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
  • C08F114/00—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 a halogen
  • C08F114/18—Monomers containing fluorine
  • C08F114/26—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
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
• • 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
  • C08F2/04—Polymerisation in solution
  • C08F2/06—Organic solvent
• • 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
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • 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
• • 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
  • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
• • 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
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/38—Thiocarbonic acids; Derivatives thereof, e.g. xanthates ; i.e. compounds containing -X-C(=X)- groups, X being oxygen or sulfur, at least one X being sulfur
• • 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
  • C08F2438/00—Living radical polymerisation
  • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

• the present disclosure relates to a method for producing a fluoropolymer and a fluoropolymer.
• Emulsion polymerization and solution polymerization are adopted as a method for producing a fluoropolymer.
• Patent Document 2 describes a method for preparing a copolymer by controlled free radical copolymerization, wherein in the presence of an initiator and a chain transfer agent, a trifluoroethylene monomer and at least one additional monomer different from trifluoroethylene.
• said chain transfer agent is a xanthate compound, a trithiocarbonate compound or a monoiodized compound, where the copolymer prepared is a block copolymer and is present during the copolymerization step.
• the monomer consists of vinylidene fluoride and trifluoroethylene; or contains vinylidene fluoride, trifluoroethylene and at least one additional monomer, and the molar ratio of the amount of chain transfer agent to the amount of monomer is from 0.001. Methods have been described which are 0.020 and the initial molar ratio of the amount of TrFE monomer to the amount of copolymer is 10% to 90%, preferably 20% to 50%.
• Patent Document 3 describes a method for producing a polymer that polymerizes a haloolefin in the presence of a specific organic tellurium compound.
• Patent Document 4 butyl acetate is charged as a solvent and a vinyl ester monomer in the autoclave, perbutyl PV (product name, manufactured by Nichiyu Co., Ltd.) is added as a polymerization initiator, the autoclave is vacuum-substituted, and the tank temperature is changed. The temperature is raised to 60 ° C., and the reaction is started by encapsulating tetrafluoroethylene with stirring.
• perbutyl PV product name, manufactured by Nichiyu Co., Ltd.
• Non-Patent Document 1 describes that TFE and isobutyl vinyl ether were alternately copolymerized in an organic solvent using solution polymerization.
• the present disclosure is a method for producing a fluoropolymer by solution polymerization or dispersion polymerization, wherein (i) a step of homopolymerizing tetrafluoroethylene in the presence of an initiator, a chain transfer agent and a solvent, or (ii).
• the chain transfer agent comprises a step of randomly copolymerizing a tetrafluoroethylene with a monomer represented by the following general formula (1) and / or a monomer represented by the general formula (2), wherein the chain transfer agent is a dithioester compound or dithiocarbamate.
• the fluoropolymer is characterized by having a polymerization unit based on tetrafluoroethylene of 50 to 100 mol%.
• General formula (1): CF 2 CR 1 R 2 (In the formula, R 1 is H or F; R 2 is -Cl, -R a , -COOR b , -OCOR C , -CONR d 2 , -CN, -COR e , -Rf a ; R a , R.
• R b, R c, R d and R e are the same or different, H, or a substituent;
• Rf a is the same or different and may have a substituent group, include an oxygen atom between carbon atoms May be, a fluorine-containing alkyl group, a fluorine-containing vinyl group, or a fluorine-containing alkoxy group;
• R 1 and R 2 may be bonded to each other to form a ring).
• Af is a fluoropolymer segment composed of only a monomer unit derived from tetrafluoroethylene, or a monomer unit derived from tetrafluoroethylene, and the following general formula (1) and / or general formula ( It is a fluoropolymer segment in which the monomer unit derived from the monomer represented by 2) is randomly copolymerized, and the polymerization unit based on tetrafluoroethylene is 50 to 100 mol%.
• CRP is from the following formula (CRP1) to. (CRP5).)
• CRP5 is a fluoropolymer characterized by being represented by (CRP5).
• General formula (1): CF 2 CR 1 R 2 (In the formula, R 1 is H or F; R 2 is -Cl, -R a , -COOR b , -OCOR C , -CONR d 2 , -CN, -COR e , -Rf a ; R a , R.
• R b, R c, R d and R e are the same or different, H, or a substituent;
• Rf a is the same or different and may have a substituent group, include an oxygen atom between carbon atoms May be, a fluorine-containing alkyl group, a fluorine-containing vinyl group, or a fluorine-containing alkoxy group;
• R 1 and R 2 may be bonded to each other to form a ring).
• Bf is a fluoropolymer segment consisting only of a monomer unit derived from tetrafluoroethylene.
• CRP is represented by any of the following formulas (CRP1) to (CRP5)).
• CRP1 is represented by any of the following formulas (CRP1) to (CRP5)).
• CRP5 is represented by any of the following formulas (CRP1) to (CRP5)).
• the present disclosure is a method for producing a fluoropolymer by solution polymerization or dispersion polymerization, wherein (iii) tetrafluoroethylene is homopolymerized in the presence of an initiator, a chain transfer agent and a solvent, and then the following general formula is used.
• the chain transfer agent comprises a step of block copolymerizing fluoroethylene, and the chain transfer agent is at least one selected from the group consisting of a dithioester compound, a dithiocarbamate compound, a trithiocarbonate compound and a xantate compound.
• CF 2 CR 1 R 2 (In the formula, R 1 is H or F; R 2 is -Cl, -R a , -COOR b , -OCOR C , -CONR d 2 , -CN, -COR e , -Rf a ; R a , R.
• R b, R c, R d and R e are the same or different, H, or a substituent;
• Rf a is the same or different and may have a substituent group, include an oxygen atom between carbon atoms May be, a fluorine-containing alkyl group, a fluorine-containing vinyl group, or a fluorine-containing alkoxy group;
• R 1 and R 2 may be bonded to each other to form a ring).
• R 3 is R g , CF 3 or F;
• R 4 is -Cl, -R h , -COOR i , -OCOR j , -CONR k 2 , -CN, -COR m , Rf c ;
• R g and R h are the same or different, H, or a hydrocarbon group or heterocyclic group which may have a substituent;
• Ri , R j , R k and R m are the same or different, H or substituent;
• Rf c may have the same or different substituents and may contain an oxygen atom between carbon atoms, a fluorine-containing alkyl group, a fluorine-containing vinyl group or a fluorine-containing alkoxy.
• the solvent is preferably a non-fluorine-based organic solvent or a fluorine-based organic solvent.
• the concentration of the monomer represented by the general formula (1) and / or the general formula (2) with respect to the solvent is preferably 0.1 to 20 mol / L.
• the present disclosure also includes segment A containing a monomeric unit derived from tetrafluoroethylene and also provided is a fluoropolymer characterized by being a fluoropolymer comprising segment B containing a monomeric unit derived from the general formula (1) and / or the general formula (2).
• General formula (1): CF 2 CR 1 R 2 (In the formula, R 1 is H or F; R 2 is -Cl, -R a , -COOR b , -OCOR C , -CONR d 2 , -CN, -COR e , -Rf a ; R a , R.
• R b, R c, R d and R e are the same or different, H, or a substituent;
• Rf a is the same or different and may have a substituent group, include an oxygen atom between carbon atoms May be, a fluorine-containing alkyl group, a fluorine-containing vinyl group, or a fluorine-containing alkoxy group;
• R 1 and R 2 may be bonded to each other to form a ring).
• R 3 is R g , CF 3 or F;
• R 4 is -Cl, -R h , -COOR i , -OCOR j , -CONR k 2 , -CN, -COR m , Rf c ;
• R g and R h are the same or different, H, or a hydrocarbon group or heterocyclic group which may have a substituent;
• Ri , R j , R k and R m are the same or different, H or substituent;
• Rf c may have the same or different substituents and may contain an oxygen atom between carbon atoms, a fluorine-containing alkyl group, a fluorine-containing vinyl group or a fluorine-containing alkoxy.
• the segment A preferably consists of only monomeric units derived from tetrafluoroethylene.
• the segment B includes hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, trifluoroethylene, fluoroalkyl vinyl ether, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, and the like.
• the segment B is preferably a segment composed of polyvinyl ester, polyvinyl amide or polyvinylidene fluoride.
• the fluoropolymer of the present disclosure preferably has a mass ratio (A / B) of the segment A to the segment B of 99/1 to 1/99.
• the production method of the present disclosure can produce a fluoropolymer by a novel method.
• the fluoropolymers of the present disclosure are novel.
• the fluororesin is a partially crystalline fluoropolymer and is a fluoroplastics.
• the fluororesin has a melting point and is thermoplastic, but may be melt-processable or non-melt-processable.
• the melt processability means that the polymer can be melted and processed by using conventional processing equipment such as an extruder and an injection molding machine. Therefore, in the melt processable fluororesin, the melt flow rate measured by the measuring method described later is usually 0.01 to 500 g / 10 minutes.
• fluororubber is an amorphous fluoropolymer. “Amorphous” refers to the melting peak ( ⁇ H) that appears in differential scanning calorimetry [DSC] (warming temperature 10 ° C./min) or differential thermal analysis [DTA] (heating rate 10 ° C./min) of fluoropolymer. ) Is 4.5 J / g or less. Fluororubber exhibits elastomeric properties by cross-linking. Elastomer properties mean properties that allow the polymer to be stretched and retain its original length when the forces required to stretch the polymer are no longer applied.
• the partially fluoropolymer is a fluoropolymer containing a fluoromonomer unit and having a perfluoromonomer unit content of less than 90 mol% with respect to all polymerization units, and has a glass transition temperature of 20 ° C. or less. It is a fluoropolymer having a melting peak ( ⁇ H) of 4.5 J / g or less.
• the perfluoro rubber is a fluoropolymer having a perfluoromonomer unit content of 90 mol% or more with respect to all polymerization units, having a glass transition temperature of 20 ° C. or less, and 4.5 J / g. It is a fluoropolymer having the following melting peak ( ⁇ H) magnitude, and further, it is a polymer in which the concentration of fluoropolymers contained in the fluoropolymer is 71% by mass or more.
• the concentration of fluorine atoms contained in the fluoropolymer is obtained by calculating the concentration (mass%) of the fluorine atoms contained in the fluoropolymer from the type and content of each monomer constituting the fluoropolymer. ..
• the perfluoromonomer is a monomer that does not contain a carbon atom-hydrogen atom bond in the molecule.
• the perfluoromonomer may be a monomer in which some of the fluorine atoms bonded to carbon atoms are replaced with chlorine atoms, and in addition to carbon atoms, nitrogen atoms and oxygen atoms. , Sulfur atom, phosphorus atom, boron atom or silicon atom.
• the perfluoromonomer is preferably a monomer in which all hydrogen atoms are replaced with fluorine atoms.
• the perfluoromonomer does not contain a monomer that provides a cross-linking site.
• the monomer that gives a cross-linking site is a monomer (curesite monomer) having a cross-linking group that gives a cross-linking site to the fluoropolymer for forming a cross-link with a curing agent.
• the polytetrafluoroethylene [PTFE] is preferably a fluoropolymer in which the content of tetrafluoroethylene with respect to all the polymerization units is 99 mol% or more.
