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
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C395/00—Compounds containing tellurium
• • 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
  • C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
• • 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
• • 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
  • C08F214/182—Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28
• • 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
  • C08F214/24—Trifluorochloroethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
  • C08F30/00—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F30/04—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
• • 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

Definitions

• the present disclosure relates to tellurium-containing compounds, polymers, and methods for producing polymers.
• the radical polymerization reaction is widely used industrially because it has excellent monomer versatility and can be easily performed even in a polar medium such as water.
• the control of the molecular weight by a general radical polymerization method is limited, and the molecular weight distribution of the obtained polymer tends to be wide.
• the living radical polymerization method has attracted attention as a polymerization method for obtaining a controlled molecular structure, and various polymerization control agents have been developed.
• the living radical polymerization method is a polymerization method in which the radical polymerization rate is controlled by reversibly protecting the growth radical with a protecting group which is a dormant species, whereby the molecular weight distribution can be controlled.
• Patent Document 1 describes a living radical polymerization method for producing a haloolefin polymer or a copolymer by radically polymerizing a specific haloolefin in the presence of a specific organic tellurium compound. This method is based on a method called a TERP (organotellurium mediated living radical polymerization) method.
• TERP organotellurium mediated living radical polymerization
• the branched polymer has various properties different from those of the linear polymer. For example, since the branched polymer has a large number of terminal groups, when used as a molding material, the crosslink density of the molded product can be increased and the curability can be improved. Branched polymers are also known to have lower intrinsic viscosities and lower glass transition temperatures than linear polymers. As described above, the branched polymer has unique properties different from those of the linear polymer, and its industrial usefulness is high.
• Non-Patent Document 1 discloses a controlled polymerization method for producing a highly branched polymer by copolymerizing vinyl telluride and an acrylic acid monomer in the presence of a tellurium compound which is a chain transfer agent, based on the TERP method. ..
• the first embodiment of the present disclosure is a novel tellurium-containing compound that can be used to prepare a polymer having a controlled molecular structure and a branched structure, and a polymer prepared by using the tellurium-containing compound. Regarding providing.
• a second embodiment of the present disclosure relates to providing a novel polymer having a controlled molecular structure and a branched structure.
• a third embodiment of the present disclosure relates to providing a polymer having a controlled molecular structure and a branched structure, which is obtained by polymerizing a fluorine-containing monomer.
• a fourth embodiment of the present disclosure relates to providing a method for producing a polymer having a controlled molecular structure and a branched structure.
• a fifth embodiment of the present disclosure relates to providing a method for producing a novel polymer having a controlled molecular structure and a branched structure.
• a sixth embodiment of the present disclosure relates to a method for producing a polymer obtained by polymerizing a fluorine-containing monomer having a controlled molecular structure and a branched structure.
• X 1 , Y 1 , and Z 1 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and are X 1 , Y 1 , and Z. At least one of 1 represents a fluorine atom, R 1 represents an organic group having 1 to 20 carbon atoms.
• R 1 is an substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted oxyalkylene structure.
• the tellurium-containing compound according to ⁇ 1> which is a monovalent hydrocarbon group having 1 to 20 carbon atoms or an substituted or unsubstituted aryl group having 3 to 20 carbon atoms.
• X 1 , Y 1 , and Z 1 are independently hydrogen atom, fluorine atom, chlorine atom, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or substituted.
• the tellurium contained in ⁇ 1> or ⁇ 2> which is a monovalent hydrocarbon group having 1 to 20 carbon atoms having an unsubstituted oxyalkylene structure or an aryl group having 3 to 20 carbon atoms which is substituted or unsubstituted.
• Compound. ⁇ 4> A polymer obtained by polymerizing at least the tellurium-containing compound according to any one of ⁇ 1> to ⁇ 3>.
• X 11 to X 14 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and X 11 to X 14 thereof. At least one represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.
• M2 A polymer obtained by polymerizing at least a tellurium-containing compound represented by the following formula (M2):
• X 2 , Y 2 , and Z 2 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and X 2 , Y 2 , and Z. At least one of 2 represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group.
• R2 represents an organic group having 1 to 20 carbon atoms.
• X 11 to X 14 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and X 11 to X 14 thereof. At least one represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.
• M3 tellurium-containing compound represented by the following formula (M3) and a compound represented by the following formula (M11):
• X 3 , Y 3 , and Z 3 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms.
• R 3 represents an organic group having 1 to 20 carbon atoms.
• X 11 to X 14 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and X 11 to X 14 thereof. At least one represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.
• ⁇ 11> At least any of ⁇ 1> to ⁇ 3> in the presence of at least one compound selected from the group consisting of the compound represented by the following formula (T1) and the compound represented by the following formula (T2).
• a method for producing a polymer which comprises polymerizing the tellurium-containing compound according to item 1.
• R 6 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms.
• R 7 and R 8 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.
• R 9 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, and an acyl group having 2 to 8 carbon atoms.
• R 10 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms.
• R 10 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms.
• X 11 to X 14 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and X 11 to X 14 thereof. At least one represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.
• R 6 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms.
• R 7 and R 8 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.
• R 9 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, and an acyl group having 2 to 8 carbon atoms.
• R 10 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms.
• X 2 , Y 2 , and Z 2 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and X 2 , Y 2 , and Z. At least one of 2 represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group.
• R2 represents an organic group having 1 to 20 carbon atoms.
• X 11 to X 14 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and X 11 to X 14 thereof. At least one represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.
• T1 the compound represented by the following formula (T2)
• T3 the compound represented by the following formula (M3).
• R 6 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms.
• R 7 and R 8 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.
• R 9 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, and an acyl group having 2 to 8 carbon atoms.
• R 10 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms.
• X 3 , Y 3 , and Z 3 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms.
• R 3 represents an organic group having 1 to 20 carbon atoms.
• X 11 to X 14 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and X 11 to X 14 thereof. At least one represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.
• a novel tellurium-containing compound that can be used to prepare a polymer having a controlled molecular structure and a branched structure, and the tellurium-containing compound are used.
• Polymers are provided.
• a novel polymer having a controlled molecular structure and a branched structure is provided.
• a polymer obtained by polymerizing a fluorine-containing monomer having a controlled molecular structure and a branched structure is provided.
• a method for producing a polymer having a controlled molecular structure and a branched structure there is provided a method for producing a polymer having a controlled molecular structure and a branched structure.
