerization vessel and the stirring blade after the aqueous dispersion is extracted from the polymerization vessel after the completion of polymerization, and the polymer that is released from the aqueous dispersion due to aggregation and Also included are polymers that are suspended or precipitated without being dispersed in a liquid. The mass of the polymer deposit is the mass after removing moisture contained in the polymer deposit by drying at 120°C.
Polymer adhesion rate (% by mass) = mass of polymer deposit/mass of obtained polymer (including deposit) x 100
Mass of polymer obtained = mass of aqueous dispersion x solid content concentration (% by mass) of aqueous dispersion/100 + mass of polymer deposit

In the production method of the present disclosure, an aqueous dispersion of a fluorine-containing elastomer is obtained by polymerizing a fluorine-containing monomer. The fluorine-containing monomer is preferably a fluorine-containing monomer (excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)), and more preferably does not contain a hydrophilic group.

Examples of fluorine-containing monomers include vinylidene fluoride (vinylidene fluoride) (VdF), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE), chlorotrifluoroethylene (CTFE ), trifluoroethylene, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, iodine-containing fluorinated vinyl ether, general formula (2):
CHX ¹ =CX ² Rf (2)
(Wherein, one of X ¹ and X ² is H, the other is F, and Rf is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms) A fluorine-containing monomer ( 2) and other fluorine-containing monomers.

As PAVE, perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) (PEVE), and perfluoro(propyl vinyl ether) (PPVE) are more preferable, and PMVE is particularly preferable.

PAVE has the formula: CF ₂ ═CFOCF ₂ ORf ^c (wherein Rf ^c is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, or a cyclic perfluoroalkyl group having 5 to 6 carbon atoms). An alkyl group, or a linear or branched perfluorooxyalkyl group having 2 to 6 carbon atoms containing 1 to 3 oxygen atoms) can also be used. _PAVE is preferably _CF2 ₌ _CFOCF2OCF3 _, _CF2 ₌ _{CFOCF2OCF2CF3} or _CF2 ₌ _{CFOCF2OCF2CF2OCF3} _, for example.

As the fluorine-containing monomer (2), a monomer in which Rf is a linear fluoroalkyl group is preferable, and a monomer in which Rf is a linear perfluoroalkyl group is more preferable. Rf preferably has 1 to 6 carbon atoms.

As the fluorine-containing monomer ( ₂ ), _CH2 = _CFCF3 , _CH2 = _CFCF2CF3 _, _CH2 ₌ _CFCF2CF2CF3 , _CH2 ₌ _{CFCF2CF2CF2CF3} _, CHF= _CHCF ₃ (1,3,3,3-tetrafluoropropene), CHF=CHCF ₃ (E-form), CHF=CHCF ₃ (Z-form) and the like, among which CH ₂ =CFCF ₃ 2, 3,3,3-tetrafluoropropylene is preferred.

In the production method of the present disclosure, it is preferable to polymerize at least vinylidene fluoride or tetrafluoroethylene as the fluorine-containing monomer because adhesion of the fluorine-containing elastomer to the polymerization tank can be further suppressed, and vinylidene fluoride is polymerized. is more preferable.

In the production method of the present disclosure, fluorine-free monomers may be polymerized together with fluorine-containing monomers. Examples of fluorine-free monomers include α-olefin monomers having 2 to 10 carbon atoms such as ethylene, propylene, butene and pentene; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, butyl vinyl ether and alkyl vinyl ethers having 1 to 20 carbon atoms in the alkyl group such as , and these monomers and compounds can be used singly or in combination of two or more.

According to the production method of the present disclosure, an aqueous dispersion containing a fluorine-containing elastomer can be produced. The fluorine-containing elastomer obtained by the production method of the present disclosure contains methylene groups ₍ --CH.sub.2--) in its main chain. The fluorine-containing elastomer containing —CH ₂ — in the main chain is not particularly limited as long as it includes a chemical structure represented by —CH ₂ —. Examples include —CH ₂ —CF ₂ — and —CH ₂ —. Fluorine-containing elastomers containing structures such as CH(CH ₃ )—, —CH ₂ —CH ₂ —, —CH ₂ —CF ₂ —(CF ₃ )—, such as vinylidene fluoride, propylene, It can be introduced into the main chain of the fluorine-containing elastomer by polymerizing ethylene, 2,3,3,3-tetrafluoropropylene, or the like. The content of tetrafluoroethylene units in the fluorine-containing elastomer (the content of monomer units based on tetrafluoroethylene with respect to the total monomer units of the fluorine-containing elastomer) may be less than 40 mol %.

As the fluoroelastomer, a partially fluorinated elastomer is preferable because it can generate more fluoroelastomer particles and can further suppress adhesion of the fluoroelastomer to the polymerization tank. A partially fluorinated elastomer is a fluoropolymer containing fluorine-containing monomer units and having a perfluoromonomer unit content of less than 90 mol% with respect to the total monomer units, and having a glass transition temperature of 20°C or less. and a melting peak (ΔH) magnitude of 4.5 J/g or less.

Examples of fluorine-containing elastomers include tetrafluoroethylene (TFE), vinylidene fluoride (VdF) and general formula: CF ₂ =CF-Rf ^a (wherein Rf ^a is —CF ₃ or —ORf ^b (Rf ^b is carbon At least one selected from the group consisting of perfluoroethylenically unsaturated compounds (for example, hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE), etc.) represented by perfluoroalkyl groups of numbers 1 to 5) It preferably contains monomeric units based on the species monomer. Among others, the fluorine-containing elastomer preferably contains VdF units or TFE units, and more preferably contains VDF units.

More specifically, the fluorine-containing elastomer includes VdF-based fluorine-containing elastomer, TFE/propylene (Pr)-based fluorine-containing elastomer, TFE/Pr/VdF-based fluorine-containing elastomer, ethylene (Et)/HFP-based fluorine-containing elastomer, Et/ HFP/VdF fluorine-containing elastomer, Et/HFP/TFE fluorine-containing elastomer, Et/TFE/PAVE fluorine-containing elastomer, and the like. Among these, VdF-based fluorine-containing elastomer, TFE/Pr-based fluorine-containing elastomer, TFE/Pr/VdF-based fluorine-containing elastomer, or Et/TFE/PAVE-based fluorine-containing elastomer have good heat aging resistance and oil resistance. It is more suitable.

A VdF-based fluorine-containing elastomer is a fluorine-containing elastomer having VdF units. The content of VdF units in the fluoroelastomer is preferably 20 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, relative to all monomer units, Particularly preferably, it is 60 mol % or more. In the VdF-based fluorine-containing elastomer, the VdF unit is preferably 20 mol% or more and 90 mol% or less, and preferably 40 mol% or more and 85 mol% of the total number of moles of the VdF unit and the monomer units based on other monomers. % or less, more preferably 45 mol % or more and 80 mol % or less, and particularly preferably 50 mol % or more and 80 mol % or less.

Other monomers in the VdF-based fluorine-containing elastomer are not particularly limited as long as they are copolymerizable with VdF, and for example, the above-mentioned fluorine-containing monomers can be used.

VdF-based fluorine-containing elastomers include VdF/HFP copolymers, VdF/TFE/HFP copolymers, VdF/CTFE copolymers, VdF/CTFE/TFE copolymers, VdF/PAVE copolymers, and VdF/TFE. /PAVE copolymer, VdF/HFP/PAVE copolymer, VdF/HFP/TFE/PAVE copolymer, VdF/TFE/Pr copolymer, VdF/Et/HFP copolymer and VdF/fluorinated monomer At least one copolymer selected from the group consisting of the copolymers of body (2) is preferred. Moreover, it is more preferable to have at least one monomer selected from the group consisting of TFE, HFP and PAVE as a monomer other than VdF.

Among these, VdF-based fluorine-containing elastomers include VdF/HFP copolymers, VdF/TFE/HFP copolymers, VdF/fluorine-containing monomer (2) copolymers, and VdF/PAVE copolymers. , VdF/TFE/PAVE copolymer, VdF/HFP/PAVE copolymer and at least one copolymer selected from the group consisting of VdF/HFP/TFE/PAVE copolymer is preferred, and VdF/HFP copolymer At least one copolymer selected from the group consisting of polymers, VdF/HFP/TFE copolymers, VdF/fluoromonomer (2) copolymers and VdF/PAVE copolymers is more preferred. .

The VdF/PAVE copolymer preferably has a VdF/PAVE composition of (65-90)/(35-10) (mol %).
In addition, the composition of VdF/PAVE is also one of the preferred forms in which it is (50 to 78)/(50 to 22) (mol %).

