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
  • C08F4/00—Polymerisation catalysts
  • C08F4/28—Oxygen or compounds releasing free oxygen
  • C08F4/32—Organic compounds
  • C08F4/34—Per-compounds with one peroxy-radical
• • 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
  • C08F114/22—Vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F14/18—Monomers containing fluorine
  • C08F14/22—Vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
  • 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
  • C08F214/22—Vinylidene fluoride

Definitions

• the present disclosure relates to a method for producing a fluorine-containing copolymer.
• fluoropolymers are polymeric materials with excellent heat resistance, solvent resistance, chemical resistance, etc., and have been used for various purposes by taking advantage of these characteristics.
• Polymerization methods such as solution polymerization, suspension polymerization, and emulsion polymerization are known as methods for producing fluoropolymers.
• Patent Document 1 and Patent Document 2 describe a polymerization reaction using vinylidene fluoride.
• Patent Document 1 and Patent Document 2 have a slow polymerization rate, and a method for obtaining a fluorine-containing copolymer more efficiently is desired.
• An object of an embodiment of the present invention is to provide a method for producing a fluorine-containing copolymer that has a faster polymerization rate than conventional methods.
• the present disclosure includes the following aspects. ⁇ 1> In a polymerization medium containing at least one polymerization solvent A selected from the group consisting of compounds represented by the following formula (1) and formula (2), A method for producing a fluoropolymer, which involves polymerization using a monomer containing vinylidene fluoride.
• Y 1 represents an oxygen atom
• Z 1 is each independently a group represented by any one of the following formulas (T1) to (T14)
• Y3 represents a carbon atom or a silicon atom
• R 1 to R 4 each independently represent a methyl group, a tert-butyl group, or a tert-butoxy group.
• a 1 each independently represents a hydrogen atom, a chlorine atom, a methyl group, a tert-butyl group, -OR, -NR 2 , or -SR
• a 2 each independently represents , represents a chlorine atom, a methyl group, a tert-butyl group, -OR, -NR 2 , or -SR
• a 3 is a hydrogen atom, a chlorine atom, a tert-butyl group, a tert-butoxy group, -NR 2 , or - represents SR
• each R independently represents a methyl group or a tert-butyl group
• * represents a bonding site.
• the monomer further includes a fluorine-containing monomer having a fluorine atom other than the vinylidene fluoride
• the fluorine-containing monomer described in ⁇ 1> includes at least one selected from the group consisting of fluorine-containing monomers represented by the following formula (X1), formula (X2), and formula (X3).
• X1 In formula (X1), X 1 , X 2 , and X 3 each independently represent a hydrogen atom or a fluorine atom, Rf 1 represents a perfluoroalkylene group having 1 to 5 carbon atoms, and an ether oxygen atom may be included between the carbon-carbon bonds of the perfluoroalkylene group, R 10 represents a hydrogen atom, a fluorine atom, -SO 2 R 11 , -COR 11 , or a cyano group, R 11 each independently represents a hydrogen atom, a fluorine atom, a hydroxyl group, or an alkoxy group, n1 is 0 or 1,
• X 4 and X 5 each independently represent a hydrogen atom or a fluorine atom
• Rf 2 and Rf 3 each independently represent a perfluoroalkyl group having 1 to 5 carbon atoms or a fluorine atom
• an ether oxygen atom may be included between the carbon-carbon bonds of
• ⁇ 3> The method for producing a fluoropolymer according to ⁇ 1> or ⁇ 2>, wherein the monomer further contains at least one fluoromonomer selected from the group consisting of hexafluoropropylene and tetrafluoroethylene.
• ⁇ 4> The method for producing a fluorine-containing copolymer according to any one of ⁇ 1> to ⁇ 3>, wherein the monomer does not have a fluorine atom and further contains a non-fluorine monomer having an ethylenically unsaturated group.
• the above monomer does not have a fluorine atom, has an ethylenically unsaturated group, and has a reactive silyl group, amino group, isocyanato group, hydroxyl group, epoxy group, acid anhydride residue, alkoxycarbonyl group, or carboxy group.
• the monomer does not have a fluorine atom, has an ethylenically unsaturated group, and has at least one selected from the group consisting of a hydroxyl group, an acid anhydride residue, an alkoxyl carbonyl group, a carboxy group, and a carboxylic acid acyl group.
• the proportion of water in the polymerization medium is less than 10% by volume
• the monomer is at least one selected from the group consisting of compounds represented by the above formula (1) and the above formula (2), and is in a polymerization medium containing water and a polymerization solvent A that is incompatible with water.