• a method for producing a polymer having a controlled molecular structure and a branched structure which is obtained by polymerizing a fluorine-containing monomer.
• the term "process” includes, in addition to a process independent of other processes, the process as long as the purpose of the process is achieved even if it cannot be clearly distinguished from the other process. ..
• the numerical range indicated by using "-" includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
• each component may contain a plurality of applicable substances. When a plurality of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
• the reactive carbon-carbon double bond means a carbon-carbon double bond that can react in various ways as an olefin, and does not include an aromatic double bond.
• the organic group or the hydrocarbon group may or may not have a substituent.
• the carbon number of a compound or a constituent thereof in the present disclosure means a number including the carbon number of the substituent when the compound or the constituent has a substituent.
• (meth) acrylic acid is a general term for acrylic acid and methacrylic acid.
• (Meta) acrylate is a general term for acrylate and methacrylate.
• (Meta) acrylamide is a general term for acrylamide and methacrylamide.
• the "polymer” is a compound obtained by polymerizing a monomer. That is, the “polymer” has a plurality of structural units.
• the statements “polymerize compound A” and “polymerize at least compound A” are used when only compound A is polymerized or compound A is polymerized with another compound. It includes any of the cases where it is caused.
• the descriptions of “polymerizing compound A and compound B” and “polymerizing at least compound A and compound B” are used when only compound A and compound B are polymerized, and compound A, compound B and others. This includes all cases where the compound of the above is polymerized.
• compound A and compound B represent any compound described in the present disclosure having a carbon-carbon double bond in the molecule.
• the polymer described in the present disclosure may be a homopolymer of one kind of compound or a copolymer of two or more kinds of compounds.
• the term "polymer” does not exclude mixtures containing raw materials (monomers, catalysts), by-products, impurities, etc., in addition to polymers.
• the present disclosure relates to controlled polymerization for producing a polymer having a branched structure using a tellurium-containing compound having a reactive carbon-carbon double bond.
• the findings of the present disclosure can be used to obtain polymers with a controlled molecular structure and a branched structure.
• the embodiment of the present disclosure is not limited in any way, it is found that the tellurium-containing compound, the polymer, and the method for producing the polymer described in detail in the present disclosure are also useful for the polymerization of the fluorine-containing monomer. It has been issued. In general, controlled polymerization of fluorine-containing monomers is more difficult than controlled polymerization of hydrocarbon-based monomers.
• the controlled polymerization method is not yet efficient for the polymerization of highly reactive and gaseous fluoroalkenes such as tetrafluoroethylene. Further, in the controlled polymerization of the fluorine-containing monomer, the knowledge about the method of introducing the branched structure into the molecule of the polymer has not been reported so far. The inventor has found that the tellurium-containing compounds, polymers, and methods for producing polymers detailed in the present disclosure are suitably applicable to the polymerization of fluorine-containing monomers.
• the tellurium-containing compound according to the first embodiment is a tellurium-containing compound represented by the following formula (M1).
• X 1 , Y 1 , and Z 1 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and are X 1 , Y 1 , and Z. At least one of 1 represents a fluorine atom, R 1 represents an organic group having 1 to 20 carbon atoms.
• the tellurium-containing compound according to the first embodiment can introduce a branched chain into the polymer to be produced by controlled polymerization, a polymer having a controlled molecular structure and a branched structure can be produced. Can be suitably used for.
• R 1 represents an organic group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, and a substituted moiety. Alternatively, it is preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms having an unsubstituted oxyalkylene structure, or an substituted or unsubstituted aryl group having 3 to 20 carbon atoms. It should be noted that R 1 is not connected to any of X 1 , Y 1 , and Z 1 .
• the unsubstituted alkyl group having 1 to 20 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and a cyclobutyl group.
• Examples thereof include linear, branched or cyclic alkyl groups such as n-pentyl group, n-hexyl group, n-heptyl group and n-octyl group. Of these, a methyl group, an ethyl group, or an n-butyl group is more preferable.
• the substituted alkyl group having 1 to 20 carbon atoms the hydrogen atom at an arbitrary position of the above-mentioned unsubstituted alkyl group having 1 to 20 carbon atoms is substituted with a fluorine atom, a chlorine atom, an alkoxy group, a fluoroalkoxy group or the like. Examples include alkyl groups substituted with groups. Of these, a perfluoroalkyl group is preferable.
• perfluoroalkyl group examples include perfluoromethyl group, perfluoroethyl group, perfluoron-propyl group, perfluoroisopropyl group, perfluoron-butyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoron-pentyl group and perfluoron.
• -Hexyl group, perfluoro n-heptyl group, perfluoro n-octyl group and the like can be mentioned.
• the monovalent hydrocarbon group having 1 to 20 carbon atoms having a substituted or unsubstituted oxyalkylene structure preferably has 1 to 12 carbon atoms, and more preferably 1 to 6 carbon atoms.
• Examples of the monovalent hydrocarbon group having an unsubstituted oxyalkylene structure include a hydrocarbon group having an oxyalkylene structure having 1 to 4 carbon atoms as a constituent unit, and more specifically,-((CH). 2 ) m -O) Groups represented by n -CH 3 can be mentioned.
• m represents the number of repetitions of the methylene group, and is preferably an integer of 0 to 4 independently.
• n represents the number of repetitions of a-((CH 2 ) m -O) -structure of 1 or more, and is preferably an integer of 1 to 15.
• the hydrogen atom at an arbitrary position of the oxyalkylene structure in the monovalent hydrocarbon group having the unsubstituted oxyalkylene structure described above is a fluorine atom or a chlorine atom.
• a monovalent hydrocarbon group having an oxyperfluoroalkylene structure is preferable, and from the viewpoint of ease of synthesis, a monovalent perfluorohydrocarbon group having an oxyperfluoroalkylene structure having 1 to 4 carbon atoms as a unit is more preferable.
• -((CF 2 ) m -O) n The perfluorohydrocarbon group represented by CF 3 is more preferable.
• m represents the number of repetitions of the difluoromethylene group, and is preferably an integer of 0 to 4 independently.
• n represents the number of repetitions of a-((CF 2 ) m -O) -structure of 1 or more, and is preferably an integer of 1 to 15.
• the hydrogen atom of the hydrocarbon group may be substituted with a fluorine atom or the like.