The VdF/TFE/PAVE copolymer preferably has a VdF/TFE/PAVE composition of (40-80)/(3-40)/(15-35) (mol %).

The VdF/HFP/PAVE copolymer preferably has a VdF/HFP/PAVE composition of (65-90)/(3-25)/(3-25) (mol %).

As the VdF/HFP/TFE/PAVE copolymer, the composition of VdF/HFP/TFE/PAVE is (40-90)/(0-25)/(0-40)/(3-35) (mol%) is preferred, and (40 to 80)/(3 to 25)/(3 to 40)/(3 to 25) (mol%) is more preferred.

The copolymer of VdF/fluorine-containing monomer (2) has a VdF/fluorine-containing monomer (2) unit of (85 to 20)/(15 to 80) (mol %), and contains VdF and Monomer units other than the fluorine-containing monomer (2) are preferably 0 to 50 mol% of the total monomer units, and the mol% ratio of VdF/fluorine-containing monomer (2) units is (80 ~20)/(20-80) is more preferred. In addition, it is also one of preferred forms that the composition of VdF/fluorine-containing monomer (2) units is (78-50)/(22-50) (mol %).

Further, as a copolymer of VdF/fluorine-containing monomer (2), the VdF/fluorine-containing monomer (2) unit is (85 to 50)/(15 to 50) (mol%), and VdF And it is also preferable that monomer units other than the fluorine-containing monomer (2) are 1 to 50 mol % of the total monomer units. Other monomers other than VdF and the fluorine-containing monomer (2) include TFE, HFP, PMVE, perfluoroethyl vinyl ether (PEVE), PPVE, CTFE, trifluoroethylene, hexafluoroisobutene, vinyl fluoride, The monomers exemplified as other monomers in the VdF fluorine-containing elastomer, such as Et, Pr, alkyl vinyl ethers, and monomers that provide crosslinkable groups, are preferred, among which PMVE, CTFE, HFP, and TFE are preferred. more preferred.

A TFE/Pr-based fluorine-containing elastomer refers to a fluorine-containing copolymer composed of 45 to 70 mol% of TFE and 55 to 30 mol% of Pr. In addition to these two components, a specific third component may be included.

Specific third components include, for example, fluorine-containing olefins other than TFE (e.g., VdF, HFP, CTFE, perfluoro(butyl ethylene), etc.), fluorine-containing vinyl ethers (perfluoro(propyl vinyl ether), perfluoro(methyl vinyl ether) etc.); α-olefins (ethylene, 1-butene, etc.), vinyl ethers (ethyl vinyl ether, butyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl benzoate, crotonic acid (vinyl, vinyl methacrylate, etc.); The specific third component may be used alone or in combination of two or more.

The TFE/Pr-based fluorine-containing elastomer preferably contains VdF, and among the TFE/Pr-based fluorine-containing elastomers, an elastomer composed of TFE, Pr, and VdF is called a TFE/Pr/VdF-based fluorine-containing elastomer.

The TFE/Pr/VdF fluorine-containing elastomer may further contain the above specific third component other than VdF. The specific third component may be used alone or in combination of two or more. The total content of the third component in the TFE/Pr fluorine-containing elastomer is preferably 35 mol% or less, more preferably 33 mol% or less, and even more preferably 31 mol% or less.

The Et/HFP copolymer preferably has an Et/HFP composition of (35 to 80)/(65 to 20) (mol %), (40 to 75)/(60 to 25) (mol %) is more preferred.

The Et/HFP/TFE copolymer preferably has an Et/HFP/TFE composition of (35 to 75)/(25 to 50)/(0 to 15) (mol%), and (45 to 75 )/(25-45)/(0-10) (mol %) is more preferred.

The Et/TFE/PAVE copolymer preferably has an Et/TFE/PAVE composition of (10 to 40)/(32 to 60)/(20 to 40) (mol%), and (20 to 40 )/(40 to 50)/(20 to 30) (mol %) is more preferable. PMVE is preferred as PAVE.

The fluorine-containing elastomer is preferably a fluorine-containing elastomer containing VdF units, more preferably a VdF/HFP copolymer or a VdF/HFP/TFE copolymer, and the composition of VdF/HFP/TFE is (32 to 85)/( 10-34)/(0-40) (mol %) is particularly preferred. The composition of VdF / HFP / TFE is more preferably (32-85) / (15-34) / (0-34) (mol%), (47-81) / (17-32) / (0- 26) (mol%) is more preferred.

For example, in the VdF/HFP copolymer, the composition of VdF/HFP is preferably (45 to 85) / (15 to 55) (mol%), more preferably (50 to 83) / (17 ~ 50) (mol%), more preferably (55 to 81) / (19 to 45) (mol%), particularly preferably (60 to 80) / (20 to 40) (mol%) be.

The configuration described above is the configuration of the main monomer of the fluorine-containing elastomer, and in addition to the main monomer, a monomer that provides a crosslinkable group may be copolymerized. As the monomer that provides the crosslinkable group, any monomer can be used as long as it can introduce an appropriate crosslinkable group into the fluorine-containing elastomer depending on the production method and the crosslinking system. Known polymerizable compounds containing crosslinkable groups such as bonds, cyano groups, carboxyl groups, hydroxyl groups, amino groups, and ester groups can be mentioned.

As a monomer that provides a preferred crosslinkable group, general formula (3):
CY ¹ ₂ =CY ² R _f ² X ¹ (3)
(Wherein, Y ¹ and Y ² are fluorine atoms, hydrogen atoms or —CH ₃ ; R _f ² may have one or more etheric oxygen atoms, may have an aromatic ring, a linear or branched fluorine-containing alkylene group in which some or all of the hydrogen atoms are substituted with fluorine atoms; X ¹ is an iodine atom or a bromine atom)
The compound represented by can be mentioned.

Specific examples of monomers that provide a crosslinkable group include general formula (4):
CY ¹ ₂ = CY ² R _f ³ CHR ¹ -X ¹ (4)
(Wherein, Y ¹ , Y ² and X ¹ are as defined above, R _f ³ may have one or more etheric oxygen atoms, and some or all of the hydrogen atoms may be substituted with fluorine atoms. linear or branched chain fluorine-containing alkylene group, that is, a linear or branched chain fluorine-containing alkylene group in which some or all of the hydrogen atoms are substituted with fluorine atoms, some or all of the hydrogen atoms A linear or branched fluorine-containing oxyalkylene group in which is substituted with a fluorine atom, or a linear or branched fluorine-containing polyoxyalkylene group in which some or all of the hydrogen atoms are substituted with fluorine atoms ; R ¹ is a hydrogen atom or a methyl group)
An iodine- or bromine-containing monomer represented by general formulas (5) to (22):
CY ⁴ ₂ = CY ⁴ (CF ₂ ) _n - X ¹ (5)
(Wherein, Y ⁴ are the same or different, a hydrogen atom or a fluorine atom, n is an integer of 1 to 8)
CF2 ₌ _CFCF2Rf4 _- ^X1 ( ⁶ )
(wherein R ⁴ is —(OCF ₂ ) _n — or —(OCF(CF ₃ )) _n —, where n is an integer of 0 to 5)
CF2 ₌ _CFCF2 ₍ OCF ₍ _CF3 ) _CF2 ) _m ₍ _OCH2CF2CF2 ) _nOCH2CF2 _- X1 ( ⁷ )
(Wherein, m is an integer of 0 to 5, n is an integer of 0 to 5)
CF ₂ =CFCF ₂ (OCH ₂ CF ₂ CF ₂ ) _m (OCF(CF ₃ )CF ₂ ) _n OCF(CF ₃ )-X ¹ (8)
(Wherein, m is an integer of 0 to 5, n is an integer of 0 to 5)
CF ₂ =CF(OCF ₂ CF(CF ₃ )) _m O(CF ₂ ) _n -X ¹ (9)
(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 8)
CF ₂ = CF (OCF ₂ CF (CF ₃ )) _m - X ¹ (10)
(In the formula, m is an integer of 1 to 5)
CF ₂ = CFOCF ₂ (CF(CF ₃ )OCF ₂ ) _n CF(−X ¹ )CF ₃ (11)
(Wherein, n is an integer of 1 to 4)
CF ₂ = CFO(CF ₂ ) _n OCF(CF ₃ )−X ¹ (12)
(Wherein, n is an integer of 2 to 5)
CF2 ₌ CFO( _CF2 ) _n- ( _C6H4 ) ^-X1 ( ₁₃ )
(Wherein, n is an integer of 1 to 6)
CF ₂ =CF(OCF ₂ CF(CF ₃ )) _n OCF ₂ CF(CF ₃ )−X ¹ (14)
(Wherein, n is an integer of 1 to 2)
CH ₂ ═CFCF ₂ O(CF(CF ₃ )CF ₂ O) _n CF(CF ₃ )—X ¹ (15)
(wherein n is an integer of 0 to 5),
CF ₂ =CFO(CF ₂ CF(CF ₃ )O) _m (CF ₂ ) _n −X ¹ (16)
(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3)
_CH2 = _CFCF2OCF ( _CF3 )OCF( _CF3 ) ^-X1 (17)
_CH2 ₌ _CFCF2OCH2CF2 _- ^X1 (18)
CF ₂ =CFO(CF ₂ CF(CF ₃ )O) _m CF ₂ CF(CF ₃ )−X ¹ (19)
(In the formula, m is an integer of 0 or more)
CF2 ₌ _CFOCF ( _CF3 )CF2O(CF2) _n ^- X1 ( ₂₀ )
(In the formula, n is an integer of 1 or more)
CF2 ₌ _CFOCF2OCF2CF ₍ _CF3 ) ^OCF2 _- X1 (21)
CH ₂ ═CH—(CF ₂ ) _n X ¹ (22)
(Wherein, n is an integer of 2 to 8)
(In general formulas (5) to (22), X ¹ is the same as above)
and iodine- or bromine-containing monomers represented by and these may be used alone or in any combination.

