WO2022071232A1 - 含フッ素重合体の製造方法、含フッ素重合体水性分散液および重合体組成物 - Google Patents
含フッ素重合体の製造方法、含フッ素重合体水性分散液および重合体組成物 Download PDFInfo
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- WO2022071232A1 WO2022071232A1 PCT/JP2021/035415 JP2021035415W WO2022071232A1 WO 2022071232 A1 WO2022071232 A1 WO 2022071232A1 JP 2021035415 W JP2021035415 W JP 2021035415W WO 2022071232 A1 WO2022071232 A1 WO 2022071232A1
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- Prior art keywords
- polymer
- fluorine
- mass
- tetrafluoroethylene
- equation
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 198
- 239000011737 fluorine Substances 0.000 title claims abstract description 193
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 46
- 239000006185 dispersion Substances 0.000 title claims description 62
- 239000000203 mixture Substances 0.000 title claims description 31
- 239000007788 liquid Substances 0.000 title description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 111
- 150000001875 compounds Chemical class 0.000 claims abstract description 95
- 239000000178 monomer Substances 0.000 claims abstract description 88
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 19
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 62
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 30
- 125000005843 halogen group Chemical group 0.000 claims description 27
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 238000005481 NMR spectroscopy Methods 0.000 description 2
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 235000014786 phosphorus Nutrition 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
- C08F14/22—Vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
- C08F14/24—Trifluorochloroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
- C08F14/26—Tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F118/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F118/02—Esters of monocarboxylic acids
- C08F118/12—Esters of monocarboxylic acids with unsaturated alcohols containing three or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
Definitions
- the present invention relates to a method for producing a fluorinated polymer, an aqueous dispersion containing a fluorinated polymer, and a polymer composition.
- Fluorine-containing polymers such as ethylene / tetrafluoroethylene-based copolymers and tetrafluoroethylene / perfluoroalkyl vinyl ether-based copolymers are excellent in heat resistance, chemical resistance, flame retardancy, weather resistance, etc. It is used in the industrial field of.
- Examples of the method for producing a fluorine-containing polymer include a method of emulsion-polymerizing a fluorine-containing monomer in an aqueous medium using a fluorine-containing emulsifier (see Patent Document 1).
- Patent Document 1 uses an aqueous medium and therefore has a small environmental load, but if a large amount of an emulsifier, which is an essential component, remains in the aqueous dispersion obtained by polymerization, it may be necessary to remove the emulsifier depending on the application.
- a fluoropolymer is produced by polymerizing at least one fluorine-containing monomer selected from tetrafluoroethylene, chlorotrifluoroethylene and vinylidene fluoride underneath (however, when the tetrafluoroethylene is polymerized). Tetrafluoroethylene is copolymerized so that the content of the unit based on tetrafluoroethylene in the fluoropolymer is less than 99% by mass with respect to all the units of the fluoropolymer). Method for producing polymer.
- X and Y independently represent a hydrogen atom, a halogen atom or a methyl group.
- R 1 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.
- R 2 represents an alkyl group, an alkyl group in which at least one of the alkyl groups -CH 2- is replaced with -CO-, or a group represented by the following formula (3).
- R 3 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or -CO-OCH 3 .
- R4 represents an alkyl group.
- L represents an alkylene group.
- Z represents -CO-O- * or -O-CO- *. However, * represents the connection position with R4 .
- m represents 0 or 1
- n represents an integer of 1 or more.
- Equation (3): -CO-CR 1 CXY In equation (3), X, Y and R 1 are the same as the definitions of X, Y and R 1 in equation (1), respectively. [2] The production method according to [1], wherein the abundance of the specific polymer is 0.0001 to 1.0 part by mass with respect to 100 parts by mass of the aqueous medium.
- An aqueous medium in which a specific polymer is present is obtained by polymerizing at least one specific compound selected from the compound represented by the following formula (1) and the compound represented by the following formula (2) in an aqueous medium. Then, in an aqueous medium in which the specific polymer is present, at least one fluorine-containing monomer selected from tetrafluoroethylene, chlorotrifluoroethylene and vinylidene fluoride is polymerized to produce a fluorine-containing polymer. (However, when the tetrafluoroethylene is polymerized, the content of the unit based on tetrafluoroethylene in the fluoropolymer is less than 99% by mass with respect to all the units of the fluoropolymer.
- X and Y independently represent a hydrogen atom, a halogen atom or a methyl group.
- R 1 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.
- R 2 represents an alkyl group, an alkyl group in which at least one of the alkyl groups -CH 2- is replaced with -CO-, or a group represented by the following formula (3).
- R 3 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or -CO-OCH 3 .
- R4 represents an alkyl group.
- L represents an alkylene group.
- Z represents -CO-O- * or -O-CO- *. However, * represents the connection position with R4 .
- m represents 0 or 1
- n represents an integer of 1 or more.
- Equation (3): -CO-CR 1 CXY
- X, Y and R 1 are the same as the definitions of X, Y and R 1 in equation (1), respectively.
- the production method according to [3], wherein the aqueous medium in which the specific polymer is present is an aqueous medium used in the production of the specific polymer to lead to the presence of the specific polymer.
- the abundance of the specific polymer in the polymerization of the fluorine-containing monomer is 0.0001 to 1.0 part by mass with respect to 100 parts by mass of the aqueous medium. The manufacturing method described.
- tetrafluoroethylene is polymerized, the content of the unit based on tetrafluoroethylene in the fluoroethylene-containing polymer becomes all the units of the fluoropolymer.
- tetrafluoroethylene is copolymerized so as to be less than 99% by mass.
- a fluorinated polymer having a unit based on an aqueous medium and at least one fluorinated monomer selected from tetrafluoroethylene, chlorotrifluoroethylene and vinylidene fluoride (provided that the fluorinated polymer contains a unit).
- the content of the unit based on tetrafluoroethylene in the fluorine-containing polymer is less than 99% by mass with respect to all the units of the fluorine-containing polymer.
- a specific polymer containing a seed unit which comprises a specific polymer contained as particles in the aqueous medium or contained in particles containing the fluorine-containing polymer, and substantially contains an emulsifier.
- X and Y independently represent a hydrogen atom, a halogen atom or a methyl group.
- R 1 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.
- R 2 represents an alkyl group, an alkyl group in which at least one of the alkyl groups -CH 2- is replaced with -CO-, or a group represented by the following formula (3).
- R 3 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or -CO-OCH 3 .
- R4 represents an alkyl group.
- L represents an alkylene group.
- Z represents -CO-O- * or -O-CO- *. However, * represents the connection position with R4 .
- m represents 0 or 1
- n represents an integer of 1 or more.
- Equation (3): -CO-CR 1 CXY In equation (3), X, Y and R 1 are the same as the definitions of X, Y and R 1 in equation (1), respectively.
- a fluorinated polymer having a unit based on an aqueous medium and at least one fluorinated monomer selected from tetrafluoroethylene, chlorotrifluoroethylene and vinylidene fluoride (provided that the fluorinated polymer contains a unit).
- the unit based on tetrafluoroethylene is contained, the content of the unit based on tetrafluoroethylene in the fluorine-containing polymer is less than 99% by mass with respect to all the units of the fluorine-containing polymer).
- a fluorine-containing polymer aqueous dispersion containing particles having a volume-based cumulative 50% diameter of 20 to 3000 nm and a polyalkylene oxide compound and substantially free of emulsifiers.
- a fluoropolymer having a unit based on at least one fluorine-containing monomer selected from tetrafluoroethylene, chlorotrifluoroethylene and vinylidene fluoride (provided that the tetrafluoroethylene is contained in the fluoropolymer.
- the unit based on the above is included, the content of the unit based on tetrafluoroethylene in the fluoropolymer is less than 99% by mass with respect to all the units of the fluoropolymer).
- X and Y independently represent a hydrogen atom, a halogen atom or a methyl group.
- R 1 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.
- R 2 represents an alkyl group, an alkyl group in which at least one of the alkyl groups -CH 2- is replaced with -CO-, or a group represented by the following formula (3).
- R 3 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or -CO-OCH 3 .
- R4 represents an alkyl group.
- L represents an alkylene group.
- Z represents -CO-O- * or -O-CO- *. However, * represents the connection position with R4 .
- m represents 0 or 1
- n represents an integer of 1 or more.
- Equation (3): -CO-CR 1 CXY In equation (3), X, Y and R 1 are the same as the definitions of X, Y and R 1 in equation (1), respectively.
- a fluorine-containing polymer having a unit based on at least one fluorine-containing monomer selected from tetrafluoroethylene, chlorotrifluoroethylene and vinylidene fluoride (however, the tetrafluoroethylene in the fluorine-containing polymer).
- fluorine-containing monomer selected from tetrafluoroethylene, chlorotrifluoroethylene and vinylidene fluoride (however, the tetrafluoroethylene in the fluorine-containing polymer).
- the unit based on is contained, the content of the unit based on tetrafluoroethylene in the fluorine-containing polymer is less than 99% by mass with respect to all the units of the fluorine-containing polymer) and polyalkylene.
- a polymer composition containing an oxide compound and substantially free of emulsifiers.
- a fluorine-containing polymer that does not require an emulsifier while using an aqueous medium having a small environmental load.
- a fluorine-containing polymer aqueous dispersion and a polymer composition can also be provided.
- the meanings of the terms in the present invention are as follows.
- the content (% by mass) of each unit with respect to all the units contained in the polymer is obtained by analyzing the polymer by the solid-state nuclear magnetic resonance spectroscopy (NMR) method, and can be estimated from the amount of each monomer charged. ..
- NMR solid-state nuclear magnetic resonance spectroscopy
- the content of each unit calculated from the charged amount of each monomer is substantially the same as the actual content of each unit.
- “Volume-based cumulative 50% diameter” is the point where the particle size distribution is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the particle population as 100%, and the cumulative volume is 50% on the cumulative curve. Particle size.
- D50 particle size
- the first embodiment of the method for producing a fluorine-containing polymer of the present invention is a unit based on the compound represented by the following formula (1) (hereinafter, also referred to as “compound (1)”) and the following formula (2).
- compound (1) the compound represented by the following formula (1)
- compound (2) the compound represented by the following formula (2)
- tetrafluoroethylene and chlorotrifluoro tetrafluoroethylene and chlorotrifluoro in an aqueous medium.
- This is a method for polymerizing at least one fluorine-containing monomer (hereinafter, also referred to as “specific fluorine-containing monomer”) selected from ethylene and vinylidene fluoride.
- tetrafluoroethylene when polymerized, tetrafluoroethylene is added so that the content of the unit based on tetrafluoroethylene in the fluorine-containing polymer is less than 99% by mass with respect to all the units of the fluorine-containing polymer. Copolymerize.
- a specific polymer obtained by separately polymerizing may be used, the specific polymer is polymerized in an aqueous medium, and the specific polymer is continuously contained in the same polymerization system. Fluorine monomers may be polymerized.
- Subsequent polymerization in the same polymerization system means using an aqueous medium used in the production of the specific polymer that has led to the presence of the specific polymer, and the specific fluorine-containing monomer in the aqueous medium in which the specific polymer is present. It means to polymerize.
- a commercially available product may be used as the specific polymer obtained by separately polymerizing.
- a specific polymer is present by polymerizing at least one specific compound selected from the compound (1) and the compound (2) in an aqueous medium.
- a method of obtaining an aqueous medium and then polymerizing the specific fluorine-containing monomer in the aqueous medium in which the specific polymer is present to produce the fluorine-containing polymer is preferable.
- the step of obtaining an aqueous medium in which the specific polymer of the first stage is present is hereinafter referred to as "step 1”
- the step of producing the fluorine-containing polymer of the latter stage is hereinafter referred to as "step 2”.
- the polymerization of the compound (1) in the step 1 and the polymerization of the specific fluorine-containing monomer in the step 2 are carried out in the presence of a polymerization initiator, respectively.
- a polymerization initiator a water-soluble polymerization initiator is preferable.
- Step 1 At least one specific compound selected from compound (1) and compound (2) is used.
- the specific compound may be used in combination of two or more kinds.
- X and Y independently represent a hydrogen atom, a halogen atom or a methyl group.
- R 1 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.
- R 2 is represented by an alkyl group, an alkyl group in which at least one of the alkyl groups -CH 2- is replaced with -CO- (hereinafter, also referred to as "substituted alkyl group”) or the following formula (3).
- R 3 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or -CO-OCH 3 .
- R4 represents an alkyl group.
- L represents an alkylene group.
