Tellurium-containing compound and method for manufacturing polymer

Abstract

Provided is a tellurium-containing compound represented by the formula below and a method for manufacturing a polymer using the same: (R-Te-CXY)nZ. In the formula, n represents an integer of 2 to 4; each R independently 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 forming an aromatic ring; each X independently represents a fluorine atom or a CF2-A group; each of A and Y independently represents a hydrogen atom, a fluorine atom, a chlorine atom, or an organic group having 1 to 12 carbon atoms; Z represents a single bond or an n-valent group; and each of X and Y may be independently linked to each other to form a cyclic structure.

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) method.

[0004] International Publication No. 2018 / 164147

[0005] In general free radical polymerization methods, the polymerization reaction proceeds rapidly, making it difficult to control the molecular weight distribution, but it is easy to obtain high molecular weight polymers. On the other hand, in controlled polymerization methods, it is possible to control the molecular weight distribution, but it is difficult to increase the molecular weight of the polymer. In view of this situation, the present disclosure relates to a method for producing a polymer that allows the molecular weight of the polymer to be controlled and increased, and a tellurium-containing compound that can be used in the method for producing the polymer.

[0006] Means for solving the above problems include the following aspects: <1> A tellurium-containing compound represented by the following formula (1): (R-Te-CXY) ｎZ ... (1) In formula (1), n ​​represents an integer of 2 to 4; each R independently 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; each X independently represents a fluorine atom or CF ２-A group, A and Y each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or an organic group having 1 to 12 carbon atoms, Z represents a single bond or an n-valent group, and X and Y each independently bond to each other to form a cyclic structure or not. <2> The tellurium-containing compound according to <1>, wherein in formula (1), Z represents a single bond, an oxygen atom, or a fluoroalkylene group having 1 to 12 carbon atoms and containing or not containing an oxygen atom. <3> A method for producing a polymer, comprising polymerizing a compound having a carbon-carbon double bond in the presence of the tellurium-containing compound according to <1> or <2>. <4> The method for producing a polymer according to <3>, 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), perfluoro(n-propyl vinyl ether), perfluoro(3-butenyl vinyl ether), (perfluoro-n-butyl)ethylene, (perfluoro-n-hexyl)ethylene, 1,4-divinylperfluorobutane, perfluoro(2,2-dimethyl-1,3-dioxole), and 1,6-divinylperfluorohexane. <5> The method for producing a polymer according to <3> or <4>, wherein the method is carried out in the presence of an azo radical initiator. <6> The method for producing a polymer according to <5>, wherein 0.01 to 100 mol of the azo radical initiator is used per 1 mol of the compound represented by formula (1). <7> The method for producing a polymer according to any one of <3> to <6>, wherein the polydispersity of the obtained polymer is 2.0 or less. <8> The method for producing a polymer according to any one of <3> to <7>, 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.<9> The method for producing a polymer according to any one of <3> to <7>, 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.

[0007] According to the present disclosure, there are provided a method for producing a polymer that allows the molecular weight of the polymer to be controlled and increased, and a tellurium-containing compound that can be used in the method for producing the polymer.

[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 "step" includes not only a step that is independent of other steps, but also a step that cannot be clearly distinguished from other steps, as long as the purpose of that step 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 those 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 value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with the value shown in the examples. In this disclosure, even when an element is expressed in the singular, this does not exclude the presence of multiple elements unless a technical contradiction arises, unless otherwise specified. In this disclosure, unless otherwise specified, organic groups or hydrocarbon groups may or may not have a substituent. In this disclosure, the number of carbon atoms in a compound or a constituent part thereof means the number including the carbon atom of the substituent when the compound or constituent part has a substituent. In this 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 this disclosure, a "polymer" is a compound obtained by polymerizing a monomer. In other words, a "polymer" has multiple structural units. In this disclosure, unless otherwise specified, the terms "polymerizing compound A" and "polymerizing at least compound A" encompass both polymerizing only compound A and polymerizing compound A with another compound. Furthermore, the terms "polymerizing compound A and compound B" and "polymerizing at least compound A and compound B" encompass both polymerizing only compound A and compound B, and polymerizing compound A, compound B, and another compound. Here, Compound A and Compound B represent any compound described in this disclosure that has a carbon-carbon double bond in the molecule.Unless otherwise specified, the polymers described in this disclosure may be homopolymers of one type of compound or copolymers of two or more types of compounds. In this disclosure, the term "polymer" does not exclude mixtures containing raw materials (monomers, catalysts), by-products, impurities, etc. in addition to the polymer.

