JPWO2015111729A1 - Fluorine-containing elastic copolymer and method for producing the same - Google Patents

Abstract

Provision of a fluorinated elastic copolymer excellent in adhesiveness and flexibility and a method for producing the same It has a structural unit (A) based on the following monomer (a), a structural unit (B) based on the following monomer (b), and a structural unit (C) based on the following monomer (c). A fluorine-containing elastic copolymer characterized by Monomer (a): represented by tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, and CF2 = CF-O-Rf (Rf is a C1-C8 perfluoroalkyl group, etc.) Perfluoro (at least one selected from the group consisting of alkyl vinyl ethers. Monomer (b): at least selected from the group consisting of the compound represented by the following formula (II) and the compound represented by the following formula (III) Monomer (c): at least one selected from the group consisting of propylene and ethylene [Chemical Formula 1] (n is 0 or 1, m is an integer of 0 to 2, and R1 is carbon number. 1 to 8 (m + 2) -valent saturated hydrocarbon group, etc., R2 is a C1-C8 divalent saturated hydrocarbon group, etc., and R3 is a C1-C8 alkylene group, etc.)

Description

  The present invention relates to a fluorinated elastic copolymer and a method for producing the same.

  Since the fluorine-containing elastic copolymer exhibits excellent chemical resistance, solvent resistance, heat resistance, etc., taking advantage of these characteristics, in a wide range of industrial fields such as the automobile industry, semiconductor industry, chemical industry, paints, for example, Used for sealing materials such as O-rings, packings, oil seals, gaskets, and electric wires. In many cases, these materials are structures in which a molded body of a fluorinated elastic copolymer and a metal are combined.

In order to improve the vulcanization adhesion between a molded product of a fluorinated elastic copolymer and a metal, it has been proposed that the fluorinated elastic copolymer contains a fluorine-substituted aliphatic sulfonyl compound as an adhesion promoter. (For example, refer to Patent Document 1). As the fluorine-substituted aliphatic sulfonyl compound, polyfluoroalkyl-N-substituted sulfonamide and the like are used.
However, if the content of the fluorine-substituted aliphatic sulfonyl compound is increased to an amount that provides sufficient adhesion to metal, sufficient flexibility (for example, elongation characteristics) of the molded product of the fluorinated elastic copolymer is ensured. There is a problem that will not be done.

Japanese Patent No. 2963729

  An object of this invention is to provide the fluorine-containing elastic copolymer excellent in adhesiveness and a softness | flexibility, and its manufacturing method.

The present invention is a fluorinated elastic copolymer having the following constitutions [1] to [8] and a method for producing the same.
[1] A structural unit (A) based on the following monomer (a), a structural unit (B) based on the following monomer (b), and a structural unit (C) based on the following monomer (c) A fluorine-containing elastic copolymer characterized by comprising:
Monomer (a): At least one selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, and perfluoro (alkyl vinyl ether) represented by the following formula (I).
CF ₂ = CF—O—R ^f (I)
Here, ^Rf represents a C1-C8 perfluoroalkyl group or a C2-C8 perfluoro (alkoxyalkyl) group.
Monomer (b): At least one selected from the group consisting of a compound represented by the following formula (II) and a compound represented by the following formula (III).

Here, n is 0 or 1, m is an integer of 0 to 2, R ¹ is a (m + 2) -valent saturated hydrocarbon group having 1 to 8 carbon atoms, or 2 carbon atoms having an etheric oxygen atom. Represents an (m + 2) -valent saturated hydrocarbon group having ˜8, R ² is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a divalent saturated carbon atom having 2 to 8 carbon atoms having an etheric oxygen atom Represents a hydrogen group, and R ³ represents an alkylene group having 1 to 8 carbon atoms or an alkylene group having 2 to 8 carbon atoms having an etheric oxygen atom.
Monomer (c): At least one selected from the group consisting of propylene and ethylene.
[2] In the formula (II), R ¹ is an alkylene group having 1 or 2 carbon atoms, or an alkylene group having 2 to 6 carbon atoms having 1 to 3 etheric oxygen atoms. In the formula (III), , R ³ is an alkylene group having 1 to 4 carbon atoms, the fluorinated elastic copolymer according to the above [1].
[3] The above [1], wherein the monomer (b) is at least one selected from the group consisting of 4-hydroxybutyl vinyl ether, allyl glycidyl ether, and 3-allyloxy-1,2-propanediol. The fluorinated elastic copolymer according to [2].
[4] The content of the structural unit (B) is 0.0005 / 100 to 10.0 / 100 in a molar ratio with respect to the total of all the structural units excluding the structural unit (B). [1] The fluorinated elastic copolymer according to any one of [3].
[5] The fluorinated elastic copolymer according to any one of [1] to [4], wherein the monomer (a) is tetrafluoroethylene and the monomer (c) is propylene.
[6] The above [1] to [5], wherein the molar ratio [(C) / (A)] of the structural unit (A) to the structural unit (C) is 20/80 to 70/30. The fluorinated elastic copolymer according to any one of the above.
[7] A method for producing a fluorinated elastic copolymer according to any one of [1] to [6] above,
A monomer component containing the monomer (a), the monomer (b), and the monomer (c) is polymerized in the presence of an aqueous medium, an emulsifier, and a radical polymerization initiator. A method for producing a fluorinated elastic copolymer.
[8] After supplying a part of the monomer component to be polymerized to a reactor charged with an aqueous medium, an emulsifier and a radical polymerization initiator and starting the polymerization reaction, Polymerizing by supplying the remainder of the body components,
The method for producing a fluorinated elastic copolymer according to the above [7], wherein the whole amount of the monomer (b) is supplied to the reactor as the remaining monomer component.