• both the fluororesin (excluding polytetrafluoroethylene) and the fluororubber are preferably fluoropolymers in which the content of tetrafluoroethylene with respect to the total polymerization units is less than 99 mol%.
• the content of each monomer constituting the fluoropolymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis according to the type of monomer.
• organic group means a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound.
• An example of the "organic group” is Alkyl groups, which may have one or more substituents, An alkenyl group which may have one or more substituents, An alkynyl group, which may have one or more substituents, A cycloalkyl group which may have one or more substituents, Cycloalkenyl groups, which may have one or more substituents, A cycloalkazienyl group which may have one or more substituents, Aryl groups, which may have one or more substituents, An aralkyl group which may have one or more substituents, A non-aromatic heterocyclic group, which may have one or more substituents, Heteroaryl groups, which may have one or more substituents, Cyano group, Holmil group, RaO-, RaCO-, RaSO 2- , RaCOO-,
• substituteduent group means a substitutable group.
• substitutable group examples include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, a sulfonyl group, a fluorine-containing sulfonyl group, an aliphatic oxy group, an aromatic oxy group, and a heterocycle.
• the aliphatic group may be saturated or unsaturated, and may be a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, or an aliphatic amino group. , Acylamino group, carbamoylamino group and the like.
• the aliphatic group include an alkyl group having a total carbon atom number of 1 to 8, preferably 1 to 4, such as a methyl group, an ethyl group, a vinyl group, a cyclohexyl group, and a carbamoylmethyl group.
• the aromatic group includes, for example, a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group and the like. You may be doing it.
• the aromatic group include aryl groups having 6 to 12 carbon atoms, preferably 6 to 10 total carbon atoms, for example, a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, and a 4-methanesulfonylphenyl group. And so on.
• the heterocyclic group has a halogen atom, a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group and the like. You may.
• Examples of the heterocyclic group include a 5- to 6-membered heterocycle having a total carbon number of 2 to 12, preferably 2 to 10, such as a 2-tetrahydrofuryl group and a 2-pyrimidyl group.
• the acyl group includes an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a hydroxy group, a halogen atom, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, and an amino group. , It may have an aliphatic amino group, an acylamino group, a carbamoylamino group and the like.
• acyl group examples include an acyl group having a total carbon atom number of 2 to 8, preferably 2 to 4, such as an acetyl group, a propanoyl group, a benzoyl group, and a 3-pyridinecarbonyl group.
• the acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group and the like, and has, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group and the like. You may be.
• Examples of the acylamino group include an acylamino group having a total carbon number of 2 to 12, preferably 2 to 8, and an alkylcarbonylamino group having a total carbon number of 2 to 8, such as an acetylamino group, a benzoylamino group, and a 2-pyridinecarbonylamino group.
• Groups, propanoylamino groups and the like can be mentioned.
• the aliphatic oxycarbonyl group may be saturated or unsaturated, and may be a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, or an aliphatic group. It may have an amino group, an acylamino group, a carbamoylamino group and the like.
• Examples of the aliphatic oxycarbonyl group include an alkoxycarbonyl group having a total carbon number of 2 to 8 and preferably 2 to 4, such as methoxycarbonyl, ethoxycarbonyl, and (t) -butoxycarbonyl group.
• the carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group and the like.
• Examples of the carbamoyl group include an unsubstituted carbamoyl group, an alkylcarbamoyl group having a total carbon number of 2 to 9, preferably an unsubstituted carbamoyl group, and an alkylcarbamoyl group having a total carbon number of 2 to 5, for example, an N-methylcarbamoyl group. Examples thereof include N, N-dimethylcarbamoyl group and N-phenylcarbamoyl group.
• the aliphatic sulfonyl group may be saturated or unsaturated, and may be a hydroxy group, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, or an amino group. , It may have an aliphatic amino group, an acylamino group, a carbamoylamino group and the like.
• Examples of the aliphatic sulfonyl group include alkylsulfonyl groups having a total carbon number of 1 to 6, preferably 1 to 4 total carbon atoms, such as methanesulfonyl.
• the aromatic sulfonyl group includes a hydroxy group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group and the like. You may be doing it.
• Examples of the aromatic sulfonyl group include arylsulfonyl groups having a total carbon atom number of 6 to 10, such as benzenesulfonyl.
• the amino group may have an aliphatic group, an aromatic group, a heterocyclic group and the like.
• the acylamino group may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group and the like.
• the acylamino group includes an acylamino group having a total carbon number of 2 to 12, preferably a total carbon number of 2 to 8, and more preferably an alkylcarbonylamino group having a total carbon number of 2 to 8, such as an acetylamino group and a benzoylamino group. Examples include a group, a 2-pyridinecarbonylamino group, a propanoylamino group and the like.
• the aliphatic sulfonamide group, aromatic sulfonamide group, and heterocyclic sulfonamide group may be, for example, a methanesulfonamide group, a benzenesulfonamide group, a 2-pyridinesulfonamide group, or the like.
• the sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group and the like.
• the sulfamoyl group includes a sulfamoyl group, an alkylsulfamoyl group having a total carbon number of 1 to 9, a dialkylsulfamoyl group having a total carbon number of 2 to 10, and an arylsulfamoyl group having a total carbon number of 7 to 13.
• Heterocyclic sulfamoyl group having 2 to 12 total carbon atoms more preferably sulfamoyl group, alkyl sulfamoyl group having 1 to 7 total carbon atoms, dialkyl sulfamoyl group having 3 to 6 total carbon atoms, total carbon
• Examples include groups, 4-pyridinesulfamoyl groups and the like.
• the aliphatic oxy group may be saturated or unsaturated, and may have a methoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxy group, a methoxyethoxy group, or the like.
• Examples of the aliphatic oxy group include an alkoxy group having a total carbon atom number of 1 to 8, preferably 1 to 6, such as a methoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxy group, and a methoxyethoxy group.
• the aromatic amino group and heterocyclic amino group are an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic group fused with the aryl group, an aliphatic oxycarbonyl group, and preferably a total carbon atom.
• the aliphatic thio group may be saturated or unsaturated, and an alkylthio group having a total carbon number of 1 to 8, more preferably a total carbon number of 1 to 6, such as a methylthio group and an ethylthio group. , Carbamoylmethylthio group, t-butylthio group and the like.
• the carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group and the like.
• Examples of the carbamoylamino group include a carbamoylamino group, an alkylcarbamoylamino group having a total carbon number of 2 to 9, a dialkylcarbamoylamino group having a total carbon number of 3 to 10, and an arylcarbamoylamino group having a total carbon number of 7 to 13.
• Heterocyclic carbamoylamino group having 3 to 12 total carbon atoms preferably carbamoylamino group, alkylcarbamoylamino group having 2 to 7 total carbon atoms, dialkylcarbamoylamino group having 3 to 6 total carbon atoms, total number of carbon atoms 7-11 arylcarbamoylamino groups, heterocyclic carbamoylamino groups with 3-10 total carbon atoms, such as carbamoylamino groups, methylcarbamoylamino groups, N, N-dimethylcarbamoylamino groups, phenylcarbamoylamino, 4-pyridine Examples thereof include a carbamoylamino group.
• the range represented by the end points includes all the numerical values included in the range (for example, 1 to 10 are 1.4, 1.9, 2.33, 5. 75, 9.98, etc. are included).
• At least 1 includes all numbers greater than or equal to 1 (eg, at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least. 100 etc.).
• the production method of the present disclosure is a method of producing a fluoropolymer by solution polymerization or dispersion polymerization, and is a step of (i) homopolymerizing tetrafluoroethylene in the presence of an initiator, a chain transfer agent and a solvent, or (Ii)
• the chain transfer agent comprises a step of randomly copolymerizing tetrafluoroethylene with a monomer represented by the following general formula (1) and / or general formula (2), and the chain transfer agent is a dithioester compound or a dithiocarbamate compound.
• General formula (1): CF 2 CR 1 R 2 (In the formula, R 1 is H or F; R 2 is -Cl, -R a , -COOR b , -OCOR C , -CONR d 2 , -CN, -COR e , -Rf a ; R a , R.
• R b, R c, R d and R e are the same or different, H, or a substituent;
• Rf a is the same or different and may have a substituent group, include an oxygen atom between carbon atoms May be, a fluorine-containing alkyl group, a fluorine-containing vinyl group, or a fluorine-containing alkoxy group;
• R 1 and R 2 may be bonded to each other to form a ring).
• solution polymerization or dispersion polymerization is selected as the polymerization method, and a specific compound is selected as the chain transfer agent, whereby block copolymerization is possible even with a TFE-based polymer. It was completed by discovering that it is possible to produce a fluoropolymer. According to the first production method of the present disclosure, a fluoropolymer having a terminal group based on a specific chain transfer agent is obtained, which enables block copolymerization.
• the above random copolymerization is a copolymerization in which two or more kinds of monomer units are randomly arranged.
• the chain transfer agent is at least one selected from the group consisting of a dithioester compound, a dithiocarbamate compound, a trithiocarbonate compound, and a xanthate compound.
• a dithioester represented by the formula (c1-1) a trithiocarbonate represented by the formula (c1-2) or the formula (c1-2')
• a dithioester represented by the formula (c1-3) examples thereof include carbamate and xanthate represented by the formula (c1-4).
• Z c1 is an aryl group or an alkyl group, for example, an aryl group having 6 to 20 carbon atoms such as a phenyl group and a cyanophenyl group, and an ethyl group having 1 carbon atom. ⁇ 15 alkyl groups.
• Z c2 is an aryl group or an alkyl group, for example, an alkyl group having 1 to 15 carbon atoms such as a dodecyl group.
• Z c3 and Z c4 are independently alkyl groups, aryl groups or 4-pyridyl groups, for example, alkyl groups having 1 to 15 carbon atoms such as methyl groups and aryl groups having 6 to 20 carbon atoms such as phenyl groups. .. Z c3 and Z c4 may be bonded to each other to form a heterocycle such as a pyrrole ring or a pyrrolidone ring together with the N atom in the formula (c1-3).
• Z c5 is an aryl group or an alkyl group, for example, an alkyl group having 1 to 15 carbon atoms such as an ethyl group and a trifluoroethyl group, and an aryl group having 6 to 20 carbon atoms such as a phenyl group and a perfluorophenyl group.
• the aryl group is preferably a phenyl group, a cyanophenyl group or a perfluorophenyl group, and more preferably a phenyl group or a perfluorophenyl group.
• the alkyl group is preferably a methyl group, an ethyl group, a butyl group, a dodecyl group, or a trifluoroethyl group, and more preferably a methyl group, an ethyl group, or a trifluoroethyl group.
• R c is a monovalent organic group, for example, one or more of (i) an alkyl group, and (ii) a hydrogen atom of the alkyl group , A phenyl group, a cyano group, a hydroxyl group, a carboxyl group, an alkoxycarbonyl group having 1 to 4 carbon atoms, a phenoxycarbonyl group, an acetoxy group and a group substituted with at least one group selected from the group consisting of c1 to c4 below. Can be mentioned.
• the two R c may each be the same or different.
• the number of carbon atoms in the alkyl group in R c is usually 1 to 18, preferably from 2 to 12.