- Z represents -CO-O- * or -O-CO- * (where * represents the bonding position with R4 ).
- m represents 0 or 1
- n represents an integer of 1 or more.
- Equation (3): -CO-CR 1 CXY In equation (3), X, Y and R 1 are the same as the definitions of X, Y and R 1 in equation (1), respectively.
- each group in the formula (1) is preferably shown below. It is preferable that X and Y are hydrogen atoms, fluorine atoms or chlorine atoms independently of each other, and it is more preferable that both are hydrogen atoms.
- R 1 an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
- L an alkylene group having 2 to 6 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an ethylene group is further preferable.
- the alkylene group of L may be linear or branched.
- alkyl group of R2 an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
- the number of groups represented by —CO— in the substituted alkyl group of R2 is preferably 1 to 3, and more preferably 2.
- the position of -CO- in the substituted alkyl group may be the terminal in the substituted alkyl group or may be between -CH 2- and -CH 2- .
- substituted alkyl group of R 2 -CO-CH 2 -CO-CH 3 is preferable.
- X, Y and R 1 in the group represented by the formula (3) of R 2 are the same as the definitions of X, Y and R 1 in the formula (1), respectively, and the preferred embodiments are also the same.
- n 1 to 100 is preferable, and 1 to 50 is more preferable.
- X, Y, R 1 , L and n are the same as the definitions of X, Y, R 1 , L and n in formula (1), respectively. ..
- R 2a represents an alkyl group.
- R 2b represents a substituted alkyl group.
- each group in the formula (2) is preferably shown below.
- the preferred ranges of X and Y are the same as the preferred ranges of X and Y in the formula (1), respectively.
- R 3 an alkyl group having 1 to 3 carbon atoms or -CO-OCH 3 is preferable.
- Z —O—CO— * is preferable.
- R4 an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
- m is preferably 0.
- X, Y and R 4 are the same as the definitions of X, Y and R 4 in formula (2), respectively.
- R 3a represents an alkyl group having 1 to 3 carbon atoms.
- aqueous medium examples include water and water and a mixture of water and a water-soluble organic solvent.
- water-soluble organic solvent examples include tert-butanol, propylene glycol and dipropylene glycol.
- concentration of the water-soluble organic solvent is preferably 10% by mass or less.
- the aqueous medium is preferably water only.
- Water-soluble polymerization initiator As the water-soluble polymerization initiator, a water-soluble radical initiator and a water-soluble redox catalyst are preferable.
- As the water-soluble radical initiator persulfates such as ammonium persulfate and potassium persulfate, water-soluble organic peroxides such as disuccinic acid peroxide, bisglutaric acid peroxide, and tert-butyl hydroperoxide are preferable.
- water-soluble redox catalyst examples include bromic acid or a salt thereof, chloric acid or a salt thereof, persulfate or a salt thereof, permanganic acid or a salt thereof, an oxidizing agent such as hydrogen peroxide, sulfurous acid or a salt thereof, and hydrogen sulfite.
- a combination thereof with a reducing agent such as a salt thereof, thiosulfate or a salt thereof, an organic acid, an inorganic salt or the like is preferable.
- a reducing agent such as a salt thereof, thiosulfate or a salt thereof, an organic acid, an inorganic salt or the like is preferable.
- the persulfate potassium persulfate and ammonium persulfate are preferable.
- As the sulfite sodium sulfite is preferable.
- the inorganic salt examples include a combination of a sulfate anion, a sulfite anion or a chloride anion and a metal ion.
- the metal ion examples include transition metal ions, manganese, iron, cobalt, nickel, copper, zinc, cerium and silver ions, and iron ions are preferable.
- Iron (II) sulfate is preferable as the inorganic salt.
- a water-soluble redox catalyst is preferable, a combination of potassium persulfate and sodium sulfite, a combination of potassium persulfate, sodium sulfite and an inorganic salt is preferable, and potassium persulfate and sodium sulfite are used. More preferred are combinations and combinations of potassium persulfate, sodium sulfite and iron (II) sulfate. Since the polymerization of the specific compound is easy to proceed, the pH of the reaction system is preferably 3 to 10, preferably 6 to 8. Sulfites such as sodium sulfite, ammonia, sodium hydroxide, hydrochloric acid and the like may be added as necessary for adjustment.
- Two or more kinds of water-soluble polymerization initiators may be used in combination.
- the entire amount of the water-soluble polymerization initiator may be charged into the reaction system before the polymerization reaction is started, or may be continuously or intermittently added to the reaction system.
- the amount of the specific compound used is preferably 0.0001 to 1.0 part by mass, more preferably 0.001 to 0.5 part by mass, based on 100 parts by mass of the aqueous medium. Within this range, it is possible to prevent a decrease in the polymerization rate and reduce the amount of the specific polymer mixed in the fluorine-containing polymer when the fluorine-containing polymer is produced in the step 2.
- As a method for charging the specific compound it is preferable to charge the entire amount into the reaction system before starting the polymerization reaction, which is the initial batch addition.
- the amount of the water-soluble polymerization initiator used is preferably 0.1 to 50.0 mol, more preferably 0.1 to 40.0 mol, and 0.5 to 10.0 mol with respect to 1 mol of the specific compound. More preferred.
- the polymerization temperature of the specific compound is preferably 10 to 95 ° C, more preferably 50 to 90 ° C.
- the polymerization time is preferably 5 to 400 minutes, more preferably 5 to 300 minutes in the case of batch treatment.
- the pressure condition at the time of polymerization is preferably a reduced pressure condition or a normal pressure condition.
- an aqueous dispersion containing the specific polymer can be obtained.
- the specific polymer is in the form of particles and is uniformly dispersed in the aqueous medium.
- the aqueous dispersion is colloidal.
- the particles of the specific polymer (hereinafter, also referred to as “specific particles”) adsorb the specific fluorine-containing monomer at the hydrophobic portion and take in the specific fluorine-containing monomer during the polymerization of the specific fluorine-containing monomer described later. It is presumed that the specific fluorine-containing monomer is polymerized in the particles of the specific particles by solubilizing the polymer and adding an initiator thereof.
- the specific particles contribute to dispersion stabilization in an aqueous medium and an organic solvent.
- the D50 of the specific particles is preferably 10 to 1000 nm, more preferably 10 to 300 nm, still more preferably 10 to 200 nm, and particularly preferably 10 to 150 nm.
- the specific particles are composed of a specific polymer containing a unit based on the specific compound (a unit based on the compound (1) and a unit based on the compound (2)).
- the content of the unit based on the specific compound in the specific polymer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, based on all the units of the specific polymer.
- the upper limit is 100% by mass.
- a fluorine-containing polymer aqueous dispersion containing 0.0001 to 1.0 part by mass of specific particles having a D50 of 10 to 1000 nm with respect to 100 parts by mass of the aqueous medium.
- the specific particles are preferably contained in an amount of 0.0001 to 0.5 parts by mass, more preferably 0.0005 to 0.1 parts by mass with respect to 100 parts by mass of the aqueous medium.
- Step 2 At least one fluorine-containing monomer selected from tetrafluoroethylene, chlorotrifluoroethylene and vinylidene fluoride in the aqueous medium in which the specific polymer is present, which was obtained in step 1, is specified.
- This is a process for producing a fluorine-containing polymer, which polymerizes a fluorine-containing monomer).
- the polymerization of the specific fluorine-containing monomer is preferably carried out using a water-soluble polymerization initiator, and examples of the water-soluble polymerization initiator include the water-soluble polymerization initiator described in Step 1.
- the fluorine-containing polymer is a tetrafluoroethylene-based polymer having a unit based on tetrafluoroethylene (TFE) (hereinafter, also referred to as “TFE unit”), polyvinylidene fluoride (hereinafter, also referred to as “PVdF”), and poly.
- TFE tetrafluoroethylene
- PVdF polyvinylidene fluoride
- poly examples thereof include chlorotrifluoroethylene and a copolymer of ethylene and chlorotrifluoroethylene. Of these, a tetrafluoroethylene polymer is preferable.
- the fluorine-containing polymer may have a unit based on a monomer other than the specific fluorine-containing monomer.
- monomers include hexafluoropropylene (hereinafter, also referred to as “HFP”), perfluoro (alkyl vinyl ether) (hereinafter, also referred to as “PAVE”), and fluoroalkylethylene (hereinafter, also referred to as “PAVE”) as fluorine-containing monomers. , Also referred to as "FAE”.).
- examples of other monomers include ethylene, propylene, vinyl chloride, vinylidene chloride, and vinyl fluoride. Further, as another monomer, a monomer having an oxygen-containing polar group can also be mentioned.
- an acid anhydride residue As the oxygen-containing polar group, an acid anhydride residue, a hydroxyl group, a carbonyl group-containing group, an acetal group, and an oxycycloalkhan group are preferable, and an acid anhydride residue is more preferable.
- a monomer having a cyclic acid anhydride residue As the monomer having an acid anhydride residue, a monomer having a cyclic acid anhydride residue is preferable, and itaconic anhydride (hereinafter, also referred to as “IAH”), citraconic anhydride, 5-norbornen-2. , 3-Dicarboxylic acid anhydride (also known as anhydrous hymic acid; hereinafter also referred to as "NAH”) and maleic anhydride are more preferable.
- tetrafluoroethylene polymer examples include a copolymer of TFE and PAVE, a polymer of TFE and HFP (hereinafter, also referred to as “FEP”), and a polymer of TFE and ethylene (hereinafter, “ETFE”). ”), A copolymer of TFE and propylene, and a polymer of TFE and vinylidene fluoride.
- FEP polymer of TFE and HFP
- ETFE polymer of TFE and ethylene
- TFE polymer of TFE and ethylene
- the TFE is copolymerized so that the content of the TFE unit in the fluorine-containing polymer is less than 99% by mass with respect to all the units of the fluorine-containing polymer.
- the unit when the unit is not based on at least one fluorine-containing monomer selected from chlorotrifluoroethylene and vinylidene fluoride and contains TFE units, the content of TFE units is the total unit of the fluorine-containing polymer. On the other hand, it is preferably 10% by mass or more and less than 99% by mass.
- the tetrafluoroethylene polymer does not contain the following specific high heat resistant polymer. Specified high heat resistant polymer: In a differential scanning calorimeter, the first endothermic peak due to a temperature rise of 10 ° C / min is at least 330 ° C or higher, and the endothermic peak after the first endothermic peak is at least 320 ° C or higher. Combined.
- ETFE tetrafluoroethylene polymer
- PAVE and FEP a copolymer of TFE and PAVE and FEP
- ETFE and PFA described later are more preferable.
- the FEP the FEP in which the ratio of the HFP unit to the total of the TFE unit and the HFP unit is 1 to 15 mol% is preferable, and the FEP in which the ratio of the HFP unit is 5 to 13 mol% is more preferable.
- ETFE has a TFE unit and a unit based on ethylene (hereinafter, also referred to as "E unit").
- E unit ethylene
- the ratio of E units to the total of E units and TFE units is preferably 20 to 70 mol%, more preferably 25 to 60 mol%, and 35 to 55 mol%. Is even more preferable.
- the total ratio of E units and TFE units to all the units constituting ETFE is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more. It is also preferable to have a FAE unit in addition to the E unit and the TFE unit.
- the ratio of FAE units to the total of E units and TFE units is preferably 0.1 to 10 mol%, more preferably 0.1 to 5 mol%, still more preferably 0.2 to 4 mol%. Further, it is also preferable to have a monomer unit having an oxygen-containing polar group in addition to the E unit and the TFE unit. The ratio of the monomer unit having an oxygen-containing polar group to the total of the E unit and the TFE unit is preferably 0.01 to 5 mol%, more preferably 0.05 to 3 mol%.
- the method for producing a fluorine-containing polymer of the present invention is emulsion polymerization using an aqueous medium, but a monomer having an oxygen-containing polar group such as a monomer having a highly hydrophilic cyclic acid anhydride residue may also be used. It does not dissolve too much, can be easily copolymerized with tetrafluoroethylene or the like, and an oxygen-containing polar group can be easily introduced into the fluorine-containing polymer.
- the copolymer of TFE and PAVE has a TFE unit and a PAVE unit.
- a copolymer of TFE and PAVE a copolymer in which the ratio of PAVE units to the total of TFE units and PAVE units is 0.1 mol% or more and less than 20 mol% (hereinafter, also referred to as “PF1”).