• substituted or unsubstituted aryl group having 3 to 20 carbon atoms a substituted or unsubstituted aryl group having 3 to 16 carbon atoms is preferable, and a substituted or unsubstituted aryl group having 3 to 12 carbon atoms is more preferable.
• the unsubstituted aryl group having 3 to 20 carbon atoms include a homoaryl group such as a phenyl group and a naphthyl group; and a heteroaryl group such as a pyridyl group, a pyrrol group, a frill group and a thienyl group.
• any hydrogen atom bonded to the aromatic ring of the above-mentioned unsubstituted aryl group having 3 to 20 carbon atoms is a halogen atom, a hydroxyl group, an alkoxy group, an amino group, or a nitro.
• Examples thereof include an aryl group substituted with a substituent such as a group, a cyano group, a carbonyl-containing group, a sulfonyl group and a trifluoromethyl group.
• the number of substituents is not particularly limited, and may be 1 to 4, 1 to 3, 1 to 2, or 1.
• X 1 , Y 1 , and Z 1 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and X 1 , Y 1 , and Z 1 represent a fluorine atom.
• X 1 , Y 1 , and Z 1 each independently have a hydrogen atom, a fluorine atom, a chlorine atom, an substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted oxyalkylene structure. It is preferably a monovalent hydrocarbon group of 1 to 20, or a substituted or unsubstituted aryl group having 3 to 20 carbon atoms.
• Substituent or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted oxyalkylene groups having 1 to 20 carbon atoms, and substituted or unsubstituted aryl groups having 3 to 20 carbon atoms examples include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms according to R 1 , substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms having an oxyalkylene structure, and substituted or unsubstituted alkyl groups. Examples thereof include the above-mentioned examples as an unsubstituted aryl group having 3 to 20 carbon atoms.
• Examples of the compound represented by the formula (M1) include phenyl (trifluorovinyl) telluride, (2,2-difluorovinyl) phenyltelluride, (1-chlorodifluorovinyl) phenyltelluride, and butyl (trifluorovinyl) telluride. , Methyl (trifluorovinyl) telluride and the like.
• the method for producing the tellurium-containing compound represented by the formula (M1) is not particularly limited.
• X 1 , Y 1 , Z 1 , and R 1 are the same as X 1 , Y 1 , Z 1 , and R 1 in the equation (M1), respectively.
• the polymer according to the first embodiment is obtained by polymerizing at least the tellurium-containing compound according to the first embodiment.
• the polymer may be a homopolymer or a copolymer of the tellurium-containing compound according to the first embodiment.
• the copolymer may be a block copolymer, a random copolymer, or an alternate copolymer.
• the polymer is a polymerizable compound having a carbon-carbon double bond in the molecule, unlike the tellurium-containing compound represented by the formula (M1) and the tellurium-containing compound represented by the formula (M1).
• it may be a copolymer obtained by polymerizing a "first copolymerization monomer”).
• the first copolymerization monomer may be used alone or in combination of two or more.
• the first copolymerization monomer is not particularly limited.
• the first copolymerization monomer may be a compound represented by the following formula (M12).
• R 11 to R 14 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an substituted or unsubstituted organic group having 1 to 40 carbon atoms.
• R 1 and R 4 or R 2 and R 3 may be connected to form an annular structure.
• the substituted or unsubstituted organic group having 1 to 40 carbon atoms in R 11 to R 14 preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. More preferred.
• Substituted or unsubstituted organic groups having 1 to 40 carbon atoms include alkyl groups, aryl groups, heteroaryl groups, aryloxy groups, heteroaryloxy groups, alkoxy groups, arylalkyl groups, heteroarylalkyl groups, and arylalkoxy groups. , Heteroarylalkoxy group, carboxy group, alkoxycarbonyl group, carbamoyl group, acylamino group, acyloxy group, cyano group, monovalent hydrocarbon group having oxyalkylene structure and the like.
• the substituted or unsubstituted organic group having 1 to 40 carbon atoms is an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkoxy group, an arylalkyl group, a heteroarylalkyl group, an arylalkoxy group,
• a hydrocarbon group which may have a hetero atom, such as a heteroarylalkoxy group or a monovalent hydrocarbon group having an oxyalkylene structure
• the hydrocarbon group is linear, branched, or branched. It may be cyclic and may or may not contain unsaturated bonds.
• acyl group of the acylamino group or the acyloxy group examples include a group obtained by removing a hydroxy group from a carboxylic acid or a sulfonic acid.
• Examples of the substituent in the organic group having 1 to 40 carbon atoms having a substituent include a fluorine atom, a chlorine atom, a hydroxy group, an alkoxy group, an alkoxyalkyl group, an amino group, a carboxylic acid group, and a sulfonic acid group, 1, 3, and 5.
• -Triazine trion skeleton and the like can be mentioned.
• R 11 and R 13 or R 12 and R 14 may be connected to form an annular structure. That is, the compound represented by the formula (M12) may be a compound having a cyclic structure such as maleic anhydride and itaconic anhydride.
• Examples of the first copolymerization monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, and (meth) acrylic.
• (Meta) acrylic acid ester monomers such as lauryl acid, hydroxyethyl methacrylate; cycloalkyls such as (meth) cyclohexyl acrylate, methyl cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, cyclododecyl (meth) acrylate.
• Group-containing unsaturated monomer carboxyl group-containing unsaturated monomer such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, maleic anhydride, itaconic anhydride; N, N-dimethylaminopropyl Tertiary amine-containing unsaturated monomers such as (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, 2- (dimethylamino) ethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate; A quaternary ammonium base-containing unsaturated monomer such as N-2-hydroxy-3-acryloyloxypropyl-N, N, N-trimethylammonium chloride, N-methacryloylaminoethyl-N, N, N-dimethylbenzylammonium chloride; Meta) Epoxy group
• Vinylidene Chemical Acid Trifluoroethylene, Chlorotrifluoroethylene, Tetrafluoroethylene, Hexafluoro Propylene, 2,3,3,3-tetrafluoropropylene, vinylidene chloride, vinyl chloride, 1-chloro-1-fluoroethylene, or 1,2-dichloro-1,2-difluoroethylene, 1H, 1H, 2H-perfluoro ⁇ -olefins such as (n-1-hexene), 1H, 1H, 2H-perfluoro (n-1-octene); vinyl ester monomers such as vinyl acetate; 1,4-divinyl octafluorobutane, 1,6-divinyl Divinylfluoroalkanes such as dodecafluorohexane; acrylonitrile; acrylamide monomers such as acrylamide, N, N-dimethylacrylamide; methyl vinyl ethers, ethyl vinyl ethers, buty
• the first copolymerization monomer may be a compound represented by the following formula (M11).