[0010] <Tellurium-Containing Compound> In one embodiment of the present disclosure, there is provided a tellurium-containing compound represented by the following formula (1): (R-Te-CXY) ｎ Z ... (1) In formula (1), n ​​represents an integer of 2 to 4; each R independently 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; each X independently represents a fluorine atom or CF ２ A and Y each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or an organic group having 1 to 12 carbon atoms; Z represents an n-valent group; and X and Y each independently bond to each other to form or not form a cyclic structure.

[0011] The tellurium-containing compound represented by formula (1) can function as a control agent in controlled polymerization. Hereinafter, the tellurium-containing compound represented by formula (1) will also be referred to as "control agent (1)." The inventors have investigated methods for achieving both control of the molecular weight of a polymer and increasing the molecular weight, and have found that a controlled polymerization method using control agent (1) can increase the molecular weight of the resulting polymer. In controlled polymerization using control agent (1), a leaving group Z(CXY-) is released from control agent (1). ｎ is eliminated, and the remainder (R-Te) binds to the growing radical end as a protecting group. ｎ reacts with the monomer as a radical to become the initiating terminal. Protection of the growing radical by the protecting group is reversible, and the radical is deprotected by reaction with another radical. By repeating deprotection, growth (addition of monomer), and protection through this mechanism, polymerization proceeds with a controlled reaction rate. Since the leaving group of the control agent (1) has multiple reaction points with the monomer, it is believed that the progress of the above polymerization allows for a higher molecular weight than when a conventional control agent is used.

[0012] In formula (1), n ​​represents an integer of 2 to 4. From the viewpoint of easy availability of the compound, n is preferably 2 or 3, and more preferably 2. From the viewpoint of the possibility of producing a polymer with a high molecular weight or a branched polymer, n may be 3 or 4.

[0013] In formula (1), each R independently 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. As the unsubstituted alkyl group having 1 to 12 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, as a linear, branched, or cyclic alkyl group. Among these, from the viewpoints of synthesizability (i.e., ease of synthesis) and chain transfer reactivity, 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 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 18 atoms constituting the aromatic ring include homoaryl groups such as phenyl and naphthyl; and heteroaryl groups such as pyridyl, pyrrole, furyl, and thienyl. Among these, from the viewpoints of synthesis and chain transfer reactivity, 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. Among these, R is preferably an unsubstituted alkyl group having 1 to 12 carbon atoms, more preferably an unsubstituted alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group, an ethyl group, or an n-butyl group.

[0014] In formula (1), each X is independently a fluorine atom or CF ２ represents an -A group. Here, A represents a hydrogen atom, a fluorine atom, a chlorine atom, or an organic group having 1 to 12 carbon atoms. The organic group having 1 to 12 carbon atoms represented by A 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. Examples of the unsubstituted alkyl group having 1 to 12 carbon atoms include an unsubstituted alkyl group having 1 to 6 carbon atoms. 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, from the viewpoints of synthesizing ability and the balance between chain transfer reaction rate and reinitiation rate, methyl, ethyl, or n-butyl is preferred. Examples of substituted alkyl groups having 1 to 12 carbon atoms include alkyl groups in which any hydrogen atom bonded to the above-mentioned unsubstituted alkyl 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 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, pyrrole, furyl, and thienyl groups. Among these, from the viewpoint of synthetic ease, 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 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. 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 A 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 From the viewpoint of synthesis, R is preferably an unsubstituted alkylene group having 1 to 3 carbon atoms. R is preferably an unsubstituted alkyl group having 1 to 3 carbon atoms. １ ) ｎ１ Examples of the group represented by —OR include —OCH ２ OCH ３ , -OCH ２ CH ２ OCH ３、 -OCF ２ OCF ３ , -OCF ２ CF ２ OCF ３ Among these, a fluorine atom is preferred as X.