- PF2 a copolymer having a PAVE unit ratio of 20 to 70 mol%
- the ratio of PAVE units to the total of TFE units and PAVE units is preferably 0.5 to 10 mol%, more preferably 0.5 to 5.0 mol%.
- PF1 may be a copolymer consisting only of TFE units and PAVE units, or may contain one or more units based on other monomers other than these.
- the other monomer another fluorine monomer or a monomer having an oxygen-containing polar group is preferable.
- the other fluorine monomer hexafluoropropylene is preferable.
- NAH is preferable as the monomer having an oxygen-containing polar group.
- the content ratio thereof is preferably 0.1 to 10 mol%, preferably 0.1 to 10 mol%, based on the total of the TFE unit and the PAVE unit. 6 mol% is more preferred.
- the monomer having an oxygen-containing polar group is preferably 0.01 to 5 mol%, more preferably 0.05 to 3 mol%.
- the total ratio of the TFE unit and the PAVE unit to all the units constituting PF1 is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more.
- PF1 is also referred to as "PFA" below.
- the ratio of PAVE units to the total of TFE units and PAVE units is preferably 20 to 50 mol%, more preferably 25 to 45 mol%.
- a unit based on a monomer having a fluorine atom and a nitrile group hereinafter, also referred to as “CN unit”
- CN unit a monomer having a fluorine atom and a plurality of vinyl groups. It is also preferable to have a unit based on (hereinafter, also referred to as “DV unit”).
- the ratio of CN units to the total of TFE units and PAVE units is preferably 0.1 to 10.0 mol%, more preferably 0.5 to 5.0 mol%.
- the ratio of DV units to the total of TFE units and PAVE units is preferably 0.01 to 1.0 mol%, more preferably 0.01 to 0.5 mol%.
- the total ratio of the TFE unit and the PAVE unit to all the units constituting PF2 is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more.
- the specific fluorine-containing monomer and other monomers are charged into the reaction system (that is, the polymerization reaction vessel) by a conventional method.
- TFE is continuously or intermittently charged into the reaction system so that the polymerization pressure becomes a predetermined pressure.
- other monomers are dissolved in an aqueous medium, and the obtained solution is continuously or intermittently charged into the reaction system.
- the water-soluble polymerization initiator may be added collectively to the reaction system or may be added in portions.
- the chain transfer agent is preferably alcohol, a hydrocarbon, or a hydrofluorocarbon, and more preferably an alcohol or a hydrocarbon, because it has an effect of stabilizing the terminal structure of the resin.
- the alcohol methanol and ethanol are preferable because they are easily dissolved in water and easily separated from the copolymer after production.
- the hydrocarbon n-pentane, cyclohexane, methane, and propane, which have good thermal stability and high chain transfer when introduced into the terminal structure of the resin, are preferable.
- the polymerization temperature is preferably 10 to 95 ° C, more preferably 15 to 90 ° C.
- the polymerization pressure is preferably 0.5 to 4.0 MPaG, more preferably 0.6 to 3.5 MPaG.
- the polymerization time is preferably 90 to 1000 minutes, more preferably 90 to 700 minutes.
- the polymerization of the specific fluorine-containing monomer may be carried out in the absence of substantially the emulsifier.
- the emulsifier include known emulsifiers and general surfactants.
- the emulsifier does not mean the specific polymer in the present invention, the polyalkylene oxide compound described later, and the decomposition product obtained by mixing the polyalkylene oxide compound and the oxidizing agent.
- the term "under virtually no emulsifier” means an environment in which the content of the emulsifier is 0.03 mass ppm or less with respect to the total mass of the aqueous medium, preferably 0.02 mass ppm or less, and 0 mass ppm is more. preferable.
- the production of the specific polymer and the production of the fluorine-containing polymer may be continuously performed in the same polymerization reaction vessel. Further, in the production method of the present invention, it is sufficient that specific particles are formed in the production of the specific polymer, and the fluorine-containing polymer is produced before the specific compound is completely consumed in the production of the specific polymer. You may. In this case, it is considered that a fluorine-containing polymer containing a unit based on a specific compound may be produced.
- the content of the specific polymer obtained in step 1 and present in step 2 in the aqueous medium is 100 parts by mass of the aqueous medium. , 0.0001 to 1.0 part by mass, more preferably 0.0005 to 0.5 part by mass.
- step 1 can be omitted.
- a commercially available specific polymer is prepared instead of step 1, and the content of the specific polymer present in step 2 in the aqueous medium is 0.0001 to 1.0 part by mass with respect to 100 parts by mass of the aqueous medium. It is preferably 0.001 to 0.5 parts by mass, and more preferably 0.001 to 0.5 parts by mass.
- the D50 of the particles of the commercially available specific polymer is preferably 10 to 1000 nm, more preferably 10 to 300 nm, further preferably 10 to 200 nm, and particularly preferably 10 to 150 nm.
- the content of the unit based on the specific compound in the commercially available specific polymer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, based on all the units of the polymer. ..
- the upper limit is 100% by mass.
- a fluorine-containing polymer aqueous dispersion containing particles having a D50 of 20 to 3000 nm and specific particles containing a fluorine-containing polymer having a unit based on the specific fluorine-containing monomer can be easily obtained. .. Further, as described above, since it is presumed that the monomer is polymerized in the specific particles when the specific fluorine-containing monomer is polymerized, the generated fluorine-containing polymer particles take in the specific particles and become a fluorine-containing polymer. Particles containing a specific polymer may be produced.
- the specific particles have a high affinity for the specific fluorine-containing monomer (for example, when the specific particles are particles of a specific polymer having a fluorine atom), the D50 containing the fluorine-containing polymer and the specific polymer. It is considered that particles having a diameter of 20 to 3000 nm are likely to be generated.
- the fluorine-containing polymer aqueous dispersion of the present invention contains the above-mentioned aqueous medium, particles having a D50 of 20 to 3000 nm containing the fluorine-containing polymer, and particles contained in the aqueous medium or the above-mentioned fluorine-containing polymer.
- the particles containing a fluorine-containing polymer mean particles that may contain a specific polymer, unless otherwise specified.
- the fluorinated polymer aqueous dispersion preferably contains 1.0 to 50.0 parts by mass of particles containing the fluorinated polymer with respect to 100 parts by mass of the aqueous medium, and preferably contains 2.0 to 40.0 parts by mass. Is more preferable.
- the fluorine-containing polymer aqueous dispersion preferably contains 0.0001 to 1.0 part by mass of the specific polymer with respect to 100 parts by mass of the aqueous medium.
- the content of the specific polymer with respect to 100 parts by mass of the particles containing the fluorine-containing polymer is preferably 0.001 to 5.00 parts by mass, preferably 0.005 to 3.00 parts by mass. The part is more preferable.
- the D50 of the particles containing the fluorine-containing polymer is preferably 20 to 1000 nm.
- the fluorine-containing polymer aqueous dispersion liquid does not substantially contain an emulsifier.
- the emulsifier is as described above.
- the fact that the emulsifier is substantially absent in the aqueous dispersion of the fluorine-containing polymer means that the content of the emulsifier is 0.03 mass ppm or less with respect to the total mass of the aqueous medium, and 0.02 mass ppm or less. Is preferable, and 0% by mass is more preferable.
- the fluoropolymer contained in the aqueous dispersion of the fluoropolymer contains TFE units
- the content of the TFE units in the fluoropolymer is 99 with respect to all the units of the fluoropolymer. Less than% by mass.
- the fluorine-containing polymer aqueous dispersion does not require an emulsifier, and therefore, it is easy to prepare a dispersion of an organic solvent such as N-methylpyrrolidone or acetone by solvent substitution.
- a fluorine-containing polymer aqueous dispersion having particles containing a fluorine-containing polymer can be mixed with an organic solvent and dehydrated by evaporation or dehydration using anhydrous sodium sulfate or the like to obtain a dispersion of an organic solvent.
- the fluorine-containing polymer aqueous dispersion liquid stably disperses the fluorine-containing polymer even if it does not contain an emulsifier. Therefore, it can be suitably used for coating applications, binders and the like.
- the polymer composition of the present invention is preferably a composition containing a specific polymer and a fluorine-containing polymer containing a unit based on the specific fluorine-containing monomer.
- the polymer composition can be easily obtained from the fluorine-containing polymer aqueous dispersion obtained in Step 2. That is, the powder of the polymer composition can be obtained by aggregating the polymer from the above-mentioned fluorine-containing polymer aqueous dispersion. Further, the powdery polymer composition obtained by aggregation can be homogenized by melt-kneading or the like to obtain a pellet-shaped or granular molding material containing a fluorine-containing polymer and a specific polymer. Further, the powdery polymer composition obtained by aggregation can be melt-molded into a molded product.
- Examples of the aggregation method include, but are not limited to, freeze aggregation, acid aggregation, base aggregation, and aggregation using a coagulant.
- the aggregation temperature is preferably 0 to 5 ° C.
- the aggregation time is preferably 1 hour or more, more preferably 2 hours or more.
- acid aggregation a method of adding a solution containing an acid to the aqueous dispersion of the fluoropolymer is preferable.
- Examples of the acid to be added include hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, hydrofluoric acid and the like, and hydrochloric acid is preferable.
- the concentration of the acid in the solution containing the acid is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, still more preferably 1 to 10% by mass.
- a method of adding a solution containing a base to the aqueous dispersion of a fluorine-containing polymer is preferable.
- the base to be added include sodium hydroxide, potassium hydroxide, ammonium carbonate and the like, and sodium hydroxide is preferable.
- the concentration of the base in the solution containing the base is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, still more preferably 1 to 10% by mass.
- a known coagulant can be used as the agglomeration by the coagulant.
- Known coagulants include aluminum salts, calcium salts and magnesium salts.
- aluminum sulfate general formula M'Al (SO 4 ) 2.12 H 2 O [in the formula , M'is a monovalent cation other than lithium. ]
- examples thereof include alum, calcium nitrate, and magnesium sulfate, of which alum is preferable, and alum in which M is potassium is more preferable.
- base aggregation is preferable because aggregation is particularly easy to proceed.
- the melting point of the fluorine-containing polymer in the polymer composition is preferably 150 ° C. or higher, more preferably 150 to 330 ° C., still more preferably 180 to 320 ° C., particularly preferably 220 to 310 ° C., and most preferably 260 to 300 ° C. ..
- the heat resistance of the fluorine-containing polymer is high, which is preferable.
- the polymer composition preferably contains substantially no emulsifier.
- the emulsifier is as described above.
- the fact that the polymer composition contains substantially no emulsifier means that the emulsifier is contained with respect to the total mass of the specific polymer in the polymer composition and the fluorine-containing polymer containing a unit based on the specific fluorine-containing monomer. It means that the amount is 0.03 mass ppm or less, preferably 0.02 mass ppm or less, and more preferably 0 mass%.
- a second embodiment of the method for producing a fluorine-containing polymer of the present invention is a method for polymerizing a specific fluorine-containing monomer in an aqueous medium in the presence of a polyalkylene oxide compound and substantially no emulsifier. Is. However, when the TFE is polymerized, the TFE is copolymerized so that the content of the TFE unit in the fluorine-containing polymer is less than 99% by mass with respect to all the units of the fluorine-containing polymer.
- the specific fluorinated monomer is polymerized in the presence of the specific polymer, whereas the method for producing the fluorinated polymer is the first.
- the specific fluorine-containing monomer is polymerized in the presence of a polyalkylene oxide compound and substantially no emulsifier. That is, the specific polymer is used in the first embodiment of the method for producing a fluoropolymer, whereas the polyalkylene oxide compound is used in the second embodiment of the method for producing a fluoropolymer.
- the procedure for polymerizing the specific fluorine-containing monomer in the second embodiment of the method for producing a fluorine-containing polymer is the same as that for the polymerization of the specific fluorine-containing monomer in the first embodiment of the method for producing a fluorine-containing polymer. It is the same as the procedure (specifically, the procedure of step 2). Therefore, In the following, mainly, the second embodiment will be described as different from the first embodiment.
- the polyalkylene oxide compound is a compound for forming a nucleus (seed) during the polymerization of a specific fluorine-containing monomer. In other words, it corresponds to a nucleation additive.
- the polyalkylene oxide compound is a compound containing a polyoxyalkylene chain, and examples of the polyoxyalkylene chain include a polyoxyethylene chain, a polyoxypropylene chain, and a polyoxytetramethylene chain.
- the polyalkylene oxide compound preferably has a surface tension in water of more than about 40 dynes / cm at a concentration of 1000 ppm.