The fluorinated elastic copolymer of the present invention is excellent in adhesiveness and flexibility, and can be combined with a metal, a resin or the like.
According to the method for producing a fluorinated elastic copolymer of the present invention, a fluorinated elastic copolymer having excellent adhesion and flexibility can be produced.

In the present invention, the “fluorinated elastic copolymer” is a fluorinated copolymer generally referred to as a fluororubber or a fluorinated elastomer.
Below, tetrafluoroethylene is TFE, hexafluoropropylene is HFP, vinylidene fluoride is VdF, chlorotrifluoroethylene is CTFE, perfluoro (alkyl vinyl ether) is PAVE, perfluoro (methyl vinyl ether) is PMVE, and perfluoro (propyl vinyl ether) is PPVE. Hydroxyethyl vinyl ether is referred to as HEVE, 4-hydroxybutyl vinyl ether as HBVE, cyclohexanedimethanol monovinyl ether as CHMVE, diethylene glycol monovinyl ether as DEGV, ethylene as E, and propylene as P.

<Fluorine-containing elastic copolymer>
The fluorinated elastic copolymer of the present invention comprises a structural unit (A) based on the monomer (a), a structural unit (B) based on the monomer (b), and a structure based on the monomer (c). Unit (C).
The fluorinated elastic copolymer of the present invention is a monomer other than the monomers (a) to (c) in addition to the structural units (A) to (C), as long as the effects of the present invention are not impaired. You may have the structural unit (D) based on d).

The monomer (a) is at least one selected from the group consisting of TFE, HFP, VdF, CTFE and PAVE represented by the following formula (I).
CF ₂ = CF—O—R ^f (I)
Here, ^Rf represents a C1-C8 perfluoroalkyl group or a C2-C8 perfluoro (alkoxyalkyl) group.
The perfluoroalkyl group in R ^f may be linear or branched, and the carbon number thereof is preferably 1 to 6, and more preferably 1 to 5. The perfluoro (alkoxyalkyl) group may be linear or branched, and the carbon number thereof is preferably 2-6, more preferably 2-5.
Specific examples of the PAVE include PMVE, PPVE, perfluoro (3,6-dioxa-1-heptene), perfluoro (3,6-dioxa-1-octene), perfluoro (5-methyl-3,6-dioxa- 1-nonene) and the like.
The monomer (a) is preferably at least one selected from the group consisting of TFE, HFP, VdF and PAVE, and most preferably TFE.

  The monomer (b) is at least one selected from the group consisting of a compound represented by the following formula (II) and a compound represented by the following formula (III).

Here, n is 0 or 1, m is an integer of 0 to 2, R ¹ is a (m + 2) -valent saturated hydrocarbon group having 1 to 8 carbon atoms, or 2 carbon atoms having an etheric oxygen atom. Represents an (m + 2) -valent saturated hydrocarbon group having ˜8, R ² is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a divalent saturated carbon atom having 2 to 8 carbon atoms having an etheric oxygen atom Represents a hydrogen group, and R ³ represents an alkylene group having 1 to 8 carbon atoms or an alkylene group having 2 to 8 carbon atoms having an etheric oxygen atom.

In R ¹ , the (m + 2) -valent saturated hydrocarbon group may be linear, branched or include a ring structure.
When m is 0, the (m + 2) -valent saturated hydrocarbon group is a divalent saturated hydrocarbon group, and examples thereof include an alkylene group, a cycloalkylene group, and an alkylene group containing a cycloalkylene group. The alkylene group may be linear or branched. As the cycloalkylene group, a cycloalkylene group having 5 to 8 carbon atoms is preferable, and a cyclohexylene group is particularly preferable. Examples of the alkylene group containing a cycloalkylene group include —CH ₂ —C ₆ H ₈ —CH ₂ —.
Examples of the divalent saturated hydrocarbon group include a linear alkylene group having 1 or 2 carbon atoms, or an alkylene group having 2 to 6 carbon atoms having 1 to 3 etheric oxygen atoms (provided that the alkylene group has a carbon number of 1 to 2). The number of etheric oxygen atoms contained in the case of 2 is 1, and the number of etheric oxygen atoms contained in the case where the alkylene group has 3 carbon atoms is preferably 1 or 2.
When m is 1 or 2, examples of the (m + 2) -valent saturated hydrocarbon group include groups obtained by removing m hydrogen atoms from the divalent saturated hydrocarbon group.

Examples of the divalent saturated hydrocarbon group for R ² include the same divalent saturated hydrocarbon groups as those for R ¹ .
The alkylene group for R ³ may be linear or branched. R ³ is preferably an alkylene group having 1 to 4 carbon atoms.

In the formula (II), R ¹ is a linear alkylene group having 1 or 2 carbon atoms, or an alkylene group having 2 to 6 carbon atoms having 1 to 3 etheric oxygen atoms (provided that The number is preferably 3 or less.)
In the formula (III), R ³ is preferably an alkylene group having 1 to 4 carbon atoms.
Specific examples of the monomer (b) include HEVE, HBVE, CHMVE, DEGV, allyl glycidyl ether, 3-allyloxy-1,2-propanediol, 5- (2-propenyloxy) -1-pentanol, 6 -(2-propenyloxy) -1-hexanol, 2- (2-propenyloxy) -1,4-butanediol, 4- (2-propenyloxy) -1,2-butanediol, 2- [2- ( At least one selected from the group consisting of 3-butenyl) ethyl] oxirane, 2- [3- (2-butenyl) propyl] oxirane, and 2- [4- (2-butenyl) butyl] oxirane is preferred, HBVE, More preferred is at least one selected from the group consisting of allyl glycidyl ether and 3-allyloxy-1,2-propanediol. Properly, HBVE is most preferable.