As the iodine- or bromine-containing monomer represented by general formula (4), general formula (23):

(Wherein, m is an integer of 1 to 5, n is an integer of 0 to 3)
An iodine-containing fluorinated vinyl ether represented by

Among these, ICH ₂ CF ₂ CF ₂ OCF=CF ₂ is preferred.

More specifically, ICF ₂ CF ₂ CF=CH ₂ and I(CF ₂ CF ₂ ) ₂ CF=CH ₂ are preferred as the iodine- or bromine-containing monomer represented by formula (5).

More specifically, the iodine- or bromine-containing monomer represented by formula (9) is preferably I(CF ₂ CF ₂ ) ₂ OCF=CF ₂ .

More specifically, _CH2 ₌ _CHCF2CF2I and I( _CF2CF2 )2CH ₌ _CH2 _are preferable as the iodine- or bromine-containing monomer represented by the general formula (22).

Also, the formula: R ² R ³ C=CR ⁴ -Z-CR ⁵ =CR ⁶ R ⁷
(Wherein, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different, and are all H or an alkyl group having 1 to 5 carbon atoms; Z is a linear or branched , preferably an at least partially fluorinated alkylene or cycloalkylene group having 1 to 18 carbon atoms, or a (per)fluoropolyoxyalkylene group, which may contain an oxygen atom, or a bisolefin compound represented by It is preferable as a monomer that provides a crosslinkable group. In the present disclosure, "(per)fluoropolyoxyalkylene group" means "fluoropolyoxyalkylene group or perfluoropolyoxyalkylene group".

Z is preferably a (per)fluoroalkylene group having 4 to 12 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are preferably hydrogen atoms.

When Z is a (per)fluoropolyoxyalkylene group, the formula:
-(Q) _p -CF ₂ O-(CF ₂ CF ₂ O) _m -(CF ₂ O) _n -CF ₂ -(Q) _p -
(In the formula, Q is an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having 2 to 10 carbon atoms, p is 0 or 1, and m and n have an m/n ratio of 0.2 to 5. and the molecular weight of the (per)fluoropolyoxyalkylene group is an integer in the range of 500 to 10,000, preferably 1,000 to 4,000.) is preferably a (per)fluoropolyoxyalkylene group represented by . In this formula, Q is preferably selected from -CH ₂ OCH ₂ - and -CH ₂ O(CH ₂ CH ₂ O) _s CH ₂ - (s=1-3).

Preferred bis-olefins are
_CH2 =CH-(CF2) ₂ -CH ₌ _CH2 ,
_CH2 =CH-(CF2) ₄ -CH ₌ _CH2 ,
_CH2 =CH-(CF2) ₆ -CH ₌ _CH2 ,
Formula: _CH2 =CH-Z1 ^- CH= _CH2
(wherein Z ¹ is —CH ₂ OCH ₂ —CF ₂ O—(CF ₂ CF ₂ O) _m —(CF ₂ O) _n —CF ₂ —CH ₂ OCH ₂ — (m/n is 0.5) , the molecular weight is preferably 2000)
etc.

Among others, 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluoro-1, represented by CH ₂ =CH-(CF ₂ ) ₆ -CH=CH ₂ , 9-decadiene is preferred.

The number average molecular weight Mn of the fluorine-containing elastomer is preferably 1,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 20,000 to 300,000.

The fluorine content of the fluorine-containing elastomer is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more. The upper limit of the fluorine content is preferably 75% by mass or less, more preferably 73% by mass or less. The fluorine content is calculated based on the values measured by ¹⁹ F-NMR, ¹ H-NMR, elemental analysis, and the like.

The fluorine-containing elastomer preferably has a Mooney viscosity at 100°C (ML1+10 (100°C)) of 130 or less. The Mooney viscosity is more preferably 110 or less, even more preferably 90 or less. Moreover, the Mooney viscosity is more preferably 10 or more, and still more preferably 20 or more. Here, the Mooney viscosity is a value measured according to JIS K 6300-1.2013.

The fluorine-containing elastomer preferably has a glass transition temperature of -50 to 0°C. The glass transition temperature is more preferably −2° C. or lower, still more preferably −3° C. or lower. Further, the glass transition temperature is more preferably −45° C. or higher, further preferably −40° C. or higher. The glass transition temperature may be -10°C or higher, or -9°C or higher. Here, the glass transition temperature is measured using a differential scanning calorimeter (e.g., X-DSC7000 manufactured by Hitachi High-Tech Science) to obtain a DSC curve by heating 10 mg of the sample at 20 ° C./min, according to JIS K6240: 2011. , the glass transition temperature can be obtained from the DSC differential curve.

The fluorine-containing elastomer preferably has an iodine content of 0.05 to 1.0% by mass. The iodine content is more preferably 0.08% by mass or more, still more preferably 0.10% by mass or more, and more preferably 0.80% by mass or less, and even more preferably 0.60% by mass or less.

The iodine content can be determined by elemental analysis. Specifically, 12 mg of fluorine-containing elastomer was mixed with 5 mg of Na ₂ SO ₃ , and 30 mg of Na ₂ CO ₃ and K ₂ CO ₃ were mixed in 20 ml of pure water at a ratio of 1:1 (mass ratio) and dissolved in the absorbent. can be used, burned in oxygen in a quartz flask, allowed to stand for 30 minutes, and then measured using a Shimadzu 20A ion chromatograph. As a calibration curve, a KI standard solution, one containing 0.5 ppm by mass of iodine ions, and one containing 1.0 ppm by mass of iodine ions can be used.

The fluorine-containing elastomer preferably contains a —CH ₂ I structure. The inclusion of the —CH ₂ I structure can be confirmed by the ¹ H-NMR spectrum. A fluorine-containing elastomer containing a —CH ₂ I structure can be obtained by iodine transfer polymerization.

The fluorine-containing elastomer preferably contains 0.05 to 1.50 mol % of the --CH ₂ I structure relative to 100 mol % of the --CH ₂ -- structure. The amount of the —CH ₂ I structure is more preferably 0.08 mol% or more, still more preferably 0.12 mol% or more, more preferably 1.20 mol% or less, further preferably 1.00 mol% or less, and 0 0.80 mol % or less is particularly preferred. The amount of —CH ₂ I structure can be determined from the ¹ H-NMR spectrum.

The fluorine-containing elastomer more preferably contains a —CF ₂ CH ₂ I structure. A fluorine-containing elastomer containing a —CF ₂ CH ₂ I structure can be obtained by producing a VdF-based fluorine-containing elastomer by iodine transfer polymerization.

The fluorine-containing elastomer preferably contains 0.05 to 1.50 mol % of the -CF ₂ CH ₂ I structure with respect to 100 mol % of the -CH ₂ - structure. The amount of the —CF ₂ CH ₂ I structure is more preferably 0.08 mol % or more, still more preferably 0.12 mol % or more, more preferably 1.20 mol % or less, and even more preferably 1.00 mol % or less. , 0.80 mol % or less is particularly preferred. The amount of the —CF ₂ CH ₂ I structure is the integrated value A of all peak intensities observed in the chemical shift region of 3.75 to 4.05 ppm derived from —CH ₂ I in the ¹ H-NMR spectrum, and —CH It is calculated by A/B*100 from the integrated value B of all peak intensities observed in the regions of 2.3 to 2.7 ppm and 2.9 to 3.75 ppm of chemical shift derived from _2- .