[0015] In formula (1), Y represents a hydrogen atom, a fluorine atom, a chlorine atom, or an organic group having 1 to 12 carbon atoms. Examples of the organic group having 1 to 12 carbon atoms include the groups exemplified as the organic group having 1 to 12 carbon atoms represented by A. Of these, a fluorine atom is preferred as Y from the viewpoint of the balance between the chain transfer reaction rate and the reinitiation rate.

[0016] In formula (1), X and Y may or may not be independently linked to each other to form a cyclic structure. Any combination of multiple X and multiple Y in formula (1) may be linked to each other. For example, X and Y bonded to the same carbon atom may be linked, or X and X, Y and Y, or X and Y bonded to different carbon atoms may be linked.

[0017] In formula (1), Z represents a single bond or an n-valent group. The definition and details of n are as described above. Examples of Z include a single bond, an oxygen atom, a nitrogen atom, a carbon atom, a silicon atom, and an n-valent organic group having 1 to 12 carbon atoms. However, when Z is a single bond or an oxygen atom, n is 2; when Z is a nitrogen atom, n is 3; and when Z is a carbon atom or a silicon atom, n is 4.

[0018] When n is 2, examples of the divalent organic group having 1 to 12 carbon atoms represented by Z include divalent aliphatic hydrocarbon groups having 1 to 12 carbon atoms, divalent aromatic hydrocarbon groups having 5 to 12 atoms constituting the aromatic ring, and combinations thereof (wherein the carbon number is 1 to 12).

[0019] Examples of the divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms include a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms, and a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms that has an oxygen atom between carbon atoms or at least at one end. The unsubstituted alkylene group having 1 to 12 carbon atoms is preferably an unsubstituted alkylene group having 1 to 6 carbon atoms. Examples of the unsubstituted alkylene group having 1 to 12 carbon atoms include linear, branched, or cyclic alkylene groups such as methylene, ethylene, n-propylene, isopropylene, cyclopropylene, n-butylene, sec-butylene, tert-butylene, cyclobutylene, n-pentylene, cyclopentylene, n-hexylene, cyclohexylene, n-heptylene, and n-octylene. Among these, a methylene group, an ethylene group, or an n-butylene group is preferred. Examples of the substituted alkylene group having 1 to 12 carbon atoms include alkylene groups in which any hydrogen atom bonded to the unsubstituted alkylene 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 even 1. Among these, a fluoroalkylene group having 1 to 12 carbon atoms is preferred from the viewpoints of synthesis and suppression of chain transfer of carbon-hydrogen bonds, which is a side reaction during polymerization. Examples of groups having an oxygen atom between the carbon-carbon atoms or at at least one terminal of the substituted or unsubstituted alkylene group having 1 to 12 carbon atoms include groups having an oxygen atom between the carbon-carbon atoms or at at least one terminal of the substituted or unsubstituted alkylene group having 1 to 12 carbon atoms. The number of oxygen atoms may be 1 to 4, 1 to 3, 1 or 2, or even 1.

[0020] A divalent aromatic hydrocarbon group having 5 to 12 atoms constituting the aromatic ring may or may not have a substituent. Examples of unsubstituted divalent aromatic hydrocarbon groups having 5 to 12 atoms constituting the aromatic ring include aromatic rings having no heteroatoms, such as a benzene ring or a naphthalene ring; or groups obtained by removing two hydrogen atoms from heteroaromatic rings, such as a pyridine ring, a pyrrole ring, a furan ring, a thiophene ring, or a triazine ring. Examples of substituted divalent aromatic hydrocarbon groups having 5 to 12 atoms constituting the aromatic ring include groups in which any hydrogen atom bonded to the above divalent aromatic hydrocarbon group is substituted with 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 even 1.