The monomer (c) is at least one selected from the group consisting of P and E.
As the monomer (c), P is preferable.

The monomer (d) is a monomer other than the monomers (a) to (c).
As the monomer (d), vinyl fluoride, pentafluoropropylene, perfluorocyclobutene, CH ₂ = CHCF ₃ , CH ₂ = CHCF ₂ CF ₃ , CH ₂ = CHCF ₂ CF ₂ CF ₃ , CH ₂ = CHCF ₂ Fluorine-containing monomers such as (perfluoroalkyl) ethylenes such as CF ₂ CF ₂ CF ₃ , CH ₂ ═CHCF ₂ CF ₂ CF ₂ CF ₂ CF ₃ ;
Α-olefins such as isobutylene and pentene, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, etc. Non-fluorinated monomers; and the like.
These monomers (d) may be used alone or in combination of two or more.

In the fluorinated elastic copolymer, the content of the structural unit (B) is based on the total of all the structural units excluding the structural unit (B) (the total of the structural units (A), (C), and (D)). The molar ratio is preferably 0.0005 / 100 to 10.0 / 100. When the molar ratio is 0.0005 / 100 or more, the adhesion (adhesiveness) of the obtained fluorinated elastic copolymer to a metal or the like is more excellent. When the molar ratio is 10.0 / 100 or less, the monomer corresponding to each structural unit is polymerized well during the production of the fluorinated elastic polymer, and the physical properties of the resulting fluorinated elastic polymer are excellent.
The molar ratio is preferably 0.01 / 100 or more, more preferably 0.05 / 100 or more, still more preferably 0.1 / 100 or more, and particularly preferably 0.2 / 100 or more.
The molar ratio is preferably 5.0 / 100 or less, more preferably 2.0 / 100 or less, still more preferably 1.0 / 100 or less, and particularly preferably 0.5 / 100 or less.

  In the fluorinated elastic copolymer, among the total of all the structural units excluding the structural unit (B) (the total of the structural units (A), (C), and (D)), the structural units (A) and (C) The total ratio is preferably 90 mol% or more, and more preferably 95 mol% or more. The proportion is usually 80 mol% or less. That is, the proportion of the structural unit (D) in the total of all the structural units excluding the structural unit (B) is preferably 10 mol% or less, and more preferably 5 mol% or less.

  In the fluorinated elastic copolymer, the molar ratio [(C) / (A)] of the structural unit (A) to the structural unit (C) is preferably 20/80 to 70/30, and 30/70 -60/40 is more preferable, and 45 / 55-60 / 40 is most preferable. When (C) / (A) is within the above range, the fluorinated elastic copolymer has an excellent balance between strength and chemical resistance.

Specific examples of the combination of the structural unit (A) and the structural unit (C) in the fluorinated elastic copolymer include the following (1) to (9). In each combination, “unit” indicates a structural unit (monomer unit).
(1) A combination of a unit based on VdF, a unit based on HFP, a unit based on TFE, a unit based on E, and a unit based on P.
(2) A combination of a unit based on VdF, a unit based on HFP, a unit based on TFE, and a unit based on P.
(3) A combination of a unit based on VdF, a unit based on HFP, a unit based on E, and a unit based on P.
(4) A combination of a unit based on VdF, a unit based on P, and a unit based on TFE.
(5) A combination of a unit based on TFE and a unit based on P.
(6) A combination of a unit based on TFE and a unit based on PAVE.
(7) A combination of a unit based on VdF and a unit based on PAVE.
(8) A combination of a unit based on E and a unit based on PAVE.

  Among the above, in terms of excellent polymerization reactivity, any combination of (1) to (6) is preferable, (4), (5) or (6) is more preferable, and the strength of the resulting polymer The combination of (5) is most preferable in that it has an excellent balance of chemical resistance. That is, the fluorinated elastic copolymer is most preferably one in which the monomer (a) is TFE and the monomer (c) is P.

In the combination of (4), the molar ratio of units based on VdF / units based on P / units based on TFE is preferably 1 to 50/20 to 70/20 to 70, and preferably 1 to 40/20 to 60/30. 60 is more preferable (however, in this molar ratio, the sum of the unit based on VdF, the unit based on P, and the unit based on TFE is 100).
In the combination of (5), the molar ratio of units based on TFE / units based on P is preferably 30/70 to 80/20, more preferably 40/60 to 70/30, and 50/50 to 65/35. Most preferred.
In the combination of (7), the molar ratio of units based on TFE / units based on PAVE is preferably 85/15 to 25/75, and more preferably 75/25 to 40/60.

The storage elastic modulus G ′ of the fluorinated elastic copolymer of the present invention is preferably 250 kPa or more, more preferably 300 kPa or more, further preferably 350 kPa or more, and most preferably 400 kPa or more. The storage elastic modulus G ′ is a measure of the molecular weight and flexibility of the fluorinated elastic copolymer, and the fluorinated elastic copolymer having a high molecular weight exhibits a large storage elastic modulus G ′. When the storage elastic modulus G ′ is 250 kPa or more, the fluorinated elastic copolymer is excellent in adhesion, mechanical properties, chemical resistance, heat resistance and the like.
The upper limit of the storage elastic modulus G ′ of the fluorinated elastic copolymer is not particularly limited, but is preferably 700 kPa or less and more preferably 650 kPa or less in terms of excellent flexibility.
In the present invention, the storage elastic modulus G ′ is a value measured under conditions of 100 ° C. and a frequency of 0.83 Hz in accordance with ASTM D6204.