• a c is an integer of alkylene radical, n is 10 to 300 2 to 5 carbon atoms.
• Examples of the dithioester (c1-1) include the following compounds.
• Examples of the trithiocarbonate (c1-2) and (c1-2') include the following compounds.
• n is an integer from 10 to 300.
• Examples of the dithiocarbamate (c1-3) include the following compounds.
• Examples of xanthate (c1-4) include the following compounds.
• the amount of the chain transfer agent added may vary depending on the magnitude of the chain transfer constant of the compound used, but is 0.05 to 20 mol with respect to all the monomers used in the polymerization. It is preferably used in the range of%. More preferably, it is 0.06 mol% or more, further preferably 0.08 mol% or more, even more preferably 0.1 mol% or more, and even more preferably 15 mol% or less. It is even more preferably 10 mol% or less, and even more preferably 6.5 mol% or less.
• RAFT reversible additional cleavage chain transfer polymerization
• living radical polymerization can be performed in the presence of the chain transfer agent.
• the solution polymerization or dispersion polymerization is carried out in the presence of an initiator.
• Suitable initiators include peroxides and azo compounds and redox-based initiators.
• Specific examples of the peroxide initiator include hydrogen peroxide, sodium peroxide or barium peroxide, diacetyl peroxide, discussinyl peroxide, dipropionyl peroxide, dibutyryl peroxide, dibenzoyl peroxide, and benzoyl acetylper.
• diacyl peroxides such as oxides, diglutaric acid peroxides and dilauryl peroxides, and peracids and salts thereof (for example, ammonium salts, sodium salts and potassium salts).
• peracids include peracetic acid. Esters of peracid can be used as well, examples of which include tert-butylperoxyacetate and tert-butylperoxypivalate.
• the inorganic agent include persulfuric acid, permanganate or ammonium salt of manganic acid, alkaline salt or alkaline earth salt, or manganic acid.
• Persulfate initiators such as ammonium persulfate (APS), can be used alone or in combination with reducing agents.
• Suitable reducing agents include bisulfites such as, for example, ammonium bisulfite or sodium metabisulfite, such as thiosulfates such as ammonium thiosulfate, potassium or sodium, hydrazine, azodicarboxylate and azodicarboxydiamid (ADA). ).
• Further reducing agents that may be used include, for example, formaldehyde sulfoxylate sodium (Luffalit) or fluoroalkylsulfinate as disclosed in US Pat. No. 5,285,002. Reducing agents typically reduce the half-life of persulfate initiators.
• a metal salt catalyst such as copper, iron or silver salt may be added.
• azo compound examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azobis (2-cyclopropyl). Propionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile) , 2- (Carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis ( N, N'-Dimethyleneisobutyamidin), 2,2'-Azobisisobuty [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2'-Azobisisobutyamidrate, 4,4
• the initiator examples include peracid esters, persulfates, diacyl peroxides, 2,2'-azobis (2-methylbutyronitrile), or 2,2'-azobis (2-methylbutyronitrile). Is more preferable, and tert-butylperoxypivalate, dibenzoyl peroxide, tert-butylperoxyacetate, or 2,2'-azobis (2-methylbutyronitrile) is further preferable.
• the amount of the initiator added may vary depending on the compound used, but is used in the range of 5.0 to 1000 mol% with respect to the chain transfer agent. It is preferably 6.0 mol% or more, more preferably 8.0 mol% or more, further preferably 10 mol% or more, and preferably 100 mol% or less, more preferably 50 mol. % Or less, more preferably 30 mol% or less.
• the solvent is preferably a non-fluorine-based organic solvent, a fluorine-based organic solvent, or water, and more preferably a non-fluorine-based organic solvent or a fluorine-based organic solvent.
• the non-fluorinated container solvent include esters such as n-butyl acetate, t-butyl acetate, ethyl acetate, methyl acetate, propyl acetate and dimethyl carbonate; ketones such as acetone, methyl ethyl ketone and cyclohexanone; hexane, cyclohexane and octane.
• aliphatic hydrocarbons such as benzene, toluene and xylene; alcohols such as methanol, ethanol, tert-butanol and isopropanol; cyclic ethers such as tetrahydrofuran and dioxane; dimethylsulfoxide, dimethylformamide, etc.
• fluorocarbon-based organic solvent examples include HCFC-225, tetradecafluorohexane, fluoroalkane, hydrofluoroether, fluoroalcohol and the like.
• the solvent examples include acetone, dimethyl carbonate, ethyl acetate, methyl ethyl ketone, methanol, tetradecafluorohexane, 1,1,1,3,3-pentafluorobutane, methylnonafluorobutyl ether, methylnonafluoroisobutyl ether, 1, 1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) -pentane, 2,2,2-trifluoroethanol, or HCFC-225 Is more preferable, and acetone, ethyl acetate, tetradecafluorohexane, 3M (TM) Novec (TM) 7100 high-performance liquid (manufactured by 3M Japan Co., Ltd.) or Asahiclean AK225 (manufactured by AGC Co., Ltd.) is used. More preferred.
• the polymerization temperature in the step (i) is not particularly limited as long as it is a temperature at which solution polymerization or dispersion polymerization is possible, but may be, for example, 10 to 150 ° C. It is preferably 20 to 130 ° C, more preferably 40 to 110 ° C.
• the polymerization pressure in the step (i) is not particularly limited as long as it is at a temperature at which solution polymerization or dispersion polymerization is possible, but may be, for example, 0.05 to 5.0 MPaG. It is preferably 0.2 to 3.5 MPaG, and more preferably 0.5 to 1.2 MPaG.
• the polymerization temperature in the step (ii) is not particularly limited as long as it is a temperature at which solution polymerization or dispersion polymerization is possible, but may be, for example, 0.0 to 150 ° C. It is preferably 20 to 130 ° C, more preferably 40 to 110 ° C.
• the polymerization pressure in the step (ii) is not particularly limited as long as it is at a temperature at which solution polymerization or dispersion polymerization is possible, but may be, for example, 0.0 to 9.8 MPaG. It is preferably 0.2 to 6.0 MPaG, and more preferably 0.5 to 3.0 MPaG.
• solution polymerization and dispersion polymerization are polymerization methods in which a polymerization reaction is carried out in a solvent.
• Solution polymerization is a polymerization performed by a combination of a monomer and a solvent in which the monomer is soluble in a solvent and the polymer formed by the polymerization is also soluble in the solvent.
• the dispersion polymerization is a polymerization carried out by a combination of a monomer and a solvent in which the monomer is soluble in a solvent but the polymer formed by the polymerization is insoluble in the solvent. Therefore, whether it is solution polymerization or dispersion polymerization is determined by the combination of the monomer and the solvent used.
• the step (i) of homopolymerizing tetrafluoroethylene (TFE) or TFE and the monomers represented by the general formulas (1) and / or the general formula (2) are randomly selected.
• the step (ii) of copolymerizing is included.
• the step (i) is for homopolymerizing TFE.
• TFE TFE homopolymer
• the step (ii) is a step of randomly copolymerizing TFE with the monomer represented by the general formula (1) and / or the monomer represented by the general formula (2).
• the fluoropolymer is polymerized so that the polymerization unit based on TFE is 50 mol% or more and less than 100 mol%.
• the polymerization unit based on TFE is preferably 51 mol% or more, more preferably 55 mol% or more, further preferably 60 mol% or more, and particularly preferably 65 mol% or more. Further, 99 mol% or less is preferable, 95 mol% or less is more preferable, and 90 mol% or less is further preferable.
• the step (ii) may be for producing the modified PTFE described later, in which case the step (ii) is based on the monomers represented by the general formulas (1) and (2) of the fluoropolymer. It is preferable that the polymerization is carried out so that the total amount of the polymerization units is 0.00001 to 1.0% by mass. As the lower limit of the total amount, 0.0001% by mass is more preferable, 0.001% by mass is further preferable, 0.005% by mass is further more preferable, and 0.009% by mass is particularly preferable. As the upper limit, 0.90% by mass is preferable, 0.50% by mass is more preferable, 0.40% by mass is further preferable, 0.30% by mass is further more preferable, and 0.10% by mass is particularly preferable.
• R a in the general formula (1), R b, R c, R d and R e are the same or different, are H or a substituent.
• substituents include those described above, and among them, an aliphatic group, an acyl group, an aromatic group, or a heterocyclic group is preferable, an aliphatic group, an acyl group, or a heterocyclic group is more preferable, and a fat. Group groups or acyl groups are more preferred.
• the R a, R b, R c , R d and R e is preferably 1 to 10 carbon atoms, more preferably 1 to 8, 1 to 5 more preferred.
• the aliphatic group, acyl group, aromatic group and heterocyclic group may have a substituent or may have an oxygen atom between carbon atoms.
• R a , R b , R c , R d, and Re may be chain-like or branched, and may include a cyclic structure.
• the Rf a in the general formula (1) may have a substituent group, may contain an oxygen atom between carbon atoms, a fluorine-containing alkyl group, fluorine-containing vinyl group, a fluorine-containing alkoxy group, containing Fluoroalkyloxyalkyl groups and the like can be mentioned.
• the carbon number of Rf a is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6.
• Rf a may be chain-like or branched, and may include a cyclic structure.
• R 2 examples include ⁇ H, a fluorine-containing alkyl group having 1 to 10 carbon atoms which may have a substituent, and a fluorine-containing alkoxy group having 1 to 10 carbon atoms which may have a substituent.
• Cl a non-fluorinated alkyl group having 1 to 10 carbon atoms which may have a substituent, a carboxyl group, an alkyl ester group having 1 to 10 carbon atoms which may have a substituent, or a substituent.
• Examples of the monomer represented by the general formula (1) include hexafluoropropylene [HFP], chlorotrifluoroethylene [CTFE], vinylidene fluoride [VDF], trifluoroethylene, fluoroalkyl vinyl ether, trifluoropropylene, and pentafluoropropylene.
• Trifluorobutene, tetrafluoroisobutene and hexafluoroisobutene are preferably at least one selected from the group.
• General formula (120): CF 2 CF-OCH 2- Rf 121 (In the formula, Rf 121 is a perfluoroalkyl group having 1 to 5 carbon atoms).
• CF 2 CFOCF 2 ORf 131
• Rf 131 is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, and 2 to 6 carbon atoms containing 1 to 3 oxygen atoms. It is a linear or branched perfluorooxyalkyl group of.), And a fluoromonomer.
• General formula (140): CF 2 CFO (CF 2 CF (Y 141 ) O) m (CF 2 ) n F (In the formula, Y 141 represents a fluorine atom or a trifluoromethyl group. M is an integer of 1 to 4. n is an integer of 1 to 4.) Selected from the group consisting of fluoromonomers. It is preferable that the amount is at least one.
• Examples of the fluoromonomer represented by the general formula (110) include a fluoromonomer in which Rf 111 is a perfluoroalkyl group having 1 to 10 carbon atoms.
• the number of carbon atoms of the perfluoroalkyl group is preferably 1 to 5.
• Examples of the perfluoroalkyl group in the general formula (110) include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group and the like.
• Rf 111 is a perfluoro (alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf 111 is the following formula:
• Rf 111 is the following formula:
• n an integer of 1 to 4.