[0021] Examples of combinations of divalent aliphatic hydrocarbon groups having 1 to 12 carbon atoms and divalent aromatic hydrocarbon groups having 5 to 12 atoms constituting the aromatic ring (provided that the number of carbon atoms is 1 to 12) include groups combining the above-mentioned divalent aromatic hydrocarbon groups having 5 to 12 atoms constituting the aromatic ring with a substituted or unsubstituted alkylene group. Examples of unsubstituted alkylene groups include unsubstituted alkylene groups having 1 to 6 carbon atoms, such as methylene, ethylene, n-propylene, isopropylene, cyclopropylene, n-butylene, sec-butylene, tert-butylene, n-pentylene, cyclopentylene, and n-hexylene. Examples of substituted alkylene groups include alkylene groups in which any hydrogen atom bonded to the above-mentioned unsubstituted alkylene groups 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 or 2, or 1.

[0022] When n is 3, examples of the trivalent organic group having 1 to 12 carbon atoms and represented by Z include trivalent aliphatic hydrocarbon groups having 1 to 12 carbon atoms, trivalent aromatic hydrocarbon groups having 5 to 12 atoms constituting the aromatic ring, and trivalent organic groups having 1 to 12 carbon atoms in combination with an aromatic hydrocarbon group and an aliphatic hydrocarbon group.

[0023] The trivalent aliphatic hydrocarbon group having 1 to 12 carbon atoms includes a substituted or unsubstituted branched or cyclic aliphatic hydrocarbon group. Examples of the substituent include a fluorine atom, a chlorine atom, an alkoxy group, and a fluoroalkoxy group.

[0024] A trivalent aromatic hydrocarbon group having 5 to 12 atoms constituting the aromatic ring may or may not have a substituent. Examples of unsubstituted trivalent aromatic hydrocarbon groups having 5 to 12 atoms constituting the aromatic ring include aromatic rings having no heteroatoms, such as a benzene ring or a naphthalene ring; or groups in which three hydrogen atoms have been removed from a heteroaromatic ring, such as a pyridine ring, a pyrrole ring, a furan ring, a thiophene ring, or a triazine ring. Examples of substituted divalent aromatic hydrocarbon groups having 5 to 12 atoms constituting the aromatic ring include groups in which any hydrogen atom bonded to the above-mentioned trivalent aromatic hydrocarbon group has been substituted with 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 even 1.

[0025] Examples of trivalent organic groups having 1 to 12 carbon atoms and combining an aromatic hydrocarbon group and an aliphatic hydrocarbon group include groups combining the above-mentioned trivalent aromatic hydrocarbon group having 5 to 12 atoms constituting the aromatic ring with a substituted or unsubstituted alkylene group. Examples of unsubstituted alkylene groups include unsubstituted alkylene groups having 1 to 6 carbon atoms, such as methylene, ethylene, n-propylene, isopropylene, cyclopropylene, n-butylene, sec-butylene, tert-butylene, n-pentylene, cyclopentylene, and n-hexylene. Examples of substituted alkylene groups include alkylene groups in which any hydrogen atom bonded to the above-mentioned unsubstituted alkylene group 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.

[0026] When n is 4, examples of the tetravalent organic group having 1 to 12 carbon atoms represented by Z include a tetravalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a tetravalent aromatic hydrocarbon group having 5 to 12 atoms constituting the aromatic ring, and a tetravalent organic group having 1 to 12 carbon atoms in combination with an aromatic hydrocarbon group and an aliphatic hydrocarbon group.

[0027] The tetravalent aliphatic hydrocarbon group having 1 to 12 carbon atoms includes a substituted or unsubstituted branched or cyclic aliphatic hydrocarbon group. Examples of the substituent include a fluorine atom, a chlorine atom, an alkoxy group, and a fluoroalkoxy group.