As the fluoromonomer used in the production method of the present disclosure, the fluoromonomers described for the fluoroelastomer can be appropriately used.

According to the production method of the present disclosure, an aqueous dispersion of a fluorine-containing elastomer is obtained. The solid content concentration (content of the fluoroelastomer) of the fluoroelastomer aqueous dispersion to be obtained is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, at the time of completion of polymerization, More preferably, it is 20 to 30% by mass.

The aqueous dispersion of the fluoroelastomer may contain fluoroelastomer particles. The average particle size of the fluorine-containing elastomer particles is preferably 10 to 800 nm, more preferably 50 to 500 nm, still more preferably 70 to 300 nm. The average particle size of the fluorine-containing elastomer particles is the cumulant average size, which can be measured by a dynamic light scattering method.

The number of fluorine-containing elastomer particles contained in the aqueous dispersion of the fluorine-containing elastomer is preferably 1.0×10 ¹² particles/cc or more, more preferably 5.0×10 ¹² particles/cc or more. More preferably, it is 1.0×10 ¹³ particles/cc or more, particularly preferably 1.2×10 ¹⁴ particles/cc or more, and most preferably 1.3×10 ¹⁴ particles/cc or more. The number of particles (the number of polymer particles) can be calculated according to the following formula.

The number of fluorine-containing elastomer particles obtained by the above formula is the number per 1 cc of water. The specific gravity is the specific gravity of the fluorine-containing elastomer. The specific gravity of the fluorine-containing elastomer can be obtained according to JIS Z 8807:2012.

The aqueous dispersion of the fluorine-containing elastomer may be subjected to treatments such as coagulation and heating.

The above coagulation can be carried out by adding alkaline earth and earth metal salts to the aqueous dispersion. Alkaline earth and earth metal salts include sulfates, nitrates, hydrochlorides, acetates, etc. of calcium, magnesium, aluminum, and the like.

The coagulated fluorine-containing elastomer may be washed with water to remove impurities such as a small amount of buffer solution and salt present in the fluorine-containing elastomer, and then the washed fluorine-containing elastomer may be dried. The drying temperature is preferably 40 to 200°C, more preferably 60 to 180°C, still more preferably 80 to 150°C.

The form of the fluorine-containing elastomer obtained after coagulation is not particularly limited, but may be gum, crumb, powder, pellet, etc., preferably gum or crumb. Gum is a small granular lump made of a fluorine-containing elastomer, and crumb is a fluorine-containing elastomer that cannot maintain its shape as a gum at room temperature and fuses with each other. It is in the shape of an amorphous mass. The gum or crumb is preferably obtained from the aqueous dispersion obtained by the production method of the present disclosure by coagulation, drying, etc. by conventionally known methods.

A composition (crosslinkable composition) can be produced by adding a crosslinking agent or the like to the aqueous dispersion of the fluoroelastomer or the fluoroelastomer obtained by the production method of the present disclosure. The type and amount of the cross-linking agent are not particularly limited, and can be used within a known range.

When the fluorine-containing elastomer is an uncrosslinked elastomer, the crosslinked system includes, for example, a peroxide crosslinked system, a polyol crosslinked system, a polyamine crosslinked system, etc., and is selected from the group consisting of a peroxide crosslinked system and a polyol crosslinked system. At least one selected is preferred. From the viewpoint of chemical resistance, a peroxide crosslinked system is preferred, and from the viewpoint of heat resistance, a polyol crosslinked system is preferred.

Therefore, the cross-linking agent is preferably at least one cross-linking agent selected from the group consisting of a polyol cross-linking agent and a peroxide cross-linking agent, more preferably a peroxide cross-linking agent.

The amount of the cross-linking agent to be blended may be appropriately selected according to the type of the cross-linking agent, etc., but it is preferably 0.2 to 6.0 parts by mass, more preferably 0.3 parts by mass, per 100 parts by mass of the fluorine-containing elastomer. ~5.0 parts by mass.

Peroxide crosslinking can be performed by using an uncrosslinked elastomer capable of peroxide crosslinking as the fluorine-containing elastomer and an organic peroxide as the crosslinking agent.

The uncrosslinked elastomer that can be peroxide-crosslinked is not particularly limited as long as it has a site that can be peroxide-crosslinked. The peroxide-crosslinkable site is not particularly limited, and examples thereof include a site having an iodine atom, a site having a bromine atom, and the like.

The organic peroxide may be any organic peroxide that can easily generate peroxy radicals in the presence of heat or a redox system, such as 1,1-bis(t-butylperoxy)-3, 5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,α-bis(t- Butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)-hexyne -3, benzoyl peroxide, t-butylperoxybenzene, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, t-butylperoxybenzoate and the like. Among these, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and 2,5-dimethyl-2,5-di(t-butylperoxy)-hexyne-3 are preferred.

The blending amount of the organic peroxide is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 5 parts by mass, per 100 parts by mass of the fluorine-containing elastomer.

When the cross-linking agent is an organic peroxide, the fluorine-containing elastomer composition preferably further contains a cross-linking aid. Examples of crosslinking aids include triallyl cyanurate, triallyl isocyanurate (TAIC), triacrylformal, triallyl trimellitate, N,N'-m-phenylenebismaleimide, dipropagyl terephthalate, diallyl phthalate, Tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris(2,3,3-trifluoro-2-propenyl)-1,3,5-triazine-2 ,4,6-trione), tris(diallylamine)-S-triazine, N,N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallylphosphoramide, N,N,N',N'-tetra allyl phthalamide, N,N,N',N'-tetraallylmalonamide, trivinyl isocyanurate, 2,4,6-trivinylmethyltrisiloxane, tri(5-norbornene-2-methylene)cyanurate, triallyl Phosphite, trimethallyl isocyanurate and the like. Among these, triallyl isocyanurate (TAIC) is preferable because of its excellent crosslinkability, mechanical properties, and flexibility.

The amount of the cross-linking aid compounded is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 7.0 parts by mass, and still more preferably 0 parts by mass with respect to 100 parts by mass of the fluorine-containing elastomer. .1 to 5.0 parts by mass. If the cross-linking coagent is less than 0.01 part by mass, the mechanical properties and the flexibility may deteriorate. If the amount exceeds 10 parts by mass, the heat resistance tends to be poor and the durability of the molded product tends to decrease.

Polyol crosslinking can be performed by using an uncrosslinked elastomer that can be polyol-crosslinked as a fluorine-containing elastomer and a polyhydroxy compound as a crosslinking agent. The blending amount of the polyhydroxy compound in the polyol cross-linkable system is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the uncrosslinked elastomer capable of being polyol-crosslinked. When the blending amount of the polyhydroxy compound is within such a range, the polyol crosslinking can be sufficiently advanced. More preferably, it is 0.02 to 8 parts by mass. More preferably, it is 0.03 to 4 parts by mass.

The polyol-crosslinkable uncrosslinked elastomer is not particularly limited as long as it has a polyol-crosslinkable site. The polyol-crosslinkable site is not particularly limited, and examples thereof include sites having vinylidene fluoride (VdF) units. Examples of the method for introducing the cross-linking site include a method of copolymerizing a monomer that provides the cross-linking site during polymerization of the uncrosslinked elastomer.

As the polyhydroxy compound, a polyhydroxy aromatic compound is preferably used because of its excellent heat resistance.

The polyhydroxyaromatic compound is not particularly limited, and examples thereof include 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A), 2,2-bis(4-hydroxyphenyl)perfluoropropane. (hereinafter referred to as bisphenol AF. Bisphenol AF is available from, for example, Fuji Film Wako Pure Chemical Industries, Ltd., Central Glass Co., Ltd., etc.), 1,3-dihydroxybenzene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene , 1,6-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxystilbene, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2-bis(4-hydroxyphenyl)butane (hereinafter referred to as bisphenol B), 4,4-bis(4-hydroxyphenyl)valeric acid, 2,2-bis(4-hydroxyphenyl)tetrafluorodichloropropane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy diphenyl ketone, tri(4-hydroxyphenyl)methane, 3,3′,5,5′-tetrachlorobisphenol A, 3,3′,5,5′-tetrabromobisphenol A and the like. These polyhydroxyaromatic compounds may be alkali metal salts, alkaline earth metal salts, etc. However, when the copolymer is coagulated using an acid, it is preferable not to use the above metal salts. The blending amount of the polyhydroxyaromatic compound is 0.1 to 15 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the uncrosslinked elastomer.