• Y 1 represents an oxygen atom
• Z 1 is each independently a group represented by any one of the above formulas (T1) to (T3), formula (T7), formula (T8), and formula (T10)
• Y 3 represents a carbon atom or a silicon atom
• R 1 to R 4 each independently represent a methyl group, a tert-butyl group, or a tert-butoxy group
• a 1 is each independently a hydrogen atom, a methyl group, a tert-butyl group, -OR, or
• R each independently represents a methyl group or a tert-butyl group, and * represents a bonding site, the method for producing a fluoropolymer according to any one of ⁇ 1> to ⁇ 7>.
• Z 1 is each independently a group represented by any one of formulas (T1) to (T3), as described in any one of ⁇ 1> to ⁇ 8>.
• ⁇ 10> The method for producing a fluorine-containing copolymer according to any one of ⁇ 1> to ⁇ 9>, wherein in the above formula (1), Z 1 is each independently a group represented by formula (T1).
• Y 3 represents a carbon atom, the method for producing a fluorine-containing copolymer according to any one of ⁇ 1> to ⁇ 10>.
• a method for producing a fluorine-containing copolymer with a faster polymerization rate than conventional methods is provided.
• a numerical range indicated using “ ⁇ ” means a range that includes the numerical values listed before and after " ⁇ " as the minimum and maximum values, respectively.
• the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step.
• the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.
• a combination of two or more preferred embodiments is a more preferred embodiment.
• the amount of each component means the total amount of the multiple types of substances, unless otherwise specified.
• tBu means "tert-butyl group.”
• the method for producing a fluorine-containing copolymer of the present disclosure includes a method for producing a fluorine-containing copolymer in a polymerization medium containing at least one polymerization solvent A selected from the group consisting of compounds represented by the following formula (1) and formula (2). This is a method in which polymerization is performed using a monomer containing vinylidene chloride.
• Y 1 represents an oxygen atom
• Z 1 is each independently a group represented by any one of the following formulas (T1) to (T14)
• Y3 represents a carbon atom or a silicon atom
• R 1 to R 4 each independently represent a methyl group, a tert-butyl group, or a tert-butoxy group.
• a 1 each independently represents a hydrogen atom, a chlorine atom, a methyl group, a tert-butyl group, -OR, -NR 2 , or -SR
• a 2 each independently represents , represents a chlorine atom, a methyl group, a tert-butyl group, -OR, -NR 2 , or -SR
• a 3 is a hydrogen atom, a chlorine atom, a tert-butyl group, a tert-butoxy group, -NR 2 , or - represents SR
• each R independently represents a methyl group or a tert-butyl group
• * represents a bonding site.
• the plural A 1 's may be the same or different from each other.
• the plural A 2 's may be the same or different from each other.
• polymerization is performed in a polymerization medium containing at least one polymerization solvent A selected from the group consisting of compounds represented by formula (1) and formula (2). be exposed. All polymerization solvents A have low chain transfer properties. Therefore, it is presumed that the polymerization of the monomer containing vinylidene fluoride proceeds smoothly.
• the polymerization medium contains at least one polymerization solvent A selected from the group consisting of compounds represented by formula (1) and formula (2).
• Y 1 represents an oxygen atom.
• p is 1 or more
• n is 1 or more.
• Each Z 1 is independently a group represented by any one of the following formulas (T1) to (T14).
• a 1 each independently represents a hydrogen atom, a chlorine atom, a methyl group, a tert-butyl group, -OR, -NR 2 , or -SR
• a 2 each independently represents , represents a chlorine atom, a methyl group, a tert-butyl group, -OR, -NR 2 , or -SR
• a 3 is a hydrogen atom, a chlorine atom, a tert-butyl group, a tert-butoxy group, -NR 2 , or - represents SR
• each R independently represents a methyl group or a tert-butyl group
• * represents a bonding site.
• combinations of p, m, n, and k include the following embodiments.
• (p, m, n, k) (0, 1, 0, 1), (0, 1, 1, 0), (1, 0, 1, 0), (0, 2, 0, 0)
• the combination of p, m, n, and k in formula (1) is such that (p, m, n, k) is (0, 1, 0, 1). , (0, 1, 1, 0), or (1, 0, 1, 0).
• each Z 1 is independently a group represented by any one of formulas (T1) to (T14);
• T7) is preferably a group represented by any one of formulas (T1) to (T3), and more preferably a group represented by any one of formulas (T1) to (T3). More preferably, it is a group.
• a 1 each independently represents a hydrogen atom, a chlorine atom, a methyl group, a tert-butyl group, -OR, -NR 2 , or -SR
• a 2 each independently represents , represents a chlorine atom, a methyl group, a tert-butyl group, -OR, -NR 2 , or -SR
• a 3 is a hydrogen atom, a chlorine atom, a tert-butyl group, a tert-butoxy group, -NR 2 , or - represents SR
• each R independently represents a methyl group or a tert-butyl group
• * represents a bonding site.
• a 1 each independently represents a methyl group, a tert-butyl group, -OR, or -NR 2
• a 2 each independently represents a methyl group, a tert-butyl group, -OR, or -NR 2 and each R independently represents a methyl group or a tert-butyl group.