• CF 2 CF-ORf 161
• Rf 161 represents a perfluoroalkyl group having 1 to 10 carbon atoms.
• a fluoromonomer represented by is preferable.
• Rf 161 is preferably a perfluoroalkyl group having 1 to 5 carbon atoms.
• the fluoroalkyl vinyl ether is preferably at least one selected from the group consisting of fluoromonomers represented by the general formulas (110), (130) and (140).
• the fluoromonomer represented by the general formula (110) at least one selected from the group consisting of perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), and perfluoro (propyl vinyl ether) is preferable, and per. At least one selected from the group consisting of fluoro (methyl vinyl ether) and perfluoro (propyl vinyl ether) is more preferable.
• CF 2 CFOCF 2 CF (CF 3 ) O (CF 2 ) 3 F
• CF 2 CFO (CF 2 CF (CF 3 ) O) 2 (CF 2 ) ) 3 F
• CF 2 CFO (CF 2 CF (CF 3 ) O) 2 (CF 2 )
• CF 2 CF-O- (CF 2 ) n- A
• n stands for an integer of 1 ⁇ 10
• A is -CH 2 OH, -COOM, is -SO 3 M or -OSO 3 M (M, -H, a metal atom, -NR 7 4, It is imidazolium which may have a substituent, pyridinium which may have a substituent or phosphonium which may have a substituent, and R 7 is H or an organic group).
• CF 2 CF -O- (CF 2 CFX 1 O) n -CF 2 CF 2 -A
• n represents an integer of 1 to 10
• X 1 represents F or CF 3
• A is the same as the above definition).
• n is preferably an integer of 5 or less.
• X 1 is preferably ⁇ CF 3 .
• R 7 is preferably an organic group H or C 1-10, more preferably an organic group of H or C 1-4, alkyl group of H or C 1-4 is more preferred.
• the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li are preferable.
• M is, -H, preferably is a metal atom or -NR 7 4, -H, alkali metal (Group 1), alkaline earth metal (Group 2) or -NR 7 4, more preferably, -H, -Na, - K, -Li or -NH 4 is more preferred.
• vinylidene fluoride, hexafluoropropylene, perfluoro (methyl vinyl ether), perfluorosulfonyl vinyl fluoride ether, trifluoroethylene, chlorotrifluoroethylene or trifluoropropylene are preferable.
• Vinylidene fluoride, hexafluoropropylene, perfluoro (methyl vinyl ether), perfluorosulfonyl vinyl ether or trifluoropropylene are more preferred, with vinylidene fluoride, hexafluoropropylene, perfluoro (methyl vinyl ether) or perfluorosulfonyl vinyl ether. More preferred.
• the monomer represented by the general formula (1) is a monomer different from TFE.
• R g and R h are hydrocarbon groups or heterocyclic groups that are the same or different and may have H or a substituent.
• the hydrocarbon group include an alkyl group, an alkylene group, an aryl group, a vinyl group and the like.
• the hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms.
• the heterocyclic group a group having a lactam structure having 2 to 7 carbon atoms is preferable, a group having a lactam structure having 3 to 6 carbon atoms is more preferable, and a group having a lactam structure having 4 carbon atoms is further preferable.
• R g and R h may be chain-like or branched, and may include a cyclic structure.
• R i , R j , R k and R m in the general formula (2) are the same or different, and are H or a substituent.
• substituents include those described above, and among them, an aliphatic group, an acyl group, an aromatic group or a heterocyclic group is preferable, an aliphatic group, an acyl group or a heterocyclic group is more preferable, and an aliphatic group is preferable. Groups or acyl groups are more preferred.
• the aliphatic group, acyl group, aromatic group and heterocyclic group may have a substituent or may have an oxygen atom between carbon atoms.
• R i , R j , R k and R m preferably have 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms.
• R i , R j , R k and R m may be chain-like or branched, and may include a cyclic structure.
• the Rf c in the general formula (2) may have a substituent group, may contain an oxygen atom between carbon atoms, a fluorine-containing alkyl group, fluorine-containing vinyl group, a fluorine-containing alkoxy group, containing Fluoroalkyloxyalkyl groups and the like can be mentioned.
• the carbon number of Rf c is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6.
• Rf c may be chain-like or branched, and may include a cyclic structure.
• the R 3 is preferably H, F, CH 3 or CF 3 , and more preferably H, F, or CF 3 .
• R 4 examples include a non-fluorinated alkyl group having 1 to 10 carbon atoms which may have a substituent, a fluorine-containing alkyl group having 1 to 10 carbon atoms which may have a substituent, and ⁇ COOR i. , -OCOR j , -CONR k 2 , -NR x COR y , -NR z 2 , or a group having a lactam structure having 2 to 7 carbon atoms is preferable.
• the R x , R y and R z are the same or different, H or an alkyl group having 1 to 10 carbon atoms.
• Examples of the monomer represented by the general formula (2) include alkenes such as ethylene, propylene, butylene, and isobutylene; vinyl acetate, vinyl propionate, n-vinyl butyrate, vinyl isobutyrate, vinyl valerate, and vinyl pivalate.
• Examples of the monomer represented by the above general formula (2) include (meth) acrylic acid esters such as methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate; itaconic acid; glycidyl such as glycidyl vinyl ether and glycidyl allyl ether.
• Fluorine-free monomers having a group fluorine-free monomers having an amino group such as aminoalkylvinyl ether and aminoalkylallyl ether; fluorine-free monomers having an amide bond such as (meth) acrylamide and methylolacrylamide can be mentioned.
• Fluoromonomer represented by (fluoroalkyl group), general formula (300): CH 2 CFCF 2- O- (CF (CF 3 ) CF 2 O) n- CF (CF 3 ) -A
• n is represents an integer of 0 or 1 ⁇ 10
• a is, -CH 2 OH, -COOM, -SO 3 M or -OSO 3 M
• M is, -H, a metal atom, -NR 7 4, substituted Imidazolium which may be, pyridinium which may have a substituent or phosphonium which may have a substituent
• R 7 is a fluoromonomer represented by H or an organic group).
• n is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1.
• R 7 an organic group of H or C 1-10 is preferable, an organic group of H or C 1-4 is more preferable, and an alkyl group of H or C 1-4 is further preferable.
• the metal atom include alkali metals (Group 1) and alkaline earth metals (Group 2), and Na, K or Li are preferable.
• -H preferably is a metal atom or -NR 7 4, -H, alkali metal (Group 1), alkaline earth metal (Group 2) or -NR 7 4, more preferably, -H, -Na , -K, -Li or -NH 4 is more preferred.
• Y 241 is, for example, a linear or branched aliphatic group having 1 to 20 carbon atoms (particularly, an alkylene group), for example, the formula ⁇ (CH 2 ) x ⁇ (in the formula, x is 1 to 10). ) May be the group.
• Rf 241 is preferably a perfluoroalkyl group.
• the carbon number of Rf 241 is preferably 4 to 8, and more preferably 4 to 6.
• Rf 241 includes -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ) 2 , -C (CF 3 ) 3 ,-(CF 2 ) 4 CF 3 ,-(CF 2 ) 2 CF ( CF 3 ) 2 , -CF 2 C (CF 3 ) 3 , -CF (CF 3 ) CF 2 CF 2 CF 3 ,-(CF 2 ) 5 CF 3 ,-(CF 2 ) 3 CF (CF 3 ) 2 , -(CF 2 ) 4 CF (CF 3 ) 2 , -C 8 F 17 and the like.
• fluorine-containing acrylate monomer examples include, but are not limited to, the following.
• the fluorine-free monomer having an amide bond for example, the above-mentioned -CONR k 2 , -NR x COR y , or a monomer having a group having a lactam structure having 2 to 7 carbon atoms is preferable.
• the amide bond refers to a bond between a carbonyl group and a nitrogen atom.
• fluorine-free monomer having an amide bond examples include N-vinyl- ⁇ -propiolactam, N-vinyl-2-pyrrolidone, N-vinyl- ⁇ -valerolactam, N-vinyl-2-piperidone, and N-vinyl.
• -N-vinyllactam compounds such as heptactam
• acyclic N-vinylamide compounds such as N-vinylformamide, N-methyl-N-vinylacetamide
• acyclic N- such as N-allyl-N-methylformamide, allylurea.
• Examples thereof include allylamide compounds, N-allylactam compounds such as 1- (2-propenyl) -2-pyrrolidone, and acrylamide compounds such as (meth) acrylamide, N, N-dimethylacrylamide, and N-isopropylacrylamide.
• R x and R y are independently H or an alkyl group having 1 to 10 carbon atoms.
• R z is independently H or an alkyl group having 1 to 10 carbon atoms, and the like can also be mentioned.
• an N-vinyllactam compound or an acyclic N-vinylamide compound is preferable, and N-vinyl- ⁇ -propiolactam, N-vinyl-2-pyrrolidone, and N are preferable.
• At least one selected from the group consisting of -vinyl- ⁇ -valerolactam, N-vinyl-2-piperidone, and N-vinyl-heptalactam is more preferable, and N-vinyl-2-pyrrolidone and N-vinyl are preferable.
• At least one selected from the group consisting of -2-piperidone is more preferable, and N-vinyl-2-pyrrolidone is particularly preferable.
• R 4 includes -OCOCH 3 , -H, -COOCH 3 , -NH (C 3 H 7 ), -C 4 F 9 , -CH 3, or the following formula (3): It is preferably a group represented by, more preferably -OCOCH 3 , -H, -COOCH 3 or a group represented by the above formula (3), and -OCOCH 3 , -H or the above formula (3). It is more preferable that the group is represented by.
• Examples of the monomer represented by the general formula (1) or the general formula (2) include HFP, CTFE, VDF, vinyl fluoride, trifluoroethylene, fluoroalkyl vinyl ether, trifluoropropylene, pentafluoropropylene, and trifluorobutene. At least one selected from the group consisting of tetrafluoroisobutene, hexafluoroisobutene, vinyl esters, (meth) acrylic acid ester, alkene, fluorine-free monomer having an amide bond, fluoroalkylethylene and fluorine-containing acrylate monomer is preferable.
• Examples of the fluoropolymer obtained by the first production method of the present disclosure include the first fluoropolymer of the present disclosure described later, the second fluoropolymer of the present disclosure, and the like.
• the fluoropolymer of the present disclosure has the following formula: Af-CRP (In the formula, Af is a fluoropolymer segment composed of only a monomer unit derived from tetrafluoroethylene, or a monomer unit derived from tetrafluoroethylene, and the general formula (1) and / or the general formula (2). It is a fluoropolymer segment in which the monomer unit derived from the monomer represented by is randomly copolymerized, and the polymerization unit based on tetrafluoroethylene is 50 to 100 mol%.
• the CRP has the following formulas (CRP1) to (CRP5).
• the first fluoropolymer of the present disclosure can be block copolymerized by having the above-mentioned specific group at the end. Therefore, the first fluoropolymer of the present disclosure is useful as an intermediate for producing block copolymers. Further, the first fluoropolymer of the present disclosure can be used as it is not only as an intermediate but also for applications as described later.
• Examples of Z c11 in the formula (CRP1) include those similar to Z c1 in the above-mentioned formula (c1-1).