<Method for producing fluorinated elastic copolymer>
The fluorinated elastic copolymer of the present invention is a copolymer of the monomer (a), the monomer (b), the monomer (c), and the monomer (d) as necessary. Can be manufactured.
Examples of the polymerization method include an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, and a bulk polymerization method. An emulsion polymerization method in which a monomer is polymerized in the presence of an aqueous medium and an emulsifier is preferable because the molecular weight and copolymer composition of the fluorinated elastic copolymer can be easily adjusted and the productivity is excellent.
In the emulsion polymerization method, a monomer component containing the monomer (a), the monomer (b), and the monomer (c) is polymerized (emulsified) in the presence of an aqueous medium, an emulsifier, and a radical polymerization initiator. The latex of the fluorinated elastic copolymer is obtained through a step of polymerization (hereinafter also referred to as an emulsion polymerization step). In the emulsion polymerization step, a pH adjuster may be added.

(Aqueous medium)
The aqueous medium is water alone or a mixture of water and a water-soluble organic solvent.
As the water-soluble organic solvent, a known compound that can be dissolved in water at an arbitrary ratio can be appropriately used. As the water-soluble organic solvent, alcohols are preferable, and examples thereof include tert-butanol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol. Of these, tert-butanol, propylene glycol, dipropylene glycol, or dipropylene glycol monomethyl ether is preferred.
The aqueous medium is preferably water, a mixture of water and tert-butanol or a mixture of water and propylene glycol, more preferably a mixture of water and tert-butanol.
Further, the amount of the aqueous medium used is preferably 40 to 80%, more preferably 50 to 70% with respect to the reaction vessel volume.

(emulsifier)
As the emulsifier, a known emulsifier used in the emulsion polymerization method can be appropriately used. From the viewpoint of excellent mechanical and chemical stability of the latex, an ionic emulsifier is preferable, and an anionic emulsifier is more preferable.
As the anionic emulsifier, those known in the emulsion polymerization method can be used. Specific examples include hydrocarbon emulsifiers such as sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium alkyl sulfonate, sodium alkyl benzene sulfonate, sodium dialkyl ester sulfonate succinate, sodium alkyl diphenyl ether disulfonate; ammonium perfluorooctanoate, Fluorine-containing alkyl carboxylates such as ammonium perfluorohexanoate; compounds represented by the following formula (V) (hereinafter referred to as compound (V)) and the like.

_{F (CF 2) p O (} CF (X) CF 2 O) q CF (X) COOA ··· (V).
In formula (V), X represents a fluorine atom or perfluoroalkyl group having 1 to 3 carbon atoms, A represents a hydrogen atom, an alkali metal atom or an NH _4,, p represents an integer of 1 to 10, q Represents an integer of 0 to 3.
X is preferably a fluorine atom or a trifluoromethyl group. A is preferably Na or NH ₄ . p is preferably 1 to 5. q is preferably 1 to 2.

As the anionic emulsifier, sodium lauryl sulfate is particularly preferable because of excellent polymerization characteristics and dispersion stability and low cost.
The amount of the anionic emulsifier used is preferably 1.5 to 5.0 parts by mass, and 1.5 to 4.5 parts by mass with respect to 100 parts by mass of the fluorinated elastic copolymer produced in the emulsion polymerization step. Is more preferable and 1.7-4.0 mass parts is especially preferable. When the content of the emulsifier in the latex of the fluorinated elastic copolymer obtained by emulsion polymerization is within this range, the stability of the latex is excellent.

(PH adjuster)
The pH adjuster is preferably an inorganic salt. As the inorganic salt, a known inorganic salt can be used as a pH adjuster in emulsion polymerization. Specific examples of the pH adjuster include phosphates such as disodium hydrogen phosphate and sodium dihydrogen phosphate; carbonates such as sodium bicarbonate and sodium carbonate; and the like. More preferable specific examples of the phosphate include disodium hydrogen phosphate dihydrate and disodium hydrogen phosphate dodecahydrate.
You may use pH adjusters other than the said inorganic salt. For example, in order to adjust to a desired pH, bases such as sodium hydroxide and potassium hydroxide; acids such as sulfuric acid, hydrochloric acid and nitric acid may be used in combination.
4-12 are preferable and, as for pH in the aqueous medium in the emulsion polymerization process mentioned later, 6-11 are more preferable.
However, from the viewpoint of reducing the content of metal in the latex of the fluorinated elastic copolymer, it is preferable that the amount of the pH adjuster used is as small as possible.

(Radical polymerization initiator)
The radical polymerization initiator used in emulsion polymerization is preferably a water-soluble polymerization initiator. Examples of the water-soluble polymerization initiator include persulfates such as ammonium persulfate; organic initiators such as disuccinic acid peroxide and azobisisobutylamidine dihydrochloride; and the like. Of these, persulfates such as ammonium persulfate are preferred.

The mechanism for initiating the radical polymerization reaction may be (i) a thermal decomposition polymerization initiator system in which heat is applied to cause radical decomposition in the presence of a thermal decomposition type radical polymerization initiator. (Ii) radical polymerization A redox polymerization initiator system in which an initiator and a redox catalyst (so-called redox catalyst) are used in combination may be used.
In any system, the amount of the water-soluble polymerization initiator used is preferably 0.0001 to 3 parts by mass with respect to 100 parts by mass of the fluorinated elastic copolymer produced in the emulsion polymerization step. Part by mass is more preferable.

  The thermal decomposition type radical polymerization initiator used in the thermal decomposition type polymerization initiator system (i) is preferably water-soluble and has a one-hour half-life temperature of 50 to 100 ° C. It can be appropriately selected from water-soluble polymerization initiators used in ordinary emulsion polymerization. Specific examples of the thermal decomposition type radical polymerization initiator include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate; organic initiators such as disuccinic acid peroxide and azobisisobutylamidine dihydrochloride. Can be mentioned. Of these, persulfates are preferred, and ammonium persulfate is particularly preferred.