• X 11 to X 14 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and X 11 to X 14 thereof. At least one represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.
• the compound represented by the formula (M1) can introduce a branched chain into the fluorine-containing polymer by copolymerizing with a fluorine-containing monomer represented by the compound represented by the formula (M11).
• the organic group having 1 to 20 carbon atoms represented by X 11 to X 14 includes an substituted or unsubstituted alkyl group having 1 to 20 carbon atoms and a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Examples thereof include the aryl group of.
• the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms includes an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkoxy group, an arylalkyl group, a heteroarylalkyl group, and an arylalkoxy group.
• Heteroarylalkoxy group carboxy group, alkoxycarbonyl group, carbamoyl group, acylamino group, acyloxy group, cyano group and the like.
• the substituted or unsubstituted organic group having 1 to 20 carbon atoms is an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkoxy group, an arylalkyl group, a heteroarylalkyl group, an arylalkoxy group, Alternatively, when it is a hydrocarbon group which may have a hetero atom such as a heteroarylalkoxy group, the hydrocarbon group may be linear, branched, or cyclic, and may have an unsaturated bond. May or may not be included.
• acyl group of the acylamino group or the acyloxy group examples include a group obtained by removing a hydroxy group from a carboxylic acid or a sulfonic acid.
• Examples of the substituent in the organic group having 1 to 20 carbon atoms having a substituent include a fluorine atom, a chlorine atom, a hydroxy group, an alkoxy group, an alkoxyalkyl group, an amino group, a carboxylic acid group, a sulfonic acid group and the like.
• perfluoroalkyl group examples include perfluoromethyl group, perfluoroethyl group, perfluoron-propyl group, perfluoroisopropyl group, perfluoron-butyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoron-pentyl group and perfluoron.
• -Hexyl group, perfluoro n-heptyl group, perfluoro n-octyl group and the like can be mentioned.
• a monovalent perfluorohydrocarbon group having an oxyperfluoroalkylene structure having 1 to 4 carbon atoms as a unit is more preferable, and-((CF 2 ) m -O).
• a perfluorohydrocarbon group represented by n -CF 3 is more preferable.
• m represents the number of repetitions of the difluoromethylene group, and is preferably an integer of 0 to 4 independently.
• n represents the number of repetitions of the ⁇ ((CF 2 ) m ⁇ O) ⁇ structure, and is preferably an integer of 1 to 15.
• Examples of the compound represented by the formula (M11) include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 1,3.
• Examples of the compound represented by the formula (M11) include vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and 2,3 from the viewpoint of polymerization reactivity when obtaining a polymer. , 3,3-Tetrafluoropropylene is preferred.
• the polymer according to the first embodiment can be obtained, for example, by the polymer polymerization method according to the fourth embodiment described later.
• the polymer according to the second embodiment is obtained by polymerizing at least a tellurium-containing compound represented by the following formula (M2).
• X 2 , Y 2 , and Z 2 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and X 2 , Y 2 , and Z. At least one of 2 represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group.
• R2 represents an organic group having 1 to 20 carbon atoms.
• At least one of X 1 , Y 1 , and Z 1 in formula (M1) being a fluorine atom at least one of X 2 , Y 2 , and Z 2 in formula (M2) is a chlorine atom, a perfluoroalkyl group.
• X2, Y2 , and Z2 in formula ( M2 ) except that they are monovalent hydrocarbon groups or phenyl groups with an oxyperfluoroalkylene structure, the details of X1, Y in formula (M1). Same as the details of 1 and Z1 .
• perfluoroalkyl group examples include perfluoromethyl group, perfluoroethyl group, perfluoron-propyl group, perfluoroisopropyl group, perfluoron-butyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoron-pentyl group and perfluoron.
• -Hexyl group, perfluoro n-heptyl group, perfluoro n-octyl group and the like can be mentioned.
• Examples of the monovalent hydrocarbon group having an oxyperfluoroalkylene structure include a perfluorohydrocarbon group having an oxyperfluoroalkylene structure having 1 to 4 carbon atoms as a constituent unit.
• the phenyl group may or may not have a substituent, and preferably does not have a substituent.
• Substituents include a substituted or unsubstituted alkyl group, a monovalent hydrocarbon group having a substituted or unsubstituted oxyalkylene structure, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group.
• Groups are preferred.
• Examples of the compound represented by the formula (M2) include (1-chlorodifluorovinyl) phenylterlide, (2-nonafluorobutylvinyl) phenylterlide, (1-chlorovinyl) phenylterlide, and (2-chlorovinyl). ) Phenylterlide, (1-phenylvinyl) phenylterlide and the like.
• the method for producing the tellurium-containing compound represented by the formula (M2) is not particularly limited.
• X 2 , Y 2 , Z 2 , and R 2 are the same as X 2 , Y 2 , Z 2 , and R 2 in the equation (M2), respectively.
• An example of a specific synthetic scheme is based on the example of the method for producing a tellurium-containing compound represented by the formula (M1) in the first embodiment.
• the polymer according to the second embodiment may be a homopolymer of the tellurium-containing compound represented by the formula (M2) or a copolymer.
• the copolymer may be a block copolymer, a random copolymer, or an alternating copolymer.
• the polymer is a polymerizable compound having a carbon-carbon double bond in the molecule, unlike the tellurium-containing compound represented by the formula (M2) and the tellurium-containing compound represented by the formula (M2).
• it may be a copolymer obtained by polymerizing a "second copolymer monomer").
• the second copolymerization monomer may be used alone or in combination of two or more.
• the second copolymerization monomer is not particularly limited.
• the details of the second copolymerization monomer are different from the tellurium-containing compound represented by the formula (M2) in place of the tellurium-containing compound represented by the formula (M1). It is the same as the details of the polymerization monomer.
• the second copolymerization monomer may be a compound represented by the above formula (M11).
• the compound represented by the formula (M2) can introduce a branched chain into the fluorine-containing polymer by copolymerizing with a fluorine-containing monomer represented by the compound represented by the formula (M11).