[0028] A tetravalent aromatic hydrocarbon group having 5 to 12 atoms constituting the aromatic ring may or may not have a substituent. Examples of unsubstituted tetravalent aromatic hydrocarbon groups having 5 to 12 atoms constituting the aromatic ring include aromatic rings having no heteroatoms, such as a benzene ring or a naphthalene ring; or groups obtained by removing four hydrogen atoms from heteroaromatic rings, such as a pyridine ring, a pyrrole ring, a furan ring, or a thiophene ring. Examples of substituted tetravalent aromatic hydrocarbon groups having 5 to 12 atoms constituting the aromatic ring include groups in which any hydrogen atom bonded to the above tetravalent aromatic hydrocarbon group has been substituted with 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 even 1.

[0029] Examples of tetravalent organic groups having 1 to 12 carbon atoms and combining an aromatic hydrocarbon group and an aliphatic hydrocarbon group include groups combining an aromatic ring having no heteroatoms, such as a benzene ring or a naphthalene ring; or a heteroaromatic ring, such as a pyridine ring, a pyrrole ring, a furan ring, or a thiophene ring, with a substituted or unsubstituted alkylene group. Examples of unsubstituted alkylene groups include unsubstituted alkylene groups having 1 to 6 carbon atoms, and specific examples include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, a cyclopropylene group, an n-butylene group, a sec-butylene group, a tert-butylene group, an n-pentylene group, a cyclopentylene group, and an n-hexylene group. Examples of substituted alkylene groups include alkylene groups in which any hydrogen atom bonded to the above unsubstituted alkylene group 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 or 2, or 1.

[0030] Among these, Z is preferably a single bond, an oxygen atom, or a fluoroalkylene group having 1 to 12 carbon atoms which may or may not contain an oxygen atom. Here, the "fluoroalkylene group having 1 to 12 carbon atoms which may or may not contain an oxygen atom" refers to a fluoroalkylene group having 1 to 12 carbon atoms which does not contain an oxygen atom, or a group which has an oxygen atom between carbon atoms or at least at one end of a fluoroalkylene group having 1 to 12 carbon atoms. The number of carbon atoms in the fluoroalkylene group having 1 to 12 carbon atoms may be 1 to 6 or 1 to 4. The fluoroalkylene group may be a perfluoroalkylene group in which all hydrogen atoms bonded to the carbon chain are substituted with fluorine atoms, or a fluoroalkylene group in which some of the hydrogen atoms bonded to the carbon chain are substituted with fluorine atoms. Examples of the fluoroalkylene group having 1 to 12 carbon atoms which contains an oxygen atom include -(OC ２ F ４ ) ｎ２ -O-, -(OC ２ F ４ ) ｎ２ -, - (OCF ２ CF (CF ３ )) ｎ２ -O-, -(OCF ２ CF (CF ３ )) ｎ２ -, - (OC ４ F ８ ) ｎ２ -O-, -(OC ４ F ８ ) ｎ２ Here, n2 is a positive number in the range of 1 to 12 carbon atoms in the fluoroalkylene group.

[0031] [Method for producing the control agent (1)] The method for producing the control agent (1) is not particularly limited. For example, the control agent (1) can be produced by reacting a tellurium-containing active species R-TeM with a Z(CXYW) ｎ where M is a hydrogen atom, a lithium atom, or MgX ２ represents X ２represents a halogen atom, W represents a bromine atom or an iodine atom, and R, X, Y, Z, and n are the same as R, X, Y, Z, and n in formula (1), respectively. The tellurium-containing active species R-TeM can be, for example, (R-Te) ２ and a reducing agent, or by reacting a ditelluride compound represented by the formula: ２ The reducing agent can be a borohydride compound such as sodium borohydride or lithium borohydride, or an aluminum hydride compound such as lithium aluminum hydride or diisobutylaluminum hydride.