• Examples of Z c12 in the formula (CRP2) include those similar to Z c2 in the above-mentioned formula (c1-2).
• Examples of R c11 in the formula (CRP3) include those similar to R c in the above-mentioned formula (c1-2').
• Examples of Z c13 in the formula (CRP4) include those similar to Z c3 and Z c4 in the above formula (c1-3).
• Examples of Z c14 in the formula (CRP5) include those similar to Z c5 in the above formula (c1-4).
• As the CRP CRP5 is preferable from the viewpoint of the polymerization rate.
• the above formulas (CRP1) to (CRP5) are groups derived from the chain transfer agent described in the first production method of the present disclosure.
• the above formulas (CRP1) to (CRP5) are portions in which at least a part of the structure of the chain transfer agent is incorporated into a fluoropolymer (preferably the main chain terminal of the fluoropolymer).
• the first fluoropolymer of the present disclosure is based on tetrafluoroethylene and has a polymerization unit of 50 to 100 mol%.
• the polymerization unit based on tetrafluoroethylene is preferably 51 to 100 mol%, more preferably 55 to 100 mol%, further preferably 60 to 100 mol%, and particularly preferably 65 to 100 mol%.
• the Af is a fluoropolymer segment composed of only monomer units derived from tetrafluoroethylene.
• PTFE fluoropolymer in which the Af is a fluoropolymer segment consisting only of monomer units derived from tetrafluoroethylene.
• PTFE fluoropolymer segment consisting only of monomer units derived from tetrafluoroethylene
• the PTFE obtained by the production method of the present disclosure may be low molecular weight PTFE or high molecular weight PTFE.
• Low molecular weight PTFE also called PTFE micropowder
• PTFE micropowder with a molecular weight of 600,000 or less has excellent chemical stability, extremely low surface energy, and is less likely to cause fibrillation, thus improving slipperiness and the texture of the coating film surface. It is suitable for producing plastics, inks, cosmetics, paints, greases, office automation equipment members, toners and the like as additives for the purpose of making them (see, for example, Japanese Patent Application Laid-Open No. 10-147617).
• the low molecular weight PTFE obtained by the above polymerization is used as a powder, it can be made into powder particles by coagulating a dispersion of PTFE.
• the high molecular weight PTFE means a PTFE having non-melt processability and fibrillation property.
• the low molecular weight PTFE means PTFE having melt processability and not fibrillation property.
• the non-melt processability means a property that the melt flow rate cannot be measured at a temperature higher than the crystallization melting point in accordance with ASTM D-1238 and D-2116.
• the presence or absence of fibrillation can be determined by "paste extrusion", which is a typical method for molding "high molecular weight PTFE powder” which is a powder made from a polymer of TFE. Generally, paste extrusion is possible because high molecular weight PTFE has fibrillation properties.
• the high molecular weight PTFE preferably has a standard specific gravity (SSG) of 2.130 to 2.280.
• the standard specific gravity is measured by a water substitution method based on ASTM D-792 using a sample molded according to ASTM D4895-89.
• High molecular weight means that the standard specific gravity is within the above range.
• the low molecular weight PTFE has a complex viscosity at 380 ° C. of 1 ⁇ 10 2 to 7 ⁇ 10 5 Pa ⁇ s.
• Low molecular weight means that the complex viscosity is within the above range.
• the high molecular weight PTFE has an extremely higher complex viscosity than the low molecular weight PTFE, and it is difficult to accurately measure the complex viscosity.
• the complex viscosity of the low molecular weight PTFE can be measured, it is difficult to obtain a molded product that can be used for measuring the standard specific gravity from the low molecular weight PTFE, and it is difficult to measure the accurate standard specific gravity. Is. Therefore, the standard specific gravity is adopted as an index of the molecular weight of the high molecular weight PTFE, and the complex viscosity is adopted as an index of the molecular weight of the low molecular weight PTFE. There is no known measurement method capable of directly specifying the molecular weight of either the high molecular weight PTFE or the low molecular weight PTFE.
• the high molecular weight PTFE preferably has a peak temperature of 333 to 347 ° C, more preferably 335 to 345 ° C.
• the low molecular weight PTFE preferably has a peak temperature of 322 to 333 ° C, more preferably 324 to 332 ° C.
• the peak temperature corresponds to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimeter [DSC] for a PTFE that has no history of heating to a temperature of 300 ° C. or higher. Is.
• the high molecular weight PTFE is 333 to 347 ° C. in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimeter [DSC] for a PTFE having no history of heating to a temperature of 300 ° C. or higher. It is preferable that at least one heat absorption peak appears in the range of 1 and the amount of heat of fusion calculated from the heat of fusion curve at 290 to 350 ° C. is 62 mJ / mg or more.
• the above PTFE can be used as an aqueous dispersion or a fine powder.
• the fine powder of PTFE is preferable for molding, and suitable applications include hydraulic systems such as aircraft and automobiles, fuel system tubes and the like, flexible hoses such as chemicals and steam, and electric wire coating applications.
• the aqueous dispersion of PTFE can also be used for various purposes as a composition in which a nonionic surfactant is added to stabilize and further concentrate the mixture, and an organic or inorganic filler is added depending on the purpose. preferable.
• the above composition has a non-adhesive and low coefficient of friction by coating on a base material made of metal or ceramics, and has excellent gloss, smoothness, abrasion resistance, weather resistance and heat resistance. It is suitable for painting rolls and cooking utensils, impregnating glass cloth, and the like.
• An organosol of PTFE can also be prepared from the above aqueous dispersion.
• the organosol can contain the PTFE and the organic solvent, and the organic solvent includes an ether solvent, a ketone solvent, an alcohol solvent, an amide solvent, an ester solvent, an aliphatic hydrocarbon solvent, and an aromatic solvent. Examples thereof include a hydrocarbon solvent and a halogenated hydrocarbon solvent, and N-methyl-2-pyrrolidone, dimethylacetamide and the like can be preferably used.
• the preparation of the organosol can be carried out, for example, by the method described in International Publication No. 2012/002038.
• the aqueous dispersion of PTFE or the fine powder of PTFE is also preferably used as a processing aid.
• a processing aid by mixing the aqueous dispersion or the fine powder with a host polymer or the like, the melt strength during melt processing of the host polymer can be improved, and the mechanical strength, electrical properties, and difficulties of the obtained polymer can be improved. It is possible to improve flammability, dripping prevention property during combustion, and slidability.
• the aqueous dispersion of PTFE or the fine PTFE powder is also preferably used as a binder for batteries and dustproof.
• An unfired tape (raw tape) can also be obtained from the PTFE fine powder obtained by the production method of the present disclosure.
• the aqueous dispersion of PTFE or the PTFE fine powder is used as a processing aid after being combined with a resin other than PTFE.
• the aqueous dispersion or the fine powder is, for example, a raw material for PTFE described in JP-A-11-49912, US Pat. No. 5,804,654, JP-A-11-29679, and JP-A-2003-2980. Is suitable as.
• the processing aid using the aqueous dispersion or the fine powder is not inferior to the processing aids described in the respective publications.
• the aqueous dispersion of PTFE is mixed with an aqueous dispersion of a melt-processable fluororesin and coagulated to obtain a co-coagulation powder.
• the co-coagulation powder is suitable as a processing aid.
• the melt-processable fluororesin include FEP, PFA, ETFE, ethylene / TFE / HFP copolymer [EFEP], and FEP is preferable.
• the aqueous dispersion preferably contains the melt-processable fluororesin.
• the melt-processable fluororesin include FEP, PFA, ETFE, and EFEP.
• the aqueous dispersion containing the melt-processable fluororesin can be used as a coating material.
• the melt-processable fluororesin can sufficiently fuse the PTFE particles to each other, the film-forming property can be improved and the obtained film can be glossed.
• the fluorine-free resin to which the co-coagulation powder is added may be in the form of a powder, in the form of pellets, or in the form of an emulsion. The above addition is preferably carried out while applying a shearing force by a known method such as extrusion kneading or roll kneading, in that each resin is sufficiently mixed.
• the aqueous dispersion of PTFE is also preferably used as a dust control treatment agent.
• the dust control treatment agent is a method of fibrillating PTFE by mixing with a dust generating substance and applying a compression-shearing action to the mixture at a temperature of 20 to 200 ° C. to suppress dust of the dust generating substance, for example. It can be used in methods such as Japanese Patent No. 2827152 and Japanese Patent No. 2538783.
• the aqueous dispersion of PTFE can be suitably used, for example, in the dust control agent composition described in International Publication No. 2007/004250, and also in the dust control treatment method described in International Publication No. 2007/000812. It can be preferably used.
• the dust control treatment agent includes building materials, soil stabilizers, solidifying materials, fertilizers, incineration ash and harmful substances in landfills, explosion-proofing, cosmetics, sand for pet excretion represented by cat sand, etc. It is suitably used for the dust control treatment of.
• aqueous dispersion of PTFE as a raw material for obtaining PTFE fibers by a dispersion spinning method.
• the aqueous dispersion of PTFE and the aqueous dispersion of a matrix polymer are mixed, the mixture is extruded to form an intermediate fiber structure, and the intermediate fiber structure is fired.
• This is a method for obtaining PTFE fibers by decomposing the matrix polymer and sintering the PTFE particles.
• the high molecular weight PTFE powder obtained by polymerization has stretchability and non-melt processability, and is also useful as a raw material for a stretched body (porous body).
• this stretched body is a membrane (PTFE stretched membrane or PTFE porous membrane), it can be stretched by a known PTFE stretching method.
• the high molecular weight PTFE is easily fibrillated into a PTFE porous body (membrane) composed of nodules and fibers.
• a uniaxially stretched film can be obtained by roll-stretching a sheet-shaped or rod-shaped paste extruded product in the extrusion direction.
• a biaxially stretched film can also be obtained by stretching in the width direction with a tenter or the like. It is also preferable to perform a semi-baking treatment before stretching.
• This PTFE stretched body is a porous body having a high porosity, and is It can be suitably used as a filter medium for various microfiltration filters such as an air filter and a chemical solution filter, and a support material for a polymer electrolyte membrane. It is also useful as a material for products used in the textile field, medical field, electrochemical field, sealing material field, air filtration field, ventilation / internal pressure adjustment field, liquid filtration field, general consumer material field, and the like. Specific uses will be illustrated below.
• Electrochemical field Dielectric material prepreg EMI shielding material, heat transfer material, etc. More specifically, printed wiring boards, electromagnetic shielding shield materials, insulating heat transfer materials, insulating materials, etc. Sealing material field Gaskets, packings, pump diaphragms, pump tubes, aircraft sealing materials, etc.
• Air filtration field ULPA filter for semiconductor manufacturing
• HEPA filter for hospital / semiconductor manufacturing
• cylindrical cartridge filter for industrial use
• bug filter for industrial use
• heat-resistant bag filter- for exhaust gas treatment
• heat-resistant pleated filter for exhaust gas treatment
• SINBRAN filter for industrial use
• catalyst filter for exhaust gas treatment
• filter with adsorbent built-in HDD
• vent filter with adsorbent for built-in HDD
• vent filter for built-in HDD, etc.