• the polymer according to the second embodiment can be obtained, for example, by the method for producing a polymer according to the fifth embodiment described later.
• the polymer according to the third embodiment is obtained by polymerizing at least a tellurium-containing compound represented by the following formula (M3) and a compound represented by the following formula (M11).
• X 3 , Y 3 , and Z 3 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms.
• R 3 represents an organic group having 1 to 20 carbon atoms.
• X 11 to X 14 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and X 11 to X 14 thereof. At least one represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.
• X3, Y3, and in formula (M3) except that at least one of X1 , Y1 , and Z1 in formula (M1) is a fluorine atom, but there is no such limitation in formula (M3).
• the details of Z 3 are the same as the details of X 1 , Y 1 , and Z 1 in the equation (M1).
• the method for producing the tellurium-containing compound represented by the formula (M3) is not particularly limited.
• X 3 , Y 3 , Z 3 , and R 3 are the same as X 3 , Y 3 , Z 3 , and R 3 in the equation (M3), respectively.
• An example of a specific synthetic scheme is based on the example of the method for producing a tellurium-containing compound represented by the formula (M1) in the first embodiment.
• the polymer according to the third embodiment can be obtained, for example, by the method for producing the polymer according to the sixth embodiment described later.
• the method for producing a polymer according to the fourth embodiment is in the presence of at least one compound selected from the group consisting of the compound represented by the following formula (T1) and the compound represented by the following formula (T2). , At least the tellurium-containing compound according to the first embodiment, that is, the tellurium-containing compound represented by the formula (M1) is polymerized.
• R 6 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms.
• R 7 and R 8 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.
• R 9 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, and an acyl group having 2 to 8 carbon atoms.
• R 10 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms.
• the method for producing a polymer according to the fourth embodiment is based on the TERP method, and is at least one compound selected from the group consisting of the compound represented by the formula (T1) and the compound represented by the formula (T2).
• T1 the compound represented by the formula
• T2 the compound represented by the formula (T2)
• the unsubstituted alkyl group having 1 to 8 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, and n.
• Examples include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms, such as pentyl groups, n-hexyl groups, n-heptyl groups and n-octyl groups. Of these, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group, an ethyl group, or an n-butyl group is more preferable.
• Examples of the substituted alkyl group having 1 to 8 carbon atoms include an alkyl group having a substituent such as a fluorine atom, a chlorine atom, an alkoxy group, and a fluoroalkoxy group at an arbitrary position.
• a substituent such as a fluorine atom, a chlorine atom, an alkoxy group, and a fluoroalkoxy group at an arbitrary position.
• an alkyl group having 2 to 13 fluorine atoms is preferable, and a (perfluoroalkyl) ethyl group having 3 to 8 carbon atoms is more preferable from the viewpoint of suppressing the hydrogen atom extraction reaction by radicals.
• Examples of the unsubstituted aryl group having 3 to 16 carbon atoms include a homoaryl group such as a phenyl group and a naphthyl group; and a heteroaryl group such as a pyridyl group, a pyrrol group, a frill group and a thienyl group. Of these, a homoaryl group is preferable, and a phenyl group is more preferable.
• a halogen atom As the substituted aryl group having 3 to 16 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, a carbonyl-containing group represented by -COR a , a sulfonyl group, and a trifluoromethyl group are used at arbitrary positions. Examples thereof include an aryl group having 1 to 4, preferably 1 to 3, more preferably 1 and preferably 1 to 4 substituents such as, and preferably 1 to 4 orth groups.
• the Ra is an alkyl group having 1 to 8 carbon atoms, preferably a linear or branched alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Represents a linear or branched alkoxy group of 4; an aryl group; or an aryloxy group.
• each group represented by R 7 and R 8 is as follows.
• the substituted or unsubstituted alkyl group having 1 to 8 carbon atoms include substituted or unsubstituted alkyl groups similar to the substituted or unsubstituted alkyl group having 1 to 8 carbon atoms shown in R6.
• R 7 and R 8 a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferable.
• each group represented by R9 is as follows.
• Examples of the substituted or unsubstituted alkyl group having 1 to 8 carbon atoms and the substituted or unsubstituted aryl group having 3 to 16 carbon atoms include the same groups as those shown in R6 above.
• acyl group having 2 to 8 carbon atoms examples include an acetyl group and a benzoyl group.
• Examples of the amide group having 2 to 8 carbon atoms include a carbamoyl group-containing group such as a carbamoylmethyl group, a dicarbamoylmethyl group and a 4-carbamoylphenyl group; and a thiocarbamoyl group-containing group such as a thiocarbamoylmethyl group and a 4-thiocarbamoylphenyl group.
• a carbamoyl group-containing group such as a carbamoylmethyl group, a dicarbamoylmethyl group and a 4-carbamoylphenyl group
• a thiocarbamoyl group-containing group such as a thiocarbamoylmethyl group and a 4-thiocarbamoylphenyl group.
• Examples of the oxycarbonyl-containing group include the group represented by -COOR b .
• R b is a hydrogen atom; an alkyl group having 1 to 8 carbon atoms, preferably a linear or branched alkyl group having 1 to 4 carbon atoms; an alkenyl group having 2 to 8 carbon atoms, preferably carbon.
• the alkyl group having 1 to 8 carbon atoms, the alkenyl group having 2 to 8 carbon atoms, the alkynyl group having 2 to 8 carbon atoms, and the aryl group having 3 to 12 carbon atoms represented by Rb have halogen atoms and hydroxyl groups at arbitrary positions.
• Examples of the oxycarbonyl-containing group include a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an n-butoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, an n-pentoxycarbonyl group, and a phenoxycarbonyl group. And so on. Of these, a methoxycarbonyl group or an ethoxycarbonyl group is preferable.
• R9 an aryl group having 5 to 12 carbon atoms, an alkoxycarbonyl group, or a cyano group is preferable.
• R 6 is an alkyl group or a phenyl group having 1 to 4 carbon atoms
• R 7 and R 8 are independently hydrogen atoms or an alkyl having 1 to 4 carbon atoms, respectively.
• the group, R9 may be a compound represented by an aryl group or an alkoxycarbonyl group having 5 to 12 carbon atoms.
• R 6 is an alkyl group or a phenyl group having 1 to 4 carbon atoms
• R 7 and R 8 are independently hydrogen atoms or carbon atoms 1 to 4, respectively.
