Tellurium-containing compound and method for producing polymer

Abstract

Provided are a tellurium-containing compound represented by any of formulae (1) to (4) and a method for producing a polymer using the tellurium-containing compound: R1 represents an unsubstituted C2-6 alkyl group, R2 and R3 each independently represent a hydrogen atom or a substituted or unsubstituted C1-6 alkyl group, Ar represents a substituted or unsubstituted aryl group having 5-18 atoms constituting an aromatic ring, Rf represents a C1-12 perfluoroalkyl group, A represents a substituted or unsubstituted C1-12 alkyl group or a substituted or unsubstituted aryl group having 5-18 atoms constituting an aromatic ring, X represents a hydrogen atom, a fluorine atom, a CF2-Z group, or a CHF-Z group, Y represents a CF2-Z group or a CHF-Z group, and Z represents a fluorine atom or a C1-12 organic group.

Description

Methods for producing tellurium-containing compounds and polymers

[0001] The present disclosure relates to methods for making tellurium-containing compounds and polymers.

[0002] Radical polymerization reactions are widely used industrially because of their excellent monomer versatility and their ease of use in polar media such as water. However, conventional radical polymerization methods tend to produce polymers with broad molecular weight distributions. Controlled polymerization, on the other hand, has attracted attention as a polymerization method that can produce controlled molecular structures, and various polymerization inhibitors have been developed. Controlled polymerization is a polymerization method that controls the radical polymerization rate by reversibly protecting propagating radicals with dormant protecting groups, thereby enabling control of molecular weight distribution.

[0003] Patent Document 1 describes a controlled polymerization method for producing a haloolefin polymer or copolymer by radically polymerizing a specific haloolefin in the presence of a specific organotellurium compound. This method is based on a method called TERP (organotellurium-mediated living radical polymerization).

[0004] International Publication No. 2018 / 164147

[0005] On the other hand, even when a controlled polymerization method based on the TERP method is used, conventional methods have room for improvement, such as insufficient control of molecular weight distribution depending on the type of monomer. In view of this situation, the present disclosure relates to a novel tellurium-containing compound that can be used in a controlled polymerization method that has excellent controllability of molecular weight distribution, and a method for producing a polymer using the same.

[0006] Means for solving the above problems include the following aspects: <1> A tellurium-containing compound represented by any one of the following formulas (1) to (4). In formulas (1) to (4), R １ represents an unsubstituted alkyl group having 2 to 6 carbon atoms; R ２ and R ３each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, Ar represents a substituted or unsubstituted aryl group having 5 to 18 atoms constituting an aromatic ring, R ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms, A represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 5 to 18 atoms constituting the aromatic ring, and X represents a hydrogen atom, a fluorine atom, or CF ２ -Z group or CHF-Z group, Y is CF ２ -Z group or CHF-Z group, Z represents a fluorine atom or an organic group having 1 to 12 carbon atoms, and in formula (2) and formula (3), Y and R ｆ are linked to each other to form a cyclic structure, or not. <2> In the formulas (1) to (4), Ar represents a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group, A represents an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 hydrogen atoms of the unsubstituted alkyl group are each independently substituted with a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group, or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group, Z is a fluorine atom; an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 hydrogen atoms of the unsubstituted alkyl group are each independently substituted with a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group; a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group; or -O-Z １ represents a group, where Z １represents an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 of the hydrogen atoms of the unsubstituted alkyl group are each independently substituted with a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group; or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group. <3> A method for producing a polymer, comprising polymerizing a compound having a carbon-carbon double bond in the presence of at least one compound selected from the group consisting of compounds represented by the following formulas (1) to (4): In formulas (1) to (4), R １ represents an unsubstituted alkyl group having 2 to 6 carbon atoms; R ２ and R ３ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, Ar represents a substituted or unsubstituted aryl group having 5 to 18 atoms constituting an aromatic ring, R ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms, A represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 5 to 18 atoms constituting the aromatic ring, and X represents a hydrogen atom, a fluorine atom, or CF ２ -Z group or CHF-Z group, Y is CF ２ -Z group or CHF-Z group, Z represents a fluorine atom or an organic group having 1 to 12 carbon atoms, and in formula (2) and formula (3), Y and R ｆare linked to each other to form a cyclic structure, or not. <4> In the formulas (1) to (4), Ar represents a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group, A represents an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 hydrogen atoms of the unsubstituted alkyl group are each independently substituted with a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group, or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group, Z is a fluorine atom; an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 hydrogen atoms of the unsubstituted alkyl group are each independently substituted with a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group; a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group; or -O-Z １ represents a group, where Z １ represents an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 of the hydrogen atoms of the unsubstituted alkyl group are each independently substituted with a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group; or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group. <5> The method for producing a polymer according to <3> or <4>, wherein the at least one compound selected from the group consisting of compounds represented by formulas (1) to (4) is a compound represented by formula (1), and the compound having a carbon-carbon double bond includes a compound represented by the following formula (5): In formula (5), A １ and A ２ each independently represents 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.１ and A ２ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group.<7> The method for producing a polymer according to <3> or <4>, wherein the at least one compound selected from the group consisting of compounds represented by formulas (1) to (4) is a compound represented by formula (2), and the compound having a carbon-carbon double bond includes a compound represented by formula (6): In formula (6), A １ and A ２ each independently represents 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 ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms. １ and A ２ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group. <9> The method for producing a polymer according to <3> or <4>, wherein the at least one compound selected from the group consisting of compounds represented by formulas (1) to (4) is a compound represented by formula (3), and the compound having a carbon-carbon double bond includes a compound represented by formula (7): In formula (7), A １ and A ２ each independently represents 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 ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms. １ and A ２each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group. <11> The method for producing a polymer according to <3> or <4>, wherein the at least one compound selected from the group consisting of compounds represented by formulas (1) to (4) is a compound represented by formula (4), and the compound having a carbon-carbon double bond includes a compound represented by formula (8): In formula (8), A １ and A ２ each independently represents 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. １ and A ２each independently represents a hydrogen atom; a fluorine atom; a chlorine atom; a bromine atom; an iodine atom; a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms; or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group. <13> The method for producing a polymer according to <3> or <4>, wherein the compound having a carbon-carbon double bond includes at least one selected from the group consisting of vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, perfluoro(methyl vinyl ether), vinylidene chloride, vinyl chloride, perfluoro(n-propyl vinyl ether), perfluoro(3-butenyl vinyl ether), (perfluoro-n-butyl)ethylene, (perfluoro-n-hexyl)ethylene, 1,4-divinylperfluorobutane, 1,6-divinylperfluorohexane, ethylene, and propylene. <14> The method for producing a polymer according to any one of <3> to <13>, wherein the method is carried out in the presence of an azo-based radical initiator. <15> The method for producing a polymer according to <14>, wherein 0.01 to 100 mol of the azo radical initiator is used per 1 mol of at least one compound selected from the group consisting of compounds represented by formulas (1) to (4). <16> The method for producing a polymer according to any one of <3> to <15>, wherein 0.001 to 1 mol of the compounds represented by formulas (1) to (4) are used per 1 mol of the compound having a carbon-carbon double bond. <17> The method for producing a polymer according to any one of <3> to <16>, wherein the weight-average molecular weight of the resulting polymer is 1,000 to 500,000. <18> The method for producing a polymer according to any one of <3> to <17>, wherein the polydispersity of the resulting polymer is 2.0 or less.<19> The method for producing a polymer according to any one of <3> to <18>, wherein the compound having a carbon-carbon double bond includes a compound having a first carbon-carbon double bond, and the compound having the first carbon-carbon double bond and a compound having a second carbon-carbon double bond different from the compound having the first carbon-carbon double bond are block copolymerized. <20> The method for producing a polymer according to any one of <3> to <18>, wherein the compound having a carbon-carbon double bond includes a compound having a first carbon-carbon double bond and a compound having a second carbon-carbon double bond different from the compound having the first carbon-carbon double bond, and the compound having the first carbon-carbon double bond and the compound having the second carbon-carbon double bond are random copolymerized.

[0007] According to the present disclosure, there are provided novel tellurium-containing compounds that can be used in controlled polymerization methods and have excellent controllability over molecular weight distribution, as well as methods for producing polymers using the same.

[0008] Hereinafter, modes for carrying out embodiments of the present disclosure will be described in detail. However, the embodiments of the present disclosure are not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and they do not limit the embodiments of the present disclosure.

[0009] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In this disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In this disclosure, each component may contain multiple corresponding substances. When multiple substances corresponding to each component are present in a composition or system, the content or amount of each component refers to the total content or amount of the multiple substances present in the composition or system, unless otherwise specified. In numerical ranges described in stages in this disclosure, the upper or lower limit of one numerical range may be replaced by the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described in this disclosure, the upper or lower limit of that numerical range may be replaced by a value shown in the examples. In this disclosure, unless otherwise specified, organic groups or hydrocarbon groups may or may not have a substituent. In the present disclosure, the number of carbon atoms in a compound or a constituent part thereof means the number including the number of carbon atoms in the substituent when the compound or constituent part has a substituent. In the present disclosure, a carbon-carbon double bond means a carbon-carbon double bond that can undergo various reactions as an olefin, and does not include aromatic double bonds. In the present disclosure, (meth)acrylic acid is a general term for acrylic acid and methacrylic acid. (Meth)acrylate is a general term for acrylate and methacrylate. (Meth)acrylamide is a general term for acrylamide and methacrylamide. In the present disclosure, a "polymer" or a "polymer" is a compound obtained by polymerizing a monomer. In other words, has a plurality of structural units. In the present disclosure, unless otherwise specified, the expressions "polymerizing compound A" and "polymerizing at least compound A" encompass both the case where only compound A is polymerized and the case where compound A is polymerized with another compound. Furthermore, the expressions "polymerizing compound A and compound B" and "polymerizing at least compound A and compound B" encompass both the case where only compound A and compound B are polymerized, and the case where compound A, compound B, and another compound are polymerized.Here, Compound A and Compound B represent any compound described in the present disclosure that has a carbon-carbon double bond in the molecule. Furthermore, unless otherwise specified, the polymer described in the present disclosure may be a homopolymer of one type of compound or a copolymer of two or more types of compounds. In the present disclosure, the term "polymer" or "polymeric polymer" does not exclude a mixture that contains raw materials (monomers, catalysts), by-products, impurities, etc. in addition to the polymer.