  As the redox polymerization initiator system (ii), a known radical polymerization initiator and a redox catalyst can be used in combination, and ammonium persulfate, sodium hydroxymethanesulfinate, and ethylenediaminetetraacetic acid disodium salt dihydrate. A system that uses a combination of potassium and ferrous sulfate, a system that uses potassium permanganate and oxalic acid, a system that uses potassium bromate and ammonium sulfite, or a system that uses ammonium persulfate and ammonium sulfite. preferable. Among these, a system using ammonium persulfate, sodium hydroxymethanesulfinate (also referred to as Rongalite), ethylenediaminetetraacetic acid disodium salt dihydrate, and ferrous sulfate is particularly preferable.

(Emulsion polymerization process)
The emulsion polymerization step can be performed by a known emulsion polymerization method.
In the emulsion polymerization step, after supplying a part of the monomer component to be polymerized (initially charged monomer component) to the reactor charged with the aqueous medium, the emulsifier and the radical polymerization initiator, and starting the polymerization reaction The polymerization is preferably advanced by supplying the remainder of the monomer component (post-added monomer component) as the polymerization reaction proceeds. Moreover, it is preferable that the whole amount of the monomer (b) is supplied to the reactor as the remaining monomer component.
The monomer (b) has a higher polymerization rate than the monomer (a) and the monomer (c), and when the entire amount of the monomer (b) is supplied all at once, the fluorinated elastic copolymer Variations are likely to occur in the amount and distribution of the structural unit (B) introduced.
By gradually supplying the monomer (b) during the polymerization reaction as the polymerization reaction proceeds, it is easy to obtain a fluorinated elastic copolymer in which the structural unit (B) is uniformly introduced. Such a fluorinated elastic copolymer is more excellent in adhesion to a metal or the like.

An emulsion polymerization process can be performed in the following procedures, for example.
First, after deaeration of the pressure-resistant reactor, an aqueous medium, an emulsifier, a radical polymerization initiator, a pH adjuster as required, and a redox catalyst in a redox polymerization initiator system are charged into the reactor. Next, after raising the temperature to a predetermined polymerization temperature, a monomer mixture containing the monomer (a) and the monomer (c) (initially charged monomer component) is injected. Further, a catalyst (such as a Rongalite catalyst in a redox polymerization initiator system) is supplied as necessary. As the polymerization reaction begins, the pressure in the reactor begins to drop.

After confirming the pressure drop in the reactor, the monomer mixture containing the monomer (a) and the monomer (c) is maintained at the predetermined polymerization pressure while maintaining the predetermined polymerization temperature. And the monomer (b) is added thereto to carry out the polymerization reaction.
It is preferable that the composition of the monomer supplied into the reactor during the polymerization is the same as the ratio of the structural units in the fluorinated elastic copolymer to be obtained.

When the total amount of monomers supplied to the reactor during the polymerization reaction period reaches a predetermined value, the inside of the reactor is cooled to stop the polymerization reaction, and a latex of a fluorinated elastic copolymer is obtained.
The latex of the fluorinated elastic copolymer thus obtained contains particles of the fluorinated elastic copolymer and an emulsifier in an aqueous medium.

When the mechanism for initiating the radical polymerization reaction is the above (i) thermal decomposition polymerization initiator system, the polymerization temperature during the polymerization reaction period is preferably 50 to 100 ° C, more preferably 60 to 90 ° C, 65 ˜80 ° C. is particularly preferred. When the polymerization temperature is within this range, the polymerization rate is appropriate and easy to control, the productivity is excellent, and good stability of the latex is easily obtained.
The polymerization pressure during the polymerization reaction period is preferably 1.0 to 10 MPaG, more preferably 1.5 to 5.0 MPaG, and particularly preferably 1.7 to 3.0 MPaG. When the polymerization pressure is less than 1.0 MPaG, the polymerization rate may be too slow. Within the above range, the polymerization rate is appropriate and easy to control, and the productivity is excellent. “G” in “MPaG” means gauge pressure.

When the mechanism for initiating the radical polymerization reaction is the above (ii) redox polymerization initiator system, the polymerization temperature during the polymerization reaction period is preferably 0 to 100 ° C, more preferably 10 to 90 ° C, and more preferably 20 to 60 ° C. Is particularly preferred. When the polymerization temperature is within this range, the polymerization rate is appropriate and easy to control, the productivity is excellent, and good stability of the latex is easily obtained.
The polymerization pressure during the polymerization reaction period is preferably 1.0 to 10 MPaG, more preferably 1.5 to 5.0 MPaG, and particularly preferably 1.7 to 3.0 MPaG. When the polymerization pressure is less than 1.0 MPaG, the polymerization rate may be too slow. Within the above range, the polymerization rate is appropriate and easy to control, and the productivity is excellent.

The average particle size of the fluorinated elastic copolymer particles contained in the latex obtained in the emulsion polymerization step is preferably 10 to 200 nm, more preferably 20 to 150 nm, still more preferably 20 to 130 nm, and more preferably 30 to 100 nm. Particularly preferred. When the average particle size is 200 nm or less, a latex having good polymerization stability and storage stability is easily obtained. On the other hand, when the average particle size is 10 nm or more, a latex having good cohesion is easily obtained.
The average particle size of the fluorinated elastic copolymer particles contained in the latex can be adjusted by a known method such as the type and amount of the emulsifier.

  The fluorinated elastic copolymer in the latex obtained in the emulsion polymerization step can be isolated by agglomeration by a known method. For the aggregation, a known method such as addition of a metal salt, addition of an inorganic acid such as hydrochloric acid, mechanical shearing, freeze-thawing, or the like can be used. For example, latex is added to an aqueous solution of a metal salt such as calcium chloride and salted out to agglomerate and precipitate the fluorinated elastic copolymer. The precipitated agglomerate is washed with ion-exchanged water, dried, and then fluorinated. It is preferable to obtain an elastic copolymer.