- the surface tension is more preferably more than about 42 dynes / cm, and even more preferably more than about 45 dynes / cm.
- the surface tension is preferably about 73 dynes / cm or less.
- the number average molecular weight of the polyalkylene oxide compound is preferably 50 to 2000, more preferably 100 to 1500, and even more preferably 150 to 1300.
- Equation (4) Ra- (OR c ) p - OR b
- Ra and R b independently represent a hydrogen atom, an alkyl group, an acryloyl group or a methacryloyl group, respectively.
- R c represents an alkylene group having 2 to 4 carbon atoms, and may be linear or branched.
- p represents an integer from 1 to 50.
- polyalkylene oxide compound examples include polyethylene glycol, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol monobutyl ether, polypropylene glycol, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, and polypropylene glycol di.
- examples thereof include methacrylate, polypropylene glycol monomethyl ether, polypropylene glycol dimethyl ether, polypropylene glycol monobutyl ether, and polytetramethylene glycol.
- the polyalkylene oxide compound may be used alone or in combination of two or more.
- the amount of the polyalkylene oxide compound used is preferably 0.1 to 10% by mass, more preferably 1 to 10% by mass, based on the total mass of the aqueous medium.
- the specific fluorine-containing monomer is polymerized in the absence of an emulsifier.
- the emulsifier is as described above.
- the term "lower" in which the emulsifier is substantially absent means an environment in which the amount of the emulsifier used is 0.03 mass ppm or less with respect to the total mass of the aqueous medium, preferably 0.02 mass ppm or less, and 0% by mass is more. preferable.
- the polyalkylene oxide compound and the oxidizing agent are mixed in an aqueous medium to obtain a dispersion liquid, and then the specific fluorine-containing monomer is polymerized in the obtained dispersion liquid to obtain a fluorine-containing liquid. It is preferable to produce a polymer.
- oxidizing agent examples include hydrogen peroxide and a polymerization initiator.
- polymerization initiator examples include the compounds exemplified by the water-soluble polymerization initiator described in the above-mentioned step 1.
- persulfate is preferable, and ammonium persulfate and potassium persulfate are more preferable.
- Mixing the polyalkylene oxide compound and the oxidizing agent in an aqueous medium gives a dispersion in which the lipophilic nucleation site is dispersed in the aqueous medium. More specifically, when the polyalkylene oxide compound and the oxidizing agent are mixed, the hydrophilic portion of the polyalkylene oxide compound is decomposed, and the hydrophobic portion of the polyalkylene oxide compound becomes a lipophilic nucleation site. The lipophilic nucleation site is dispersed in the aqueous medium, and the fluorine-containing polymer can be finely dispersed in these sites.
- the lipophilic nucleation site has an excellent affinity with the specific fluorine-containing monomer, the polymerization of the specific fluorine-containing monomer is likely to proceed in the dispersion liquid containing the lipophilic nucleation site. That is, the lipophilic nucleation site can be a place for a hydrophobic environment for the specific fluorine-containing monomer to polymerize.
- the amount of the oxidizing agent used is preferably 0.01 to 1.00% by mass, more preferably 0.05 to 0.5% by mass, based on the total mass of the aqueous medium.
- the temperature at which the polyalkylene oxide compound and the oxidizing agent are mixed is preferably 20 to 120 ° C, more preferably 40 to 120 ° C.
- the mixing time when the polyalkylene oxide compound and the oxidizing agent are mixed is preferably 0.05 to 1.00 hours.
- the amount of the water-soluble inorganic salt used is preferably 1 to 1000 mass ppm, more preferably 10 to 1000 mass ppm, based on the total mass of the aqueous medium.
- the water-soluble inorganic salt include sodium bisulfite, sodium hydrogen sulfite, sodium chloride, potassium sulfite, potassium hydrogen sulfite, potassium carbonate, ammonium oxalate, sodium tetraborate, sodium acetate, ammonium carbonate, ammonium dihydrogen phosphate, and phosphorus.
- diammonium acid preferably sodium bisulfite, and more preferably sodium bisulfite and ammonium sulfite.
- a fluorine-containing polymer aqueous dispersion containing particles having a D50 of 20 to 3000 nm and a polyalkylene oxide compound containing a fluorine-containing polymer having a unit based on a specific fluorine-containing monomer can be easily prepared. can get.
- the fluorine-containing polymer aqueous dispersion preferably contains 1.0 to 50.0 parts by mass of particles containing the fluorine-containing polymer with respect to 100 parts by mass of the aqueous medium, and more preferably 3 to 40 parts by mass.
- the fluorine-containing polymer aqueous dispersion preferably contains a polyalkylene oxide compound in an amount of 0.1 to 10 mass ppm based on the total mass of the fluorine-containing polymer aqueous dispersion, and preferably contains 1 to 10 mass ppm. Further, in the fluorine-containing polymer aqueous dispersion, the content of the polyalkylene oxide compound with respect to 100 parts by mass of the particles containing the fluorine-containing polymer is preferably 0.001 to 5.00 parts by mass, preferably 0.005 to 3.00. Parts by mass are more preferred.
- the D50 of the particles containing the fluorine-containing polymer is preferably 20 to 1000 nm.
- the fluorine-containing polymer aqueous dispersion liquid does not substantially contain an emulsifier.
- the emulsifier is as described above.
- the fact that the emulsifier is substantially absent in the aqueous dispersion of the fluorine-containing polymer means that the content of the emulsifier is 0.03 mass ppm or less with respect to the total mass of the aqueous medium, and 0.02 mass ppm or less. Is preferable, and 0% by mass is more preferable.
- the fluoropolymer contained in the aqueous dispersion of the fluoropolymer contains TFE units
- the content of the TFE units in the fluoropolymer is 99 with respect to all the units of the fluoropolymer. Less than% by mass.
- the fluorine-containing polymer aqueous dispersion does not require an emulsifier, and therefore, it is easy to prepare a dispersion of an organic solvent such as N-methylpyrrolidone or acetone by solvent substitution.
- a fluorine-containing polymer aqueous dispersion having particles containing a fluorine-containing polymer can be mixed with an organic solvent and dehydrated by evaporation or dehydration using anhydrous sodium sulfate or the like to obtain a dispersion of an organic solvent.
- the fluorine-containing polymer aqueous dispersion liquid stably disperses the fluorine-containing polymer even if it does not contain an emulsifier. Therefore, it can be suitably used for coating applications, binders and the like.
- the polymer composition of the present invention is preferably a composition containing a polyalkylene oxide compound and a fluorine-containing polymer containing a unit based on a specific fluorine-containing monomer.
- the polymer composition can be easily obtained from the aqueous dispersion of a fluorine-containing polymer. That is, the powder of the polymer composition can be obtained by aggregating the polymer from the above-mentioned fluorine-containing polymer aqueous dispersion. Further, the powdery polymer composition obtained by aggregation can be homogenized by melt-kneading or the like to obtain a pellet-shaped or granular molding material containing a fluorine-containing polymer and a polyalkylene oxide compound. It can also be made into a molded product by melt molding or the like from the powdery polymer composition obtained by aggregation. The aggregation method is as described above.
- the polymer composition preferably contains substantially no emulsifier.
- the emulsifier is as described above.
- the fact that the polymer composition is substantially free of emulsifier means that the emulsifier is based on the total mass of the polyalkylene oxide compound in the polymer composition and the fluorine-containing polymer containing a unit based on the specific fluorine-containing monomer. It means that the content is 0.03% by mass or less, preferably 0.02% by mass or less, and more preferably 0% by mass.
- Examples 1 to 7 correspond to Examples.
- Percentage of each unit in the polymer The proportion of each unit in the polymer was determined from 19 F-NMR analysis, fluorine content analysis, and infrared absorption spectrum analysis.
- the melting point is the temperature at the endothermic peak due to melting measured under a nitrogen atmosphere using a differential scanning heat analyzer (DSC 3500Sirius manufactured by NETZSCH).
- the temperature transition program during measurement is ⁇ 20 ° C. ⁇ 310 ° C. ⁇ ⁇ 70 ° C. ⁇ 310 ° C., each temperature rise rate is 10 ° C./min, and the temperature drop rate is 5 ° C./min.
- the temperature at the endothermic peak due to the heat of fusion at the time of the second temperature rise after the temperature is lowered to ⁇ 70 ° C. is defined as the “melting point”.
- KPS potassium persulfate
- the polymerization tank was cooled to room temperature, and the gas in the polymerization tank was released to the atmosphere.
- the polymerization time was 329 minutes.
- the solid content concentration of the obtained fluorine-containing polymer in the aqueous dispersion of the fluorine-containing polymer was about 3.7%.
- the D50 of the fluorine-containing polymer particles in the fluorine-containing polymer aqueous dispersion was 92 nm.
- the fluorinated polymer aqueous dispersion was cooled and the fluorinated polymer particles were aggregated to obtain a powder. Next, this fluorine-containing polymer powder was dried at 150 ° C.
- the Q value of the obtained fluorine-containing polymer powder under a load of 50 kg was 8.3 mm 3 / s, and the molar ratio of TFE units / E units / PFBE units in the fluorine-containing polymer was 53.0 / 46.0 / 1. It was 0.
- the melting point of the obtained fluorine-containing polymer was 266 ° C.
- Example 2 A fluorine-containing polymer was produced according to the same procedure as in Example 1 except that a predetermined amount of the compound shown in Table 1 was used instead of MEM. The results are summarized in Table 1. The symbols of the compounds shown in Table 1 represent the following.
- DiGMEMA Diethylene glycol monomethyl ether methacrylate (see the structural formula below)
- TeEDGDMA Tetraethylene glycol dimethacrylate (see structural formula below)
- ECMMMA Ethylene glycol monoacetate acetate monomethacrylate (see structural formula below)
- the “Mass part” column of the “Compound” column represents the abundance of the specific polymer with respect to 100 parts by mass of the aqueous medium for Examples 1 to 5 and 7, and 100 parts by mass of the aqueous medium for Example 6. Or represents the abundance of the polyalkylene oxide compound.
- the column “Amount of initiator used when polymerizing the specific compound” represents the amount (g) of the water-soluble polymerization initiator used when polymerizing the specific compound in Examples 1 to 5 and 7. .
- the “solid content (%)” column represents the solid content concentration of the fluorine-containing polymer in the aqueous dispersion of the fluorine-containing polymer.
- the “D50 (nm)” column represents the D50 (nm) of the fluorine-containing polymer particles.
- the “Q value (mm 3 / g)” column represents the Q value (mm 3 / g) of the fluorine-containing polymer powder under a load of 50 kg.
- the “melting point (° C.)” column represents the melting point (° C.) of the fluorine-containing polymer.
- TFE unit (mol%)”, “E unit (mol%)”, and “PFBE unit (mol%)” are TFE unit, E unit, and PFBE unit in the obtained fluorine-containing polymer, respectively. Represents the content of. In Examples 1 to 7, the emulsifier was not substantially present when the fluorine-containing monomer was polymerized.