[0010] <Tellurium-Containing Compound> The tellurium-containing compound in one embodiment of the present disclosure is a compound represented by any one of the following formulas (1) to (4).

[0011]

[0012] In formulas (1) to (4), R １ represents an unsubstituted alkyl group having 2 to 6 carbon atoms; R ２ and R ３ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, Ar represents a substituted or unsubstituted aryl group having 5 to 18 atoms constituting an aromatic ring, R ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms, A represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 5 to 18 atoms constituting the aromatic ring, and X represents a hydrogen atom, a fluorine atom, or CF ２ -Z group or CHF-Z group, Y is CF ２ -Z group or CHF-Z group, Z represents a fluorine atom or an organic group having 1 to 12 carbon atoms, and in formula (2) and formula (3), Y and R ｆ may or may not be linked to form a ring structure.

[0013] The compounds represented by formulas (1) to (4) can function as control agents in controlled polymerization. Hereinafter, the compounds represented by formulas (1) to (4) will also be collectively referred to as "specific control agents." The compounds represented by formulas (1) to (4) will also be referred to as "specific control agent (1)," "specific control agent (2)," "specific control agent (3)," and "specific control agent (4)," respectively. The inventors have found that, in controlled polymerization based on the TERP method, using a specific control agent instead of a conventional control agent as the control agent can favorably control the molecular weight distribution. The mechanism behind this is not clear, but is presumed to be as follows. In controlled polymerization based on the TERP method, a propagating radical reacts with the control agent (R ａ -Te-X ａ ; where R ａ is a non-leaving group, X ａ is a leaving group), the control agent releases the leaving group (X ａ ) is eliminated, and the remainder (R ａ -Te) binds to the growing radical end as a protecting group. ａ ) reacts with the monomer as a radical to become the initiating terminal. The protection of the growing radical by the protecting group is reversible, and the protecting group is deprotected by reaction with another radical. By repeating deprotection, growth (addition of monomer), and protection in this mechanism, polymerization with a controlled reaction rate proceeds. Here, when a specific control agent is used as the control agent, the non-leaving group (R ａ ) while maintaining a necessary and sufficient rate of protection of the polymer end with a leaving group (X ａ The faster the rate of protection of the polymer ends, the more likely it is that two molecules will terminate, and the faster the rate of reinitiation, the less variation there will be in the timing of polymer generation. These factors are thought to enable the formation of polymers with narrower molecular weight distributions than conventional methods.

[0014] Specific control agent (1) is -CF ２ X is -CFR in the specific control agent (2). ｆ In the specific control agent (3), Y is -CHR ｆ Y is -CHFCR in the specific control agent (4). ２ R ３X each serves as a leaving group. It is presumed that the structure of these leaving groups allows the ease of radical generation and radical stability to fall within appropriate ranges, thereby accelerating the re-initiation rate of the leaving group and the monomer. When the re-initiation rate relative to the initiation reaction rate, which is the reaction rate of the radical derived from the radical initiator and the monomer, is equal to or higher than a certain level, the induction period until polymerization begins tends to be shortened, and the reaction time can be shortened. Note that the embodiments of the present disclosure are not bound by the above-mentioned presumed mechanism.

[0015] In formula (1), R １ represents an unsubstituted alkyl group having 2 to 6 carbon atoms. Examples of the unsubstituted alkyl group having 2 to 6 carbon atoms include a linear, branched, or cyclic alkyl group such as 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, an n-pentyl group, a cyclopentyl group, an n-hexyl group, and a cyclohexyl group. In one embodiment, R １ As the alkyl group, a linear alkyl group is preferred, and an n-butyl group is more preferred.

[0016] In formula (4), R ２ and R ３ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. ２ and R ３are each independently preferably a hydrogen atom, and more preferably all are a hydrogen atom. Examples of unsubstituted alkyl groups having 1 to 6 carbon atoms include linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, and cyclohexyl. Examples of substituted alkyl groups having 1 to 6 carbon atoms include alkyl groups in which any hydrogen atom bonded to the unsubstituted alkyl group having 1 to 6 carbon atoms is substituted with a substituent such as a fluorine atom, a chlorine atom, an alkoxy group, or a fluoroalkoxy group. The number of substituents is not particularly limited, and may be 1 to 4, 1 to 3, 1 to 2, or even 1. In one aspect, the substituted alkyl group having 1 to 6 carbon atoms is preferably a fluoroalkyl group having 1 to 6 carbon atoms. Examples of the fluoroalkyl group having 1 to 6 carbon atoms include a fluoroalkyl group in which some or all of the hydrogen atoms bonded to the above-mentioned unsubstituted alkyl group having 1 to 6 carbon atoms have been substituted with fluorine atoms. Here, the term "fluoroalkyl group" refers to an alkyl group consisting only of C, F, and H (if present).

[0017] In formula (2), Ar represents a substituted or unsubstituted aryl group having 5 to 18 atoms constituting the aromatic ring. Ar is preferably a substituted or unsubstituted aryl group having 5 to 12 atoms constituting the aromatic ring. Here, the "number of atoms constituting the aromatic ring" refers to the number of atoms constituting the aromatic ring itself, and does not include the number of hydrogen atoms or atoms of substituents. Examples of unsubstituted aryl groups having 5 to 18 atoms constituting the aromatic ring include homoaryl groups such as phenyl and naphthyl; and heteroaryl groups such as pyridyl, imidazolyl, pyrrolyl, furyl, and thienyl. Among these, homoaryl groups are preferred, and phenyl groups are more preferred. Examples of substituted aryl groups having 5 to 18 atoms constituting the aromatic ring include aryl groups in which any hydrogen atom bonded to the aromatic ring of the unsubstituted aryl group is substituted with a substituent such as a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, a carbonyl-containing group, a sulfonyl group, or 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. In one embodiment, Ar is preferably a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group.

[0018] In formulas (2) and (3), R ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms. ｆ is preferably a perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of perfluoroalkyl groups having 1 to 12 carbon atoms include a perfluoromethyl group, a perfluoroethyl group, a perfluoro n-propyl group, a perfluoroisopropyl group, a perfluoro n-butyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoro n-pentyl group, a perfluoro n-hexyl group, a perfluoro n-heptyl group, and a perfluoro n-octyl group. In one embodiment, R ｆ is preferably a perfluoromethyl group.

[0019] In formulas (3) and (4), A represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 5 to 18 atoms constituting the aromatic ring. As the unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted alkyl group having 1 to 6 carbon atoms is preferred. Examples of the unsubstituted alkyl group having 1 to 12 carbon atoms include linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, and n-octyl. Of these, methyl, ethyl, and n-butyl are preferred. Examples of substituted alkyl groups having 1 to 12 carbon atoms include alkyl groups in which any hydrogen atom bonded to the unsubstituted alkyl groups having 1 to 12 carbon atoms is substituted with a substituent such as a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group. Examples of carbonyl-containing groups include an acyl group, a formyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, and an acylamino group. Examples of sulfonyl-containing groups include a sulfo group, an alkoxysulfonyl group, an aryloxysulfonyl group, a sulfonyloxy group, a sulfamoyl group, and a sulfonylamino group. The number of substituents is not particularly limited and may be 1 to 4, 1 to 3, 1 to 2, or even 1. Examples of unsubstituted aryl groups having 5 to 18 atoms constituting the aromatic ring include homoaryl groups such as phenyl and naphthyl groups; and heteroaryl groups such as pyridyl, imidazolyl, pyrrolyl, furyl, and thienyl groups. Of these, homoaryl groups are preferred, and phenyl groups are more preferred. Examples of substituted aryl groups having 5 to 18 atoms constituting the aromatic ring include aryl groups in which any hydrogen atom bonded to the aromatic ring of the above-mentioned unsubstituted aryl group has been substituted with a substituent such as a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, a carbonyl-containing group, a sulfonyl group, or 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. In one embodiment, A is preferably an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 of the hydrogen atoms of the unsubstituted alkyl group are each independently substituted with a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group; or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group.

[0020] In formulas (1) and (4), X represents a hydrogen atom, a fluorine atom, or CF ２ The group represents a -Z group or a CHF-Z group, where Z represents a fluorine atom or an organic group having 1 to 12 carbon atoms. The organic group having 1 to 12 carbon atoms represented by Z includes a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 5 to 12 atoms constituting an aromatic ring, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a -(OX １ ) ｎ１ A group represented by —OR (wherein X １each independently represent a substituted or unsubstituted alkylene group having 1 to 11 carbon atoms, R represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 11 carbon atoms, and n1 represents an integer of 1 to 11. As the unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted alkyl group having 1 to 6 carbon atoms is preferred. As the unsubstituted alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkyl group such as 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, an n-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, or an n-octyl group is preferred. Of these, a methyl group, an ethyl group, or an n-butyl group is preferred. Examples of substituted alkyl groups having 1 to 12 carbon atoms include alkyl groups in which any hydrogen atom bonded to the unsubstituted alkyl groups having 1 to 12 carbon atoms is substituted with a substituent such as a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group. Examples of carbonyl-containing groups include an acyl group, a formyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, and an acylamino group. Examples of sulfonyl-containing groups include a sulfo group, an alkoxysulfonyl group, an aryloxysulfonyl group, a sulfonyloxy group, a sulfamoyl group, and a sulfonylamino group. The number of substituents is not particularly limited and may be 1 to 4, 1 to 3, 1 to 2, or even 1. Examples of unsubstituted aryl groups having 5 to 12 atoms constituting the aromatic ring include homoaryl groups such as phenyl and naphthyl groups; and heteroaryl groups such as pyridyl, imidazolyl, pyrrolyl, furyl, and thienyl groups. Of these, homoaryl groups are preferred, and phenyl groups are more preferred. Examples of substituted aryl groups having 5 to 12 atoms constituting the aromatic ring include aryl groups in which any hydrogen atom bonded to the aromatic ring of the above-mentioned unsubstituted aryl group has been substituted with a substituent such as a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, a carbonyl-containing group, a sulfonyl group, or 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. The unsubstituted alkoxy group having 1 to 12 carbon atoms includes —OR. ｕ In this case, R ｕ represents an unsubstituted alkyl group having 1 to 12 carbon atoms, and examples of the unsubstituted alkyl group having 1 to 12 carbon atoms represented by Z include those mentioned above. Examples of the substituted alkoxy group having 1 to 12 carbon atoms include alkoxy groups in which any hydrogen atom bonded to the unsubstituted alkoxy group having 1 to 12 carbon atoms is substituted with a substituent such as a fluorine atom, a chlorine atom, an alkoxy group, or a fluoroalkoxy group. The number of substituents is not particularly limited, and may be 1 to 4, 1 to 3, 1 to 2, or 1. -(OX １ ) ｎ１ In the group represented by —OR, X １ When R has a substituent, examples of the substituent include a fluorine atom, a chlorine atom, an alkoxy group, a fluoroalkoxy group, etc. The number of the substituents is not particularly limited, and may be 1 to 4, 1 to 3, 1 to 2, or 1, independently of each other. １ As R, an unsubstituted alkylene group having 1 to 3 carbon atoms is preferred. As R, an unsubstituted alkyl group having 1 to 3 carbon atoms is preferred. １ ) ｎ１ Examples of the group represented by —OR include —OCH ２ OCH ３ , -OCH ２ CH ２ OCH ３ In one embodiment, Z is a fluorine atom, an unsubstituted alkyl group having 1 to 12 carbon atoms, a perfluoroalkyl group having 1 to 12 carbon atoms, a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 hydrogen atoms of the unsubstituted alkyl group are each independently substituted with a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group, a substituted or unsubstituted phenyl group, a naphthyl group, a pyridyl group, or an imidazolyl group, or -O-Z１ The group is preferred. １ represents an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 of the hydrogen atoms of the unsubstituted alkyl group are each independently substituted with a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group; or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group. ２ The group -Z is preferred.