When the cross-linking agent is a polyhydroxy compound, the fluorine-containing elastomer composition preferably further contains a cross-linking accelerator. The cross-linking accelerator promotes the formation of intramolecular double bonds in the dehydrofluoric acid reaction of the polymer main chain and the addition of the polyhydroxy compound to the generated double bonds.

The cross-linking accelerator may be used in combination with an acid acceptor such as magnesium oxide, or a cross-linking aid.

Examples of the crosslinking accelerator include onium compounds. Among the onium compounds, ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, and 1 It is preferably at least one selected from the group consisting of functional amine compounds, more preferably at least one selected from the group consisting of quaternary ammonium salts and quaternary phosphonium salts.

The quaternary ammonium salt is not particularly limited, and examples include 8-methyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride, 8-methyl-1,8-diazabicyclo[5, 4,0]-7-undecenium iodide, 8-methyl-1,8-diazabicyclo[5,4,0]-7-undecenium hydroxide, 8-methyl-1,8-diazabicyclo[5 ,4,0]-7-undecenium methyl sulfate, 8-ethyl-1,8-diazabicyclo[5,4,0]-7-undecenium bromide, 8-propyl-1,8-diazabicyclo[5 ,4,0]-7-undecenium bromide, 8-dodecyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride, 8-dodecyl-1,8-diazabicyclo[5,4 ,0]-7-undecenium hydroxide, 8-eicosyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride, 8-tetracosyl-1,8-diazabicyclo[5,4 ,0]-7-undecenium chloride, 8-benzyl-1,8-diazabicyclo[5,4,0]-7-undecenium chloride (hereinafter referred to as DBU-B. DBU-B is, for example, available from Fuji Film Wako Pure Chemical Industries, Ltd.), 8-benzyl-1,8-diazabicyclo[5,4,0]-7-undecenium hydroxide, 8-phenethyl-1,8-diazabicyclo[5 ,4,0]-7-undecenium chloride, 8-(3-phenylpropyl)-1,8-diazabicyclo[5,4,0]-7-undecenium chloride, tetrabutylammonium hydrogen sulfate, tetra butylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide and the like. Among these, DBU-B is preferable from the viewpoint of crosslinkability, mechanical properties and flexibility.

The quaternary phosphonium salt is not particularly limited, and examples thereof include tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl -2-methoxypropyl phosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride, and the like. Among them, benzyltriphenylphosphonium chloride (BTPPC) is preferred from the viewpoint of crosslinkability, mechanical properties, and flexibility. preferable.

Further, as a cross-linking accelerator, a solid solution of a quaternary ammonium salt and bisphenol AF, a solid solution of a quaternary phosphonium salt and bisphenol AF, and a chlorine-free cross-linking accelerator disclosed in JP-A-11-147891 are used. can also

The amount of the crosslinking accelerator to be blended is preferably 0.01 to 8.00 parts by mass, more preferably 0.02 to 5.00 parts by mass, per 100 parts by mass of the uncrosslinked elastomer. More preferably, it is 0.03 to 3.00 parts by mass. If the amount of the cross-linking accelerator is less than 0.01 parts by mass, the cross-linking of the uncross-linked elastomer may not proceed sufficiently, and the resulting molded article may have reduced heat resistance. If it exceeds 8.00 parts by mass, there is a possibility that the molding processability of the fluorine-containing elastomer composition will be deteriorated, the elongation in mechanical properties will be deteriorated, and the flexibility will also tend to be deteriorated.

Acid acceptors are used to neutralize acidic substances generated during polyol cross-linking. #2000, CALDIC #1000 (manufactured by Ohmi Chemical Industry Co., Ltd.)), calcium oxide, litharge (lead oxide), zinc white, dibasic lead phosphite, hydrotalcite, etc., and highly active magnesium oxide and low It is preferably at least one selected from the group consisting of active magnesium.

Polyamine crosslinking can be performed by using a polyamine-crosslinkable fluorine-containing elastomer as a fluorine-containing elastomer and a polyamine compound as a crosslinking agent.

The polyamine-crosslinkable fluorine-containing elastomer is not particularly limited as long as it has a polyamine-crosslinkable site. The polyamine-crosslinkable site is not particularly limited, and examples thereof include sites having vinylidene fluoride (VdF) units. Examples of the method for introducing the cross-linking site include a method of copolymerizing a monomer that provides the cross-linking site during polymerization of the fluorine-containing elastomer.

Examples of polyamine compounds include hexamethylenediamine carbamate, N,N'-dicinnamylidene-1,6-hexamethylenediamine, and 4,4'-bis(aminocyclohexyl)methane carbamate. Among these, N,N'-dicinnamylidene-1,6-hexamethylenediamine is preferred.

The method for obtaining the composition containing the cross-linking agent is not particularly limited as long as the method is capable of uniformly mixing the fluorine-containing elastomer obtained by the production method of the present disclosure and the cross-linking agent. For example, there is a method of kneading a powder obtained by coagulating a fluorine-containing elastomer alone and, if necessary, other additives or compounding agents with a kneader such as an open roll.

The present disclosure contains a methylene group in the main chain and further contains a monomer unit (1) based on a fluorine-containing allyl ether (1) and a monomer unit (2) based on a fluorine-containing vinyl ether (2). It also relates to fluoroelastomers. The fluorine-containing elastomer of the present disclosure can be suitably produced by the production method of the present disclosure.

The form of the composition of the present disclosure is not particularly limited, and may be, for example, an aqueous dispersion, gum, crumb, powder, pellet, or the like. An aqueous dispersion is a dispersion system containing an aqueous medium as a dispersion medium and a fluorine-containing elastomer as a dispersoid. The aqueous medium is not particularly limited as long as it is a liquid containing water, and in addition to water, it may contain, for example, an organic solvent such as alcohol, ether, ketone, or paraffin wax.

A suitable configuration of the fluorine-containing elastomer is the same as the configuration of the fluorine-containing elastomer obtained by the production method of the present disclosure.

Suitable configurations of the fluorine-containing allyl ether (1) and the fluorine-containing vinyl ether (2) are the same as the configurations of the fluorine-containing allyl ether (1) and the fluorine-containing vinyl ether (2) used in the production method of the present disclosure.

The content of the monomer units (1) based on the fluorine-containing allyl ether (1) in the fluorine-containing elastomer is preferably 0.0009 to 1.5% by mass with respect to the total monomer units, and more It is preferably 0.0015% by mass or more, more preferably 0.0030% by mass or more, particularly preferably 0.0060% by mass or more, most preferably 0.0090% by mass or more, and more preferably It is 0.30% by mass or less, more preferably 0.15% by mass or less, particularly preferably 0.09% by mass or less, and most preferably 0.06% by mass or less. If the content of the monomer units (1) based on the fluorine-containing allyl ether (1) is too high, the properties required for the fluorine-containing elastomer may be impaired.

The content of the monomer units (2) based on the fluorine-containing vinyl ether (2) in the fluorine-containing elastomer is preferably 0.0009 to 1.5% by mass, more preferably 0.0009 to 1.5% by mass, based on the total monomer units. is 0.0015% by mass or more, more preferably 0.0030% by mass or more, particularly preferably 0.0060% by mass or more, most preferably 0.0090% by mass or more, more preferably 0 0.30% by mass or less, more preferably 0.15% by mass or less, particularly preferably 0.09% by mass or less, and most preferably 0.06% by mass or less. If the content of the monomer units (2) based on the fluorine-containing vinyl ether (2) is too high, the properties required for the fluorine-containing elastomer may be impaired.

The content of monomer unit (1) and monomer unit (2) in the fluorine-containing elastomer is calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer. can.

In one embodiment of the fluoroelastomer of the present disclosure, the composition and the aqueous dispersion to be described later, it contains a fluorosurfactant (excluding the fluorinated allyl ether (1) and the fluorinated vinyl ether (2)). . A fluorine-containing surfactant-containing fluorine-containing elastomer, composition, and aqueous dispersion can be obtained by using a fluorine-containing surfactant (except for the fluorine-containing allyl ether (1) and the fluorine-containing vinyl ether (2)). There is an advantage that it can be manufactured stably with productivity. Examples of the fluorine-containing surfactant include fluorine-containing surfactants (provided that fluorine-containing allyl ether (1), fluorine-containing vinyl ether (2) and fluorine-containing compounds represented by the general formula: X—(CF ₂ ) _m2 —Y ) are preferred, and those exemplified as fluorine-containing surfactants that can be present during polymerization can be mentioned. As the fluorine-containing surfactant, a fluorine-containing surfactant (excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)) is more preferred. The aqueous dispersion may not contain a fluorine-containing compound represented by the general formula: X-(CF ₂ ) _m2 -Y.