• a 3 represents a tert-butyl group or a tert-butoxy group.
• examples of Z 1 include the following compounds.
• Y 3 represents a carbon atom or a silicon atom.
• R 1 to R 4 each independently represent a methyl group, a tert-butyl group, or a tert-butoxy group.
• Y 3 in formula (2) is preferably a carbon atom.
• R 1 to R 4 in formula (2) are preferably methyl groups.
• a compound that corresponds to the compound represented by formula (1) and also corresponds to the compound represented by formula (2) is a compound represented by formula (1). . That is, the compound represented by formula (2) does not include the compound represented by formula (1).
• di-tert-butyl ether corresponds to a compound represented by formula (1) and also corresponds to a compound represented by formula (2), but it is considered a compound represented by formula (1). That is, the compound represented by formula (2) does not include di-tert-butyl ether.
• the proportion of polymerization solvent A in the polymerization medium is preferably 70 mol% or more, more preferably 95 mol% or more.
• the polymerization medium may contain a polymerization solvent other than polymerization solvent A.
• polymerization solvents include, for example, aromatic hydrocarbon solvents such as benzene, toluene, and xylene; sulfoxide solvents such as dimethyl sulfoxide (DMSO); ketone solvents such as acetone and 2-butanone (methyl ethyl ketone); tetrahydrofuran (ether solvents such as THF), dioxane; ester solvents such as ethyl acetate; hexafluoroisopropanol, chloroform, 1H-perfluorohexane, 1H,1H,1H,2H,2H-perfluorooctane, 1,3-bis(trifluoro Examples include halogenated solvents such as methyl)benzene, 1,4-bis(trifluoromethyl)benzene, benzotrifluoride, chlorobenzene, and 1,2-dichlorobenzene, and water.
• aromatic hydrocarbon solvents such as benzene,
• Polymerization in the method for producing a fluorine-containing copolymer of the present disclosure may be solution polymerization or suspension polymerization.
• the solution polymerization method is a method in which polymerization is carried out in a state in which monomers are dissolved in a polymerization medium.
• the suspension polymerization method is a method in which monomers are polymerized in a state in which they are suspended in a polymerization medium containing water.
• solution polymerization In the method for producing a fluorine-containing copolymer of the present disclosure, it is preferable to carry out solution polymerization using the above monomer in a polymerization medium.
• the proportion of water in the polymerization medium is preferably less than 10% by volume.
• the polymerization medium is not particularly limited as long as it contains at least one polymerization solvent A selected from the group consisting of compounds represented by formula (1) and formula (2) above. Preferred embodiments of the compounds represented by formula (1) and formula (2) are as described above.
• each Z 1 is preferably independently a group represented by any one of formulas (T1) to (T7); ) to (T3) is more preferable, and a group represented by formula (T1) is even more preferable.
• Y 3 in formula (2) is preferably a carbon atom.
• R 1 to R 4 in formula (2) are preferably methyl groups.
• the polymerization medium preferably does not contain other polymerization solvents, and preferably consists of only polymerization solvent A.
• a polymerization solvent A that is at least one selected from the group consisting of compounds represented by formula (1) and formula (2) and is incompatible with water;
• suspension polymerization is carried out using the monomers described above in a polymerization medium containing water.
• the proportion of water in the polymerization medium is preferably 10% to 80% by volume.
• Y 1 represents an oxygen atom
• Z 1 is each independently a group represented by any one of formulas (T1) to (T3), formula (T7), formula (T8), and formula (T10)
• Y3 represents a carbon atom or a silicon atom
• R 1 to R 4 each independently represent a methyl group, a tert-butyl group, or a tert-butoxy group
• a 1 is each independently a hydrogen atom, a methyl group, a tert-butyl group, -OR, or - NR 2
• a 2 each independently represents a methyl group, a tert-butyl group, -OR
• each Z 1 is preferably independently a group represented by any one of formulas (T1) to (T3); ) is more preferable.
• Y 3 in formula (2) is preferably a carbon atom.
• R 1 to R 4 in formula (2) are preferably methyl groups.
• the polymerization medium preferably does not contain other polymerization solvents from the viewpoint of increasing the polymerization rate.
• the proportion of polymerization solvent A and water in the polymerization medium is preferably 90 mol % or more, and more preferably consists only of polymerization solvent A and water.
• VDF vinylidene fluoride
• the fluorine-containing copolymer obtained by the method for producing a fluorine-containing copolymer of the present disclosure contains a structural unit derived from VDF.
• the fluorine-containing copolymer may be a homopolymer consisting only of VDF, that is, polyvinylidene fluoride (PVDF).