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Abstract
Description
含フッ素重合体の製造方法として、含フッ素乳化剤を使用し、水性媒体中で含フッ素モノマーを乳化重合する方法が挙げられる(特許文献1参照)。
また、本発明は、含フッ素重合体水性分散液および重合体組成物も提供することも課題とする。
式(1): CXY=CR1-COO-(L-O)n-R2
式(2): CXY=CR3-(O)m-CH2-Z-R4
式(1)および式(2)中の各記号は以下のものを表す。
XおよびYは、相互に独立して、水素原子、ハロゲン原子またはメチル基を表す。
R1は、水素原子、ハロゲン原子または炭素数1~3のアルキル基を表す。
R2は、アルキル基、アルキル基中の少なくとも1つの-CH2-が-CO-に置き換えられたアルキル基または下式(3)で表される基を表す。
R3は、水素原子、ハロゲン原子、炭素数1~3のアルキル基または-CO-OCH3を表す。
R4は、アルキル基を表す。
Lは、アルキレン基を表す。
Zは、-CO-O-*または-O-CO-*を表す。ただし、*はR4との結合位置を表す。
mは0または1を表し、nは1以上の整数を表す。
式(3): -CO-CR1=CXY
式(3)中、X、YおよびR1は、それぞれ式(1)におけるX、YおよびR1の定義と同じである。
[2] 前記特定重合体の存在量が、前記水性媒体100質量部に対して0.0001~1.0質量部である、[1]に記載の製造方法。
式(1): CXY=CR1-COO-(L-O)n-R2
式(2): CXY=CR3-(O)m-CH2-Z-R4
式(1)および式(2)中の各記号は以下のものを表す。
XおよびYは、相互に独立して、水素原子、ハロゲン原子またはメチル基を表す。
R1は、水素原子、ハロゲン原子または炭素数1~3のアルキル基を表す。
R2は、アルキル基、アルキル基中の少なくとも1つの-CH2-が-CO-に置き換えられたアルキル基または下式(3)で表される基を表す。
R3は、水素原子、ハロゲン原子、炭素数1~3のアルキル基または-CO-OCH3を表す。
R4は、アルキル基を表す。
Lは、アルキレン基を表す。
Zは、-CO-O-*または-O-CO-*を表す。ただし、*はR4との結合位置を表す。
mは0または1を表し、nは1以上の整数を表す。
式(3): -CO-CR1=CXY
式(3)中、X、YおよびR1は、それぞれ式(1)におけるX、YおよびR1の定義と同じである。
[4] 前記特定重合体が存在する水性媒体が、前記特定重合体の製造に使用されて特定重合体が存在するに至った水性媒体である、[3]に記載の製造方法。
[5] 前記含フッ素単量体の重合における前記特定重合体の存在量が、前記水性媒体100質量部に対して0.0001~1.0質量部である、[3]または[4]に記載の製造方法。
式(1): CXY=CR1-COO-(L-O)n-R2
式(2): CXY=CR3-(O)m-CH2-Z-R4
式(1)および式(2)中の各記号は以下のものを表す。
XおよびYは、相互に独立して、水素原子、ハロゲン原子またはメチル基を表す。
R1は、水素原子、ハロゲン原子または炭素数1~3のアルキル基を表す。
R2は、アルキル基、アルキル基中の少なくとも1つの-CH2-が-CO-に置き換えられたアルキル基または下式(3)で表される基を表す。
R3は、水素原子、ハロゲン原子、炭素数1~3のアルキル基または-CO-OCH3を表す。
R4は、アルキル基を表す。
Lは、アルキレン基を表す。
Zは、-CO-O-*または-O-CO-*を表す。ただし、*はR4との結合位置を表す。
mは0または1を表し、nは1以上の整数を表す。
式(3): -CO-CR1=CXY
式(3)中、X、YおよびR1は、それぞれ式(1)におけるX、YおよびR1の定義と同じである。
[8] 前記含フッ素重合体を含む粒子を、水性媒体100質量部に対して1.0~50.0質量部含む、[7]に記載の含フッ素重合体水性分散液。
[9] 前記特定重合体の粒子を、水性媒体100質量部に対して0.0001~1.0質量部含む、[7]または[8]に記載の含フッ素重合体水性分散液。
[10] 前記特定重合体の粒子を、前記含フッ素重合体を含む粒子100質量部に対して0.001~5.00質量部含む、[7]~[9]のいずれかに記載の含フッ素重合体水性分散液。
式(1): CXY=CR1-COO-(L-O)n-R2
式(2): CXY=CR3-(O)m-CH2-Z-R4
式(1)および式(2)中の各記号は以下のものを表す。
XおよびYは、相互に独立して、水素原子、ハロゲン原子またはメチル基を表す。
R1は、水素原子、ハロゲン原子または炭素数1~3のアルキル基を表す。
R2は、アルキル基、アルキル基中の少なくとも1つの-CH2-が-CO-に置き換えられたアルキル基または下式(3)で表される基を表す。
R3は、水素原子、ハロゲン原子、炭素数1~3のアルキル基または-CO-OCH3を表す。
R4は、アルキル基を表す。
Lは、アルキレン基を表す。
Zは、-CO-O-*または-O-CO-*を表す。ただし、*はR4との結合位置を表す。
mは0または1を表し、nは1以上の整数を表す。
式(3): -CO-CR1=CXY
式(3)中、X、YおよびR1は、それぞれ式(1)におけるX、YおよびR1の定義と同じである。
[13] 前記含フッ素重合体100質量部に対する前記特定重合体の含有量が、0.001~5.00質量部である、[12]に記載の重合体組成物。
また、本発明によれば、含フッ素重合体水性分散液および重合体組成物も提供できる。
重合体が含む全単位に対する、それぞれの単位の含有量(質量%)は、重合体を固体核磁気共鳴スペクトル(NMR)法により分析して求められるが、各単量体の仕込み量から推算できる。通常、各単量体の仕込み量から計算される各単位の含有量は、実際の各単位の含有量と略一致している。
「体積基準累積50%径」は、レーザー回折・散乱法によって粒度分布を測定し、粒子の集団の全体積を100%として累積カーブを求め、その累積カーブ上で累積体積が50%となる点の粒子径である。以下、「D50」とも記す。
本発明の含フッ素重合体の製造方法の第1実施態様は、下式(1)で表される化合物(以下、「化合物(1)」とも記す。)に基づく単位および下式(2)で表される化合物(以下、「化合物(2)」とも記す。)に基づく単位から選ばれる少なくとも1種の単位を含む特定重合体の存在下に、水性媒体中で、テトラフルオロエチレン、クロロトリフルオロエチレンおよびフッ化ビニリデンから選ばれる少なくとも1種の含フッ素単量体(以下、「特定含フッ素単量体」とも記す。)を重合する方法である。ただし、テトラフルオロエチレンを重合させる場合、含フッ素重合体中におけるテトラフルオロエチレンに基づく単位の含有量が、含フッ素重合体の全単位に対して、99質量%未満となるようにテトラフルオロエチレンを共重合させる。
本発明の含フッ素重合体の製造方法の第1実施態様は、別途重合して得た特定重合体を用いてもよく、水性媒体中で特定重合体を重合し、引き続き同じ重合系で特定含フッ素単量体を重合してもよい。引き続き同じ重合系で重合するとは、特定重合体の製造に使用されて特定重合体が存在するに至った水性媒体を用い、かかる特定重合体が存在する水性媒体中で特定含フッ素単量体を重合することを意味する。別途重合して得た特定重合体としては市販品を用いてもよい。
本発明の含フッ素重合体の製造方法の第1実施態様としては、化合物(1)および化合物(2)から選ばれる少なくとも1種の特定化合物を水性媒体中で重合して特定重合体が存在する水性媒体を得、次いで、特定重合体が存在する水性媒体中で特定含フッ素単量体を重合して含フッ素重合体を製造する方法が好ましい。この2段階の製造方法において、前段の特定重合体が存在する水性媒体を得る段階を以下「工程1」といい、後段の含フッ素重合体を製造する段階を以下「工程2」という。
工程1における化合物(1)の重合および工程2における特定含フッ素単量体の重合は、それぞれ、重合開始剤の存在下に行われることが好ましい。重合開始剤としては、水溶性重合開始剤が好ましい。
(特定化合物)
工程1において、化合物(1)および化合物(2)から選ばれる少なくとも1種の特定化合物が使用される。特定化合物は、2種以上を組み合わせて用いてもよい。
式(1): CXY=CR1-COO-(L-O)n-R2
式(2): CXY=CR3-(O)m-CH2-Z-R4
式(1)および式(2)中の各記号は以下のものを表す。
XおよびYは、相互に独立して、水素原子、ハロゲン原子またはメチル基を表す。
R1は、水素原子、ハロゲン原子または炭素数1~3のアルキル基を表す。R2は、アルキル基、アルキル基中の少なくとも1つの-CH2-が-CO-に置き換えられたアルキル基(以下、「置換アルキル基」とも記す。)または下式(3)で表される基を表す。R3は、水素原子、ハロゲン原子、炭素数1~3のアルキル基または-CO-OCH3を表す。R4は、アルキル基を表す。
Lは、アルキレン基を表す。Zは、-CO-O-*または-O-CO-*を表す(ただし、*はR4との結合位置を表す。)。mは0または1を表し、nは1以上の整数を表す。
式(3): -CO-CR1=CXY
式(3)中、X、YおよびR1は、それぞれ式(1)におけるX、YおよびR1の定義と同じである。
XおよびYは、相互に独立して、水素原子、フッ素原子または塩素原子であるのが好ましく、いずれも水素原子であるのがより好ましい。
R1としては、炭素数1~3のアルキル基が好ましく、メチル基がより好ましい。
Lとしては、炭素数2~6のアルキレン基が好ましく、炭素数2または3のアルキレン基がより好ましく、エチレン基がさらに好ましい。Lのアルキレン基は、直鎖状でも、分岐鎖状でもよい。
R2のアルキル基としては、炭素数1~3のアルキル基が好ましく、メチル基がより好ましい。
R2の置換アルキル基中における-CO-で表される基の数としては、1~3が好ましく、2がより好ましい。置換アルキル基中の-CO-の位置は、置換アルキル基中の末端でもよいし、-CH2-と-CH2-との間でもよい。R2の置換アルキル基としては、-CO-CH2-CO-CH3が好ましい。
R2の式(3)で表される基中におけるX、YおよびR1は、それぞれ式(1)におけるX、YおよびR1の定義と同じであり、好適態様も同じである。
nとしては、1~100が好ましく、1~50がより好ましい。
式(1A): CXY=CR1-COO-(L-O)n-R2a
式(1B): CXY=CR1-COO-(L-O)n-CO-CR1=CXY
式(1C): CXY=CR1-COO-L-O-R2b
式(1A)、式(1B)、式(1C)中、X、Y、R1、Lおよびnは、それぞれ式(1)におけるX、Y、R1、Lおよびnの定義と同じである。
式(1A)中、R2aは、アルキル基を表す。
式(1C)中、R2bは、置換アルキル基を表す。
式(2)中、XおよびYの好適範囲は、それぞれ式(1)におけるXおよびYの好適範囲と同じである。
R3としては、炭素数1~3のアルキル基または-CO-OCH3が好ましい。
Zとしては、-O-CO-*が好ましい。
R4としては、炭素数1~3のアルキル基が好ましく、メチル基がより好ましい。
mは、0が好ましい。
式(2A) CXY=CR3a-CH2-O-CO-R4
式(2A)中、X、YおよびR4は、それぞれ式(2)におけるX、YおよびR4の定義と同じである。
R3aとしては、炭素数1~3のアルキル基を表す。
水性媒体としては、例えば、水、水と水溶性有機溶媒との混合物が挙げられる。
水溶性有機溶媒としては、例えば、tert-ブタノール、プロピレングリコール、ジプロピレングリコールが挙げられる。水と水溶性有機溶媒との混合物の場合、水溶性有機溶媒濃度は、10質量%以下が好ましい。水性媒体としては、水のみであることが好ましい。
水溶性重合開始剤としては、水溶性ラジカル開始剤、水溶性酸化還元系触媒が好ましい。
水溶性ラジカル開始剤としては、過硫酸アンモニウム、過硫酸カリウム等の過硫酸塩、ジコハク酸過酸化物、ビスグルタル酸過酸化物、tert-ブチルヒドロパーオキシド等の水溶性有機過酸化物が好ましい。
水溶性酸化還元系触媒としては、臭素酸またはその塩、塩素酸またはその塩、過硫酸またはその塩、過マンガン酸またはその塩、過酸化水素等の酸化剤と、亜硫酸またはその塩、亜硫酸水素またはその塩、チオ硫酸またはその塩、有機酸、無機塩等の還元剤と、の組み合わせが好ましい。過硫酸塩としては、過硫酸カリウム、過硫酸アンモニウムが好ましい。亜硫酸塩としては、亜硫酸ナトリウムが好ましい。無機塩としては、硫酸アニオン、亜硫酸アニオンまたは塩化物アニオンと、金属イオンとの組み合わせが挙げられる。金属イオンとしては、遷移金属のイオンが好ましく、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、セリウムおよび銀のイオンが挙げられ、鉄イオンが好ましい。無機塩としては硫酸鉄(II)が好ましい。