[0021] In formulas (2) and (3), Y is CF ２ -Z group or CHF-Z group, where Z represents a fluorine atom or an organic group having 1 to 12 carbon atoms. Details of Z are as described above. In one embodiment, Y is CF ２ The -Z group is preferred, and CF ３ is more preferred.

[0022] Examples of the specific control agent (1) include (ethyl)pentafluoroethyl telluride, (ethyl)n-nonafluorobutyl telluride, (ethyl)n-tridecafluorohexyl telluride, (n-butyl)pentafluoroethyl telluride, (n-butyl)n-nonafluorobutyl telluride, (sec-butyl)n-nonafluorobutyl telluride, (tert-butyl)n-nonafluorobutyl telluride, (n-hexyl)n-nonafluorobutyl telluride, etc. Examples of the specific control agent (2) include (1,1,1,2,3,3,3-heptafluoroisopropyl)phenyl telluride, (1,1,2,2,3,3,4,4,5,5,6-undecafluorocyclohexyl)phenyl telluride, (1,1,1,2,2,3,4,4,4-nonafluorobutyl)phenyl telluride, etc. Examples of the specific control agent (3) include (1,1,1,3,3,3-hexafluoroisopropyl)methyl telluride, (ethyl) 1,1,1,3,3,3-hexafluoroisopropyl telluride, (n-butyl) 1,1,1,3,3,3-hexafluoroisopropyl telluride, (1,1,1,3,3,3-hexafluoroisopropyl)phenyl telluride, and (n-butyl) 1,1,1-trifluoroisopropyl telluride. Examples of the specific control agent (4) include (1,3,3,3-tetrafluoropropyl)methyl telluride, (n-butyl) 1,3,3,3-tetrafluoropropyl telluride, and (1,3,3,3-tetrafluoropropyl)phenyl telluride. In one embodiment, the type of specific control agent is preferably selected depending on the monomers used in the polymerization.

[0023] The specific control agent (1) is, for example, a compound (R １ Te) ２ and compound CXF ２ It can be synthesized by reacting R １ and X is defined as R in formula (1). １ and X are defined as above. The specific control agents (2) to (4) can also be synthesized in a similar manner.

[0024] <Method for Producing Polymer> A method for producing a polymer in one embodiment of the present disclosure includes polymerizing a compound having a carbon-carbon double bond in the presence of a specific control agent. Hereinafter, a compound having a carbon-carbon double bond will also be referred to as a "polymerizable monomer." The method for producing a polymer in this embodiment has excellent controllability over the molecular weight of the resulting polymer, and is likely to produce a polymer with a narrow molecular weight distribution.

[0025] In the method for producing a polymer according to the present embodiment, in addition to the specific control agent and the polymerizable monomer, other components such as a radical initiator, a solvent, an emulsifier, a suspending aid, an acid or an alkali may be further used. Hereinafter, each component used in the method for producing a polymer according to the present embodiment, the polymer produced therefrom, and the polymerization method will be described in detail.

[0026] [Specific Control Agent] The specific control agent is as described above in the section “Tellurium-containing compound.” The specific control agent may be used alone or in combination of two or more.

[0027] The amount of the specific control agent used per 1 mol of polymerizable monomer is preferably 0.001 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. Therefore, the amount used is preferably 0.001 to 1 mol, more preferably 0.005 to 0.5 mol, and even more preferably 0.01 to 0.1 mol.

[0028] [Compound Having a Carbon-Carbon Double Bond] The compound having a carbon-carbon double bond (polymerizable monomer) may contain at least one carbon-carbon double bond, or may contain two or more, or may contain three or more, and may be selected depending on the polymer to be synthesized. The polymerizable monomer preferably has one or two carbon-carbon double bonds. One type of polymerizable monomer may be used alone, or two or more types may be used in combination.

[0029] The polymerizable monomer may be a monomer containing a fluorine atom (fluorine-containing monomer), or may be a monomer not containing a fluorine atom. In one embodiment, the polymerizable monomer preferably contains a fluorine-containing monomer. In general, controlled polymerization of a fluorine-containing monomer is often difficult from the viewpoint of reaction kinetics. For example, polymerization of a fluorine-containing monomer tends to be disadvantageous for controlled polymerization because the propagation reaction rate is high, the initiation reaction rate and the exchange chain transfer reaction rate are low, and the side reaction rate is high. However, according to the method for producing a polymer of this embodiment, the controlled polymerization of a fluorine-containing monomer can also be favorably progressed, and a polymer with a narrow molecular weight distribution can easily be formed.

[0030] In one embodiment, the polymerizable monomer may be a compound represented by the following formula (M1):

[0031]

[0032] In formula (M1), R １１ ~R １４ R each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 40 carbon atoms. １１ and R １３ , or R １２ and R １４ may or may not be linked to form a cyclic structure.

[0033] R １１ ~R １４ The organic group having 1 to 40 carbon atoms preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 12 carbon atoms.

[0034] Examples of the organic group having 1 to 40 carbon atoms include 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 heteroarylalkoxy group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, an acylamino group, an acyloxy group, a cyano group, and a monovalent hydrocarbon group having an oxyalkylene structure. The organic group having 1 to 40 carbon atoms may be an organic group having a substituent such as a fluorine atom, a chlorine atom, a hydroxy group, an alkoxy group, an alkoxyalkyl group, an amino group, a carboxylic acid group, or a sulfonic acid group in addition to the above organic group.

[0035] When the organic group having 1 to 40 carbon atoms is a hydrocarbon group with or without a heteroatom, such as 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 heteroarylalkoxy group, an alkoxycarbonyl group, or a monovalent hydrocarbon group having an oxyalkylene structure, the hydrocarbon group may be linear, branched, or cyclic, and may or may not contain an unsaturated bond.

[0036] The acyl group of the acylamino group or acyloxy group includes groups obtained by removing the hydroxy group from a carboxylic acid or sulfonic acid.

[0037] In formula (M1), R １１ and R １３ , or R １２ and R １４ may or may not be linked to form a cyclic structure. That is, the compound represented by formula (M1) may be a compound having a cyclic structure such as maleic anhydride or itaconic anhydride.

[0038] Examples of the polymerizable monomer include (meth)acrylic acid ester monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, and hydroxyethyl methacrylate; cycloalkyl group-containing unsaturated monomers such as cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and cyclododecyl (meth)acrylate; carboxyl group-containing unsaturated monomers such as (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, maleic anhydride, and itaconic anhydride; tertiary amine-containing unsaturated monomers such as N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylamide, 2-(dimethylamino)ethyl (meth)acrylate, and N,N-dimethylaminopropyl (meth)acrylate; N-2-hydroxy- quaternary ammonium base-containing unsaturated monomers such as 3-acryloyloxypropyl-N,N,N-trimethylammonium chloride and N-methacryloylaminoethyl-N,N,N-dimethylbenzylammonium chloride; epoxy group-containing unsaturated monomers such as glycidyl (meth)acrylate; styrene monomers such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 2-chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 1-vinylnaphthalene, divinylbenzene, 4-(chloromethyl)styrene, 2-(chloromethyl)styrene, 3-(chloromethyl)styrene, 4-styrenesulfonic acid or an alkali metal salt thereof (sodium salt, potassium salt, etc.); heterocycle-containing unsaturated monomers such as 2-vinylthiophene and N-methyl-2-vinylpyrrole; vinylamides such as N-vinylformamide and N-vinylacetamide;α-olefins such as diallylamine, triallyl isocyanurate, tri(2-methyl-allyl) isocyanurate, ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-octene, 1-decene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, vinylidene chloride, vinyl chloride, 1-chloro-1-fluoroethylene, or 1,2-dichloro-1,2-difluoroethylene, 1H,1H,2H-perfluoro(n-1-hexene), 1H,1H,2H-perfluoro(n-1-octene), (perfluoro-n-butyl)ethylene, and (perfluoro-n-hexyl)ethylene; vinyl acetate divinylfluoroalkanes such as 1,4-divinylperfluorobutane and 1,6-divinylperfluorohexane; acrylonitrile; acrylamide monomers such as acrylamide and N,N-dimethylacrylamide; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, and hydroxybutyl vinyl ether; perfluoro(alkyl vinyl ethers) such as perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(n-propyl vinyl ether), and perfluoro(3-butenyl vinyl ether);

[0039] Among these, the polymerizable monomer preferably includes at least one selected from the group consisting of vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, perfluoro(methyl vinyl ether), vinylidene chloride, vinyl chloride, perfluoro(n-propyl vinyl ether), perfluoro(3-butenyl vinyl ether), (perfluoro-n-butyl)ethylene, (perfluoro-n-hexyl)ethylene, 1,4-divinylperfluorobutane, 1,6-divinylperfluorohexane, ethylene, and propylene.