• cleaning Machine filters for vacuum cleaners
• general-purpose multi-layer felt materials for GT cartridge filters (for GT compatible products), cooling filters (for electronic device housings), etc.
• Ventilation / internal pressure adjustment field Freezing and drying materials such as containers for freezing and drying, ventilation materials for automobiles for electronic circuits and lamps, container applications such as container caps, electronic devices including small terminals such as tablet terminals and mobile phone terminals For protective ventilation applications, medical ventilation applications, etc.
• Liquid filtration field Semiconductor liquid filtration filter (for semiconductor manufacturing), hydrophilic PTFE filter (for semiconductor manufacturing), filter for chemicals (for chemical treatment), filter for pure water production line (for pure water production), backwash type liquid Filtration filter (for industrial wastewater treatment), etc.
• Textile field PTFE fiber fiber material
• sewing thread textile
• weaving thread textile
• rope etc.
• the fluoropolymer in which the Af is a fluoropolymer segment composed of only a monomer unit derived from tetrafluoroethylene can be produced by the method including step (i) in the first production method of the present disclosure.
• the Af is a fluoropolymer segment in which a monomer unit derived from tetrafluoroethylene and a monomer unit derived from a monomer represented by the general formula (1) and / or the general formula (2) are randomly copolymerized.
• the monomer represented by the general formula (1) and / or the monomer represented by the general formula (2) is the same as that described in the first production method of the present disclosure.
• the Af preferably has a TFE-based polymerization unit of 50 mol% or more and less than 100 mol%.
• the polymerization unit based on TFE is preferably 51 mol% or more, more preferably 55 mol% or more, further preferably 60 mol% or more, and particularly preferably 65 mol% or more. Further, 99 mol% or less is preferable, 95 mol% or less is more preferable, and 90 mol% or less is further preferable.
• the Af is a fluoropolymer segment in which a monomer unit derived from TFE and a monomer unit derived from a monomer represented by the general formula (1) and / or the general formula (2) are randomly copolymerized.
• the fluoropolymer is a copolymer of TFE and a monomer represented by the general formula (1) and / or the general formula (2), for example, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene.
• -Melt-processable fluororesin such as perfluoro (alkyl vinyl ether) copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), TFE / VDF copolymer; tetrafluoroethylene-propylene rubber (FEPM), etc. Fluoro rubber; etc.
• the FEP may be further modified by using perfluoro (alkyl vinyl ether) as the third component within a range of 0.1 to 2% by mass of all the monomers.
• the FEP can be used for manufacturing various molded products such as coating materials such as electric wires, foamed electric wires, cables and wires, tubes, films, sheets and filaments.
• molded products can be obtained from the above PFA.
• molded products include sheets, films, packings, round bars, square bars, pipes, tubes, round tanks, square tanks, tanks, wafer carriers, wafer boxes, beakers, filter housings, flow meters, pumps, valves, etc.
• tubes, pipes, tanks, connectors, etc. used for various chemical reaction devices, semiconductor manufacturing devices, and acid-based or alkaline-based chemical supply devices that require impermeable chemical solutions. Can be used.
• a primer composition can also be obtained by dissolving or dispersing PFA alone or, if necessary, a polyether sulfone, a polyamide-imide, a polyimide, a metal powder or the like in an organic solvent.
• This primer composition is applied to a metal surface, a melt-processable fluororesin composition is applied onto the thus formed primer layer, and the melt-processable fluororesin composition layer is fired together with the primer layer to form fluorine on the metal surface. It can also be used as a resin coating method.
• the ETFE may be further modified by using a third monomer in a range of 0 to 20% by mass of all the monomers.
• TFE: ethylene: third monomer (63 to 94) :( 27 to 2) :( 1 to 10).
• ETFE can also be extruded into a sheet.
• ETFE powder or ETFE pellets can be melted, continuously extruded from the die, and cooled to form a sheet-like molded product.
• Additives may be added to ETFE.
• a known additive can be appropriately used. Specific examples include ultraviolet absorbers, light stabilizers, antioxidants, infrared absorbers, flame retardants, flame retardant fillers, organic pigments, inorganic pigments, dyes and the like. Inorganic additives are preferable from the viewpoint of excellent weather resistance.
• the content of the additive in the ETFE sheet is preferably 20% by mass or less, and particularly preferably 10% by mass or less, based on the total mass of the ETFE sheet.
• membrane materials for membrane structure buildings (athletic facilities, gardening facilities, atriums, etc.) ) Is suitable.
• membrane materials for membrane structures for example, outdoor board materials (soundproof walls, windbreak fences, overwave fences, garage canopies, shopping malls, pedestrian walls, roofing materials), glass shatterproof films, heat and water resistance Sheets, building materials, etc. (tent materials for tent warehouses, membrane materials for sunshades, partial roofing materials for lighting, window materials that replace glass, membrane materials for flameproof partitions, curtains, exterior wall reinforcement, waterproof membranes, smokeproof membranes, etc.
• Non-combustible transparent partition road reinforcement, interior (lighting, wall surface, brand, etc.), exterior (tent, signboard, etc.), daily leisure goods (fishing rod, racket, golf club, projection curtain, etc.), automobile materials (roof) , Vibration damping material, body, etc.), aircraft materials, ship materials, home appliance exteriors, tanks, container inner walls, filters, construction membrane materials, electronic materials (printed substrates, wiring substrates, insulating films, release films, etc.), solar cells It is useful as a surface material for modules, a mirror protective material for solar thermal power generation, a surface material for solar water heaters, and the like.
• the TFE / VDF copolymer may also be modified by using a third monomer in a range of 0 to 50 mol% of all the monomers.
• TFE: ethylene: third monomer (50 to 85) :( 10 to 44.9) :( 0.1 to 10).
• Formula: CX 11 X 12 CX 13 (CX 14 X 15 ) n11 X 16 (In the formula, X 11 to X 16 represent H, F or Cl in the same or different manner, and n 11 represents an integer of 0 to 8.
• the monomer represented by Formula: CX 21 X 22 CX 23- O (CX 24 X 25 ) n21 X 26 (In the formula, X 21 to X 26 represent H, F or Cl in the same or different manner, and n 21 represents an integer of 0 to 8).
• the third monomer may be a fluorine-free ethylenic monomer.
• the fluorine-free ethylenic monomer is preferably selected from ethylenic monomers having 6 or less carbon atoms in terms of maintaining heat resistance and chemical resistance.
• TFE / VDF copolymer may be amidated by contacting it with aqueous ammonia, ammonia gas or a nitrogen compound capable of producing ammonia.
• the TFE / VDF copolymer is also preferably used as a raw material for obtaining TFE / VDF copolymer fibers by a spinning and drawing method.
• a TFE / VDF copolymer is melt-spun and then cooled and solidified to obtain an undrawn yarn, and then the undrawn yarn is run in a heated tubular body and drawn to form a TFE.
• a method for obtaining VDF copolymer fibers is also preferably used as a raw material for obtaining TFE / VDF copolymer fibers by a spinning and drawing method.
• the TFE / VDF copolymer can also be dissolved in an organic solvent to obtain a solution of the TFE / VDF copolymer.
• organic solvent include nitrogen-containing organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and dimethylformamide; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone; ethyl acetate.
• Ester solvents such as butyl acetate; ether solvents such as tetrahydrofuran and dioxane; further, general-purpose organic solvents having a low boiling point such as mixed solvents thereof can be mentioned.
• the above solution can be used as a binder for batteries.
• the aqueous dispersion of the TFE / VDF copolymer on a porous substrate made of a polyolefin resin and use it as a composite porous film. It is also preferable to disperse inorganic particles or organic particles in an aqueous dispersion and coat it on a porous substrate to use it as a composite porous membrane.
• the composite porous membrane thus obtained can be used as a separator for a lithium secondary battery or the like.
• the melt-processable fluororesin powder can be suitably used as a powder coating material.
• a powder coating material made of the melt-processable fluororesin powder is applied to a base material, a film having a smooth surface can be obtained.
• the melt-processable fluororesin powder having an average particle size of 1 ⁇ m or more and less than 100 ⁇ m is particularly suitable as a powder coating used for electrostatic coating, and the melt-processable fluororesin powder having an average particle size of 100 ⁇ m or more and 1000 ⁇ m or less is particularly suitable.
• the melt-processable fluororesin powder can be produced by a method of obtaining a powder by drying and pulverizing the melt-processable fluororesin obtained by the above-described production method of the present disclosure.
• the fluororubber may be a partially fluororubber or a perfluororubber.
• As the partially fluorinated rubber at least one selected from the group consisting of tetrafluoroethylene (TFE) / propylene (Pr) -based fluororubber and tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) -based fluororubber. Is preferable.
• the tetrafluoroethylene / propylene-based fluororubber is preferably a copolymer composed of 45 to 70 mol% of tetrafluoroethylene, 55 to 30 mol% of propylene, and 0 to 5 mol% of fluoromonomer that provides a crosslinked site. ..
• the fluororubber may be a perfluoro rubber.
• the perfluoro rubber include perfluoro rubber containing TFE, for example, a fluoromonomer copolymer represented by TFE / general formula (160), (130) or (140) and TFE / general formula (160), (130). ) Or (140), at least one selected from the group consisting of a fluoromonomer / a monomer copolymer giving a cross-linking site is preferable.
• the composition is preferably 50 to 90/10 to 50 (mol%), more preferably 55 to 80/20 to 45, and even more preferably 55 to. It is 70 / 30-45.
• a monomer copolymer that provides a TFE / PMVE / cross-linking site it is preferably 50 to 89.9 / 10 to 49.9 / 0.01 to 4 (mol%), and more preferably 55 to 77. It is 9/20 to 49.9 / 0.1 to 3.5, and more preferably 55 to 69.8 / 30 to 44.8 / 0.2 to 3.
• the fluoromonomer copolymer represented by the general formula (160), (130) or (140) having TFE / carbon number of 4 to 12 it is preferably 50 to 90/10 to 50 (mol%). , More preferably 60 to 88/12 to 40, and even more preferably 65 to 85/15 to 35.
• perfluoro rubber examples include TFE / a fluoromonomer represented by the general formula (140) / a fluoromonomer copolymer giving a crosslinked site, TFE / a perfluorovinyl ether copolymer represented by the general formula (140), and TFE. / At least one selected from the group consisting of a fluoromonomer copolymer represented by the general formula (160) and a TFE / fluoromonomer represented by the general formula (160) / a monomer copolymer giving a cross-linking site. Is preferable.
• perfluoro rubber examples include perfluoro rubbers described in International Publication No. 97/24381, Japanese Patent Publication No. 61-57324, Japanese Patent Publication No. 4-81608, Japanese Patent Publication No. 5-13961, and the like. Can be done.
• the fluororubber is preferably having a glass transition temperature of ⁇ 70 ° C. or higher, more preferably ⁇ 60 ° C. or higher, and further preferably ⁇ 50 ° C. or higher, from the viewpoint of excellent compression set at high temperature. .. Further, from the viewpoint of good cold resistance, it is preferably 5 ° C. or lower, more preferably 0 ° C. or lower, and even more preferably -3 ° C. or lower.