An embodiment of the fluorine-containing elastomer, composition and aqueous dispersion does not substantially contain a fluorine-containing surfactant (excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)). Fluorine-containing surfactants (excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)) are used for fluorine-containing elastomers, compositions and aqueous dispersions that do not substantially contain fluorine-containing surfactants. However, the method for producing a fluorine-containing elastomer aqueous dispersion of the present disclosure, which uses the fluorine-containing allyl ether (1) and the fluorine-containing vinyl ether (2), can be produced. It has become possible.

In the present disclosure, "substantially free of fluorine-containing surfactant" means the fluorine-containing elastomer, the composition, and the fluorine-containing surfactant in the aqueous dispersion (however, the fluorine-containing allyl ether (1) and fluorine-containing (excluding vinyl ether (2)) is 10 mass ppm or less, preferably 1 mass ppm or less, more preferably 100 mass ppb or less, still more preferably 10 mass ppb or less. more preferably 1 mass ppb or less, and particularly preferably less than the detection limit of the fluorine-containing surfactant as measured by liquid chromatography-mass spectrometry (LC/MS).

The content of the fluorine-containing surfactant (excluding fluorine-containing allyl ether (1) and fluorine-containing vinyl ether (2)) can be quantified by a known method, for example, by LC/MS analysis. .
First, methanol is added to the fluoroelastomer, the composition or the aqueous dispersion for extraction, and the resulting extract is subjected to LC/MS analysis. In order to further increase the extraction efficiency, a treatment such as Soxhlet extraction, ultrasonic treatment, or the like may be performed.
Molecular weight information is extracted from the obtained LC/MS spectrum, and conformity with the structural formula of the candidate fluorine-containing surfactant is confirmed.
After that, aqueous solutions with five or more levels of content of the confirmed fluorosurfactant were prepared, and the aqueous solutions with each content were analyzed by LC/MS to determine the content and the relationship between the area area and the content. Plot and draw a standard curve.
Then, using the calibration curve, the area area of the LC/MS chromatogram of the fluorine-containing surfactant in the extract can be converted to the content of the fluorine-containing surfactant.

The present disclosure also relates to compositions containing fluorine-containing elastomers. The composition of the present disclosure may be an aqueous dispersion containing a fluorine-containing elastomer and an aqueous medium. The upper limit of the solid content concentration of the aqueous dispersion is preferably 50% by mass, more preferably 40% by mass, still more preferably 35% by mass, and particularly preferably 30% by mass, relative to the aqueous dispersion. The lower limit of the solid content concentration of the aqueous dispersion is preferably 5% by mass, more preferably 10% by mass, still more preferably 15% by mass, and particularly preferably 20% by mass. The solid content concentration of the aqueous dispersion can be adjusted by diluting or concentrating the aqueous dispersion obtained by polymerization.

The solid content concentration of the aqueous dispersion is the concentration of the solid content contained in the aqueous dispersion. A fluorine-containing elastomer etc. are mentioned as solid content. Moreover, the solid content concentration of the aqueous dispersion may be the content of the fluorine-containing elastomer in the aqueous dispersion. The solid content concentration of the aqueous dispersion is obtained by drying 1 g of the aqueous dispersion under the conditions of 150 ° C. for 180 minutes, measuring the mass of the heating residue, and calculating the ratio of the mass of the heating residue to the mass of the aqueous dispersion. can be identified by

The aqueous dispersion can further contain a cross-linking agent, a filler, and the like. A preferred configuration of the cross-linking agent is the same as the configuration of the composition (crosslinkable composition) obtained by the production method of the present disclosure.

If necessary, the aqueous dispersion can be made into a dispersion suitable for rubber molding by adding a dispersion stabilizer such as a hydrocarbon surfactant or by concentrating it. The dispersion is processed by pH adjustment, coagulation, heating, and the like.

The composition of the present disclosure may be a coagulate, gum, crumb, powder, pellet, etc. obtained by coagulating the fluorine-containing elastomer contained in the aqueous dispersion, and may be gum or crumb. is preferably Gum is a small granular lump made of a fluorine-containing elastomer, and crumb is a fluorine-containing elastomer that cannot maintain its shape as a gum at room temperature and fuses with each other. It is in the shape of an amorphous mass. The gum or crumb is preferably obtained from the aqueous dispersion obtained by the production method of the present disclosure by coagulation, drying, etc. by conventionally known methods.

The water content of the composition is not particularly limited, but is preferably 1% by mass or less, more preferably 0.1% by mass or less, and still more preferably 0.01% by mass or less, relative to the mass of the composition. is. The moisture content of the composition can be determined, for example, by sufficiently drying the composition by heating it to 120°C or higher, measuring the weight of the composition before and after heating, and dividing the weight loss by the weight before heating. can be calculated.

The composition can contain a cross-linking agent. A preferred configuration of the cross-linking agent is the same as the configuration of the composition (crosslinkable composition) obtained by the production method of the present disclosure.

The composition may contain at least one polyfunctional compound. A polyfunctional compound is a compound having two or more functional groups with the same or different structures in one molecule. Functional groups possessed by polyfunctional compounds include functional groups generally known to have reactivity, such as carbonyl groups, carboxyl groups, haloformyl groups, amide groups, olefin groups, amino groups, isocyanate groups, hydroxy groups, and epoxy groups. Any group can be used.

The composition may contain usual additives that are blended into elastomers, such as fillers (carbon black, barium sulfate, etc.), processing aids (wax, etc.), plasticizers, colorants, stabilizers, tackifiers, etc., if necessary. Various additives such as imparting agents (coumarone resin, cumarone-indene resin, etc.), release agents, conductivity imparting agents, thermal conductivity imparting agents, surface non-adhesive agents, flexibility imparting agents, heat resistance improving agents, flame retardants, etc. and one or more commonly used cross-linking agents and cross-linking accelerators different from those described above may be blended.

The content of the filler such as carbon black is not particularly limited, but is preferably 0 to 300 parts by mass, more preferably 1 to 150 parts by mass, relative to 100 parts by mass of the fluorine-containing elastomer. It is more preferably 2 to 100 parts by mass, and particularly preferably 2 to 75 parts by mass.

The content of processing aids such as wax is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, per 100 parts by mass of the fluorine-containing elastomer. The use of processing aids, plasticizers and release agents tends to reduce the mechanical properties and sealability of the resulting molded product. need to be adjusted.

A molded product can be obtained by molding the composition. A molded article can also be obtained by molding the composition and cross-linking it. The composition can be molded by a conventionally known method. The method and conditions for molding and crosslinking may be within the range of known methods and conditions for molding and crosslinking to be employed. The order of molding and crosslinking is not limited, and crosslinking may be performed after molding, molding may be performed after crosslinking, or molding and crosslinking may be performed simultaneously.

Examples of molding methods include compression molding, injection molding, injection molding, extrusion molding, and molding using a roto-curing method, but are not limited to these. As the cross-linking method, a steam cross-linking method, a cross-linking method by heating, a radiation cross-linking method, or the like can be employed. Among them, the steam cross-linking method and the cross-linking method by heat are preferable. Specific cross-linking conditions, which are not limited, are usually within a temperature range of 140 to 250° C. and a cross-linking time of 1 minute to 24 hours.

Also, by heating the resulting molded product in an oven or the like, it is possible to improve mechanical properties and compression set characteristics at high temperatures. Specific cross-linking conditions, which are not limited, are usually in the temperature range of 140 to 300° C. and in the range of 30 minutes to 72 hours.

The resulting molded products can be used as various parts in various fields such as the automobile industry, aircraft industry, and semiconductor industry. Molded products include, for example, sealing materials, sliding members, non-adhesive members, crosslinked rubber molded products described in JP-A-2013-216915, and fluororubber molded products described in JP-A-2019-94430. can be used for

Examples of usage forms of molded products include various sealing materials and packings such as rings, packings, gaskets, diaphragms, oil seals, and bearing seals. As a sealing material, it can be used in applications requiring excellent non-adhesiveness and low friction properties. In particular, it can be suitably used for various sealing materials in the automobile industry and the like.

Also used as tubes, hoses, rolls, various rubber rolls, flexible joints, rubber plates, coatings, belts, dampers, valves, valve seats, valve bodies, chemical-resistant coating materials, laminating materials, lining materials, etc. can.

Although the embodiments have been described above, it will be understood that various changes in form and detail are possible without departing from the spirit and scope of the claims.

Next, the embodiments of the present disclosure will be described with examples, but the present disclosure is not limited only to these examples.

Each numerical value in the examples was measured by the following method.