• a "monomer” is a compound used for polymerization, and means a polymerizable compound having a polymerizable group. Furthermore, in the present disclosure, a “monomer” means a compound having a number average molecular weight of 1000 or less, and is distinguished from an oligomer and a polymer.
• the monomers used in the polymerization may contain monomers other than VDF. That is, the fluorine-containing copolymer may contain structural units other than the structural unit derived from VDF. Further, the number of monomers other than VDF may be one, or two or more.
• Monomers other than VDF are not particularly limited as long as they have a polymerizable group.
• the polymerizable group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group.
• the ethylenically unsaturated group include a vinyl group, a vinyl ether group, a vinyl ester group, and a (meth)acryloyl group.
• Examples of monomers other than VDF include olefins, vinyl ethers, vinyl esters, vinylamides, styrenes, maleimides, (meth)acrylic esters, (meth)acrylic acid, (meth)acrylamides, and (meth)acrylonitrile. Can be mentioned.
• the monomer used in the polymerization preferably further includes a fluorine-containing monomer having a fluorine atom other than VDF, and the fluorine-containing monomer is represented by the following formula (X1), formula (X2), and formula (X3). It is preferable that at least one selected from the group consisting of fluorine-containing monomers is included.
• X 1 , X 2 , and X 3 each independently represent a hydrogen atom or a fluorine atom
• Rf 1 represents a perfluoroalkylene group having 1 to 5 carbon atoms
• an ether oxygen atom may be included between the carbon-carbon bonds of the perfluoroalkylene group
• R 10 represents a hydrogen atom, a fluorine atom, -SO 2 R 11 , -COR 11 , or a cyano group
• R 11 each independently represents a hydrogen atom, a fluorine atom, a hydroxyl group, or an alkoxy group
• n1 is 0 or 1.
• X 4 and X 5 each independently represent a hydrogen atom or a fluorine atom
• Rf 2 and Rf 3 each independently represent a perfluoroalkyl group having 1 to 5 carbon atoms or a fluorine atom
• an ether oxygen atom may be included between the carbon-carbon bonds of the perfluoroalkyl group.
• X 6 , X 8 , and X 9 each independently represent a hydrogen atom or a fluorine atom
• X 7 each independently represents a hydrogen atom, a fluorine atom, or a trifluoromethyl group
• R 20 each independently represents a fluorine atom or -Rf 4 -R 30
• R 40 each independently represents a fluorine atom or -Rf 5 -R 50
• Rf 4 and Rf 5 each independently represent a perfluoroalkylene group having 1 to 5 carbon atoms
• an etheric oxygen atom may be included between the carbon-carbon bonds of the perfluoroalkylene group
• R 30 and R 50 each independently represent -SO 2 R 11 , -COR 11 or a cyano group.
• the perfluoroalkylene group represented by Rf 1 preferably has 1 to 3 carbon atoms.
• R 10 is preferably a hydrogen atom or a fluorine atom.
• examples of the compound where n1 is 1 include perfluoro(alkyl vinyl ether) (hereinafter also referred to as "PAVE").
• PAVE is preferably PMVE or PPVE.
• examples of compounds where n1 is 0 include hexafluoropropylene (hereinafter also referred to as "HFP”) and fluoroalkylethylene (hereinafter also referred to as "FAE").
• HFP hexafluoropropylene
• FEE fluoroalkylethylene
• FAE is preferably PFEE or PFBE.
• the number of carbon atoms in the perfluoroalkyl groups represented by Rf 2 and Rf 3 is preferably 1 to 3, each independently.
• Examples of the fluorine-containing monomer represented by formula (2) include the following compounds.
• Examples of the fluorine-containing monomer represented by formula (X3) include the following compounds.
• the monomers used in the polymerization may contain fluorine-containing monomers other than the fluorine-containing monomers represented by the above (X1), formula (X2), and formula (X3).
• TFE tetrafluoroethylene
• vinyl fluoride vinyl fluoride
• trifluoroethylene hexafluoroisobutylene
• the monomer used in the polymerization further contains at least one fluorine-containing monomer selected from the group consisting of HFP and TFE.
• the fluorine-containing copolymer obtained by the method for producing a fluorine-containing copolymer of the present disclosure is selected from the group consisting of a structural unit derived from VDF, a structural unit derived from HFP, and a structural unit derived from TFE. It is preferable that the copolymer is a copolymer containing at least one kind of.
• a preferred embodiment includes a copolymer containing a structural unit derived from VDF and a structural unit derived from HFP. This copolymer is called "FKM”.
• the monomer used in the polymerization may include a monomer that does not have a fluorine atom (hereinafter referred to as a "non-fluorine monomer").
• the non-fluorine monomer is not particularly limited as long as it does not have a fluorine atom and has a polymerizable group.
• the polymerizable group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group.
• the ethylenically unsaturated group include a vinyl group, a vinyl ether group, a vinyl ester group, and a (meth)acryloyl group.