• the alkyl group and R9 may be a compound represented by a phenyl group, a methoxycarbonyl group or an ethoxycarbonyl group.
• Specific examples of the compound represented by the formula (T1) include (methylteranylmethyl) benzene, (methylteranylmethyl) naphthalene, ethyl-2-methyl-2-methylteranyl-propionate, and ethyl-2-methyl.
• -2-n-Butylteranyl-propionate (2-trimethylsiloxyethyl) -2-methyl-2-methylteranyl-propinate, (2-hydroxyethyl) -2-methyl-2-methylteranyl-propinate, (3-trimethylsilylpropargyl)
• Examples thereof include the compounds described in International Publication No. 2004/01/4848 and International Publication No. 2004/014962, such as -2-methyl-2-methylteranyl-propinate.
• the method for producing the compound represented by the formula (T1) is not particularly limited, and is according to the known methods described in International Publication No. 2004/014948, International Publication No. 2004/014962, and International Publication No. 2018/164147. Can be manufactured.
• the compound represented by the formula (T2) In the formula (T2), the details of R 10 are independently the same as the details of R 6 in the above formula (T1).
• the compound represented by the formula (T2) may be a compound in which R 10 is independently represented by an alkyl group or a phenyl group having 1 to 4 carbon atoms.
• Specific examples of the compound represented by the formula (T2) include dimethylditelluide, diethylditelluride, di-n-propylditelluride, diisopropylditelluride, dicyclopropylditelluride, and di-.
• n-butyl ditelluride di-sec-butyl ditelluride, di-tert-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis- (p-methoxyphenyl) ditelluide, bis- (p-aminophenyl) diterlide, bis- Examples thereof include (p-nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthylditelluride, dipyridylditelluride and the like.
• the compound represented by the formula (T2) may be used alone or in combination of two or more.
• dimethyl ditelluride diethyl ditelluride, di-n-propyl ditelluride, di-n-butyl ditelluride, or diphenyl ditelluride is preferable.
• radical initiator examples include an azo-based radical initiator, a peroxide-based radical initiator, and the like.
• the radical initiator may be used alone or in combination of two or more.
• azo-based radical initiator examples include 2,2'-azobis (isobutyronitrile) (AIBN), 2,2'-azobis (2-methylbutyronitrile) (AMBN), and 2,2'-azobis (2).
• AIBN isobutyronitrile
• AMBN 2,2'-azobis (2-methylbutyronitrile
• 2,2'-azobis (2) 4-dimethylvaleronitrile) (ADVN), 1,1'-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2'-azobisisobutyrate (MAIB), 4,4'-azobis (4-cyanovalerian acid) (ACVA), 1,1'-azobis (1-acetoxy-1-phenylethane), 2,2'-azobis (2-methylbutylamide), 2,2'-azobis (4) -Methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylamidinopropane) dihydrochloride, 2,2'-azo
• peroxide-based radical initiator examples include diisopropylperoxydicarbonate, tert-butylperoxypivalate, and benzoyl peroxide.
• solvent examples include organic solvents and aqueous solvents.
• the solvent one type may be used alone or two or more types may be used in combination.
• organic solvent examples include benzene, toluene, N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), acetone, 2-butanone (methylethylketone), dioxane, hexafluoroisopropanol, chloroform, carbon tetrachloride, tetrahydrofuran (THF).
• DMF N, N-dimethylformamide
• DMSO dimethylsulfoxide
• acetone 2-butanone (methylethylketone)
• dioxane hexafluoroisopropanol
• chloroform carbon tetrachloride
• THF tetrahydrofuran
• N-methyl-N-methoxymethylpyrrolidium tetrafluoroborate N-methyl-N-ethoxymethyltetrafluoroborate, 1-methyl-3-methylimidazolium tetrafluoroborate, 1-methyl-3-methylimidazolium
• An ionic liquid such as hexafluorophosphate or 1-methyl-3-methylimidazolium chloride may be used.
• aqueous solvent examples include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, diacetone alcohol and the like.
• the method for producing the polymer according to the fourth embodiment includes the tellurium-containing compound according to the first embodiment (that is, the tellurium-containing compound represented by the formula (M1)) and the first embodiment.
• a polymerizable compound having a carbon-carbon double bond in the molecule that is, the first copolymer in the first embodiment, unlike the tellurium-containing compound according to the above (that is, the tellurium-containing compound represented by the formula (M1)).
• Polymerization monomer and. The details of the first copolymerization monomer are as described above.
• the amount of the compound represented by the formula (T2) or the compound represented by the formula (T2) (when the compound represented by the formula (T1) and the compound represented by the formula (T2) are used in combination, the total of these) is 0. It is preferably 001 mol or more, more preferably 0.005 mol or more, and even more preferably 0.01 mol or more.
• the amount used is preferably 1 mol or less, more preferably 0.5 mol or less, and even more preferably 0.1 mol or less.
• a compound represented by the formula (T1) or a compound represented by the formula (T2) (a compound represented by the formula (T1) and a compound represented by the formula (T2)) may be used.
• the total amount of the azo-based polymerization initiator used per 1 mol is preferably 0.01 mol or more, more preferably 0.05 mol or more, and more preferably 0.1 mol or more. preferable.
• the amount used is preferably 50 mol or less, more preferably 10 mol or less, and further preferably 5 mol or less.
• the amount of the compound represented by the formula (T2) to be used for 1 mol of the compound represented by the formula (T1) is determined. It is preferably 0.01 mol or more, more preferably 0.05 mol or more, and further preferably 0.1 mol or more. The amount used is preferably 100 mol or less, more preferably 10 mol or less, and further preferably 5 mol or less.
• the above polymerization reaction can be carried out without a solvent, but it can also be carried out using an organic solvent or an aqueous solvent generally used in radical polymerization.
• the amount of solvent used can be adjusted as appropriate.
• the amount of the solvent with respect to 1000 g of the obtained polymer is preferably 0.01 L or more, more preferably 0.05 L or more, and further preferably 0.1 L or more.
• the amount of the solvent with respect to 1000 g of the obtained polymer is preferably 50 L or less, more preferably 10 L or less, and further preferably 5 L or less.
• the reaction temperature and reaction time may be appropriately adjusted according to the molecular weight or molecular weight distribution of the obtained polymer, and may be stirred at 60 ° C. to 150 ° C. for 5 hours to 100 hours. Alternatively, the mixture may be stirred at 80 ° C. to 120 ° C. for 10 hours to 30 hours.