<Mooney viscosity>
Mooney viscosity was measured according to JIS K 6300-1.2013 at 100° C. using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES.

<Composition of fluorine-containing elastomer>
Obtained by NMR analysis.

<Polymer adhesion rate>
The ratio of the mass of the polymer deposit adhering to the polymerization tank after the polymerization to the total amount of the polymer (fluorine-containing elastomer) after the polymerization (percentage of adhesion to the polymerization tank) was determined by the following formula.
Polymer deposition rate (% by mass) = mass of polymer deposit/mass of obtained polymer (including polymer deposit) x 100
Mass of obtained polymer = mass of aqueous dispersion x solid content concentration of aqueous dispersion (% by mass)/100 + mass of polymer deposits. , polymer adhering to the inside of the polymerization vessel such as the inner wall of the polymerization vessel and stirring blades, and the polymer released from the aqueous dispersion due to aggregation and floating or precipitated without being dispersed in the aqueous dispersion. . The mass of the polymer deposit is the mass after removing moisture contained in the polymer deposit by drying at 120°C.

<Solid content concentration of aqueous dispersion>
1 g of the aqueous dispersion is dried in a blower dryer at 150 ° C. for 180 minutes, the mass of the heating residue is measured, and the ratio of the mass of the heating residue to the mass of the aqueous dispersion (1 g) (mass %) was obtained.

<Average particle size>
The average particle size (cumulant average size) of the fluorine-containing elastomer particles in the aqueous dispersion was measured by the dynamic light scattering method using ELSZ-1000S (manufactured by Otsuka Electronics Co., Ltd.) and calculated by the cumulant method.

<Number of fluorine-containing elastomer particles in aqueous dispersion>
It was calculated by the following formula.

In the formula, the average particle diameter is the cumulant average diameter calculated by the method described above, the number of polymer particles (the number of fluorine-containing elastomer particles) is the number per 1 cc of water, and all fluorine-containing particles of Examples and Comparative Examples The specific gravity of the elastomer was set to 1.8.

Example 1
1500 g of deionized water, 0.75 g of a 10% by mass aqueous solution of CH ₂ =CF-CF ₂ OCF (CF ₃ )COONH ₄ , and 1.0394 g of CF ₂ =CF-O were placed in a SUS polymerization vessel having an internal volume of 3 L. A 7.22% by mass aqueous solution of CF ₂ CF ₂ SO ₃ Na was added, the polymerization tank was sealed, and the atmosphere in the system was replaced with nitrogen to remove oxygen. The temperature of the polymerization tank was raised to 80° C., and polymerization was carried out with stirring at a molar ratio of vinylidene fluoride [VDF]/tetrafluoroethylene [TFE]/hexafluoropropylene [HFP] (=19/11/70 mol %). The monomer (initial monomer) was pressurized so that the internal pressure of the tank was 2.03 MPaG.

Next, an aqueous polymerization initiator solution prepared by dissolving 0.030 g of ammonium persulfate (APS) in deionized water was pressurized with nitrogen gas to initiate polymerization. As the polymerization progressed, when the internal pressure dropped to 2.00 MPaG, a mixed monomer of VDF/TFE/HFP (=50/20/30 mol%) was charged so that the internal pressure was kept constant at 2.03 MPaG. is.

When 10 g of mixed monomer was added, 2.45 g of diiodine compound I(CF ₂ ) ₄ I was injected with nitrogen gas.

3.0 hours after the initiation of polymerization, 0.030 g of APS in the polymerization initiator aqueous solution was injected with nitrogen gas.

When 500 g of the mixed monomer was added, the stirring was stopped and the pressure in the polymerization vessel was released until it reached atmospheric pressure. The polymerization tank was cooled to obtain an aqueous dispersion. Table 1 shows the polymer adhesion rate, the solid content concentration of the aqueous dispersion, the mass of the aqueous dispersion, the average particle size and the number of particles.

An aqueous solution of aluminum sulfate was added to the above aqueous dispersion for coagulation. The obtained coagulate was washed with water and dried to obtain a fluorine-containing elastomer. The Mooney viscosity of the fluorine-containing elastomer was ML1+10 (100° C.)=52.7. When the composition of the copolymer was examined by NMR analysis, it was found to be VDF/TFE/HFP=50/20/30 (mol %).

Example 2
Same as Example 1, except that the amount of deionized water was changed from 1500 g to 1496 g, and the amount of the aqueous solution of CF ₂ =CF-O-CF ₂ CF ₂ SO ₃ Na was changed from 1.0394 g to 4.157 g. Polymerization was carried out with

An aqueous solution of aluminum sulfate was added to the above aqueous dispersion for coagulation. The obtained coagulate was washed with water and dried to obtain a fluorine-containing elastomer. The Mooney viscosity of the fluorine-containing elastomer was ML1+10 (100° C.)=59.3. When the composition of the copolymer was examined by NMR analysis, it was found to be VDF/TFE/HFP=50/20/30 (mol %).

Example 3
In the same manner as in Example 1, except that 0.750 g of a 10% by mass aqueous solution of CF ₂ ═CFOCF ₂ CF ₂ COONH ₄ was added instead of the aqueous solution of CF ₂ ═CF—O—CF ₂ CF ₂ SO ₃ Na. Polymerization was carried out.

An aqueous solution of aluminum sulfate was added to the above aqueous dispersion for coagulation. The obtained coagulate was washed with water and dried to obtain a fluorine-containing elastomer. The Mooney viscosity of the fluorine-containing elastomer was ML1+10 (100° C.)=58.8. When the composition of the copolymer was examined by NMR analysis, it was found to be VDF/TFE/HFP=50/20/30 (mol %).

Example 4
Except that 0.750 g of a ₁₀ wt% aqueous solution of CF2 ₌ _CFOCF2CF ₍ _CF3 ) _{OCF2CF2COONH4} was added instead of the aqueous solution of CF2 ₌ CF _- O _- _CF2CF2SO3Na . , the polymerization was carried out in the same manner as in Example 1.

An aqueous solution of aluminum sulfate was added to the above aqueous dispersion for coagulation. The obtained coagulate was washed with water and dried to obtain a fluorine-containing elastomer. The Mooney viscosity of the fluorine-containing elastomer was ML1+10 (100° C.)=55.6. When the composition of the copolymer was examined by NMR analysis, it was found to be VDF/TFE/HFP=50/20/30 (mol %).

Comparative example 1
Same as Example 1, except that the aqueous solution of CH ₂ ═CF—CF ₂ OCF(CF ₃ )COONH ₄ was not added, and 0.030 g of APS aqueous solution of polymerization initiator was injected with nitrogen gas 6.0 hours after the initiation of polymerization. Polymerization was carried out with

An aqueous solution of aluminum sulfate was added to the above aqueous dispersion for coagulation. The obtained coagulate was washed with water and dried to obtain a fluorine-containing elastomer. The Mooney viscosity of the fluorine-containing elastomer was ML1+10 (100° C.)=43.9. When the composition of the copolymer was examined by NMR analysis, it was found to be VDF/TFE/HFP=50/20/30 (mol %).

Comparative example 2
Polymerization was carried out in the same manner as in Example 1, except that the aqueous solution of CF ₂ =CF--O--CF ₂ CF ₂ SO ₃ Na was not added.

An aqueous solution of aluminum sulfate was added to the above aqueous dispersion for coagulation. The obtained coagulate was washed with water and dried to obtain a fluorine-containing elastomer. The Mooney viscosity of the fluorine-containing elastomer was ML1+10 (100° C.)=53.1. When the composition of the copolymer was examined by NMR analysis, it was found to be VDF/TFE/HFP=50/20/30 (mol %).

<Crosslinking properties>
The fluorine-containing elastomer obtained above was kneaded according to the formulation shown in Table 2 to obtain a fluorine-containing elastomer composition. For the obtained fluorine-containing elastomer composition, a rubber vulcanization tester MDRH2030 (manufactured by M&K Co., Ltd.) was used during press crosslinking to obtain a crosslinking curve. ) and the optimum vulcanization time (T90) were determined. Further, a crosslinked molded article sheet was obtained by cross-linking the fluorine-containing elastomer composition by press cross-linking and oven cross-linking subsequent to press cross-linking.
Kneading method: Roll kneading Press cross-linking: 160°C for 10 minutes Oven cross-linking: 180°C for 4 hours

The materials shown in Table 2 are as follows.
MT carbon: Thermax N-990 Cancarb TAIC: triallyl isocyanurate, Tyke Nippon Kasei Co., Ltd. Perhexa 25B: 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, NOF Corporation

<Normal physical properties>
Using the crosslinked molded product sheet, according to JIS K6251, a dumbbell No. 6-shaped test piece was prepared, and the 100% modulus (M100) of the prepared test piece in the normal state, the tensile strength at break (TB), at break Elongation (EB) was measured.