• the glass transition temperature is determined by using a differential scanning calorimeter (DSC822e, manufactured by METTLER TOLEDO) to raise the temperature of 10 mg of the sample at 10 ° C./min to obtain a DSC curve, which is the base before and after the secondary transition of the DSC curve. It can be obtained as the temperature indicating the midpoint of the intersection of the extension line of the line and the tangent line at the turning point of the DSC curve.
• DSC822e differential scanning calorimeter
• the fluororubber preferably has a Mooney viscosity ML (1 + 20) at 170 ° C. of 30 or more, more preferably 40 or more, and even more preferably 50 or more. Further, in terms of good workability, it is preferably 150 or less, more preferably 120 or less, and further preferably 110 or less.
• the fluororubber preferably has a Mooney viscosity ML (1 + 20) at 140 ° C. of 30 or more, more preferably 40 or more, and even more preferably 50 or more. Further, in terms of good workability, it is preferably 180 or less, more preferably 150 or less, and further preferably 110 or less.
• the fluororubber has a Mooney viscosity ML (1 + 10) at 100 ° C. of preferably 10 or more, more preferably 20 or more, and further preferably 30 or more in terms of good heat resistance. Further, in terms of good workability, it is preferably 120 or less, more preferably 100 or less, and further preferably 80 or less.
• the Mooney viscosity can be measured according to JIS K6300 at 170 ° C., 140 ° C., or 100 ° C. using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES.
• the fluororubber can be processed into a fluororubber composition by adding a curing agent, a filler and the like.
• curing agent examples include polyols, polyamines, organic peroxides, organic tins, bis (aminophenol) tetraamines, bis (thioaminophenol) and the like.
• the fluororubber composition is made of the above-mentioned fluororubber, it is excellent in that it does not contain an emulsifier and is easily crosslinked during molding.
• a fluororubber molded product can be obtained by molding using the above-mentioned fluororubber.
• the molding process is not particularly limited, and examples thereof include known methods using the above-mentioned curing agent.
• the fluororubber molded product is suitable as a seal, gasket, electric wire coating, hose, tube, laminate, accessory, etc., and is particularly suitable for parts for semiconductor manufacturing equipment, automobile parts, and the like.
• the fluoropolymer obtained in the above step (ii) has a monomer unit derived from TFE of 99.0% by mass or more and the general formula (1) and / or the general formula (2) of 1.0% by mass or less. It may be a modified PTFE containing a monomer unit derived from the indicated monomer.
• the total amount of the monomers represented by the general formula (1) and the general formula (2) is in the range of 0.00001 to 1.0% by mass with respect to the fluoropolymer obtained in the step (ii). Is preferable.
• As the lower limit of the total amount 0.0001% by mass is more preferable, 0.001% by mass is further preferable, 0.005% by mass is further more preferable, and 0.009% by mass is particularly preferable.
• As the upper limit 0.90% by mass is preferable, 0.50% by mass is more preferable, 0.40% by mass is further preferable, 0.30% by mass is further more preferable, and 0.10% by mass is particularly preferable.
• the Af is a fluoropolymer segment in which a monomer unit derived from tetrafluoroethylene and a monomer unit derived from a monomer represented by the general formula (1) and / or the general formula (2) are randomly copolymerized.
• a fluoropolymer can be produced by a method including step (ii) in the first production method of the present disclosure.
• the fluoropolymers of the present disclosure are: Bf-CRP (In the formula, Bf is a fluoropolymer segment composed of only a monomer unit derived from tetrafluoroethylene.
• CRP is one of the following formulas (CRP1) to (CRP5)). (Hereinafter, also referred to as "the second fluoropolymer of the present disclosure").
• the second fluoropolymer of the present disclosure can be block copolymerized by having the above-mentioned specific group at the end. Therefore, the second fluoropolymer of the present disclosure is useful as an intermediate for producing block copolymers.
• Examples of Z c11 in the formula (CRP1) include those similar to Z c1 in the above-mentioned formula (c1-1).
• Examples of Z c12 in the formula (CRP2) include those similar to Z c2 in the above-mentioned formula (c1-2).
• Examples of R c11 in the formula (CRP3) include those similar to R c in the above-mentioned formula (c1-2').
• Examples of Z c13 in the formula (CRP4) include those similar to Z c3 and Z c4 in the above formula (c1-3).
• Examples of Z c14 in the formula (CRP5) include those similar to Z c5 in the above formula (c1-4).
• As the CRP CRP5 is preferable from the viewpoint of the polymerization rate.
• the above formulas (CRP1) to (CRP5) are groups derived from the chain transfer agent described in the first production method of the present disclosure.
• the above formulas (CRP1) to (CRP5) are portions in which at least a part of the structure of the chain transfer agent is incorporated into a fluoropolymer (preferably the main chain terminal of the fluoropolymer).
• the Bf is a fluoropolymer segment composed of only a monomer unit derived from tetrafluoroethylene.
• the second fluoropolymer of the present disclosure is a so-called PTFE, and all the characteristics of PTFE described for the first fluoropolymer of the present disclosure can be applied.
• the second fluoropolymer of the present disclosure can be produced by the method including the step (i) in the first production method of the present disclosure.
• the production method of the present disclosure is also a method of producing a fluoropolymer by solution polymerization or dispersion polymerization, in which (iii) tetrafluoroethylene is homopolymerized in the presence of an initiator, a chain transfer agent and a solvent, and then A step of block copolymerizing the monomers represented by the following general formulas (1) and / or the general formula (2), or (iv) polymerizing the following general formulas (1) and / or the general formula (2).
• the chain transfer agent is then at least one selected from the group consisting of dithioester compounds, dithiocarbamate compounds, trithiocarbonate compounds and xantate compounds, which comprises a step of block copolymerizing tetrafluoroethylene.
• a method for producing a fluoropolymer (hereinafter, also referred to as "the second production method of the present disclosure”).
• General formula (1): CF 2 CR 1 R 2 (In the formula, R 1 is H or F; R 2 is -Cl, -R a , -COOR b , -OCOR C , -CONR d 2 , -CN, -COR e , -Rf a ; R a , R.
• R b, R c, R d and R e are the same or different, H, or a substituent;
• Rf a is the same or different and may have a substituent group, include an oxygen atom between carbon atoms May be, a fluorine-containing alkyl group, a fluorine-containing vinyl group, or a fluorine-containing alkoxy group;
• R 1 and R 2 may be bonded to each other to form a ring).
• a block copolymer can be produced from a tetrafluoroethylene-based polymer.
• the initiator, chain transfer agent, solvent, and monomer represented by the general formula (1) or the general formula (2) are described in the first production method of the present disclosure. It is the same as the one.
• step (iii) the method of homopolymerizing tetrafluoroethylene can be carried out in the same manner as in the step (i) of the first production method of the present disclosure.
• polymers having CRP at the terminal such as the first and second fluoropolymers of the present disclosure described above, are obtained, whereby the general formula is obtained.
• the monomer represented by (1) and / or the general formula (2) can be block copolymerized.
• tetrafluoroethylene is homopolymerized in the presence of an initiator, a chain transfer agent and a solvent, and then the monomers represented by the general formulas (1) and / or the general formulas (2) are obtained.
• the homopolymerization may be carried out in the presence of an initiator, a chain transfer agent and a solvent, and the block copolymerization may be carried out in the presence of an initiator, a chain transfer agent and a solvent. Good.
• the amount of the chain transfer agent added may vary depending on the magnitude of the chain transfer constant of the compound used, but it should be used in the range of 0.05 to 20 mol% with respect to tetrafluoroethylene. Is preferable. It is preferably 0.06 mol% or more, more preferably 0.08 mol% or more, further preferably 0.1 mol% or more, and preferably 15 mol% or less, more preferably. It is 10 mol% or less, more preferably 6.5 mol% or less.
• the amount of the initiator added may vary depending on the compound used, but is used in the range of 5.0 to 1000 mol% with respect to the chain transfer agent. It is preferably 6.0 mol% or more, more preferably 8.0 mol% or more, further preferably 10 mol% or more, and preferably 100 mol% or less, more preferably 50 mol. % Or less, more preferably 30 mol% or less.
• the homopolymerization and the block copolymerization of the monomers represented by the general formulas (1) and / or the general formula (2) may be continuously carried out, or may be obtained by the homopolymerization.
• the polymer may be recovered, the recovered polymer may be added to a solvent, and then the monomers represented by the general formula (1) and / or the general formula (2) may be added to carry out the polymerization.
• the temperature of the block copolymerization of the monomers represented by the general formulas (1) and / or the general formula (2) is not particularly limited as long as the block copolymerization is possible, but for example. , 0-150 ° C. It is preferably 20 to 130 ° C, more preferably 40 to 110 ° C.
• the pressure for block copolymerization of the monomers represented by the general formulas (1) and / or the general formula (2) is not particularly limited as long as the pressure allows block copolymerization, but for example. , 0 to 9.8 MPaG. It is preferably 0.2 to 6.0 MPaG, and more preferably 0.5 to 3.0 MPaG.
• the concentration of the monomer represented by the general formula (1) and / or the general formula (2) with respect to the solvent is 0.1 to 20 mol / L. Is preferable. It is more preferably 0.3 to 18 mol / L, and even more preferably 0.5 to 15 mol / L.
• step (iii) may be performed once, or may be performed twice or more.
• a block copolymer having a plurality of blocks (segments) can be produced by performing the process twice or more.
• step (iv) is a step of polymerizing the following general formula (1) and / or general formula (2) in the presence of an initiator, a chain transfer agent and a solvent, and then block copolymerizing tetrafluoroethylene. is there.
• the polymerization of the general formula (1) and / or the general formula (2) may be carried out in the presence of an initiator, a chain transfer agent and a solvent, and the block copolymerization may be carried out by the initiator and chain transfer. It does not have to be done in the presence of agents and solvents.
• the block copolymerization of TFE is preferably a block copolymerization of only TFE.
• the amount of the chain transfer agent added may vary depending on the magnitude of the chain transfer constant of the compound used, but the total amount of the monomers represented by the general formulas (1) and (2). On the other hand, it is preferably used in the range of 0.05 to 20 mol% with respect to tetrafluoroethylene. More preferably, it is 0.06 mol% or more, further preferably 0.08 mol% or more, even more preferably 0.1 mol% or more, and even more preferably 15 mol% or less. It is even more preferably 10 mol% or less, and even more preferably 6.5 mol% or less.
• the amount of the initiator added may vary depending on the compound used, but is used in the range of 5.0 to 1000 mol% with respect to the chain transfer agent. It is preferably 6.0 mol% or more, more preferably 8.0 mol% or more, further preferably 10 mol% or more, and preferably 100 mol% or less, more preferably 50 mol. % Or less, more preferably 30 mol% or less.
• the temperature at which the general formula (1) and / or the general formula (2) is polymerized may be, for example, 0 to 150 ° C. It is preferably 20 to 130 ° C, more preferably 40 to 110 ° C.
• the pressure for polymerizing the general formula (1) and / or the general formula (2) may be, for example, 0 to 9.8 MPaG. It is preferably 0.2 to 6.0 MPaG, and more preferably 0.5 to 3.0 MPaG.