• the reaction may be carried out under normal pressure, and may be pressurized or reduced in pressure.
• the target polymer may be taken out by removing the solvent used, residual monomers, etc. under reduced pressure by a conventional method, or the target polymer may be reprecipitated using a solvent insoluble in the target polymer. Isolate the object.
• any treatment method can be used as long as the target product is not hindered.
• a block copolymer, an alternate copolymer, or a random copolymer may be prepared by using the tellurium-containing compound represented by the formula (M1) and the first copolymer monomer.
• R represents R 1 or R 6
• n represents the number of structural units independently.
• the method for producing a polymer according to the fifth embodiment is in the presence of at least one compound selected from the group consisting of the compound represented by the following formula (T1) and the compound represented by the following formula (T2). , At least including polymerizing a tellurium-containing compound represented by the following formula (M2).
• R 6 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms.
• R 7 and R 8 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.
• R 9 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, and an acyl group having 2 to 8 carbon atoms.
• R 10 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms.
• X 2 , Y 2 , and Z 2 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and X 2 , Y 2 , and Z. At least one of 2 represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group.
• R2 represents an organic group having 1 to 20 carbon atoms.
• the method for producing a polymer according to the fifth embodiment is based on the TERP method, and is at least one compound selected from the group consisting of the compound represented by the formula (T1) and the compound represented by the formula (T2).
• Is a method for producing a polymer which comprises polymerizing at least the compound represented by the formula (M2) by using the above as a chain transfer agent.
• a polymer having a controlled molecular structure and a branched structure can be obtained.
• the obtained polymer may be the polymer according to the second embodiment.
• the method for producing a polymer according to the fifth embodiment is different from the tellurium-containing compound represented by the formula (M2) and the tellurium-containing compound represented by the formula (M2), in which carbon is contained in the molecule.
• - contains polymerizing with a polymerizable compound having a carbon double bond (ie, a second copolymerization monomer). The details of the second copolymerization monomer are as described above.
• the method for producing a polymer according to the sixth embodiment is in the presence of at least one compound selected from the group consisting of the compound represented by the following formula (T1) and the compound represented by the following formula (T2). At least, it comprises polymerizing a tellurium-containing compound represented by the following formula (M3) and a compound represented by the following formula (M11).
• R 6 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms.
• R 7 and R 8 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.
• R 9 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, and an acyl group having 2 to 8 carbon atoms.
• R 10 represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms.
• X 3 , Y 3 , and Z 3 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms.
• R 3 represents an organic group having 1 to 20 carbon atoms.
• X 11 to X 14 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and X 11 to X 14 thereof. At least one represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.
• the method for producing a polymer according to the sixth embodiment is based on the TERP method, and is at least one compound selected from the group consisting of the compound represented by the formula (T1) and the compound represented by the formula (T2).
• a polymer having a controlled molecular structure and a branched structure obtained by polymerizing a fluorine-containing monomer can be obtained.
• the obtained polymer may be the polymer according to the third embodiment.
• the nuclear magnetic resonance spectrum was measured by Fourier transform type NMR.
• 1 1 H-NMR measured tetramethylsilane at 300 MHz with a chemical shift value of 0 ppm as a reference.
• 19 F-NMR measured 1,4-bis (trifluoromethyl) benzene at 282 MHz with a chemical shift value of -63.9 ppm as a reference.
• the abbreviations used in the text have the following meanings.
• MS mass spectrum
• MS mass spectrum
• MS gas chromatograph mass spectrometer
• a magnetic rotor and 15 g (36 mmol) of diphenyl ditelluride were added to a glass flask having an internal volume of 100 mL, and the inside was replaced with nitrogen.
• 45 g of frozen and degassed tetrahydrofuran was added, and the internal temperature was cooled to 0 ° C. with stirring.
• 5.7 mL (36 mmol) of bromine was added, and the mixture was stirred for 1 hour while maintaining the internal temperature at 0 ° C. Let this solution be B.
• a magnetic rotor was added to a glass flask having an internal volume of 500 mL, and the inside was replaced with nitrogen.
• the mixture was stirred for 1 hour while maintaining the internal temperature at room temperature.
• the reaction vessel was opened in a nitrogen-substituted glove box and the reaction mixture was suction filtered to remove solids.
• the filtrate was washed 3 times with ion-exchanged water to recover the organic phase.
• the solvent of the organic phase was distilled off under reduced pressure, and the residue was purified by distillation under reduced pressure to give the title compound as an oil of 5.7 g.
• a magnetic rotor was added to a glass flask having an internal volume of 100 mL, and the inside was replaced with nitrogen. Under a nitrogen atmosphere, 6.7 g of frozen and degassed tetrahydrofuran was added, and the internal temperature was cooled to ⁇ 78 ° C. with stirring. Under a nitrogen atmosphere, 25 mL (1.3 mol / L, 33 mmol) of s-butyllithium / hexane / cyclohexane solution was added, and the mixture was stirred for 30 minutes while maintaining the internal temperature at ⁇ 78 ° C.
• the internal temperature was raised to ⁇ 78 ° C. while stirring was continued.
• the mixture was stirred for 30 minutes while maintaining the internal temperature at ⁇ 78 ° C.
• the internal temperature was raised to room temperature over 30 minutes while continuing stirring.
• the mixture was stirred for 1 hour while maintaining the internal temperature at room temperature.
• the reaction vessel was opened in a nitrogen-substituted glove box and the reaction mixture was suction filtered to remove solids.
• the filtrate was washed 3 times with ion-exchanged water to recover the organic phase.
• the solvent of the organic phase was distilled off under reduced pressure, and the residue was purified by distillation under reduced pressure to obtain 1.1 g of the title compound as an oil.
• a magnetic rotor was added to a glass flask having an internal volume of 50 mL, and the inside was replaced with nitrogen. Under a nitrogen atmosphere, 10 g (15 wt%, 39 mmol) of degassed sodium hydroxide aqueous solution and 5 g (19 mmol) of 1,2-dibromo-2-chloro-1,1-difluoroethane were added. The mixture was stirred for 30 minutes while maintaining the internal temperature at room temperature.