<Uses of fluorinated elastic copolymers>
The fluorinated elastic copolymer of the present invention is formed by a known method after preparing the fluorinated elastic copolymer as it is or by adding an optional component as necessary. To form a molded body.
Optional components include, for example, a crosslinking agent, a crosslinking aid, a filler, a stabilizer, a colorant, an antioxidant, a processing aid, a lubricant, a lubricant, a flame retardant, an antistatic agent, a pigment, a reinforcing agent, and a vulcanization. Examples include accelerators. Any one of these optional components may be used alone, or two or more thereof may be used in combination.
Examples of the molding method of the fluorinated elastic copolymer or the fluorinated elastic copolymer composition include injection molding, extrusion molding, coextrusion molding, blow molding, compression molding, inflation molding, transfer molding, and calendar molding. .
Crosslinking may be performed together with or after the molding of the fluorinated elastic copolymer or the fluorinated elastic copolymer composition. The crosslinking method is not particularly limited. For example, a chemical crosslinking method using an organic peroxide such as α, α′-bis (t-butylperoxy) -p-diisopropylbenzene, dicumyl peroxide as a crosslinking agent, X Examples include an irradiation crosslinking method using ionizing radiation such as rays, γ rays, electron rays, proton rays, deuteron rays, α rays, and β rays.

The fluorinated elastic copolymer of the present invention is excellent in adhesion to metal. Therefore, the fluorinated elastic copolymer of the present invention can be suitably used for producing a structure in which a molded body of a fluorinated elastic copolymer or a fluorinated elastic copolymer composition and a metal are combined. In the molded body constituting such a structural body, the molded body of the fluorinated elastic copolymer of the present invention and the metal adhere well.
In addition, the fluorinated elastic copolymer of the present invention is excellent in adhesion to a resin. Therefore, the fluorinated elastic copolymer of the present invention can also be used to produce a structure in which a molded product of a fluorinated elastic copolymer or a fluorinated elastic copolymer composition and a resin molded product are combined. In the molded body constituting such a structural body, the molded body of the fluorinated elastic copolymer of the present invention and the resin molded body are in good contact.
Examples of the resin constituting the resin molded body include polyacetal, polyamide, polycarbonate, polybutylene terephthalate, polyphenylene ether, polysulfone, polyether ether ketone, polyimide, polyether imide and the like.
Specific examples of the use of the fluorinated elastic copolymer of the present invention include sealing materials such as gaskets, packings, oil seals, and bearing seals. In addition to the sealing material, it can also be used as various rubber products, such as diaphragms, O-rings, tubes, hoses, bushes, cushions, various rubber rolls, and the like. Moreover, it can utilize also as a laminated tube, a hose, a sheet | seat etc. by lamination | stacking with resin.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
Measurement and evaluation in Examples and Comparative Examples were performed by the following methods.

[Copolymerization composition of fluorinated elastic copolymer]
The latex of the fluorinated elastic copolymer is added to a 1.5% by mass aqueous solution of calcium chloride, salted out to agglomerate and precipitate the fluorinated elastic copolymer, and the precipitated aggregate is washed with ion-exchanged water. And dried in an oven at 100 ° C. for 15 hours to obtain a fluorinated elastic copolymer.
The copolymer composition of the obtained fluorinated elastic copolymer was measured by ¹⁹ F-NMR and ¹ H-NMR. From the results, the molar ratio [(A) / (C)] of the structural unit (A) to the structural unit (C) in the fluorinated elastic copolymer, with respect to the total of all the structural units other than the structural unit (B). The molar ratio of the structural unit (B) was calculated.

[Storage modulus of fluorinated elastic copolymer]
A 1.5 mass% aqueous calcium chloride solution is added to the latex of the fluorinated elastic copolymer, salted out to agglomerate and precipitate the fluorinated elastic polymer, and the precipitated agglomerate is washed with ion-exchanged water. Dry in an oven at 15 ° C. for 15 hours. The fluorine-containing elastic polymer obtained by drying was used for measuring the storage elastic modulus G ′. The storage elastic modulus G ′ (kPa) of the fluorinated elastic polymer is 100% at a temperature of 0.83 Hz in accordance with ASTM D6204, and “Rubber Process Analyzer (RPA-2000)” manufactured by Alpha Technologies is used. And measured.

[Average particle diameter of fluorinated elastic copolymer]
In the present invention, the average particle size of the particles of the fluorinated elastic copolymer contained in the latex is the scattering intensity distribution by the dynamic light scattering method using ELS-8000 of a laser zeta electrometer manufactured by Otsuka Electronics Co., Ltd. It is a value measured from

[Adhesion (peel strength)]
A latex of the fluorinated elastic copolymer and a carboxymethyl cellulose solution (solid content: 2% by mass) were mixed so that the mass ratio in terms of the solid content was 1: 1 to prepare a mixed solution. The obtained mixed liquid was spread on a copper foil (width 20 mm × length 150 mm) so that the thickness after drying was 70 μm, and dried on a hot plate at 80 ° C. Thus, a laminate in which the copper foil and the fluorine-containing elastic copolymer sheet were laminated was obtained.
After drying, along the length direction of the obtained laminate, the strength (N) when the sheet of the fluorinated elastic copolymer is peeled in the direction of 180 ° C. at a speed of 50 mm / min is measured five times. The average value was defined as peel strength. It shows that it is excellent in the adhesiveness (adhesion) of a fluorine-containing elastic copolymer and a metal, so that this value is large.