水溶性重合開始剤としては、水溶性酸化還元系触媒が好ましく、過硫酸カリウムと亜硫酸ナトリウムとの組み合わせ、過硫酸カリウムと亜硫酸ナトリウムと無機塩との組み合わせが好ましく、過硫酸カリウムと亜硫酸ナトリウムとの組み合わせ、および、過硫酸カリウムと亜硫酸ナトリウムと硫酸鉄(II)との組み合わせがより好ましい。
なお、特定化合物の重合が進みやすいことから、反応系のpHを3~10とすることが好ましく、6~8とすることが好ましい。調整するために、亜硫酸ナトリウム等の亜硫酸塩、アンモニア、水酸化ナトリウム、塩酸等を必要に応じて添加してもよい。
水溶性重合開始剤は、2種以上を組み合わせて用いてもよい。
なお、水溶性重合開始剤の仕込み方法としては、重合反応を開始する前にその全量を反応系に仕込んでおいてもよく、連続的または断続的に反応系に添加してもよい。
重合時の圧力条件は、減圧条件または常圧条件が好ましい。
特定重合体の粒子(以下、「特定粒子」とも記す。)は、後述する特定含フッ素単量体の重合時に、疎水部で特定含フッ素単量体を吸着し、取り込むことにより特定含フッ素単量体を可溶化し、ここに開始剤を加えることで特定含フッ素単量体は特定粒子の粒子内で重合すると推測される。また特定粒子は水性媒体中および有機溶媒中における分散安定化に寄与すると推測される。
特定粒子のD50は、10~1000nmが好ましく、10~300nmがより好ましく、10~200nmがさらに好ましく、10~150nmが特に好ましい。
特定重合体中における特定化合物に基づく単位の含有量は、特定重合体の全単位に対して、50質量%以上が好ましく、70質量%以上がより好ましく、90質量%以上がさらに好ましい。上限としては、100質量%が挙げられる。
工程2は、工程1で得られた、特定重合体が存在する水性媒体中で、テトラフルオロエチレン、クロロトリフルオロエチレンおよびフッ化ビニリデンから選ばれる少なくとも1種の含フッ素単量体(すなわち、特定含フッ素単量体)を重合する、含フッ素重合体の製造工程である。
特定含フッ素単量体の重合は水溶性重合開始剤を用いて行われることが好ましく、水溶性重合開始剤としては、工程1で説明した水溶性重合開始剤が挙げられる。また、特定含フッ素単量体の重合は、さらに連鎖移動剤を用いて行われることも好ましい。
含フッ素重合体は、テトラフルオロエチレン(TFE)に基づく単位(以下、「TFE単位」とも記す。)を有するテトラフルオロエチレン系重合体、ポリフッ化ビニリデン(以下、「PVdF」とも記す。)、ポリクロロトリフルオロエチレン、エチレンとクロロトリフルオロエチレンとの共重合体が挙げられる。中でも、テトラフルオロエチレン系重合体が好ましい。
他の単量体としては、含フッ素単量体として、ヘキサフルオロプロピレン(以下、「HFP」とも記す。)、ペルフルオロ(アルキルビニルエーテル)(以下、「PAVE」とも記す。)、フルオロアルキルエチレン(以下、「FAE」とも記す。)が挙げられる。
PAVEとしては、CF2=CFOCF3(以下、「PMVE」とも記す。)、CF2=CFOCF2CF3、CF2=CFOCF2CF2CF3(以下、「PPVE」とも記す。)、CF2=CFOCF2CF2CF2CF3、CF2=CFO(CF2)8Fが挙げられ、PMVEおよびPPVEが好ましい。
FAEとしては、CH2=CH(CF2)2F(以下、「PFEE」とも記す。)、CH2=CH(CF2)3F、CH2=CH(CF2)4F(以下、「PFBE」とも記す。)、CH2=CF(CF2)3H、CH2=CF(CF2)4Hが挙げられ、PFEEおよびPFBEが好ましい。
また、他の単量体としては、エチレン、プロピレン、塩化ビニル、塩化ビニリデン、フッ化ビニルも挙げられる。
また、他の単量体としては、酸素含有極性基を有する単量体も挙げられる。酸素含有極性基としては、酸無水物残基、水酸基、カルボニル基含有基、アセタール基、オキシシクロアルカン基が好ましく、酸無水物残基がより好ましい。酸無水物残基を有する単量体としては、環状酸無水物残基を有する単量体が好ましく、無水イタコン酸(以下、「IAH」とも記す。)、無水シトラコン酸、5-ノルボルネン-2,3-ジカルボン酸無水物(別称:無水ハイミック酸。以下、「NAH」とも記す。)および無水マレイン酸がより好ましい。
ただし、TFEを重合させる場合、含フッ素重合体中におけるTFE単位の含有量が、含フッ素重合体の全単位に対して、99質量%未満となるようにTFEを共重合させる。また、クロロトリフルオロエチレンおよびフッ化ビニリデンから選ばれる少なくとも1種の含フッ素単量体に基づく単位を含まず、TFE単位を含む場合は、TFE単位の含有量が、含フッ素重合体の全単位に対して、10質量%以上99質量%未満であることが好ましい。
また、テトラフルオロエチレン系重合体は、下記の特定高耐熱性重合体を含まない。
特定高耐熱性重合体:示差走査熱量計で、10℃/min昇温による最初の吸熱ピークが少なくとも330℃以上であり、最初の吸熱ピークを経た後の吸熱ピークが少なくとも320℃以上である重合体。
FEPとしては、TFE単位とHFP単位との合計に対するHFP単位の割合が1~15モル%であるFEPが好ましく、5~13モル%であるFEPがより好ましい。
ETFEを構成する全単位に対して、E単位とTFE単位との合計の割合は80モル%以上が好ましく、85モル%以上がより好ましく、90モル%以上がさらに好ましい。
また、E単位とTFE単位の他に、FAE単位を有することも好ましい。E単位とTFE単位との合計に対するFAE単位の割合は、0.1~10モル%が好ましく、0.1~5モル%がより好ましく、0.2~4モル%がさらに好ましい。
また、E単位とTFE単位の他に、酸素含有極性基を有する単量体単位を有することも好ましい。E単位とTFE単位との合計に対する酸素含有極性基を有する単量体単位の割合は、0.01~5モル%が好ましく、0.05~3モル%がより好ましい。本発明の含フッ素重合体の製造方法は、水性媒体を用いた乳化重合だが、親水性の高い環状酸無水物残基を有する単量体など酸素含有極性基を有する単量体を用いても溶解し過ぎず、テトラフルオロエチレン等との共重合が容易であり、含フッ素重合体に酸素含有極性基を容易に導入できる。
PF1は、TFE単位とPAVE単位とのみからなる共重合体でもよく、これら以外の他の単量体に基づく単位の1種以上を含んでもよい。
他の単量体としては、他のフッ素単量体や酸素含有極性基を有する単量体が好ましい。他のフッ素単量体としては、ヘキサフルオロプロピレンが好ましい。酸素含有極性基を有する単量体としては、NAHが好ましい。
他の単量体に基づく単位を含む場合、その含有割合は、TFE単位とPAVE単位との合計に対して、他のフッ素単量体は0.1~10モル%が好ましく、0.1~6モル%がより好ましい。酸素含有極性基を有する単量体は、0.01~5モル%が好ましく、0.05~3モル%がより好ましい。
PF1を構成する全単位に対して、TFE単位とPAVE単位との合計の割合は80モル%以上が好ましく、85モル%以上がより好ましく、90モル%以上がさらに好ましい。
なお、PF1は、以下「PFA」とも記す。
また、TFE単位とPAVE単位との他に、フッ素原子およびニトリル基を有する単量体に基づく単位(以下、「CN単位」とも記す。)や、フッ素原子および複数のビニル基を有する単量体に基づく単位(以下、「DV単位」とも記す。)を有することも好ましい。
フッ素原子およびニトリル基を有する単量体としては、CF2=CFO(CF2)5CN、CF2=CFOCF2CF(CF3)CF2CF2CNが挙げられる。
フッ素原子および複数のビニル基を有する単量体としては、CF2=CFO(CF2)3OCF=CF2、CF2=CFO(CF2)4OCF=CF2、CH2=CH(CF2)6CH=CH2が挙げられる。
TFE単位とPAVE単位との合計に対するCN単位の割合は、0.1~10.0モル%が好ましく、0.5~5.0モル%がより好ましい。
TFE単位とPAVE単位との合計に対するDV単位の割合は、0.01~1.0モル%が好ましく、0.01~0.5モル%がより好ましい。
PF2を構成する全単位に対して、TFE単位とPAVE単位との合計の割合は、80モル%以上が好ましく、85モル%以上がより好ましく、90モル%以上がさらに好ましい。
水溶性重合開始剤を用いる場合、水溶性重合開始剤は反応系に一括して添加されてもよいし、分割して添加されてもよい。
連鎖移動剤を用いる場合、連鎖移動剤としては、樹脂の末端構造を安定化させる効果がある点から、アルコール、ハイドロカーボン、ハイドロフルオロカーボンが好ましく、アルコール、ハイドロカーボンがより好ましい。アルコールとしては、水に溶解しやすく、製造後に共重合体と分離しやすい点から、メタノール、エタノールが好ましい。ハイドロカーボンとしては、樹脂の末端構造に導入された際に熱安定性がよく、連鎖移動性も高いn-ペンタン、シクロヘキサン、メタン、プロパンが好ましい。
乳化剤としては、公知の乳化剤が挙げられ、一般的な界面活性剤が挙げられる。
なお、上記乳化剤は、本発明における特定重合体、後述するポリアルキレンオキシド化合物、および、ポリアルキレンオキシド化合物と酸化剤とを混合して得られる分解物、を意味しない。
乳化剤を実質的に存在しない下とは、水性媒体全質量に対して乳化剤の含有量が0.03質量ppm以下である環境を意味し、0.02質量ppm以下が好ましく、0質量ppmがより好ましい。
また、本発明の製造方法においては、特定重合体の製造において特定粒子が形成されればよく、特定重合体の製造において完全に特定化合物が消費される前に、含フッ素重合体の製造を実施してもよい。この場合には、特定化合物に基づく単位を含む含フッ素重合体が生成することがあると考えられる。
市販の特定重合体も、その粒子のD50は10~1000nmが好ましく、10~300nmがより好ましく、10~200nmがさらに好ましく、10~150nmが特に好ましい。
また、市販の特定重合体中における特定化合物に基づく単位の含有量は、重合体の全単位に対して、50質量%以上が好ましく、70質量%以上がより好ましく、90質量%以上がさらに好ましい。上限としては、100質量%が挙げられる。
また、上記のように、特定含フッ素単量体の重合時に特定粒子内で単量体が重合すると推測されることより、生成する含フッ素重合体粒子が特定粒子を取り込み、含フッ素重合体と特定重合体とを含む粒子が生成する場合もある。特に、特定粒子が特定含フッ素単量体と親和性が高い場合(例えば、特定粒子がフッ素原子を有する特定重合体の粒子である場合)、含フッ素重合体と特定重合体とを含む、D50が20~3000nmである粒子が生成しやすいと考えられる。
本発明の含フッ素重合体水性分散液は、上記のような、水性媒体と、含フッ素重合体を含むD50が20~3000nmである粒子と、水性媒体中に粒子として含まれるかまたは上記含フッ素重合体を含む粒子中に含まれる、特定重合体と、を含む、水性分散液であることが好ましい。
以下、含フッ素重合体を含む粒子とは、特に言及しない限り、特定重合体を含んでいてもよい粒子を意味する。
含フッ素重合体水性分散液は、含フッ素重合体を含む粒子を水性媒体100質量部に対して1.0~50.0質量部含むのが好ましく、2.0~40.0質量部含むのがより好ましい。
含フッ素重合体水性分散液は、特定重合体を水性媒体100質量部に対して0.0001~1.0質量部含むことが好ましい。
また、含フッ素重合体水性分散液において、含フッ素重合体を含む粒子100質量部に対する特定重合体の含有量は、0.001~5.00質量部が好ましく、0.005~3.00質量部がより好ましい。
含フッ素重合体を含む粒子のD50は、20~1000nmが好ましい。
乳化剤とは、上述した通りである。
含フッ素重合体水性分散液中において乳化剤を実質的に存在しないとは、水性媒体全質量に対して乳化剤の含有量が0.03質量ppm以下であることを意味し、0.02質量ppm以下が好ましく、0質量%がより好ましい。
含フッ素重合体を含む粒子を有する含フッ素重合体水性分散液を有機溶媒と混合し、蒸発または無水硫酸ナトリウム等を用いて脱水することにより、有機溶媒の分散液とすることができる。
上記重合体組成物は、工程2により得られた含フッ素重合体水性分散液から容易に得られる。すなわち、上記含フッ素重合体水性分散液から重合体を凝集させることにより、重合体組成物の粉末を得ることができる。さらに、凝集により得られた粉末状の重合体組成物を、溶融混練等により均質化して、含フッ素重合体と特定重合体とを含むペレット状、粒状等の形状の成形材料とすることができ、また、凝集により得られた粉末状の重合体組成物から溶融成形等により成形物とすることもできる。