[0040] In one embodiment, the polymerizable monomer may be a compound represented by the following formula (M2):

[0041]

[0042] In formula (M2), X １１ ~X １４ each independently represents 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; X １１ ~X １４ At least one of represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.

[0043] The monomer represented by formula (M2) is a fluorine-containing monomer, and as described above, according to the method for producing a polymer of the present embodiment, the controlled polymerization can be suitably carried out even for the monomer represented by formula (M2).

[0044] X １１ ~X １４ In the above formula, the number of carbon atoms in the organic group having 1 to 20 carbon atoms is preferably 1 to 12. Examples of the organic group having 1 to 20 carbon atoms include 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 heteroarylalkoxy group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, an acylamino group, an acyloxy group, a cyano group, and a monovalent hydrocarbon group having an oxyalkylene structure. The organic group having 1 to 20 carbon atoms may be an organic group obtained by further having a substituent such as a fluorine atom, a chlorine atom, a hydroxy group, an alkoxy group, an alkoxyalkyl group, an amino group, a carboxylic acid group, or a sulfonic acid group in addition to the above organic group.

[0045] When the organic group having 1 to 20 carbon atoms is a hydrocarbon group which may or may not have a heteroatom, such as 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 heteroarylalkoxy group, an alkoxycarbonyl group, or a monovalent hydrocarbon group having an oxyalkylene structure, the hydrocarbon group may be linear, branched, or cyclic, and may or may not contain an unsaturated bond.

[0046] The acyl group of the acylamino group or acyloxy group includes groups obtained by removing the hydroxy group from a carboxylic acid or sulfonic acid.

[0047] Examples of perfluoroalkyl groups include perfluoromethyl, perfluoroethyl, perfluoro n-propyl, perfluoroisopropyl, perfluoro n-butyl, perfluoro sec-butyl, perfluoro tert-butyl, perfluoro n-pentyl, perfluoro n-hexyl, perfluoro n-heptyl, and perfluoro n-octyl groups.

[0048] The monovalent hydrocarbon group having an oxyperfluoroalkylene structure is preferably a monovalent perfluorohydrocarbon group having an oxyperfluoroalkylene structure unit having 1 to 4 carbon atoms, such as -[(CF ２ ) ｍ -O] ｎ -CF ３ More preferred is a perfluorohydrocarbon group represented by the following formula: where m represents the number of repeating difluoromethylene groups, and each m is preferably an integer of 0 to 4 independently. n is -[(CF ２ ) ｍ —O]— structure, and is preferably an integer of 1 to 15.

[0049] Examples of the compound represented by formula (M2) include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 1,3,3,3-tetrafluoropropylene, 2,3,3,3-tetrafluoropropylene, 1-chloro-1-fluoroethylene, 1-bromo-1-fluoroethylene, 1-iodo-1-fluoroethylene, 1,1-dibromo-2,2-difluoroethylene, 1,1-difluoro-2,2-diiodoethylene, 1,2-dichloro-1,2-difluoroethylene, 1,2-dibromo-1,2-difluoroethylene, and 1,2-difluoro-1,2-diiodoethylene.

[0050] As the compound represented by formula (M2), vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and 2,3,3,3-tetrafluoropropylene are preferred from the viewpoint of polymerization reactivity when obtaining a polymer. Also preferred are compounds having two carbon-carbon double bonds, such as perfluoro(3-butenyl vinyl ether), 1,4-divinyloctafluorobutane, and 1,6-divinyldodecafluorohexane.

[0051] [Other Optional Components] In the method for producing a polymer of this embodiment, other components such as a radical initiator, a solvent, an emulsifier, a suspending aid, an acid, or an alkali may be further used.

[0052] -Radical initiator- Examples of the radical initiator include azo-based radical initiators and peroxide-based radical initiators. From the viewpoint of being less likely to inhibit the action of the specific control agent, azo-based radical initiators are preferred as the radical initiator. The radical initiators may be used alone or in combination of two or more.

[0053] Examples of azo radical initiators include 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (AMBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1'-azobis(1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2'-azobisisobutyrate (MAIB), 4,4'-azobis(4-cyanovaleric acid) (ACVA), 1,1'-azobis(1-acetoxy-1-phenylethane), 2,2'-azobis(2-methylbutyronitrile), 2,2' -azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylamidinopropane) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2,4,4-trimethylpentane), 2-cyano-2-propylazoformamide, 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), and the like.

[0054] When a polymerization reaction is carried out using an azo radical initiator, the amount of the azo radical initiator used per 1 mol of the specific control agent is preferably 0.01 mol or more, more preferably 0.05 mol or more, and even more preferably 0.1 mol or more. Furthermore, the amount used is preferably 100 mol or less, more preferably 50 mol or less, even more preferably 10 mol or less, and particularly preferably 5 mol or less. Therefore, the amount of the azo radical initiator used per 1 mol of the specific control agent is preferably 0.01 to 100 mol, more preferably 0.05 to 50 mol, even more preferably 0.1 to 10 mol, and particularly preferably 0.1 to 5 mol.

[0055] Examples of peroxide radical initiators include diisopropyl peroxydicarbonate, tert-butyl peroxypivalate, and benzoyl peroxide.

[0056] The solvent may be an organic solvent or an aqueous solvent. One type of solvent may be used alone, or two or more types may be used in combination.

[0057] Examples of organic solvents include benzene, toluene, xylene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, hexafluoroisopropanol, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, 1H-perfluorohexane, 1H,1H,1H,2H,2H-perfluorooctane, trifluoromethylbenzene, 1,3-bis(trifluoromethyl)benzene, 1,4-bis(trifluoromethyl)benzene, benzotrifluoride, chlorobenzene, acetonitrile, etc. In addition, ionic liquids such as N-methyl-N-methoxymethylpyrrolidium tetrafluoroborate, N-methyl-N-ethoxymethyl tetrafluoroborate, 1-methyl-3-methylimidazolium tetrafluoroborate, 1-methyl-3-methylimidazolium hexafluorophosphate, and 1-methyl-3-methylimidazolium chloride may also be used.

[0058] Examples of aqueous solvents include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol.

[0059] The amount of solvent used can be adjusted appropriately. For example, the amount of solvent per 1000 g of the obtained polymer is preferably 0.01 L or more, more preferably 0.05 L or more, and even more preferably 0.1 L or more. Furthermore, the amount of solvent per 1000 g of the obtained polymer is preferably 50 L or less, more preferably 10 L or less, and even more preferably 5 L or less. Therefore, the amount of solvent per 1000 g of the obtained polymer is preferably 0.01 to 50 L, more preferably 0.05 to 10 L, and even more preferably 0.1 to 5 L.

[0060] [Polymer] The resulting polymer may be a homopolymer obtained by polymerizing one type of polymerizable monomer, or a copolymer obtained by polymerizing two or more types of polymerizable monomer. The copolymer may be a block copolymer, a random copolymer, or an alternating copolymer. Depending on the type of polymerizable monomer, the polymer may be a fluorine-containing polymer or a polymer that does not contain fluorine atoms.

[0061] The molecular weight of the polymer can be adjusted by the amount of the specific control agent and the radical initiator used as needed, the reaction time, etc. For example, the number average molecular weight (Mn) of the polymer may be 100 to 1,000,000, 1,000 to 500,000, or 10,000 to 200,000. The weight average molecular weight (Mw) of the polymer may be 100 to 1,000,000, 1,000 to 500,000, or 10,000 to 200,000. The number average molecular weight (Mn) and weight average molecular weight (Mw) in the present disclosure are determined by SEC (size exclusion chromatography) measurement, and polystyrene is used as a standard substance for molecular weight conversion.

[0062] According to the method for producing a polymer of this embodiment, it is possible to control the polydispersity of the resulting polymer to, for example, 2.5 or less. According to the production method of the present disclosure, it is also possible to obtain a polymer having a very narrow molecular weight distribution, such as a polydispersity of preferably 2.1 or less, 2.0 or less, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, or 1.5 or less. The lower limit of polydispersity is 1.0 by definition. Polydispersity (PD), which is an index of molecular weight distribution, can be calculated using the following formula: PD = Mw (weight average molecular weight) / Mn (number average molecular weight)

[0063] The resulting polymer preferably has a structure derived from the leaving group of the specific control agent. For example, when the specific control agent (1) is used, the polymer has a terminal structure of -CF ２It is preferable that the polymer molecule contains a polymer molecule having a terminal structure of -CFR when the specific control agent (2) is used. ｆ When the specific control agent (3) is used, it is preferable that the polymer molecule contains a polymer molecule having a terminal structure of -CHR ｆ When the specific control agent (4) is used, it is preferable that the polymer molecule contains a polymer molecule having a terminal structure of -CHFCR. ２ R ３ It is preferable that the polymer molecule contains a polymer molecule represented by X. The ratio of the structure derived from the leaving group of the specific control agent to the number of moles of the polymer terminal is preferably 10 to 100 mol %, and more preferably 25 to 100 mol %. The ratio can be measured by NMR.

[0064] [Polymerization Method] A specific example of the polymerization method in the polymer production method of this embodiment is described below. The specific control agent and polymerizable monomer are mixed in a container purged with an inert gas or a container under vacuum pressure. Examples of inert gases include nitrogen, argon, and helium. Of these, nitrogen or argon is preferred, and nitrogen is more preferred. A radical initiator such as an azo-based radical initiator may be used in combination to accelerate the polymerization rate. The polymerization reaction can be carried out without a solvent, but can also be carried out using an organic solvent or aqueous solvent commonly used in radical polymerization.