• non-fluorine monomers examples include olefins, vinyl ethers, vinyl esters, Among vinylamides, styrenes, maleimides, (meth)acrylic esters, (meth)acrylic acid, (meth)acrylamides, and (meth)acrylonitrile, compounds that do not have a fluorine atom can be mentioned.
• the monomer used in the polymerization preferably does not have a fluorine atom and further contains a non-fluorine monomer having an ethylenically unsaturated group, from the viewpoint of polymerization rate and copolymerizability with the fluorine-containing monomer.
• the monomer used in the polymerization preferably further contains a non-fluorine monomer that does not have a fluorine atom, has an ethylenically unsaturated group, and has a reactive group.
• the reactive group is at least one selected from the group consisting of a reactive silyl group, an amino group, an isocyanato group, a hydroxyl group, an epoxy group, an acid anhydride residue, an alkoxycarbonyl group, a carboxy group, and a carboxylic acid acyl group. More preferably, it is at least one selected from the group consisting of a hydroxyl group, an acid anhydride residue, an alkoxylcarbonyl group, a carboxy group, and a carboxylic acid acyl group.
• the polymerization medium does not contain water.
• a reactive silyl group means a group in which a reactive group is bonded to a silicon atom (Si atom).
• the reactive group is preferably a hydrolyzable group or a hydroxyl group.
• a hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. That is, the hydrolyzable silyl group represented by Si-L becomes a silanol group represented by Si-OH through a hydrolysis reaction.
• the hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanato group (-NCO).
• the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms.
• the aryl group of the aryloxy group includes a heteroaryl group.
• the halogen atom is preferably a chlorine atom.
• the acyl group is preferably an acyl group having 1 to 6 carbon atoms.
• the acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms.
• R A is each independently a hydrocarbon group
• L is each independently a hydrolyzable group or a hydroxyl group
• n is an integer from 0 to 2.
• the multiple reactive silyl groups may be the same or different from each other. From the viewpoint of easy availability of raw materials and ease of manufacturing the compound, it is preferable that the plurality of reactive silyl groups are the same.
• Each R A is independently a hydrocarbon group, preferably a saturated hydrocarbon group.
• the number of carbon atoms in R A is preferably 1 to 6, more preferably 1 to 3, even more preferably 1 to 2.
• hydrolyzable group those mentioned above are preferred.
• L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of ease of manufacturing the compound.
• L is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an ethoxy group or a methoxy group, since the storage stability of the compound is better.
• w is an integer from 0 to 2, preferably 0 or 1, and more preferably 0.
• the plurality of L's present in one molecule may be the same or different from each other. From the viewpoint of ease of obtaining raw materials and ease of manufacturing the compound, it is preferable that the plurality of L's are the same.
• w 2
• multiple R A 's present in one molecule may be the same or different from each other. From the viewpoint of ease of obtaining raw materials and ease of manufacturing the compound, it is preferable that the plurality of R A be the same.
• Examples of monomers having a reactive silyl group include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, and 3-methacryltrimethoxysilane.
• Acryloxybutyltriethoxysilane is mentioned.
• Examples of monomers having an amino group include: N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, 1-(N,N-dimethylamino)-1,1-dimethylmethyl (meth)acrylate, N,N- Dimethylaminohexyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-diisopropylaminoethyl (meth)acrylate, N,N-di-n-butylaminoethyl (meth)acrylate, N,N -di-i-butylaminoethyl (meth)acrylate, morpholinoethyl (meth)acrylate, piperidinoethyl (meth)acrylate, 1-pyrrolidinoethyl (meth)acrylate, N,N-methyl-2-pyrrolidy
• Examples of monomers having an isocyanato group include 2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate, and 2-(2-methacryloyloxyethyloxy). ) ethyl isocyanate.
• the above monomer having an isocyanato group may be blocked with a blocking agent.
• the blocking agent include pyrazoles such as 3,5-dimethylpyrazole; oximes such as 2-butanone oxime; and lactams such as ⁇ -caprolactam.
• Examples of monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxybutyl (meth)acrylate.
• (Meth)acrylates such as meth)acrylate and 4-hydroxybutyl (meth)acrylate; Vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether; and Examples include allyl ethers such as hydroxyethyl allyl ether, hydroxypropyl allyl ether, and hydroxybutyl allyl ether.
• Examples of the monomer having an epoxy group include glycidyl (meth)acrylate.
• Examples of the monomer having an acid anhydride residue include itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and maleic anhydride.
• Examples of monomers having an alkoxycarbonyl group include methyl (meth)acrylate, butyl acrylate, and methyl 3-butenoate.
• Examples of the polymerizable monomer having a carboxy group include (meth)acrylic acid, itaconic acid, 2-(meth)acryloyloxyethylsuccinic acid, and 2-(meth)acryloyloxyhexahydrophthalic acid.