<Example 1: Production of fluorinated elastic copolymer A>
Using a redox polymerization initiator, a fluorinated elastic copolymer A was produced by the following procedure.
That is, after degassing the inside of a stainless steel pressure-resistant reactor having an internal volume of 3200 mL equipped with an anchor blade for stirring, 1700 g of ion-exchange water, 17.7 g of sodium lauryl sulfate as an emulsifier, pH 60 g of disodium hydrogen phosphate 12 hydrate and 0.9 g of sodium hydroxide were added as regulators, and 8.4 g of ammonium persulfate (1 hour half-life temperature 82 ° C.) as an initiator. Further, 0.4 g of ethylenediaminetetraacetic acid disodium salt dihydrate (hereinafter referred to as EDTA) and 0.3 g of ferrous sulfate heptahydrate were dissolved in 200 g of ion-exchanged water as a redox catalyst. Aqueous solution was added to the reactor. At this time, the pH of the aqueous medium in the reactor was 9.2.
Next, at 25 ° C., a monomer mixed gas of TFE / P = 88/12 (molar ratio) was injected so that the internal pressure of the reactor was 2.50 MPaG. While rotating the anchor blade at 300 rpm, 47 g of an aqueous solution of sodium hydroxymethanesulfinate dihydrate (hereinafter referred to as Rongalite) adjusted to pH 10.0 with sodium hydroxide was added to the reactor to carry out the polymerization reaction. Started.
The polymerization is continued while maintaining the polymerization temperature at 40 ° C., and the pressure in the reactor decreases with the progress of the polymerization. Therefore, when the internal pressure of the reactor drops to 2.49 MPaG, TFE / P = 56/44 (Molar ratio) monomer mixed gas was injected under its own pressure, and the internal pressure of the reactor was increased to 2.51 MPaG. This operation was repeated, and the internal pressure of the reactor was maintained at 2.49 to 2.51 MPaG, and the polymerization reaction was continued.

Subsequently, when the pressure of the TFE / P monomer mixture gas reached 20 g, 2 mL of the tert-butanol solution of HBVE (HBVE / tert-butanol = 11/57 (mass ratio)) was added to the reactor. It was press-fitted with nitrogen back pressure. Thereafter, 2 mL of the tert-butanol solution of HBVE was injected every 20 g until the injection amount of the TFE / P monomer mixed gas was 480 g, and a total of 48 mL was injected. When the total amount of the TFE / P monomer mixed gas injected reached 500 g, the internal temperature of the reactor was cooled to 10 ° C. to obtain a latex of fluorinated elastic copolymer A. The polymerization time was 4.5 hours. The content of the fluorinated elastic copolymer A in the latex was 21% by mass.
Further, HBVE remaining in the latex was not detected by gas chromatography. From this, it can be inferred that all the HBVE supplied into the reactor has reacted.

In the copolymer composition of the fluorinated elastic copolymer A, the molar ratio [(A) / (C)] of the structural unit (A) (unit based on TFE) and the structural unit (C) (unit based on P) is The molar ratio of the structural unit (B) to the total of all the structural units other than the structural unit (B) (unit based on HBVE) (that is, the total of the structural unit (A) and the structural unit (C)). [(B) / {(A) + (C)}] was 0.5 / 100.
The physical properties (storage modulus G ′ and latex particle diameter) of the fluorinated elastic copolymer A are combined with the physical properties of the fluorinated elastic copolymers B to F obtained in Examples 2 to 5 and Comparative Example 1. Table 1 shows.

<Example 2: Production of fluorinated elastic copolymer B>
A fluorinated elastic copolymer B was obtained in the same manner as in Example 1 except that the amount of HBVE added in Example 1 was changed.
That is, 2 mL of HBVE tert-butanol solution (HBVE / tert-butanol = 6/52 (mass ratio)) was added to the reactor for every 20 g of TFE / P monomer mixed gas injected into the reactor. A total of 22 mL was injected with nitrogen back pressure.
The polymerization time was 4.4 hours. The content of the fluorinated elastic copolymer B in the latex was 21% by mass.
In the copolymer composition of the fluorinated elastic copolymer B, the molar ratio [(A) / (C)] of the structural unit (A) (unit based on TFE) and the structural unit (C) (unit based on P) is The molar ratio of the structural unit (B) to the total of all the structural units other than the structural unit (B) (unit based on HBVE) (that is, the total of the structural unit (A) and the structural unit (C)). [(B) / {(A) + (C)}] was 0.2 / 100.

<Example 3: Production of fluorinated elastic copolymer C>
A latex of fluorinated elastic copolymer C was obtained in the same manner as in Example 1 except that HBVE was changed to allyl glycidyl ether.
The polymerization time was 4.5 hours. The content of the fluorinated elastic copolymer C in the latex was 22% by mass.
In the copolymer composition of the fluorinated elastic copolymer C, the molar ratio [(A) / (C)] of the structural unit (A) (unit based on TFE) and the structural unit (C) (unit based on P) is Of the structural unit (B) with respect to the total of all the structural units other than the structural unit (B) (unit based on allyl glycidyl ether) (that is, the total of the structural unit (A) and the structural unit (C)). The molar ratio [(B) / {(A) + (C)}] was 0.2 / 100.

<Example 4: Production of fluorinated elastic copolymer D>
A latex of fluorinated elastic copolymer D was obtained in the same manner as in Example 1 except that HBVE was changed to 3-allyloxy-1,2-propanediol.
The polymerization time was 4.5 hours. The content of the fluorinated elastic copolymer D in the latex was 21% by mass.
In the copolymer composition of the fluorinated elastic copolymer D, the molar ratio [(A) / (C)] of the structural unit (A) (unit based on TFE) and the structural unit (C) (unit based on P) is 56/44, and the total of all the structural units other than the structural unit (B) (units based on 3-allyloxy-1,2-propanediol) (that is, the total of the structural unit (A) and the structural unit (C)) The molar ratio [(B) / {(A) + (C)}] of the structural unit (B) to 0.5 / 100.