[0065] Next, the mixture obtained above is stirred. The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the resulting polymer, and the mixture may be stirred at 60 to 150°C for 5 to 100 hours, or at 80 to 120°C for 10 to 30 hours. The reaction may be carried out at normal pressure, or under increased or reduced pressure.

[0066] After the reaction is complete, the target polymer is isolated by removing the solvent, residual monomers, etc. under reduced pressure using conventional methods, or by reprecipitation using a solvent in which the target polymer is insoluble. Any reaction treatment can be used as long as it does not adversely affect the target product. This polymerization method allows for excellent control of molecular weight and molecular weight distribution under mild conditions.

[0067] A block copolymer, a random copolymer, or an alternating copolymer may be prepared using multiple types of polymerizable monomers. For example, the polymerizable monomers polymerized in the presence of a specific control agent may include a first polymerizable monomer, and the first polymerizable monomer may be block copolymerized with a second polymerizable monomer different from the first polymerizable monomer. In this case, the first polymerizable monomer may be polymerized in the presence of a specific control agent, and then the product may be reacted with the second polymerizable monomer in the presence of the specific control agent. Alternatively, the first polymerizable monomer may be polymerized in the presence of a specific control agent, and then the product may be reacted with the second polymerizable monomer without using a specific control agent (i.e., by a method different from the polymer production method of this embodiment). In one aspect, the polymerizable monomers polymerized in the presence of a specific control agent may include a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer, and the first polymerizable monomer and the second polymerizable monomer may be randomly copolymerized.

[0068] The first polymerizable monomer and the second polymerizable monomer may be any polymerizable monomer, and each independently may be the polymerizable monomer exemplified above. In one embodiment, it is preferable that at least the first polymerizable monomer is a fluorine-containing monomer, and it is also preferable that both the first polymerizable monomer and the second polymerizable monomer are fluorine-containing monomers.

[0069] In one embodiment, the combination of the specific control agent and the polymerizable monomer is preferably any one of the following first to fourth combinations.

[0070] (First Combination) The specific control agent is the specific control agent (1), and the polymerizable monomer contains a compound represented by the following formula (5).

[0071]

[0072] In formula (5), A １ and A ２ each independently represents 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.

[0073] (Second Combination) The specific control agent is the specific control agent (2), and the polymerizable monomer contains a compound represented by the following formula (6).

[0074]

[0075] In formula (6), A １ and A ２ each independently represents 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 ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms.

[0076] (Third Combination) The specific control agent is the specific control agent (3), and the polymerizable monomer contains a compound represented by the following formula (7).

[0077]

[0078] In formula (7), A １ and A ２ each independently represents 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 ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms.

[0079] (Fourth Combination) The specific control agent is the specific control agent (4), and the polymerizable monomer contains a compound represented by the following formula (8).

[0080]

[0081] In formula (8), A １ and A ２ each independently represents 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.

[0082] The first to fourth combinations are a combination of a carbon atom adjacent to Te of a leaving group in a specific control agent and a hydrogen atom or a substituent bonded thereto (for example, —CF ２ -, specific control agent (2) -CFR ｆ -, and specific control agent (3) is -CHR ｆ -, -CHF- in the specific control agent (4), and a partial structure of a polymerizable monomer (for example, ═CF in the formula (5)).２ , in equation (6) = CFR ｆ , in formula (7) = CHR ｆ , and =CHF in formula (8), the hydrogen atom or substituent bonded to the carbon atom is common. It is believed that the combination of a specific control agent having such a similar structure with a polymerizable monomer provides an appropriate balance between the stability of the radical and the reactivity with the monomer, increases the reinitiation rate, and enables particularly suitable molecular weight control.

[0083] In formulas (5) to (8), A １ or A ２ Examples of the organic group having 1 to 20 carbon atoms represented by the formula (I) include a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 5 to 20 atoms constituting an aromatic ring, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, and a -(OX １ ) ｎ１ A group represented by —OR (wherein X １each independently represent a substituted or unsubstituted alkylene group having 1 to 11 carbon atoms, R represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 11 carbon atoms, and n1 represents an integer of 1 to 11. As the unsubstituted alkyl group having 1 to 20 carbon atoms, an unsubstituted alkyl group having 1 to 12 carbon atoms is preferable, and an unsubstituted alkyl group having 1 to 6 carbon atoms is more preferable. As the unsubstituted alkyl group having 1 to 20 carbon atoms, 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, an n-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, or the like, may be mentioned. Among these, a methyl group, an ethyl group, or an n-butyl group is preferable. Examples of substituted alkyl groups having 1 to 20 carbon atoms include alkyl groups in which any hydrogen atom bonded to the above-mentioned unsubstituted alkyl group having 1 to 12 carbon atoms has been substituted with a substituent such as a fluorine atom, a chlorine atom, an alkoxy group, or a fluoroalkoxy group. The number of substituents is not particularly limited and may be 1 to 4, 1 to 3, 1 to 2, or even 1. Examples of unsubstituted aryl groups having 5 to 20 atoms constituting the aromatic ring include homoaryl groups such as a phenyl group or a naphthyl group; and heteroaryl groups such as a pyridyl group, an imidazolyl group, a pyrrolyl group, a furyl group, or a thienyl group. Of these, homoaryl groups are preferred, and phenyl groups are more preferred. Examples of substituted aryl groups having 5 to 20 atoms constituting the aromatic ring include aryl groups in which any hydrogen atom bonded to the aromatic ring of the above-mentioned unsubstituted aryl group has been substituted with a substituent such as a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, a carbonyl-containing group, a sulfonyl group, or 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. Examples of the unsubstituted alkoxy group having 1 to 12 carbon atoms include -OR ｕ In this case, R ｕrepresents an unsubstituted alkyl group having 1 to 12 carbon atoms, and examples of the unsubstituted alkyl group having 1 to 12 carbon atoms represented by Z include those mentioned above. Examples of the substituted alkoxy group having 1 to 12 carbon atoms include alkoxy groups in which any hydrogen atom bonded to the unsubstituted alkoxy group having 1 to 12 carbon atoms is substituted with a substituent such as a fluorine atom, a chlorine atom, an alkoxy group, or a fluoroalkoxy group. The number of substituents is not particularly limited, and may be 1 to 4, 1 to 3, 1 to 2, or 1. -(OX １ ) ｎ１ In the group represented by —OR, X １ When R has a substituent, examples of the substituent include a fluorine atom, a chlorine atom, an alkoxy group, a fluoroalkoxy group, etc. The number of the substituents is not particularly limited, and may be 1 to 4, 1 to 3, 1 to 2, or 1, independently of each other. １ As R, an unsubstituted alkylene group having 1 to 3 carbon atoms is preferred. As R, an unsubstituted alkyl group having 1 to 3 carbon atoms is preferred. １ ) ｎ１ Examples of the group represented by —OR include —OCH ２ OCH ３ , -OCH ２ CH ２ OCH ３ In one embodiment, A １ and A ２ are each independently preferably a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group. １ and A ２ The combination may be any of the combinations described above, and for example, a combination of all hydrogen atoms, a combination of all fluorine atoms, a combination of a hydrogen atom and a fluorine atom, a combination of a fluorine atom and a chlorine atom, a combination of a hydrogen atom and an organic group having 1 to 20 carbon atoms, and a combination of a fluorine atom and an organic group having 1 to 20 carbon atoms are preferred.

[0084] In formulas (5) to (8), R ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms. ｆ is preferably a perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of perfluoroalkyl groups having 1 to 12 carbon atoms include a perfluoromethyl group, a perfluoroethyl group, a perfluoro n-propyl group, a perfluoroisopropyl group, a perfluoro n-butyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoro n-pentyl group, a perfluoro n-hexyl group, a perfluoro n-heptyl group, and a perfluoro n-octyl group. In one embodiment, R ｆ A perfluoromethyl group is preferred as R ｆ is the R in the specific control agent used in combination. ｆ It is preferable that the structure is the same as that of

[0085] Next, embodiments of the present disclosure will be described in detail using examples, but the embodiments of the present disclosure are not limited to these examples. In the following examples, Examples 1 to 26 are examples, and Examples 27 to 30 are comparative examples.

[0086] In the following examples, nuclear magnetic resonance spectra (NMR) were measured by Fourier transform NMR. １ H-NMR was measured at 300 MHz using tetramethylsilane as the reference with a chemical shift value of 0 ppm. １９ F-NMR was measured at 282 MHz using 1,4-bis(trifluoromethyl)benzene as the reference with a chemical shift value of -63.9 ppm. The abbreviations used in the text have the following meanings: s: singlet, d: doublet, t: triplet, m: multiplet, br: broad, Hz: Hertz. CDCl ３ : deuterated chloroform １ H-NMR: proton nuclear magnetic resonance １９ F-NMR: fluorine-19 nuclear magnetic resonance

[0087] In the following examples, MS (mass spectrum) was measured by GC / MS (gas chromatograph mass spectrometer). EI (electron ionization) was used as the ionization method. Positive ionization mode (EI+) was used. The data reported were actual measurements (found values).

[0088] In the following examples, the number average molecular weight (Mn) and weight average molecular weight (Mw) were determined by SEC (Size Exclusion Chromatography) measurement, and polystyrene was used as a standard substance for molecular weight conversion.