• Examples of monomers having a carboxylic acid acyl group include vinyl methyl ketone, allyl methyl ketone, and vinyl acetate.
• the content of structural units derived from VDF is 30 mol% of the structural units derived from VDF with respect to the total structural units of the obtained fluorine-containing copolymer. It is preferably at least 40 mol%, more preferably at least 50 mol%, even more preferably at least 50 mol%.
• the content of structural units derived from monomers other than VDF is preferably 70 mol% or less, more preferably 60 mol% or less, based on the total structural units of the obtained fluorine-containing copolymer. More preferably, it is 50 mol% or less.
• the monomers used in the polymerization include at least one fluorine-containing monomer selected from the group consisting of HFP and TFE, and a non-fluorine monomer that does not have a fluorine atom and has a (meth)acryloyl group. Including further.
• the content of structural units derived from VDF is preferably 30 mol% or more, more preferably 40 mol% or more, based on the total structural units of the obtained fluorine-containing copolymer. It is preferably 50 mol% or more, and more preferably 50 mol% or more.
• the content of the structural unit derived from at least one fluorine-containing monomer selected from the group consisting of HFP and TFE is 60 mol% with respect to the total structural units of the obtained fluorine-containing copolymer. It is preferably at most 50 mol%, more preferably at most 40 mol%, even more preferably at most 40 mol%.
• the content of structural units derived from a non-fluorine monomer having no fluorine atoms and a (meth)acryloyl group is 1 to 20% based on the total structural units of the obtained fluorine-containing copolymer. It is preferably mol%, more preferably 1 mol% to 15 mol%, even more preferably 1 mol% to 10 mol%.
• the content of VDF is preferably 10 mol% or more, more preferably 15 mol% or more, based on the total amount of monomers used for polymerization.
• the content of other monomers other than VDF is preferably 90 mol% or less, more preferably 85 mol% or less, based on the total amount of monomers used for polymerization.
• the monomers used in the polymerization include at least one fluorine-containing monomer selected from the group consisting of HFP and TFE, and a non-fluorine monomer that does not have a fluorine atom and has a (meth)acryloyl group. Including further.
• the content of VDF is preferably 10 mol% or more, more preferably 15 mol% or more, based on the total amount of monomers used for polymerization.
• the content of at least one fluorine-containing monomer selected from the group consisting of HFP and TFE is preferably 90 mol% or less, and 85 mol% or less, based on the total amount of monomers used in the polymerization. is more preferable.
• the content of the non-fluorine monomer that does not have a fluorine atom and has a (meth)acryloyl group is preferably 1 to 20 mol%, and 1 to 15% by mole, based on the total amount of monomers used in the polymerization. It is more preferably mol%, and even more preferably 1 to 10 mol%.
• Polymerization initiator In the method for producing a fluorine-containing copolymer of the present disclosure, it is preferable to use a polymerization initiator to initiate the polymerization reaction.
• the polymerization initiator is preferably a radical polymerization initiator.
• the radical polymerization initiator include azo compounds such as azobisisobutyronitrile and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); peroxydicarbonates such as diisopropylperoxydicarbonate; Peroxy esters such as tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, and tert-butyl peroxy acetate; Non-fluorinated diacyl peroxides such as diisobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, and lauroyl peroxide; (Z( Fluorine-containing diacyl peroxides such as CF 2 ) p COO) 2 (Z is a hydrogen atom, a fluorine atom or a chlorine atom, and p is an integer of 1 to 10);
• the polymerization reaction may be performed in the presence of a chain transfer agent.
• a chain transfer agent makes it easier to adjust the molecular weight of the fluoropolymer produced.
• chain transfer agents examples include methanol, ethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoropropanol, 1,1,1,3,3,3-hexafluoroisopropanol, Alcohols such as 2,2,3,3,3-pentafluoropropanol; Hydrocarbons such as n-pentane, n-hexane, cyclohexane; Hydrofluorocarbons such as CF 2 H 2 ; Ketones such as acetone; Mercaptans such as methyl mercaptan esters such as methyl acetate and ethyl acetate; and ethers such as diethyl ether and methyl ethyl ether.
• a monomer containing VDF is added continuously or intermittently to a polymerization medium to advance the polymerization reaction.
• a fluorine-containing copolymer of the present disclosure it is preferable that there is only one reaction step.
• a polymerization reaction is carried out using only the first monomer among the monomers used for polymerization (first step), and after the completion of the reaction in the first step, the second monomer is added.
• second step By performing a polymerization reaction (second step), a structure is formed in which the first block derived from the first monomer and the second block derived from the second monomer are connected.
• a single polymerization reaction is performed using all the monomers used in the polymerization, resulting in a structure in which structural units derived from the monomers used in the polymerization are arranged randomly. Note that all of the monomers used in the polymerization need only be added to the polymerization medium before the end of the polymerization reaction, and do not need to be added all at once.