• a magnetic rotor and 2.0 g (4.8 mmol) of diphenylditelluride were added to a glass flask having an internal volume of 50 mL, and the inside was replaced with nitrogen. Under a nitrogen atmosphere, 13 g of frozen and degassed tetrahydrofuran was added, and the internal temperature was cooled to 0 ° C. with stirring. Under a nitrogen atmosphere, 0.25 mL (4.8 mmol) of bromine was added, and the mixture was stirred for 1 hour while maintaining the internal temperature at 0 ° C. Let this solution be B. A magnetic rotor was added to a glass flask having an internal volume of 300 mL, and the inside was replaced with nitrogen.
• 1 1 H NMR (300 MHz, CDCl 3 ) ⁇ 1.0 (1H, t) 19 F NMR (282 MHz, CDCl 3 ) ⁇ -86.8 (1F, dd), ⁇ -106.1 (1F, dd), ⁇ -156.6 (1F, dd) MS (EI +): [M +] 268.0
• Example 5 below is an example that is expected to be synthesizable based on the findings of the present disclosure and known methods.
• Example 6 Copolymerization of phenyltrifluorovinyltelluride and chlorotrifluoroethylene
• a nitrogen-substituted glove box 0.061 g (0.27 mmol) of azo radical initiator was placed in a stainless steel autoclave with a stirrer having an internal volume of 30 mL.
• "V-601" Flujifilm Wako Pure Chemical Industries, Ltd.
• 0.055 g (0.13 mmol) of diphenylditelluride 1.2 g (4.0 mmol) of phenyl (trifluorovinyl) telluride synthesized in Example 1.
• 0.055 g (0.13 mmol
• diphenylditelluride 1.2 g (4.0 mmol) of phenyl (trifluorovinyl) telluride synthesized in Example 1.
• a benzotrifluoride 11 g of benzotrifluoride.
• the obtained polymer solution was vacuum dried to obtain an oil.
• the oil was added to 40 mL of frozen degassed methanol in a nitrogen-substituted glove box and stirred for 5 minutes, after which the oil and supernatant were separated using a centrifuge.
• the obtained oil was vacuum dried to obtain 0.2 g of the oil.
• 19 F-NMR of the obtained oil was measured, a peak was observed at ⁇ -177 ppm. Since this is attributed to the fluorine atom bonded to the tertiary carbon atom, it was shown that the polymer has a branched main chain skeleton.
• the tertiary carbon atom means a carbon atom in which three carbon atoms are directly bonded.
• Example 7 Copolymerization of Butyltrifluorovinylterlide and Tetrafluoroethylene
• azo radical initiator "in an autoclave made of stainless steel with a stirrer having an internal volume of 30 mL. V-601 ”(Fujifilm Wako Pure Chemical Industries, Ltd.)
• 0.057 g (0.15 mmol) of dibutyl diterlide
• 1.3 g (4.6 mmol) of butyltrifluorovinylterlide synthesized in Example 4
• 13 g of 1H-perfluorohexane was charged.
• the obtained polymer solution was vacuum dried to obtain a solid.
• the solid was added to 40 mL of frozen degassed methanol in a nitrogen-substituted glove box and stirred for 5 minutes, after which the solid and supernatant were separated using a centrifuge.
• the obtained solid was vacuum dried to obtain 0.5 g of a solid.
• Examples 8 to 13 below are examples that are expected to be synthesizable based on the findings of the present disclosure and known methods. In each of the examples, since a highly reactive fluorine-containing monomer is used as the copolymerization monomer, it is considered that the copolymer can be suitably synthesized.
• Example 8 (2,2-Difluorovinyl) Copolymerization of phenyltelluride and chlorotrifluoroethylene
• an azo radical initiator "V-601" was placed in a stainless steel autoclave with a stirrer having an internal volume of 30 mL.
• diphenylditelluride, (2,2-difluorovinyl) phenylterlide synthesized in Example 2 benzotrifluoride, and chlorotrifluoroethylene are charged, and then the internal temperature is adjusted. Stirring is started and reacted while raising the temperature to 80 ° C.
• Example 9 (1-Chlorodifluorovinyl) Copolymerization of phenyltelluride and chlorotrifluoroethylene
• an azo radical initiator "V-601" is placed in a stainless steel autoclave with a stirrer having an internal volume of 30 mL.
• diphenylditelluride, (1-chlorodifluorovinyl) phenylterlide synthesized in Example 3 benzotrifluoride, and chlorotrifluoroethylene are charged, and then the internal temperature is 80 ° C. Start stirring while raising the temperature to the above level to react.
• Example 10 (2-Nonafluorobutylvinyl) Copolymerization of phenyltelluride and chlorotrifluoroethylene
• an azo radical initiator "V-601" was placed in a stainless steel autoclave with a stirrer having an internal volume of 30 mL.
• Example 11 Copolymerization of (1-chlorovinyl) phenyltelluride and chlorotrifluoroethylene
• an azo radical initiator "V-601” Azo-based radical initiator "V-601” was added to a stainless steel autoclave with a stirrer having an internal volume of 30 mL. Fujifilm Wako Junyaku Co., Ltd.), diphenylditelluride, (1-chlorovinyl) phenylterlide synthesized according to publicly known literature, benzotrifluoride, and chlorotrifluoroethylene, and then the internal temperature is raised to 80 ° C. Start stirring while warming to react.
• Example 12 (2-Chlorovinyl) Copolymerization of phenyltelluride and chlorotrifluoroethylene
• an azo radical initiator "V-601” (azo radical initiator "V-601" was added to a stainless steel autoclave with a stirrer having an internal volume of 30 mL. Fujifilm Wako Junyaku Co., Ltd.), diphenylditelluride, (2-chlorovinyl) phenylterlide synthesized according to publicly known literature, benzotrifluoride, and chlorotrifluoroethylene, and then the internal temperature is raised to 80 ° C. Start stirring while warming to react.
• Example 13 (1-Phenylvinyl) Copolymerization of phenyltelluride and chlorotrifluoroethylene
• an azo radical initiator "V-601” (azo radical initiator "V-601" was added to a stainless steel autoclave with a stirrer having an internal volume of 30 mL. Fujifilm Wako Junyaku Co., Ltd.), diphenylditelluride, (1-phenylvinyl) phenylterlide synthesized according to publicly known literature, benzotrifluoride, and chlorotrifluoroethylene, and then the internal temperature is raised to 80 ° C. Start stirring while warming to react.

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