• the polymerization of the general formula (1) and / or the general formula (2) and the block copolymerization of TFE may be continuously carried out, or the general formula (1) and / or the general formula (1) and / or the general formula ( The polymer obtained by the polymerization of 2) may be recovered, the recovered polymer may be added to a solvent, and then TFE may be added to carry out the polymerization.
• the temperature at which tetrafluoroethylene is block copolymerized may be, for example, 10 to 150 ° C. It is preferably 20 to 130 ° C, more preferably 40 to 110 ° C.
• the pressure for block copolymerizing tetrafluoroethylene may be, for example, 0.05 to 5.0 MPaG. It is preferably 0.2 to 3.5 MPaG, and more preferably 0.5 to 1.2 MPaG.
• step (iv) may be performed once or twice or more.
• a block copolymer having a plurality of blocks (segments) can be produced by performing the process twice or more.
• Examples of the fluoropolymer obtained by the second production method of the present disclosure include the third fluoropolymer of the present disclosure described later.
• the fluoropolymer of the present disclosure contains a segment A containing a monomer unit derived from tetrafluoroethylene and a segment B containing a monomer unit derived from the general formula (1) and / or the general formula (2).
• a fluoropolymer characterized by being a polymer hereinafter, also referred to as "the third fluoropolymer of the present disclosure").
• CF 2 CR 1 R 2 (In the formula, R 1 is H or F; R 2 is -Cl, -R a , -COOR b , -OCOR C , -CONR d 2 , -CN, -COR e , -Rf a ; R a , R.
• R b, R c, R d and R e are the same or different, H, or a substituent;
• Rf a is the same or different and may have a substituent group, include an oxygen atom between carbon atoms May be, a fluorine-containing alkyl group, a fluorine-containing vinyl group, or a fluorine-containing alkoxy group;
• R 1 and R 2 may be bonded to each other to form a ring).
• the segment A contains a monomer unit derived from TFE. Segment A preferably consists of only monomeric units derived from TFE.
• the segment A is a polymer segment made of a TFE homopolymer (PTFE), and all the characteristics of the above-mentioned PTFE can be adopted.
• PTFE TFE homopolymer
• the segment B may contain a monomer unit derived from the general formula (1) and / or the general formula (2), and in particular, HFP, CTFE, VDF, vinyl fluoride, trifluoroethylene, and fluoro.
• At least one selected from the group consisting of (meth) acrylic acid ester, N-acrylamide compound, alkene, N-vinylamide compound, N-vinyllactam compound, fluoroalkylethylene and fluorine-containing acrylate monomer is preferable, and HFP, VDF, and At least one selected from the group consisting of perfluoro (methyl vinyl ether), perfluorofluorinated sulfonyl vinyl ether, ethylene, N-vinylamide compound, N-vinyllactam compound, and vinyl acetate is more preferable, and HFP, VDF, and per.
• At least one selected from the group consisting of fluoro (methyl vinyl ether), perfluorofluorinated sulfonyl vinyl ether, ethylene, N-vinylamide compound, N-vinylpyrrolidone, and vinyl acetate is particularly preferable.
• the polymer constituting the segment B is not limited as long as it contains a polymerization unit based on the monomer represented by the general formula (1) and / or the general formula (2), but is not limited, for example, polyvinyl acetate such as polyvinyl acetate. Esters; polyvinylamides such as poly (N-vinylpyrrolidone); polyfluoroolefins such as PVDF and the like are particularly preferable.
• the third fluoropolymer of the present disclosure includes segment A and segment B.
• the third fluoropolymer of the present disclosure has the following formula: -ALB- (In the formula, A is segment A, B is segment B, and L represents a linking group).
• the L may be a single bond or a divalent organic group. Examples of the divalent organic group in L include an alkylene group and an oxyalkylene group.
• the L is preferably a single bond.
• the third fluoropolymer of the present disclosure preferably contains a —AB— structure in which the segment A and the segment B are bonded by a single bond.
• segment A and segment B are bonded by a single bond constitutes a monomer unit constituting the end of segment A (for example, a monomer unit derived from TFE) and an end of segment B. It means that the monomer unit (for example, the monomer unit derived from the monomer represented by the general formula (1) and / or the general formula (2)) is directly bonded.
• a monomer unit for example, the monomer unit derived from the monomer represented by the general formula (1) and / or the general formula (2)
• Such a configuration can be realized by the second manufacturing method of the present disclosure.
• At least one -ALB- structure may be present, and there may be two or more, or three or more. That is, in the third fluoropolymer of the present disclosure, at least one segment A and at least one segment B need to be bonded by L (preferably a single bond), and -ALB- is bonded twice or more. It may be a repeating one, and may have a structure repeated three times or more. For example, -ALB-, -B-LA-, -A-L-B-LA-, -B-L-A-L-B-, -A-L-B-L It may have a configuration of —ALB—, —BLBLA—, or the like.
• the third fluoropolymer of the present disclosure may have a mass ratio (A / B) of the segment A to the segment B of 99/1 to 1/99.
• the third fluoropolymer of the present disclosure is based on segment A containing a monomer unit based on a monomer derived from TFE and a monomer represented by the general formula (1) and / or the general formula (2). It can have both properties of segment B containing a monomeric unit.
• Such fluoropolymers are expected to be used, for example, as compatibilizers and adhesives for compounding fluororesins.
• the third fluoropolymer of the present disclosure can also be used for each of the fluoropolymers described in the first and second fluoropolymers of the present disclosure.
• Example 1 In the reactor, 0.031 g of t-butyl peroxypivalate as a polymerization initiator, 0.37 g of O-ethyl S- (1-methoxycarbonylethyl) dithiocarbonate as a chain transfer agent, and 39 mL of asahiclean AK as a solvent. -225 (trade name; manufactured by AGC) and 2.3 g of tetrafluoroethylene were introduced, and the mixture was heated and stirred to 80 ° C. After completion of the reaction, the reactor was cooled, degassed, and the polymer dispersion was recovered. The dispersion was filtered off and dried to give 1.8 g of a white solid.
• a peak of CF 2 linkage from the reference is taken as -120 ppm, since the peak of the -CF 2 -S- derived looked to -85 ppm, a chain transfer agent intercept the polymer terminus ( -It was confirmed that SC (S) OC 2 H 5 ) was introduced.
• the degree of polymerization estimated from the ratio of the peak integral value of ⁇ 120 ppm to the peak integral value of ⁇ 85 ppm was 16.
• Example 2 0.016 g of AIBN, 2.0 g of the polymer of Example 1, 5 mL of ethyl acetate, and 5.0 g of vinyl acetate were introduced into the reactor, and the mixture was heated and stirred to 65 ° C. Then, the polymer solution was recovered. The homopolymer was removed by filtration of the insoluble material and washing after reprecipitation to obtain 5.8 g of the desired block copolymer. From 19 F-NMR measurement, it disappeared peaks of -CF 2 -S- derived -85 ppm, 1 H-NMR measurement from the backbone resulting vinyl acetate is polymerized (1.5 ⁇ 2.3 ppm, 4.7 The presence of ⁇ 5.1 ppm) was confirmed. 19 F-NMR (CDCl 3 ) ⁇ F ppm: -105 to -125 (CF 2 CH 2 , CH (CH 3 ) CF 2 , CF 2 CF 2 CF 2 )
• Example 3 In the reactor, 0.027 g of t-butylperoxypivalate as the polymerization initiator, 0.12 g of O-ethyl S- (1-methoxycarbonylethyl) dithiocarbonate as the chain transfer agent, and 15 mL of asahiclean AK as the solvent. -225 (trade name; manufactured by AGC), 0.7 g of vinyl acetate, and 1.9 g of tetrafluoroethylene were introduced, and the mixture was heated and stirred to 70 ° C. After completion of the reaction, the reactor was cooled, degassed, and the polymer dispersion was recovered. The dispersion was filtered off and dried to give 1.1 g of a white solid.
• Example 4 In the reactor, 0.027 g of t-butyl peroxypivalate as the polymerization initiator, 0.12 g of O-ethyl S- (1-methoxycarbonylethyl) dithiocarbonate as the chain transfer agent, and 15 mL of asahiclean AK as the solvent. -225 (trade name; manufactured by AGC), 1.5 g of tetrafluoroethylene, and 0.45 g of vinylidene fluoride were introduced, and the mixture was heated and stirred to 70 ° C. After completion of the reaction, the reactor was cooled, degassed, and the polymer dispersion was recovered. The dispersion was filtered off and dried to give 1.0 g of a white solid.
• Example 5 In the reactor, 0.027 g of t-butylperoxypivalate as the polymerization initiator, 0.12 g of O-ethyl S- (1-methoxycarbonylethyl) dithiocarbonate as the chain transfer agent, and 15 mL of asahiclean AK as the solvent. -225 (trade name; manufactured by AGC), 0.9 g of N-vinylpyrrolidone, and 1.9 g of tetrafluoroethylene were introduced, and the mixture was heated and stirred to 70 ° C. After completion of the reaction, the reactor was cooled, degassed, and the polymer dispersion was recovered. The dispersion was filtered off and dried to give 1.2 g of a white solid.
• Example 6 0.024 g of t-butylperoxypivalate, 2.0 g of the polymer of Example 1, 60 mL of dimethyl carbonate, and 19 g of vinylidene fluoride were introduced into the reactor, and the mixture was heated and stirred to 70 ° C. After completion of the reaction, the reactor was cooled, degassed, and the polymer dispersion was recovered. The dispersion was dried and the homopolymer was removed by washing to obtain 10 g of the block copolymer of interest.
• Solid 19 F-NMR measurement revealed that the peak derived from -CF 2 -S- at -85 ppm disappeared, and the presence of a skeleton (-90 to -100 ppm, -110 to -120 ppm) formed by polymerization of vinylidene fluoride was confirmed. did.
• Solid 19 F-NMR ⁇ F ppm -90 to -100 (CH 2 CF 2 CH 2 ), -110 to -125 (CF 2 CF 2 CH 2 , CF 2 CF 2 CF 2 )
• Example 7 Introducing 0.024 g of t-butylperoxypivalate, 2.0 g of the polymer of Example 1, 60 mL of ethyl acetate, and 6.6 g of vinylidene fluoride and 12 g of hexafluoropropylene into the reactor. The mixture was heated and stirred up to 60 ° C. After completion of the reaction, the reactor was cooled, degassed, and the polymer dispersion was recovered. The dispersion was dried and the homopolymer was removed by washing to obtain 12 g of the block copolymer of interest.
• Solid 19 F-NMR ⁇ F ppm -70 to -80 (CF (CF 3 )), -90 to -100 (CH 2 CF 2 CH 2 ), -100 to -125 (CH 2 CF 2 CF 2 , CF 2 CF (CF 3 ), CF 2 CF 2 CF 2 ), -185 (CF (CF 3 ))
• Example 8 0.024 g of t-butylperoxypivalate, 2.0 g of the polymer of Example 1, 60 mL of acetone, and 6.5 g of N-vinylpyrrolidone were introduced into the reactor, and the mixture was heated and stirred to 70 ° C. After 6 hours, the polymer solution was recovered. The homopolymer was removed by filtration and washing of the insoluble material to obtain 6.9 g of the desired block copolymer.

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