<Hardness>
Dumbbell No. 6-shaped test pieces were produced in the same manner as above, and the hardness (Shore A) of the produced test pieces was measured according to JIS K6253 (peak value, 1 sec, 3 sec).

<Compression set>
Using the fluorine-containing elastomer composition, press cross-linking and oven cross-linking are performed under the above conditions to prepare an O-ring (P24 size), which is subjected to compression ratio of 25% at 200° C. for 72 hours according to JIS K6262. , the compression set of the produced O-ring was measured.

Table 2 shows the above results.

Example 5
1500 g of deionized water, 0.93 g of CH ₂ =CF-CF ₂ OCF (CF ₃ )COONH ₄ 10 wt% aqueous solution, and 3.00 g of CF ₂ =CFOCF ₂ CF were placed in a SUS polymerization vessel having an inner volume of 3 L. A 10% by mass aqueous solution of ₂ COONH ₄ was added, the polymerization tank was sealed, and the inside of the system was replaced with nitrogen to remove oxygen. The temperature of the polymerization tank was raised to 80° C., and polymerization was carried out at a molar ratio of vinylidene fluoride [VDF]/tetrafluoroethylene [TFE]/hexafluoropropylene [HFP] (=19/11/70 mol %) while stirring. A monomer (initial monomer) was injected so that the internal pressure of the tank was 1.47 MPaG.

Next, an aqueous polymerization initiator solution prepared by dissolving 0.0255 g of ammonium persulfate (APS) in deionized water was pressurized with nitrogen gas to initiate polymerization. As the polymerization progressed, when the internal pressure dropped to 1.44 MPaG, a mixed monomer of VDF/TFE/HFP (=50/20/30 mol%) was charged so that the internal pressure was kept constant at 1.47 MPaG. is.

When 15 g of mixed monomer was added, 2.19 g of diiodine compound I(CF ₂ ) ₄ I was injected with nitrogen gas.

3.0 hours after the initiation of polymerization, 0.0255 g of APS in the polymerization initiator aqueous solution was injected with nitrogen gas.

When 477 g of the mixed monomer was added, the stirring was stopped, and the pressure in the polymerization vessel was released until it reached atmospheric pressure. The polymerization tank was cooled to obtain an aqueous dispersion. Table 3 shows the polymer adhesion rate, the solid content concentration of the aqueous dispersion, the mass of the aqueous dispersion, the average particle size and the number of particles.

An aqueous solution of aluminum sulfate was added to the above aqueous dispersion for coagulation. The obtained coagulate was washed with water and dried to obtain a fluorine-containing elastomer. The Mooney viscosity of the fluorine-containing elastomer was ML1+10 (100° C.)=64.8. When the composition of the copolymer was examined by NMR analysis, it was found to be VDF/TFE/HFP=50/20/30 (mol %).

Comparative example 3
Polymerization was carried out in the same manner as in Example ₅ , except that the aqueous solution of _CF2 ₌ _{CFOCF2CF2COONH4} was not added.

An aqueous solution of aluminum sulfate was added to the above aqueous dispersion for coagulation. The obtained coagulate was washed with water and dried to obtain a fluorine-containing elastomer. The Mooney viscosity of the fluorine-containing elastomer was ML1+10 (100° C.)=66.7. When the composition of the copolymer was examined by NMR analysis, it was found to be VDF/TFE/HFP=50/20/30 (mol %).

Using the fluorine-containing elastomers obtained in Example 5 and Comparative Example 3, in the same manner as in Example 1, minimum viscosity (ML), maximum torque level (MH), induction time (T10) and optimum vulcanization time ( T90) was determined. Further, using the fluoroelastomers obtained in Example 5 and Comparative Example 3, a fluoroelastomer composition and a crosslinked molding sheet were produced in the same manner as in Example 1, and the physical properties, hardness and compression durability in the normal state were measured. Strain was measured.

Table 4 shows the above results.

Claims

by polymerizing a fluorine-containing monomer in the presence of a fluorine-containing allyl ether (1) represented by the general formula (1), a fluorine-containing vinyl ether (2) represented by the general formula (2), and an aqueous medium; and a method for producing an aqueous dispersion of a fluorine-containing elastomer containing a methylene group in the main chain.
CX 11 2 =CY 11 (-CZ 11 2 -O-Rf 11 -Y 12 ) (1)
(Wherein, X 11 is the same or different and is -H or -F, Y 11 is -H, -F, an alkyl group or a fluorine-containing alkyl group, Z 11 is the same or different and - H, —F, alkyl group or fluorine-containing alkyl group Rf 11 is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond Y 12 is a hydrophilic group.)
CX 21 2 = CY 21 (-O-Rf 21 -Y 22 ) (2)
(Wherein, X 21 is the same or different and is -H or -F, Y 21 is -H, -F, alkyl group or fluorine-containing alkyl group, Rf 21 is C 1-40 A fluorine alkylene group or a fluorine-containing alkylene group having an ether bond with 2 to 100 carbon atoms, and Y 22 is a hydrophilic group.)
Y 12 is —NH 2 , —P(O)(OM) 2 , —OP(O)(OM) 2 , —SO 3 M, —OSO 3 M, —COOM, —B(OM) 2 or —OB (OM) 2 ( wherein M is H, a metal atom, NR 74 , optionally substituted imidazolium, optionally substituted pyridinium or substituted R 7 is H or an organic group, which may be the same or different, any two of which may be combined with each other to form a ring. manufacturing method.
3. The production method according to claim 1 or 2, wherein all X 11 are -H.
The production method according to any one of claims 1 to 3, wherein the amount of the fluorine-containing allyl ether (1) is 3 to 5000 mass ppm with respect to the aqueous medium.
Y 22 is —NH 2 , —P(O)(OM) 2 , —OP(O)(OM) 2 , —SO 3 M, —OSO 3 M, —COOM, —B(OM) 2 or —OB (OM) 2 ( wherein M is H, a metal atom, NR 74 , optionally substituted imidazolium, optionally substituted pyridinium or substituted R 7 is H or an organic group, which may be the same or different, any two of which may combine with each other to form a ring. The manufacturing method according to any one of.
The production method according to any one of claims 1 to 5, wherein the amount of the fluorine-containing vinyl ether (2) is 3 to 5000 mass ppm with respect to the aqueous medium.
Further, the production method according to any one of claims 1 to 6, wherein the fluorine-containing monomer is polymerized in the presence of a chain transfer agent.
The production method according to any one of claims 1 to 7, wherein the fluorine-containing monomer is polymerized at 10 to 120°C.
The production method according to any one of claims 1 to 8, wherein the fluorine-containing monomer is polymerized at 0.5 to 10 MPaG.
The production method according to any one of claims 1 to 9, wherein the fluorine-containing elastomer contains vinylidene fluoride units.
The production method according to any one of claims 1 to 10, wherein the fluorine-containing elastomer contains 50 mol% or more of vinylidene fluoride units with respect to all monomer units.
The production method according to any one of claims 1 to 11, wherein the fluorine-containing elastomer has a Mooney viscosity (ML1+10 (100°C)) of 10 to 130.
A monomer unit (1) based on a fluorine-containing allyl ether (1) represented by the general formula (1) and a fluorine-containing vinyl ether (2) represented by the general formula (2) containing a methylene group in the main chain. A fluorine-containing elastomer containing monomer units (2) based on ).
CX 11 2 =CY 11 (-CZ 11 2 -O-Rf 11 -Y 12 ) (1)
(Wherein, X 11 is the same or different and is -H or -F, Y 11 is -H, -F, an alkyl group or a fluorine-containing alkyl group, Z 11 is the same or different and - H, —F, alkyl group or fluorine-containing alkyl group Rf 11 is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and an ether bond Y 12 is a hydrophilic group.)
CX 21 2 = CY 21 (-O-Rf 21 -Y 22 ) (2)
(Wherein, X 21 is the same or different and is -H or -F, Y 21 is -H, -F, alkyl group or fluorine-containing alkyl group, Rf 21 is C 1-40 A fluorine alkylene group or a fluorine-containing alkylene group having an ether bond with 2 to 100 carbon atoms, and Y 22 is a hydrophilic group.)
The fluorine-containing elastomer according to claim 13, which contains vinylidene fluoride units.
A fluorine-containing elastomer aqueous dispersion containing the fluorine-containing elastomer according to claim 13 or 14 and an aqueous medium.