• the amount (mol) of the polymerization solvent A is M sol
• the solubility (mol/mol) of VDF in the polymerization solvent A is S
• the amount (mol) of VDF dissolved in the polymerization medium is M mon
• measuring polymerization refers to a period during which a fluorine-containing copolymer containing VDF is being produced.
• M sol ⁇ S/M mon When the polymerization medium consists only of polymerization solvent A and does not contain any polymerization medium other than polymerization solvent A, M sol ⁇ S/M mon is 1.0. When the polymerization medium contains a polymerization medium other than polymerization solvent A, M sol ⁇ S/M mon is less than 1.0.
• M sol ⁇ S/M mon is 0.5 to 1.0, chain transfer by the polymerization medium is suppressed and the polymerization rate is improved. From the viewpoint of further improving the polymerization rate, M sol ⁇ S/M mon is more preferably from 0.7 to 1.0, and even more preferably from 0.85 to 1.0.
• M sol of polymerization solvent A which represents the amount of substance in polymerization solvent A, is calculated using the following formula.
• M sol (mol) weight of polymerization solvent A (g)/molecular weight of polymerization solvent A
• a value obtained by measurement under atmospheric pressure is used.
• the solubility S of VDF in polymerization solvent A is calculated by the following method. First, the vapor pressure P sol of polymerization solvent A is measured. P sol is the pressure shown when the internal temperature of the reactor is maintained at a predetermined temperature T after the polymerization medium is placed in a stainless steel autoclave equipped with a stirrer and freeze-degassed twice. T means liquidus temperature. The temperature of the gas phase is assumed to be equal to the liquid phase temperature. Put the weighed polymerization solvent A into a stainless steel autoclave equipped with a stirrer. Based on the weighed weight (g) of polymerization solvent A, the substance amount M' (mol) of polymerization solvent A is calculated.
• the partial pressure P mon of the gas in the VDF is calculated from the following formula.
• P mon P all - P sol
• the volume V of the gas phase of the stainless steel autoclave with a stirrer is calculated from the following formula.
• V volume of stainless steel autoclave with stirrer ⁇ volume of polymerization solvent A
• M g (mol) of VDF gas present in the gas phase of the stainless steel autoclave with stirrer is calculated from the following formula.
• R means a gas constant.
• M g P mon V/RT
• M' mon (mol) of the VDF gas dissolved in the polymerization solvent A is calculated from the following formula.
• M' mon M all - M g VDF solubility S in polymerization solvent A is calculated from the following formula.
• S M'mon /M'
• the amount M mon of VDF dissolved in polymerization medium is calculated by the following method.
• P'sol is the pressure shown when the internal temperature of the reactor is maintained at a predetermined temperature T after the polymerization medium is placed in a stainless steel autoclave equipped with a stirrer and freeze-degassed twice.
• T means liquidus temperature.
• the temperature of the gas phase is assumed to be equal to the liquid phase temperature.
• the weighed amount of VDF gas is put into a stainless steel autoclave equipped with a stirrer.
• the amount M' all (mol) of the VDF gas to be charged is calculated from the following formula using the weighed weight W' (g) of the gas.
• M'all W'/64
• P' mon P' all -P' sol
• the volume V' of the gas phase of the stainless steel autoclave with a stirrer is calculated from the following formula.
• V' Volume of stainless steel autoclave with stirrer - Volume of polymerization medium
• the amount M' g (mol) of VDF gas present in the gas phase of the stainless steel autoclave with stirrer is calculated from the following formula. Note that R means a gas constant.
• M'g P'mon ⁇ V'/RT
• M mon (mol) of the VDF gas dissolved in the polymerization medium is calculated from the following formula.
• M mon M' all -M' g
• the polymerization temperature is preferably 0°C to 100°C, more preferably 20°C to 90°C.
• the polymerization pressure is preferably 0.1 MPaG to 10 MPaG, more preferably 0.5 MPaG to 5 MPaG.
• the polymerization time is preferably 1 hour to 30 hours, more preferably 2 hours to 20 hours.
• the fluorine-containing copolymer of the present disclosure includes a structural unit derived from VDF.
• the fluorine-containing copolymer of the present disclosure may contain structural units other than the structural unit derived from VDF.
• Example 1 A stainless steel autoclave with an internal volume of 600 mL and equipped with a stirrer was placed in an ice water bath and held for 10 minutes, and then 360 mL (1.88 mol) of di-tert-butyl carbonate ("Boc 2 O" in the table) was charged as a polymerization medium. , freeze-degassing was performed twice. The reactor was stirred while raising the internal temperature to 45° C., and VDF was pressurized as a monomer so that the internal pressure of the reactor was 2.0 MPaG.