<Example 5: Production of fluorinated elastic copolymer E>
A fluorinated elastic copolymer E was obtained in the same manner as in Example 1 except that the amount of HBVE added in Example 1 was changed.
That is, 2 mL of HBVE tert-butanol solution (HBVE / tert-butanol = 33/57 (mass ratio)) was added to the reactor for every 20 g of TFE / P monomer mixed gas injected into the reactor. A total of 48 mL was injected with nitrogen back pressure.
The polymerization time was 5 hours. The content of the fluorinated elastic copolymer E in the latex was 23% by mass.
In the copolymer composition of the fluorinated elastic copolymer E, the molar ratio [(A) / (C)] of the structural unit (A) (unit based on TFE) and the structural unit (C) (unit based on P) is The molar ratio of the structural unit (B) to the total of all the structural units other than the structural unit (B) (unit based on HBVE) (that is, the total of the structural unit (A) and the structural unit (C)). [(B) / {(A) + (C)}] was 3.0 / 100.

<Comparative Example 1: Production of fluorinated elastic copolymer F>
A latex of fluorinated elastic copolymer F was obtained in the same manner as in Example 1 except that HBVE was not added.
The polymerization time was 4 hours. The content of the fluorinated elastic copolymer F in the latex was 22% by mass.
In the copolymer composition of the fluorinated elastic copolymer E, the molar ratio [(A) / (C)] of the structural unit (A) (unit based on TFE) and the structural unit (C) (unit based on P) is 56/44.

As shown in the above results, the fluorinated elastic copolymers A to E having the structural unit (B) based on the monomer (b) contain no structural unit (B) based on the monomer (b). Compared with Fluoroelastic Copolymer F, the adhesion to metal was excellent.
Moreover, from the measurement result of the storage elastic modulus G ′, it was confirmed that the fluorinated elastic copolymers A to E had the same or more flexibility as the fluorinated elastic copolymer F.

Since the fluorinated elastic copolymer of the present invention is excellent in adhesion to metals, resins, etc. and has flexibility, sealing materials such as gaskets, packing, oil seals, bearing seals, diaphragms, O-rings, tubes, Various rubber products such as hoses, bushes, cushions, various rubber rolls, and laminated with resin can be used as laminated tubes, hoses, sheets and the like.
It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2014-012809 filed on January 27, 2014 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (8)

It has a structural unit (A) based on the following monomer (a), a structural unit (B) based on the following monomer (b), and a structural unit (C) based on the following monomer (c). A fluorine-containing elastic copolymer characterized by
Monomer (a): At least one selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, and perfluoro (alkyl vinyl ether) represented by the following formula (I).
CF ₂ = CF—O—R ^f (I)
Here, ^Rf represents a C1-C8 perfluoroalkyl group or a C2-C8 perfluoro (alkoxyalkyl) group.
Monomer (b): At least one selected from the group consisting of a compound represented by the following formula (II) and a compound represented by the following formula (III).

Here, n is 0 or 1, m is an integer of 0 to 2, R ¹ is a (m + 2) -valent saturated hydrocarbon group having 1 to 8 carbon atoms, or 2 carbon atoms having an etheric oxygen atom. Represents an (m + 2) -valent saturated hydrocarbon group having ˜8, R ² is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a divalent saturated carbon atom having 2 to 8 carbon atoms having an etheric oxygen atom Represents a hydrogen group, and R ³ represents an alkylene group having 1 to 8 carbon atoms or an alkylene group having 2 to 8 carbon atoms having an etheric oxygen atom.
Monomer (c): At least one selected from the group consisting of propylene and ethylene. In the formula (II), R ¹ is an alkylene group having 1 or 2 carbon atoms, or an alkylene group having 2 to 6 carbon atoms having 1 to 3 etheric oxygen atoms. In the formula (III), R ³ The fluorine-containing elastic copolymer according to claim 1, wherein is an alkylene group having 1 to 4 carbon atoms.   The monomer (b) is at least one selected from the group consisting of 4-hydroxybutyl vinyl ether, allyl glycidyl ether, and 3-allyloxy-1,2-propanediol. Fluorine-containing elastic copolymer.   Content of the said structural unit (B) is 0.0005 / 100-10.0 / 100 by molar ratio with respect to the sum total of all the structural units except the said structural unit (B). The fluorinated elastic copolymer according to any one of the above.   The fluorinated elastic copolymer according to any one of claims 1 to 4, wherein the monomer (a) is tetrafluoroethylene and the monomer (c) is propylene.   The molar ratio [(C) / (A)] of the structural unit (A) and the structural unit (C) is 20/80 to 70/30, according to any one of claims 1 to 5. Fluorine-containing elastic copolymer. It is a manufacturing method of the fluorinated elastic copolymer as described in any one of Claims 1-6,
A monomer component containing the monomer (a), the monomer (b), and the monomer (c) is polymerized in the presence of an aqueous medium, an emulsifier, and a radical polymerization initiator. A method for producing a fluorinated elastic copolymer. A reactor charged with an aqueous medium, an emulsifier, and a radical polymerization initiator is supplied with a part of the monomer component to be polymerized, and after the polymerization reaction is started, the remainder of the monomer component is determined according to the progress of the polymerization reaction. To advance the polymerization by supplying
The method for producing a fluorinated elastic copolymer according to claim 7, wherein the whole amount of the monomer (b) is supplied to the reactor as the remainder of the monomer component.