凍結凝集の場合、凝集温度は0~5℃が好ましい。凝集時間は1時間以上が好ましく、2時間以上がより好ましい。
酸凝集の場合、酸を含む溶液を含フッ素重合体水性分散液に添加する方法が好ましい。添加する酸としては、塩酸、硝酸、硫酸、シュウ酸、フッ化水素酸等が挙げられ、塩酸が好ましい。酸を含む溶液中の酸の濃度は0.1~50質量%が好ましく、1~30質量%がより好ましく、1~10質量%がさらに好ましい。
塩基凝集としては、塩基を含む溶液を含フッ素重合体水性分散液に添加する方法が好ましい。添加する塩基としては、水酸化ナトリウム、水酸化カリウム、炭酸アンモニウム等が挙げられ、水酸化ナトリウムが好ましい。塩基を含む溶液中の塩基の濃度は0.1~50質量%が好ましく、1~30質量%がより好ましく、1~10質量%がさらに好ましい。
凝析剤による凝集としては、公知の凝析剤が使用できる。公知の凝析剤としては、アルミニウム塩、カルシウム塩、マグネシウム塩が挙げられる。具体的には、硫酸アルミニウム、一般式M’Al(SO4)2・12H2O〔式中、M’はリチウム以外の一価カチオンである。〕で表されるミョウバン、硝酸カルシウム、硫酸マグネシウムが挙げられ、中でもミョウバンが好ましく、Mがカリウムであるカリミョウバンがより好ましい。
凝集方法としては、凝集が特に進みやすいことから塩基凝集が好ましい。
乳化剤とは、上述した通りである。
重合体組成物が乳化剤を実質的に含まないとは、重合体組成物中の特定重合体と特定含フッ素単量体に基づく単位を含む含フッ素重合体との合計質量に対して乳化剤の含有量が0.03質量ppm以下であることを意味し、0.02質量ppm以下が好ましく、0質量%がより好ましい。
本発明の含フッ素重合体の製造方法の第2実施態様は、水性媒体中で、ポリアルキレンオキシド化合物が存在し、乳化剤が実質的に存在しない下で、特定含フッ素単量体を重合する方法である。ただし、TFEを重合させる場合、含フッ素重合体中におけるTFE単位の含有量が、含フッ素重合体の全単位に対して、99質量%未満となるようにTFEを共重合させる。
上述した含フッ素重合体の製造方法の第1実施態様においては、特定重合体の存在下にて特定含フッ素単量体の重合を行ったのに対して、含フッ素重合体の製造方法の第2実施態様においては、ポリアルキレンオキシド化合物が存在し、乳化剤が実質的に存在しない下で、特定含フッ素単量体の重合う。つまり、含フッ素重合体の製造方法の第1実施態様においては特定重合体を使用するのに対して、含フッ素重合体の製造方法の第2実施態様ではポリアルキレンオキシド化合物を使用している点で異なり、含フッ素重合体の製造方法の第2実施態様における特定含フッ素単量体の重合の手順は、含フッ素重合体の製造方法の第1実施態様における特定含フッ素単量体の重合の手順(具体的には、工程2の手順)と同じである。よって、
以下では、主に、第2実施態様において、第1実施態様と異なる点を説明する。
ポリアルキレンオキシド化合物は、特定含フッ素単量体の重合の際の核(シード)を形成するための化合物である。言い換えれば、核形成添加剤に該当する。
ポリアルキレンオキシド化合物とは、ポリオキシアルキレン鎖を含む化合物であり、ポリオキシアルキレン鎖としては、例えば、ポリオキシエチレン鎖、ポリオキシプロピレン鎖、ポリオキシテトラメチレン鎖が挙げられる。
式(4): Ra-(O-Rc)p-O-Rb
式(4)中、RaおよびRbは、それぞれ独立に、水素原子、アルキル基、アクリロイル基またはメタクリロイル基を表す。
Rcは、炭素数2~4のアルキレン基を表し、直鎖状であっても、分岐鎖状であってもよい。
pは、1~50の整数を表す。
ポリアルキレンオキシド化合物の使用量は、水性媒体全質量に対して、0.1~10質量ppmが好ましく、1~10質量ppmがより好ましい。
第2実施態様においては、乳化剤が実質的に存在しない下で、特定含フッ素単量体の重合を行う。
乳化剤とは、上述した通りである。
乳化剤を実質的に存在しない下とは、水性媒体全質量に対して乳化剤の使用量が0.03質量ppm以下である環境を意味し、0.02質量ppm以下が好ましく、0質量%がより好ましい。
酸化剤としては、例えば、過酸化水素および重合開始剤が挙げられる。
重合開始剤としては、上述した工程1で説明した水溶性重合開始剤で例示された化合物が挙げられる。重合開始剤としては、過硫酸塩が好ましく、過硫酸アンモニウム、過硫酸カリウムがより好ましい。
親油性核形成部位は特定含フッ素単量体との親和性に優れるため、親油性核形成部位が含まれる分散液中においては、特定含フッ素単量体の重合が進行しやすい。つまり、親油性核形成部位は、特定含フッ素単量体が重合するための疎水性環境の場となりえる。
ポリアルキレンオキシド化合物と酸化剤とを混合する際の温度は、20~120℃が好ましく、40~120℃がより好ましい。
ポリアルキレンオキシド化合物と酸化剤とを混合する際の混合時間は、0.05~1.00時間が好ましい。
水溶性無機塩の使用量は、水性媒体全質量に対して、1~1000質量ppmが好ましく、10~1000質量ppmがより好ましい。
水溶性無機塩としては、例えば、亜硫酸ナトリウム、亜硫酸水素ナトリウム、塩化ナトリウム、亜硫酸カリウム、亜硫酸水素カリウム、炭酸カリウム、シュウ酸アンモニウム、テトラホウ酸ナトリウム、酢酸ナトリウム、炭酸アンモニウム、リン酸二水素アンモニウム、リン酸二アンモニウムが挙げられ、亜硫酸塩が好ましく、亜硫酸ナトリウム、亜硫酸アンモニウムがより好ましい。
含フッ素重合体水性分散液は、含フッ素重合体を含む粒子を水性媒体100質量部に対して1.0~50.0質量部含むのが好ましく、3~40質量部含むのがより好ましい。
含フッ素重合体水性分散液は、ポリアルキレンオキシド化合物を含フッ素重合体水性分散液全質量に対して0.1~10質量ppm含むのが好ましく、1~10質量ppm含むのが好ましい。
また、含フッ素重合体水性分散液において、含フッ素重合体を含む粒子100質量部に対するポリアルキレンオキシド化合物の含有量は、0.001~5.00質量部が好ましく、0.005~3.00質量部がより好ましい。
含フッ素重合体を含む粒子のD50は、20~1000nmが好ましい。
乳化剤とは、上述した通りである。
含フッ素重合体水性分散液中において乳化剤を実質的に存在しないとは、水性媒体全質量に対して乳化剤の含有量が0.03質量ppm以下であることを意味し、0.02質量ppm以下が好ましく、0質量%がより好ましい。
含フッ素重合体を含む粒子を有する含フッ素重合体水性分散液を有機溶媒と混合し、蒸発または無水硫酸ナトリウム等を用いて脱水することにより、有機溶媒の分散液とすることができる。
上記重合体組成物は、上記含フッ素重合体水性分散液から容易に得られる。すなわち、上記含フッ素重合体水性分散液から重合体を凝集させることにより、重合体組成物の粉末を得ることができる。さらに、凝集により得られた粉末状の重合体組成物を、溶融混練等により均質化して、含フッ素重合体とポリアルキレンオキシド化合物とを含むペレット状、粒状等の形状の成形材料とすることができ、また、凝集により得られた粉末状の重合体組成物から溶融成形等により成形物とすることもできる。
凝集方法は、上述した通りである。
乳化剤とは、上述した通りである。
重合体組成物が乳化剤を実質的に含まないとは、重合体組成物中のポリアルキレンオキシド化合物と特定含フッ素単量体に基づく単位を含む含フッ素重合体との合計質量に対して乳化剤の含有量が0.03質量ppm以下であることを意味し、0.02質量ppm以下が好ましく、0質量%がより好ましい。
水性分散液中の重合体粒子のD50(nm):
重合体粒子の水性分散液を試料とし、レーザー回折・散乱式粒度分布測定装置(大塚電子株式会社、ELSZ)を用いて測定した。
特定重合体の確認:
特定重合体が得られていることは1H-NMR分析により確認した。
フローテスター(島津製作所社製)を用いて、ETFEのQ値(容量流速ともいう)を温度297℃、荷重50kgで測定した。
重合体における各単位の割合は、19F-NMR分析、フッ素含有量分析、赤外吸収スペクトル分析から求めた。
融点は、示差走査熱分析器(NETZSCH社製 DSC 3500Sirius)を用いて、窒素雰囲気下に測定した融解による吸熱ピークにおける温度である。測定中の温度推移プログラムは-20℃→310℃→-70℃→310℃とし、各昇温速度は10℃/分、降温速度は5℃/分とする。-70℃まで降温した後の2度目の昇温時の融解熱による吸熱ピークにおける温度を「融点」とする。
(例1)
[工程1]
2.1Lのステンレス鋼製の重合槽を窒素置換した後、-0.1MPaGまで減圧し、超純水(624g)、亜硫酸ナトリウム(74mg)、2-メトキシエチルメタクリレート(以下、「MEM」とも記す。以下構造式参照。)(34mg)を仕込んだ。次に、重合槽内の溶液を撹拌しながら60℃に昇温し、過硫酸カリウム(以下、「KPS」とも記す。)を脱イオン水に溶解させた溶液(5質量%)4.0mlを重合槽内に注入し、MEMを重合させた。MEMの仕込み量から、水性媒体100質量部中のポリMEMは、0.0054質量部である。
次に、TFE/E=86/14モル比の混合単量体で重合槽を1.9MPaGまで加圧し、KPS(5質量%)と酢酸ナトリウム(1.2質量%)を脱イオン水に溶解させた溶液10mlとPFBE(0.7g)を重合槽内に注入した。重合槽内の圧力が降下し始めたら重合槽内の内圧を1.9MPaGに保つようにTFE/E=54/46モル比の混合単量体を添加し、重合を進行させた。混合モノマーの連続仕込みが30gになった時点で重合槽を室温に冷却し、重合槽内のガスを大気放出した。重合時間は329分間であった。
得られた含フッ素重合体の含フッ素重合体水性分散液中での固形分濃度は約3.7%であった。また、含フッ素重合体水性分散液中の含フッ素重合体粒子のD50は92nmだった。
含フッ素重合体水性分散液を冷却し、含フッ素重合体粒子を凝集させ、粉末を取得した。次に、この含フッ素重合体粉末を150℃で乾燥した。得られた含フッ素重合体粉末の50kg荷重におけるQ値は8.3mm3/s、含フッ素重合体中のTFE単位/E単位/PFBE単位のモル比は53.0/46.0/1.0であった。得られた含フッ素重合体の融点は266℃であった。
MEMの代わりに、表1に記載の化合物を所定量用いた以外は、実施例1と同様の手順に従って、含フッ素重合体を製造した。結果を表1にまとめて示す。
なお、表1に記載の化合物の記号はそれぞれ以下を表す。
表1中、「特定化合物を重合する際の開始剤使用量」欄は、例1~5、7において、特定化合物を重合させる際に使用した水溶性重合開始剤の使用量(g)を表す。
表1中、「固形分(%)」欄は、含フッ素重合体の含フッ素重合体水性分散液中での固形分濃度を表す。
表1中、「D50(nm)」欄は、含フッ素重合体粒子のD50(nm)を表す。
表1中、「Q値(mm3/g)」欄は、含フッ素重合体粉末の50kg荷重におけるQ値(mm3/g)を表す。
表1中、「融点(℃)」欄は、含フッ素重合体の融点(℃)を表す。
表1中、「TFE単位(mol%)」、「E単位(mol%)」、「PFBE単位(mol%)」は、それぞれ得られた含フッ素重合体中のTFE単位、E単位、PFBE単位の含有量を表す。
なお、例1~7においては、含フッ素単量体を重合する際に、乳化剤が実質的に存在していなかった。
なお、2020年09月30日に出願された日本特許出願2020-165490号の明細書、特許請求の範囲および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (14)
- 水性媒体中で、下式(1)で表される化合物に基づく単位および下式(2)で表される化合物に基づく単位から選ばれる少なくとも1種の単位を含む特定重合体の存在下に、テトラフルオロエチレン、クロロトリフルオロエチレンおよびフッ化ビニリデンから選ばれる少なくとも1種の含フッ素単量体を重合して含フッ素重合体を製造する(ただし、前記テトラフルオロエチレンを重合させる場合、前記含フッ素重合体中におけるテトラフルオロエチレンに基づく単位の含有量が、前記含フッ素重合体の全単位に対して、99質量%未満となるようにテトラフルオロエチレンを共重合させる。)、含フッ素重合体の製造方法。
式(1): CXY=CR1-COO-(L-O)n-R2
式(2): CXY=CR3-(O)m-CH2-Z-R4
式(1)および式(2)中の各記号は以下のものを表す。
XおよびYは、相互に独立して、水素原子、ハロゲン原子またはメチル基を表す。
R1は、水素原子、ハロゲン原子または炭素数1~3のアルキル基を表す。
R2は、アルキル基、アルキル基中の少なくとも1つの-CH2-が-CO-に置き換えられたアルキル基または下式(3)で表される基を表す。
R3は、水素原子、ハロゲン原子、炭素数1~3のアルキル基または-CO-OCH3を表す。