[0089] (Example 1) (n-butyl) n-nonafluorobutyl telluride (n-BuTeC ４ F ９ Synthesis of (n-BuTe) ２ + n-C ４ F ９ I → 2n-BuTeC ４ F ９In a nitrogen-purged glove box, a magnetic rotor, 3.7 g (10 mmol) of di-n-butyl ditelluride, and 67 mL of pre-degassed ethanol were placed in a 200 mL three-neck glass flask and sealed with a three-way stopcock, septum, and flat stopper. The flask was removed from the glove box, and stirring was initiated at room temperature. The septum was removed while nitrogen was circulating through the flask. Under a nitrogen atmosphere, 9.5 g (25 mmol) of sodium borohydride was added to the flask, and the mixture was stirred at room temperature for 15 minutes. Under a nitrogen atmosphere, the flask was cooled to -73°C with stirring. Under a nitrogen atmosphere, 17 g (50 mmol) of pre-degassed n-nonafluorobutyl iodide was added to the flask at a rate that did not cause the mixture temperature to exceed -50°C. The flask was stirred at room temperature for 12 hours under a nitrogen atmosphere. Under a nitrogen atmosphere, 100 mL of saturated saline solution, previously degassed under reduced pressure, and 200 mL of pre-degassed hexane were added to the flask and stirred for 10 minutes. The organic and aqueous phases were separated, and the aqueous phase was extracted with 100 mL of pre-degassed hexane and combined with the organic phase. The organic phase was washed with pre-degassed water. In a nitrogen-purged glove box, 100 g of magnesium sulfate was added to the organic phase, and the mixture was allowed to stand for 1 hour. The mixture was then filtered and the filtrate was recovered. The solvent in the filtrate was evaporated under reduced pressure, and the residue was purified by vacuum distillation to obtain 2.4 g of the title compound as a liquid. １ H NMR (300 MHz, CDCl ３ ) δ0.95 (3H, t), δ1.37 to 1.46 (2H, m), δ1.86 to 1.94 (2H, m), δ3.15 (2H, t) １９ F NMR (282 MHz, CDCl ３ ) δ-125.4 to -125.5 (2F, m), δ-116.1 to -116.2 (2F, m), δ-85.1 to -85.2 (2F, br), δ-81.2 (3F, t) MS (EI+): [M+] 406.0

[0090] (Example 2) (1,1,1,2,3,3,3-heptafluoroisopropyl)phenyl telluride (PhTeCF(CF ３ ) ２ Synthesis of (PhTe) ２ +CF ３ CFICF ３ → 2PhTeCF (CF ３) ２ The same procedure as in Example 1 was conducted except that 3.7 g (10 mmol) of di-n-butyl ditelluride in Example 1 was changed to 4.1 g (10 mmol) of diphenyl ditelluride and 17 g (50 mmol) of n-nonafluorobutyl iodide was changed to 15 g (50 mmol) of 1,1,1,2,3,3,3-heptafluoroisopropyl iodide, thereby obtaining the title compound as 2.8 g of a liquid. １ H NMR (300 MHz, CDCl ３ ) δ7.30 to 7.46 (3H, m), δ7.75 to 7.78 (2H, m) １９ F NMR (282 MHz, CDCl ３ ) δ-176.9 to -177.1 (1F, m), δ-73.5 (6F, d) MS (EI+): [M+] 375.9

[0091] (Example 3) (1,1,1,3,3,3-hexafluoroisopropyl)phenyl telluride (PhTeCH(CF ３ ) ２ Synthesis of (PhTe) ２ +CF ３ CHICF ３ → 2PhTeCH (CF ３ ) ２ The same procedure as in Example 2 was repeated except that 15 g (50 mmol) of 1,1,1,2,3,3,3-heptafluoroisopropyl iodide in Example 2 was changed to 14 g (50 mmol) of 1,1,1,3,3,3-hexafluoroisopropyl iodide, to obtain 1.5 g of the title compound as a liquid. １ H NMR (300 MHz, CDCl ３ ) δ4.0 to 4.5 (1H, m), δ7.26 to 7.45 (3H, m), δ7.72 to 7.75 (2H, m) １９ F NMR (282 MHz, CDCl ３ ) δ-61.7 (6F, d) MS (EI+): [M+] 357.9

[0092] (Example 4) (n-butyl) 1,3,3,3-tetrafluoropropyl telluride (n-BuTeCHFCH ２ CF ３ Synthesis of (n-BuTe) ２ + n-CF ３CH ２ CHFI → 2n-BuTeCHFCH ２ CF ３ The procedure of Example 1 was repeated except that 17 g (50 mmol) of n-nonafluorobutyl iodide was changed to 12 g (50 mmol) of 1,3,3,3-tetrafluoropropyl iodide, to obtain 0.8 g of the title compound as a liquid. １ H NMR (300 MHz, CDCl ３ ) δ0.91 (3H, t), δ1.35 to 1.44 (2H, m), δ1.72 to 1.80 (2H, m), δ2.44 to 2.54 (2H, m), δ3.12 (2H, t), δ6.12.44 to 2.54 (2H, m) １９ F NMR (282 MHz, CDCl ３ ) δ-184.0 (1F, br), δ-65.6 (3F, m) MS (EI+): [M+] 302.0

[0093] The following Examples 5 to 9 are examples that are expected to be synthesizable based on the findings of the present disclosure and known techniques.

[0094] Example 5 (Ethyl) n-tridecafluorohexyl telluride (EtTeC ６ F １３ Synthesis of (EtTe) ２ + C ６ F １３ I → 2EtTeC ６ F １３ The procedure of Example 1 is repeated except that di-n-butyl ditelluride is replaced with diethyl ditelluride and n-nonafluorobutyl iodide is replaced with n-tridecafluorohexyl iodide, to give the title compound as a liquid.

[0095] (Example 6) (1,1,2,2,3,3,4,4,5,5,6-undecafluorocyclohexyl)phenyl telluride (PhTeC ６ F １１ Synthesis of (PhTe) ２ + C ６ F １１ I → 2PhTeC ６ F １１The procedure of Example 2 is repeated except that 1,1,1,2,3,3,3-heptafluoroisopropyl iodide is replaced with 1,1,2,2,3,3,4,4,5,5,6-undecafluorohexyl iodide, to give the title compound as a liquid.

[0096] (Example 7) (1,1,1,3,3,3-hexafluoroisopropyl)methyl telluride (MeTeCH(CF ３ ) ２ Synthesis of (MeTe) ２ +CF ３ CHICF ３ → 2MeTeCH (CF ３ ) ２ The procedure of Example 3 is repeated except that diphenyl ditelluride is replaced with dimethyl ditelluride to give the title compound as a liquid.

[0097] (Example 8) (n-butyl) 1,1,1,3,3,3-hexafluoroisopropyl telluride (n-BuTeCH(CF ３ ) ２ Synthesis of (n-BuTe) ２ +CF ３ CHICF ３ → 2n-BuTeCH (CF ３ ) ２ The procedure of Example 3 is repeated except that diphenyl ditelluride is replaced with di-n-butyl ditelluride to give the title compound as a liquid.

[0098] (Example 9) (1,3,3,3-tetrafluoropropyl)phenyl telluride (PhTeCHFCH ２ CF ３ Synthesis of (PhTe) ２ +CF ３ CH ２ CHFI → PhTeCHFCH ２ CF ３ The procedure of Example 4 is repeated except that di-n-butyl ditelluride is replaced with diphenyl ditelluride to give the title compound as a liquid.

[0099] (Example 10) n-BuTeC ４ F ９In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.046 g (0.18 mmol) of an azo radical initiator "V-65" (FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.074 g (0.18 mmol) of n-BuTeC synthesized in Example 1, ４ F ９ , and 25 g of 1H-perfluorohexane were charged. After 3.7 g (37 mmol) of tetrafluoroethylene was injected, stirring was initiated while raising the liquid temperature to 65°C. While maintaining the liquid temperature, stirring was carried out at 200 rpm (200 revolutions per minute) for 5 hours. After cooling the autoclave in an ice-water bath, unreacted tetrafluoroethylene was purged.

[0100] The resulting polymer solution was dried in vacuo to give 0.4 g of a solid.

[0101] (Example 11) n-BuTeC ４ F ９ In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.036 g (0.16 mmol) of an azo radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.063 g (0.16 mmol) of n-BuTeC synthesized in Example 1, ４ F ９ , and 25 g of 1H-perfluorohexane were charged. 0.41 g (15 mmol) of ethylene and 1.7 g (17 mmol) of tetrafluoroethylene were injected, and then stirring was initiated while the liquid temperature was raised to 70°C. Stirring was carried out at 200 rpm for 5 hours while maintaining the liquid temperature. The autoclave was cooled in an ice-water bath, and then unreacted ethylene and tetrafluoroethylene were purged.

[0102] The resulting polymer solution was dried under vacuum to obtain 1.2 g of a solid. The resulting solid was measured by size exclusion chromatography, and found to have Mn=14,000 and Mw=18,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.3, indicating that this radical polymerization is characteristic of living radical polymerization.

[0103] (Example 12) n-BuTeC ４ F ９ Copolymerization of tetrafluoroethylene and perfluoro(n-propyl vinyl ether) using the above copolymer In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 2.1 g (8.0 mmol) of perfluoro(n-propyl vinyl ether), 0.046 g (0.20 mmol) of an azo radical initiator “V-601” (FUJIFILM Wako Pure Chemical Industries, Ltd.), and 0.080 g (0.20 mmol) of the n-BuTeC synthesized in Example 1. ４ F ９ , and 25 g of 1H-perfluorohexane were charged. After 3.0 g (30 mmol) of tetrafluoroethylene was injected, stirring was started while the liquid temperature was raised to 80°C. Stirring was carried out at 200 rpm for 4 hours while maintaining the liquid temperature. After the autoclave was cooled in an ice-water bath, unreacted tetrafluoroethylene was purged.

[0104] The resulting polymer solution was dried in vacuo to give 1.9 g of a solid.

[0105] (Example 13) n-BuTeC ４ F ９ In a nitrogen-substituted glove box, 0.025 g (0.10 mmol) of an azo radical initiator “VR-110” (FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.040 g (0.10 mmol) of n-BuTeC synthesized in Example 1, and 0.025 g (0.10 mmol) of n-BuTeC synthesized in Example 1 were placed in a 30 mL stainless steel autoclave equipped with a stirrer. ４ F ９ , and 12 g of acetonitrile were charged. After 1.3 g (20 mmol) of vinylidene fluoride was injected, stirring was initiated while the liquid temperature was raised to 110°C. Stirring was carried out at 200 rpm for 5 hours while maintaining the liquid temperature. After the autoclave was cooled in an ice-water bath, unreacted vinylidene fluoride was purged.

[0106] The resulting polymer solution was dried in vacuo to give 0.3 g of a solid.

[0107] (Example 14) n-BuTeC ４F ９ In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.034 g (0.15 mmol) of an azo radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.059 g (0.15 mmol) of n-BuTeC synthesized in Example 1, ４ F ９ , and 12 g of acetonitrile were charged. After 2.4 g (29 mmol) of trifluoroethylene was injected, stirring was started while the liquid temperature was raised to 80°C. Stirring was carried out at 200 rpm for 5 hours while maintaining the liquid temperature. After the autoclave was cooled in an ice-water bath, unreacted trifluoroethylene was purged.