• Boc 2 O di-tert-butyl carbonate
• di-tert-butyl carbonate corresponds to a compound represented by formula (1), where Y 1 is an oxygen atom, p is 0, m is 1, n is 1, and k is 0, Z 1 is a group represented by formula (T1), in formula (T1), A 1 is -OR, and R is a tert-butyl group.
• Example 2 The polymerization medium was changed to methyl pivalate ("MePiv” in the table), and the polymerization initiator was changed to diisobutyryl peroxide (product name "Perloyl IB", manufactured by NOF Corporation, "IBPO” in the table). 2.96 g of a VDF homopolymer was obtained in the same manner as in Example 1, except that the polymerization temperature was changed to 30°C.
• methyl pivalate corresponds to a compound represented by formula (1), where Y 1 is an oxygen atom, p is 1, m is 0, n is 1, and k is 0.
• Z 1 is a group represented by formula (T1), and in formula (T1), A 3 is a tert-butyl group.
• Example 3 4.4 g of a VDF homopolymer was obtained in the same manner as in Example 2, except that the polymerization medium was changed to tetramethylsilane ("TMS" in the table). Note that tetramethylsilane corresponds to a compound represented by formula (2), where Y 3 is a silicon atom and R 1 to R 4 are methyl groups.
• Example 4 7.9 g of a VDF homopolymer was obtained in the same manner as in Example 2, except that the polymerization medium was changed to trimethyl phosphate ("TMP" in the table).
• trimethyl phosphate corresponds to a compound represented by formula (1), where Y 1 is an oxygen atom, p is 1, m is 0, n is 1, and k is 0. and Z 1 is a group represented by formula (T3), where A 2 is -OR and R is a methyl group.
• HFP hexafluoropropylene
• Example 7 VDF and 3.5 g of a copolymer of HFP and TFE was obtained.
• the molar ratio of VDF units: HFP units: TFE units was 63:16:21.
• Example 13 An attempt was made to obtain a homopolymer of VDF in the same manner as in Example 2, except that the polymerization medium was changed to tert-butyl methyl ether ("TBME" in the table). However, no copolymer was obtained. Tert-butyl methyl ether does not fall under polymerization solvent A.
• C6H 1H-perfluorohexane
• Example 16 VDF alone was prepared in the same manner as in Example 2, except that the polymerization medium was changed to a mixture of methyl pivalate and water (water content: 20% by volume) ("MePiv/water" in the table). 1.2g of polymer was obtained.
• the polymerization rate in the production methods of Examples 1 to 17 and the melt flow rate values (MFR values) of the copolymers obtained in Examples 1 to 17 were measured.
• the storage modulus was measured instead of the MFR value.
• the amount (mol) of the polymerization solvent A is M sol
• the solubility (mol/mol) of VDF in the polymerization solvent A is S
• the amount (mol) of VDF dissolved in the polymerization medium is M sol .
• M sol ⁇ S/M mon was calculated.
• the measurement method and calculation method are as follows. In addition, items that could not be measured are marked with a "-" in the table.
• Polymerization rate (g/h ⁇ L) Yield of obtained copolymer (g)/ ⁇ polymerization time (h) ⁇ volume of polymerization solvent (L) ⁇ Note that the polymerization solvent referred to herein does not include a polymerization initiator.
• ⁇ MFR value> Diameter: 2.095 mm, length under the conditions of temperature: 230°C, load: 49.0 N, using a thermal fluid evaluation device (product name "Flow Tester CFT-100EX", manufactured by Shimadzu Corporation) in accordance with ASTM D3159. : The mass (g) of the copolymer flowing out from an 8.000 mm orifice in 10 minutes was measured and defined as MFR (g/10 minutes).
• Viscosity was measured using a Mooney viscometer (Model MV2000E, manufactured by ALPHA TECHNOLOGIES) at a measurement temperature of 100° C. in accordance with ASTM-D1646 and JIS K6300-1:2013.
• ⁇ Ratio of each monomer> The proportion of each structural unit in the polymer was determined from 19 F-NMR analysis, fluorine content analysis, or infrared absorption spectrum analysis.
• M sol is the amount (mol) of the polymerization solvent A, the solubility (mol/mol) S of VDF in the polymerization solvent A, and the amount (mol) of the VDF dissolved in the polymerization medium. M mon was calculated. Thereafter, M sol ⁇ S/M mon was calculated using M sol , S, and M mon .
• Table 1 lists the types of monomers, polymerization medium, and polymerization initiator, as well as the polymerization rate, MFR (storage modulus in Example 7), and M sol ⁇ S/M mon .
• Examples 1 to 12 and Examples 16 to 17 contain at least one polymerization solvent A selected from the group consisting of compounds represented by formula (1) and formula (2). Since the polymerization was carried out using a monomer containing VDF in the polymerization medium, it was found that the polymerization rate was faster than that of the conventional method.

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