R4は、アルキル基を表す。
Lは、アルキレン基を表す。
Zは、-CO-O-*または-O-CO-*を表す。ただし、*はR4との結合位置を表す。
mは0または1を表し、nは1以上の整数を表す。
式(3): -CO-CR1=CXY
式(3)中、X、YおよびR1は、それぞれ式(1)におけるX、YおよびR1の定義と同じである。 - 前記特定重合体の存在量が、前記水性媒体100質量部に対して0.0001~1.0質量部である、請求項1に記載の製造方法。
- 下式(1)で表される化合物および下式(2)で表される化合物から選ばれる少なくとも1種の特定化合物を水性媒体中で重合して特定重合体が存在する水性媒体を得、次いで、前記特定重合体が存在する水性媒体中で、テトラフルオロエチレン、クロロトリフルオロエチレンおよびフッ化ビニリデンから選ばれる少なくとも1種の含フッ素単量体を重合して含フッ素重合体を製造する(ただし、前記テトラフルオロエチレンを重合させる場合、前記含フッ素重合体中におけるテトラフルオロエチレンに基づく単位の含有量が、前記含フッ素重合体の全単位に対して、99質量%未満となるようにテトラフルオロエチレンを共重合させる。)、含フッ素重合体の製造方法。
式(1): CXY=CR1-COO-(L-O)n-R2
式(2): CXY=CR3-(O)m-CH2-Z-R4
式(1)および式(2)中の各記号は以下のものを表す。
XおよびYは、相互に独立して、水素原子、ハロゲン原子またはメチル基を表す。
R1は、水素原子、ハロゲン原子または炭素数1~3のアルキル基を表す。
R2は、アルキル基、アルキル基中の少なくとも1つの-CH2-が-CO-に置き換えられたアルキル基または下式(3)で表される基を表す。
R3は、水素原子、ハロゲン原子、炭素数1~3のアルキル基または-CO-OCH3を表す。
R4は、アルキル基を表す。
Lは、アルキレン基を表す。
Zは、-CO-O-*または-O-CO-*を表す。ただし、*はR4との結合位置を表す。
mは0または1を表し、nは1以上の整数を表す。
式(3): -CO-CR1=CXY
式(3)中、X、YおよびR1は、それぞれ式(1)におけるX、YおよびR1の定義と同じである。 - 前記特定重合体が存在する水性媒体が、前記特定重合体の製造に使用されて特定重合体が存在するに至った水性媒体である、請求項3に記載の製造方法。
- 前記含フッ素単量体の重合における前記特定重合体の存在量が、前記水性媒体100質量部に対して0.0001~1.0質量部である、請求項3または4に記載の製造方法。
- 水性媒体中で、ポリアルキレンオキシド化合物が存在し、乳化剤が実質的に存在しない下で、テトラフルオロエチレン、クロロトリフルオロエチレンおよびフッ化ビニリデンから選ばれる少なくとも1種の含フッ素単量体を重合して含フッ素重合体を製造する(ただし、前記テトラフルオロエチレンを重合させる場合、前記含フッ素重合体中におけるテトラフルオロエチレンに基づく単位の含有量が、前記含フッ素重合体の全単位に対して、99質量%未満となるようにテトラフルオロエチレンを共重合させる。)、含フッ素重合体の製造方法。
- 水性媒体と、テトラフルオロエチレン、クロロトリフルオロエチレンおよびフッ化ビニリデンから選ばれる少なくとも1種の含フッ素単量体に基づく単位を有する含フッ素重合体(ただし、前記含フッ素重合体中に前記テトラフルオロエチレンに基づく単位が含まれる場合、前記含フッ素重合体中におけるテトラフルオロエチレンに基づく単位の含有量が、前記含フッ素重合体の全単位に対して、99質量%未満である。)を含む、体積基準累積50%径が20~3000nmである粒子と、下式(1)で表される化合物に基づく単位および下式(2)で表される化合物に基づく単位から選ばれる少なくとも1種の単位を含む特定重合体であって、前記水性媒体中に粒子として含まれるかまたは前記含フッ素重合体を含む粒子中に含まれる、特定重合体と、を含み、乳化剤を実質的に含まない、含フッ素重合体水性分散液。
式(1): CXY=CR1-COO-(L-O)n-R2
式(2): CXY=CR3-(O)m-CH2-Z-R4
式(1)および式(2)中の各記号は以下のものを表す。
XおよびYは、相互に独立して、水素原子、ハロゲン原子またはメチル基を表す。
R1は、水素原子、ハロゲン原子または炭素数1~3のアルキル基を表す。
R2は、アルキル基、アルキル基中の少なくとも1つの-CH2-が-CO-に置き換えられたアルキル基または下式(3)で表される基を表す。
R3は、水素原子、ハロゲン原子、炭素数1~3のアルキル基または-CO-OCH3を表す。
R4は、アルキル基を表す。
Lは、アルキレン基を表す。
Zは、-CO-O-*または-O-CO-*を表す。ただし、*はR4との結合位置を表す。
mは0または1を表し、nは1以上の整数を表す。
式(3): -CO-CR1=CXY
式(3)中、X、YおよびR1は、それぞれ式(1)におけるX、YおよびR1の定義と同じである。 - 前記含フッ素重合体を含む粒子を、水性媒体100質量部に対して1.0~50.0質量部含む、請求項7に記載の含フッ素重合体水性分散液。
- 前記特定重合体の粒子を、水性媒体100質量部に対して0.0001~1.0質量部含む、請求項7または8に記載の含フッ素重合体水性分散液。
- 前記特定重合体の粒子を、前記含フッ素重合体を含む粒子100質量部に対して0.001~5.00質量部含む、請求項7~9のいずれか1項に記載の含フッ素重合体水性分散液。
- 水性媒体と、テトラフルオロエチレン、クロロトリフルオロエチレンおよびフッ化ビニリデンから選ばれる少なくとも1種の含フッ素単量体に基づく単位を有する含フッ素重合体(ただし、前記含フッ素重合体中に前記テトラフルオロエチレンに基づく単位が含まれる場合、前記含フッ素重合体中におけるテトラフルオロエチレンに基づく単位の含有量が、前記含フッ素重合体の全単位に対して、99質量%未満である。)を含む、体積基準累積50%径が20~3000nmである粒子と、ポリアルキレンオキシド化合物とを含み、乳化剤を実質的に含まない、含フッ素重合体水性分散液。
- テトラフルオロエチレン、クロロトリフルオロエチレンおよびフッ化ビニリデンから選ばれる少なくとも1種の含フッ素単量体に基づく単位を有する含フッ素重合体(ただし、前記含フッ素重合体中に前記テトラフルオロエチレンに基づく単位が含まれる場合、前記含フッ素重合体中におけるテトラフルオロエチレンに基づく単位の含有量が、前記含フッ素重合体の全単位に対して、99質量%未満である。)と、下式(1)で表される化合物に基づく単位および下式(2)で表される化合物に基づく単位から選ばれる少なくとも1種の単位を含む特定重合体と、を含み、乳化剤を実質的に含まない、重合体組成物。
式(1): CXY=CR1-COO-(L-O)n-R2
式(2): CXY=CR3-(O)m-CH2-Z-R4
式(1)および式(2)中の各記号は以下のものを表す。
XおよびYは、相互に独立して、水素原子、ハロゲン原子またはメチル基を表す。
R1は、水素原子、ハロゲン原子または炭素数1~3のアルキル基を表す。
R2は、アルキル基、アルキル基中の少なくとも1つの-CH2-が-CO-に置き換えられたアルキル基または下式(3)で表される基を表す。
R3は、水素原子、ハロゲン原子、炭素数1~3のアルキル基または-CO-OCH3を表す。
R4は、アルキル基を表す。
Lは、アルキレン基を表す。
Zは、-CO-O-*または-O-CO-*を表す。ただし、*はR4との結合位置を表す。
mは0または1を表し、nは1以上の整数を表す。
式(3): -CO-CR1=CXY
式(3)中、X、YおよびR1は、それぞれ式(1)におけるX、YおよびR1の定義と同じである。 - 前記含フッ素重合体100質量部に対する前記特定重合体の含有量が、0.001~5.00質量部である、請求項12に記載の重合体組成物。
- テトラフルオロエチレン、クロロトリフルオロエチレンおよびフッ化ビニリデンから選ばれる少なくとも1種の含フッ素単量体に基づく単位を有する含フッ素重合体(ただし、前記含フッ素重合体中に前記テトラフルオロエチレンに基づく単位が含まれる場合、前記含フッ素重合体中におけるテトラフルオロエチレンに基づく単位の含有量が、前記含フッ素重合体の全単位に対して、99質量%未満である。)と、ポリアルキレンオキシド化合物とを含み、乳化剤を実質的に含まない、重合体組成物。
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JPS50143890A (ja) * | 1974-05-10 | 1975-11-19 | ||
JPS5738808A (en) * | 1980-06-28 | 1982-03-03 | Hoechst Ag | Manufacture of water colloid dispersion of tetrafluoroethylene-ethylene type copolymer |
WO2001019880A1 (fr) * | 1999-09-13 | 2001-03-22 | Asahi Glass Company, Limited | Copolymere tetrafluoroethylene/ethylene et film constitue dudit polymere |
JP2002188052A (ja) * | 2000-12-21 | 2002-07-05 | Asahi Glass Co Ltd | フッ素系共重合体の水性塗料用組成物 |
JP2002201227A (ja) * | 2000-12-28 | 2002-07-19 | Asahi Glass Co Ltd | フッ素系共重合体の水性分散液 |
JP2002226764A (ja) * | 2001-01-31 | 2002-08-14 | Asahi Glass Co Ltd | 建材用塗装物品 |
WO2007046377A1 (ja) | 2005-10-20 | 2007-04-26 | Asahi Glass Company, Limited | 溶融成形可能なフッ素樹脂の製造方法 |
JP2020165490A (ja) | 2019-03-29 | 2020-10-08 | 積水化学工業株式会社 | ダイヤフラムバルブ |
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US5952457A (en) * | 1995-09-12 | 1999-09-14 | Mitsui Chemicals, Inc. | Polymerization catalyst for alkylene oxide compound and production process of poly(alkylene oxide) |
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JPS50143890A (ja) * | 1974-05-10 | 1975-11-19 | ||
JPS5738808A (en) * | 1980-06-28 | 1982-03-03 | Hoechst Ag | Manufacture of water colloid dispersion of tetrafluoroethylene-ethylene type copolymer |
WO2001019880A1 (fr) * | 1999-09-13 | 2001-03-22 | Asahi Glass Company, Limited | Copolymere tetrafluoroethylene/ethylene et film constitue dudit polymere |
JP2002188052A (ja) * | 2000-12-21 | 2002-07-05 | Asahi Glass Co Ltd | フッ素系共重合体の水性塗料用組成物 |
JP2002201227A (ja) * | 2000-12-28 | 2002-07-19 | Asahi Glass Co Ltd | フッ素系共重合体の水性分散液 |
JP2002226764A (ja) * | 2001-01-31 | 2002-08-14 | Asahi Glass Co Ltd | 建材用塗装物品 |
WO2007046377A1 (ja) | 2005-10-20 | 2007-04-26 | Asahi Glass Company, Limited | 溶融成形可能なフッ素樹脂の製造方法 |
JP2020165490A (ja) | 2019-03-29 | 2020-10-08 | 積水化学工業株式会社 | ダイヤフラムバルブ |
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