[0108] The resulting polymer solution was dried under vacuum to obtain 0.9 g of a solid. The resulting solid was measured by size exclusion chromatography, revealing Mn = 9,000 and Mw = 11,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.2, indicating that this radical polymerization is characteristic of living radical polymerization.

[0109] Example 15 Block Copolymerization of Polytrifluoroethylene and Styrene A 30 mL glass Schlenk flask was charged with a magnetic rotor, 0.52 g of the fluoropolymer synthesized in Example 14, 0.012 g (0.050 mmol) of the azo radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.), 1.0 g (10 mmol) of styrene, and 12 g of acetonitrile. Stirring was initiated while the temperature of the water bath was raised to 80°C. Stirring was continued at 400 rpm for 2 hours while maintaining the temperature of the water bath. The Schlenk flask was cooled in a water bath.

[0110] The obtained polymer solution was added to 50 mL of pre-degassed methanol to precipitate a solid. The obtained solid was filtered and washed with 10 mL of pre-degassed methanol. The obtained solid was dried in vacuo to obtain 0.7 g of a solid. The obtained solid was measured by size exclusion chromatography to find that Mn = 11,000, Mw = 14,000, and the peak was monomodal. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.3. The formation of a block copolymer was confirmed from Mn, Mw, polydispersity, and the monomodal peak.

[0111] (Example 16) n-BuTeC ４ F ９ In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.14 g (0.60 mmol) of an azo radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.097 g (0.24 mmol) of n-BuTeC synthesized in Example 1, ４ F ９ , and 18 g of benzotrifluoride were charged. After 14 g (120 mmol) of chlorotrifluoroethylene was injected, stirring was started while the liquid temperature was raised to 80°C. Stirring was carried out at 200 rpm for 4 hours while maintaining the liquid temperature. After the autoclave was cooled in an ice-water bath, unreacted chlorotrifluoroethylene was purged.

[0112] The resulting polymer solution was dried under vacuum to obtain 4.5 g of a solid. The resulting solid was measured by size exclusion chromatography, revealing Mn = 22,000 and Mw = 27,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.2, indicating that this radical polymerization is characteristic of living radical polymerization.

[0113] (Example 17) n-BuTeC ４ F ９Copolymerization of chlorotrifluoroethylene and ethyl vinyl ether using the above-mentioned copolymer In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 2.9 g (40 mmol) of ethyl vinyl ether, 0.099 g (0.40 mmol) of an azo radical initiator “V-65” (FUJIFILM Wako Pure Chemical Industries, Ltd.), and 0.16 g (0.40 mmol) of the n-BuTeC synthesized in Example 1. ４ F ９ , and 13 g of o-xylene were charged. After 4.7 g (60 mmol) of chlorotrifluoroethylene was injected, stirring was started while the liquid temperature was raised to 65°C. Stirring was carried out at 200 rpm for 3 hours while maintaining the liquid temperature. After the autoclave was cooled in an ice-water bath, unreacted chlorotrifluoroethylene was purged.

[0114] The resulting polymer solution was dried under vacuum to obtain 4.7 g of a solid. The resulting solid was measured by size exclusion chromatography, and found to have Mn=14,000 and Mw=18,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.3, indicating that this radical polymerization is characteristic of living radical polymerization.

[0115] (Example 18) n-BuTeC ４ F ９ A 30 mL glass Schlenk tube was charged with a magnetic rotor, 5.6 g (20 mmol) of perfluoro(3-butenyl vinyl ether), 0.023 g (0.10 mmol) of an azo radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.), and 0.040 g (0.10 mmol) of n-BuTeC synthesized in Example 1. ４ F ９ , and 25 g of 1H-perfluorohexane were charged. Stirring was started while the temperature of the water bath was raised to 80°C. Stirring was carried out at 400 rpm for 4 hours while maintaining the temperature of the water bath. The Schlenk flask was cooled in the water bath.

[0116] The resulting polymer solution was dried in vacuo to give 0.8 g of a solid.

[0117] (Example 19) n-BuTeC４ F ９ In a nitrogen-substituted glove box, 0.042 g (0.18 mmol) of an azo-based radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.073 g (0.18 mmol) of n-BuTeC synthesized in Example 1, and 0.042 g (0.18 mmol) of n-BuTeC synthesized in Example 1 were placed in a 30 mL stainless steel autoclave equipped with a stirrer. ４ F ９ , and 12 g of acetonitrile were charged. 1.2 g (18 mmol) of vinylidene fluoride and 1.4 g (17 mmol) of trifluoroethylene were injected, and then stirring was initiated while the liquid temperature was raised to 65°C. Stirring was carried out at 200 rpm for 5 hours while maintaining the liquid temperature. The autoclave was cooled in an ice-water bath, and then unreacted vinylidene fluoride and trifluoroethylene were purged.

[0118] The resulting polymer solution was dried under vacuum to obtain 1.0 g of a solid. The resulting solid was measured by size exclusion chromatography, revealing Mn = 9,000 and Mw = 13,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.4, indicating that this radical polymerization is characteristic of living radical polymerization.

[0119] (Example 20) PhTeCF (CF ３ ) ２ In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.043 g (0.19 mmol) of an azo radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.070 g (0.19 mmol) of PhTeCF(CF) synthesized in Example 2, and ３ ) ２ , and 12 g of acetonitrile were charged. 2.3 g (16 mmol) of hexafluoropropylene and 1.2 g (19 mmol) of vinylidene fluoride were injected, and then stirring was initiated while the liquid temperature was raised to 80°C. Stirring was carried out at 200 rpm for 3 hours while maintaining the liquid temperature. The autoclave was cooled in an ice-water bath, and then unreacted vinylidene fluoride and hexafluoropropylene were purged.

[0120] The resulting polymer solution was dried under vacuum to obtain 0.9 g of a solid. The resulting solid was measured by size exclusion chromatography, and found to have Mn=7,000 and Mw=10,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.4, indicating that this radical polymerization is characteristic of living radical polymerization.

[0121] (Example 21) PhTeCF (CF ３ ) ２ In a nitrogen-substituted glove box, 0.043 g (0.19 mmol) of an azo-based radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.) and 0.070 g (0.19 mmol) of PhTeCF(CF) synthesized in Example 2 were placed in a 30 mL stainless steel autoclave equipped with a stirrer. ３ ) ２ , and 12 g of acetonitrile were charged. 2.0 g (18 mmol) of 2,3,3,3-tetrafluoropropene and 1.2 g (19 mmol) of vinylidene fluoride were injected, and then stirring was initiated while the liquid temperature was raised to 80°C. Stirring was carried out at 200 rpm for 5 hours while maintaining the liquid temperature. After the autoclave was cooled in an ice-water bath, unreacted vinylidene fluoride and 2,3,3,3-tetrafluoropropene were purged.

[0122] The resulting polymer solution was dried under vacuum to obtain 0.9 g of a solid. The resulting solid was measured by size exclusion chromatography to find that Mn was 8,000 and Mw was 11,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.4, indicating that this radical polymerization is characteristic of living radical polymerization.

[0123] (Example 22) PhTeCH(CF ３ ) ２A 30 mL glass Schlenk tube was charged with a magnetic rotor, 13 g (50 mmol) of 1,4-divinyloctafluorobutane, 0.064 g (0.25 mmol) of an azo radical initiator "VR-110" (FUJIFILM Wako Pure Chemical Industries, Ltd.), and 0.089 g (0.25 mmol) of PhTeCH(CF) synthesized in Example 3. ３ ) ２ , and 25 g of 1H-perfluorohexane were charged. Stirring was started while the temperature of the oil bath was raised to 110°C. Stirring was carried out at 400 rpm for 8 hours while maintaining the oil bath temperature. The Schlenk flask was cooled in a water bath.

[0124] The resulting polymer solution was dried under vacuum to obtain 2.7 g of a liquid. The resulting liquid was measured by size exclusion chromatography, revealing Mn = 4,000 and Mw = 6,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.5, indicating that this radical polymerization is characteristic of living radical polymerization.

[0125] (Example 23) PhTeCH(CF ３ ) ２ Copolymerization of (perfluoro-n-hexyl)ethylene and vinyl acetate using a 30 mL glass Schlenk tube was charged with a magnetic rotor, 5.2 g (15 mmol) of (perfluoro-n-hexyl)ethylene, 1.3 g (15 mmol) of vinyl acetate, 0.035 g (0.15 mmol) of an azo radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.), and 0.053 g (0.15 mmol) of PhTeCH(CF) synthesized in Example 3. ３ ) ２ , and 12 g of acetonitrile were charged. Stirring was started while the temperature of the water bath was raised to 80°C. Stirring was carried out at 400 rpm for 4 hours while maintaining the temperature of the water bath. The Schlenk flask was cooled in the water bath.

[0126] The resulting polymer solution was dried under vacuum to obtain 3.1 g of a liquid. The resulting liquid was measured by size exclusion chromatography, revealing Mn = 12,000 and Mw = 16,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.3, indicating that this radical polymerization is characteristic of living radical polymerization.

[0127] (Example 24) n-BuTeCHFCH ２ CF ３ In Example 14, 0.040 g (0.10 mmol) of n-BuTeC synthesized in Example 1 was used for polymerization of trifluoroethylene. ４ F ９ 0.044 g (0.10 mmol) of n-BuTeCHFCH synthesized in Example 4 ２ CF ３ The procedure of Example 14 was repeated except for changing the solvent to the following, to obtain 0.7 g of a solid.

[0128] The obtained solid was measured by size exclusion chromatography, and it was found that Mn was 10,000 and Mw was 13,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.3, and this radical polymerization shows the characteristics of living radical polymerization.

[0129] (Example 25) PhTeCH(CF ３ ) ２ In a nitrogen-purged glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.12 g (0.50 mmol) of an azo radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.18 g (0.50 mmol) of PhTeCH(CF) synthesized in Example 3, and ３ ) ２ , 1.0 g of toluene, and 14 g of ion-exchanged water were charged. After 6.3 g (100 mmol) of vinyl chloride was injected, stirring was initiated while the liquid temperature was raised to 65°C. Stirring was continued at 200 rpm for 4 hours while maintaining the liquid temperature. After the autoclave was cooled in an ice-water bath, unreacted vinyl chloride was purged.

[0130] The resulting polymer solution was dried under vacuum to give 1.2 g of a solid, which was measured by size exclusion chromatography to have an Mn of 10,000.

[0131] (Example 26) PhTeCH(CF ３ ) ２ Polymerization of vinyl chloride using Example 25-2 The procedure of Example 25 was repeated except that the heating and stirring time of 4 hours in Example 25 was changed to 8 hours, and 2.3 g of a solid was obtained.

[0132] The obtained solid was measured by size exclusion chromatography and found to have an Mn of 17,000. Compared with Example 25, the Mn increased with an increase in the monomer conversion rate, indicating that this radical polymerization is a living radical polymerization.

[0133] (Example 27) (n-BuTe) ２ Polymerization of tetrafluoroethylene using 0.074 g (0.18 mmol) of n-BuTeC synthesized in Example 1 in Example 10 ４ F ９ 0.034 g (0.092 mmol) of (n-BuTe) ２ However, the same procedure as in Example 10 was carried out except for changing the solvent to the following, but no solid was obtained.

[0134] (Example 28) (n-BuTe) ２ When 0.046 g (0.18 mmol) of the azo radical initiator "V-65" (FUJIFILM Wako Pure Chemical Industries, Ltd.) in Example 27 was changed to 0.042 g (0.18 mmol) of the azo radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.) and the polymerization time was extended, the pressure began to decrease 18 hours after the completion of temperature increase.

[0135] (Example 29) (n-BuTe) ２ Copolymerization of tetrafluoroethylene and perfluoro(n-propyl vinyl ether) using 0.080 g (0.20 mmol) of n-BuTeC synthesized in Example 1 in Example 12 ４ F ９ 0.037 g (0.099 mmol) of (n-BuTe) ２However, the same procedure as in Example 12 was carried out except for changing the solvent to the following, but no solid was obtained.

[0136] (Example 30) (n-BuTe) ２ In Example 14, 0.059 g (0.15 mmol) of n-BuTeC synthesized in Example 1 was used for polymerization of trifluoroethylene. ４ F ９ 0.027 g (0.073 mmol) of (n-BuTe) ２ However, the same procedure as in Example 14 was carried out except for changing the solvent to the following, but no solid was obtained.

[0137] (Example 31) (n-BuTe) ２ Polymerization of chlorotrifluoroethylene using 0.097 g (0.24 mmol) of n-BuTeC synthesized in Example 1 in Example 16 ４ F ９ 0.044 g (0.12 mmol) of (n-BuTe) ２ The procedure of Example 16 was repeated except for changing the solvent to the following, to obtain 3.4 g of a solid.

[0138] The obtained solid was measured by size exclusion chromatography, and it was found that Mn was 21,000 and Mw was 31,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.5, and this radical polymerization shows the characteristics of living radical polymerization, but the polydispersity is larger than that of Example 16.

[0139] Examples 10 to 26 show that the polymerization method using a specific control agent enables suitable controlled polymerization using various polymerizable monomers and produces polymers with narrow molecular weight distributions. Furthermore, when the induction period is defined as the time required from the completion of the temperature increase of the reaction solution until the gas phase pressure decreases, the induction period in Example 28 was 18 hours, whereas the induction periods in Examples 10 to 14, 16, 17, 19 to 21, and 24 to 26 were all 30 minutes or less, indicating that the induction period until the start of polymerization was short.

[0140] The disclosure of Japanese Patent Application No. 2023-192418, filed on November 10, 2023, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A tellurium-containing compound represented by any one of the following formulas (1) to (4): In formulas (1) to (4), R １ represents an unsubstituted alkyl group having 2 to 6 carbon atoms; R ２ and R ３ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; Ar represents a substituted or unsubstituted aryl group having 5 to 18 atoms constituting an aromatic ring; R ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms, A represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 5 to 18 atoms constituting an aromatic ring, and X represents a hydrogen atom, a fluorine atom, or CF ２ -Z group or CHF-Z group, Y represents CF ２ In the formula (2) and the formula (3), Y and R represent a -Z group or a CHF-Z group, Z represents a fluorine atom or an organic group having 1 to 12 carbon atoms. ｆ may or may not be linked to form a ring structure.

2. In the formulas (1) to (4), Ar represents a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group; A represents an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 hydrogen atoms of the unsubstituted alkyl group are each independently substituted with a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group; or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group; Z is a fluorine atom; an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 hydrogen atoms of the unsubstituted alkyl group are each independently substituted with a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group; a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group; or -O-Z １ represents a group, where Z １ represents an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 hydrogen atoms of the unsubstituted alkyl group are each independently substituted with a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group; or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group. The tellurium-containing compound according to claim 1, 3. A method for producing a polymer, comprising polymerizing a compound having a carbon-carbon double bond in the presence of at least one compound selected from the group consisting of compounds represented by the following formulas (1) to (4): In formulas (1) to (4), R １ represents an unsubstituted alkyl group having 2 to 6 carbon atoms; R ２ and R ３ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; Ar represents a substituted or unsubstituted aryl group having 5 to 18 atoms constituting an aromatic ring; R ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms, A represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 5 to 18 atoms constituting an aromatic ring, and X represents a hydrogen atom, a fluorine atom, or CF ２ -Z group or CHF-Z group, Y represents CF ２ In the formula (2) and the formula (3), Y and R represent a -Z group or a CHF-Z group, Z represents a fluorine atom or an organic group having 1 to 12 carbon atoms. ｆ may or may not be linked to form a ring structure.

4. In the formulas (1) to (4), Ar represents a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group; A represents an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 hydrogen atoms of the unsubstituted alkyl group are each independently substituted with a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group; or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group; Z is a fluorine atom; an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 hydrogen atoms of the unsubstituted alkyl group are each independently substituted with a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group; a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group; or -O-Z １ represents a group, where Z １ represents an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 hydrogen atoms of the unsubstituted alkyl group are each independently substituted with a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl-containing group, or a sulfonyl-containing group; or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group.

5. The method for producing a polymer according to claim 3 or 4, wherein at least one compound selected from the group consisting of compounds represented by formulas (1) to (4) is a compound represented by formula (1), and the compound having a carbon-carbon double bond includes a compound represented by formula (5): In formula (5), A １ and A ２ each independently represents 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.

6. In the formula (5), A １ and A ２ each independently represents a hydrogen atom; a fluorine atom; a chlorine atom; a bromine atom; an iodine atom; a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms; or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group.

7. The method for producing a polymer according to claim 3 or 4, wherein at least one compound selected from the group consisting of compounds represented by formulas (1) to (4) is a compound represented by formula (2), and the compound having a carbon-carbon double bond includes a compound represented by formula (6): In formula (6), A １ and A ２ each independently represents 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 ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms.

8. In the formula (6), A １ and A ２ each independently represents a hydrogen atom; a fluorine atom; a chlorine atom; a bromine atom; an iodine atom; a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms; or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group.

9. The method for producing a polymer according to claim 3 or 4, wherein at least one compound selected from the group consisting of compounds represented by formulas (1) to (4) is a compound represented by formula (3), and the compound having a carbon-carbon double bond includes a compound represented by formula (7): In formula (7), A １ and A ２ each independently represents 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 ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms.

10. In the formula (7), A １ and A ２ each independently represents a hydrogen atom; a fluorine atom; a chlorine atom; a bromine atom; an iodine atom; a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms; or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group.

11. The method for producing a polymer according to claim 3 or 4, wherein at least one compound selected from the group consisting of compounds represented by formulas (1) to (4) is a compound represented by formula (4), and the compound having a carbon-carbon double bond includes a compound represented by formula (8): In formula (8), A １ and A ２ each independently represents 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.

12. In the formula (8), A １ and A ２ each independently represents a hydrogen atom; a fluorine atom; a chlorine atom; a bromine atom; an iodine atom; a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms; or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, or imidazolyl group.

13. The method for producing a polymer according to claim 3 or 4, wherein the compound having a carbon-carbon double bond comprises at least one selected from the group consisting of vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, perfluoro(methyl vinyl ether), vinylidene chloride, vinyl chloride, perfluoro(n-propyl vinyl ether), perfluoro(3-butenyl vinyl ether), (perfluoro-n-butyl)ethylene, (perfluoro-n-hexyl)ethylene, 1,4-divinylperfluorobutane, 1,6-divinylperfluorohexane, ethylene, and propylene.

14. A method for producing the polymer according to claim 3 or 4, which is carried out in the presence of an azo-based radical initiator.

15. The method for producing a polymer according to claim 14, wherein 0.01 to 100 mol of the azo radical initiator is used per 1 mol in total of at least one compound selected from the group consisting of compounds represented by formulas (1) to (4).

16. The method for producing a polymer according to claim 3 or 4, wherein a total of 0.001 to 1 mol of at least one compound selected from the group consisting of compounds represented by formulas (1) to (4) is used relative to a total of 1 mol of the compound having a carbon-carbon double bond.

17. The method for producing a polymer according to claim 3 or 4, wherein the weight average molecular weight of the resulting polymer is 1,000 to 500,000.

18. A method for producing a polymer according to claim 3 or 4, wherein the polydispersity of the resulting polymer is 2.0 or less.

19. The method for producing a polymer according to claim 3 or 4, wherein the compound having a carbon-carbon double bond includes a compound having a first carbon-carbon double bond, and the compound having the first carbon-carbon double bond and a compound having a second carbon-carbon double bond different from the compound having the first carbon-carbon double bond are block copolymerized.

20. The method for producing a polymer according to claim 3 or 4, wherein the compound having a carbon-carbon double bond includes a compound having a first carbon-carbon double bond and a compound having a second carbon-carbon double bond different from the compound having the first carbon-carbon double bond, and the compound having the first carbon-carbon double bond and the compound having the second carbon-carbon double bond are randomly copolymerized.