[0032] <Method for Producing Polymer> In one embodiment of the present disclosure, a method for producing a polymer is provided, in which a compound having a carbon-carbon double bond is polymerized in the presence of the tellurium-containing compound of the present disclosure. In the present disclosure, the compound having a carbon-carbon double bond is also referred to as a "polymerizable monomer." In the method for producing a polymer of the present disclosure, in addition to the control agent (1), other components such as a radical initiator, a solvent, an emulsifier, a suspending aid, an acid, or an alkali may be further used. Each component used in the method for producing a polymer of the present disclosure, the polymer produced therefrom, and the polymerization method are described in detail below.

[0033] [Controller (1)] Details of the control agent (1) are as described above. From the viewpoint of improving the polymerization rate, the amount of control agent (1) used per 1 mol of polymerizable monomer is preferably 0.001 mol or more, more preferably 0.005 mol or more, and may be 0.01 mol or more. Furthermore, from the viewpoints of increasing the molecular weight, narrowing the molecular weight distribution, and facilitating heat removal, 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 may be 0.01 to 0.1 mol. One type of control agent (1) may be used alone, or two or more types may be used in combination.

[0034] [Polymerizable Monomer] 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.

[0035] 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 of a high propagation reaction rate, a low initiation reaction rate and a low exchange chain transfer reaction rate, and a high side reaction rate. However, according to the method for producing a polymer of the present disclosure, the controlled polymerization of a fluorine-containing monomer can also be favorably carried out, and a polymer with a narrow molecular weight distribution can easily be formed.

[0036] In one embodiment, the polymerizable monomer may be a compound represented by the following formula (M1):

[0037]

[0038] 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 ring structure.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] In formula (M1), R １１ and R １３ , or R １２ and R １４ may 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.

[0044] 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);

[0045] Among these, from the viewpoint of the balance between the propagation reaction rate constant, the exchange chain transfer reaction rate constant, and the chain transfer reaction rate constant for carbon-hydrogen bonding, which is one of the side reactions, it is preferable that the polymerizable monomer comprises at least one selected from the group consisting of vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 1-chloro-1-fluoroethylene, 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.

[0046] In one embodiment, the polymerizable monomer may be a compound represented by the following formula (M2):

[0047]

[0048] 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.

[0049] 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 disclosure, controlled polymerization can be favorably carried out even for the monomer represented by formula (M2).

[0050] X １１ ~X １４In 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.

[0051] When the organic group having 1 to 20 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.

[0052] 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.

[0053] 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.

[0054] 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 -[(CF２ ) 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 represents -[(CF ２ ) ｍ —O]— structure, and is preferably an integer of 1 to 15.

[0055] 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.

[0056] 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.

[0057] Among these, from the viewpoint of the balance between the propagation reaction rate constant, the exchange chain transfer reaction rate constant, and the chain transfer reaction rate constant for carbon-hydrogen bonding, which is one of the side reactions, it is preferable that the polymerizable monomer 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), perfluoro(n-propyl vinyl ether), perfluoro(3-butenyl vinyl ether), (perfluoro-n-butyl)ethylene, (perfluoro-n-hexyl)ethylene, 1,4-divinylperfluorobutane, perfluoro(2,2-dimethyl-1,3-dioxole), and 1,6-divinylperfluorohexane.

[0058] [Other Optional Components] In the method for producing a polymer of the present disclosure, other components such as a radical initiator, a solvent, an emulsifier, a suspending aid, an acid, or an alkali may be further used.

[0059] -Radical initiator- Examples of the radical initiator include azo-based radical initiators and peroxide-based radical initiators. Azo-based radical initiators are preferred because they are less likely to cause side reactions with the tellurium-containing compound. The radical initiators may be used alone or in combination of two or more.

[0060] 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.

[0061] When a polymerization reaction is carried out using an azo radical initiator, the amount of the azo radical initiator used per 1 mol of control agent (1) is preferably 0.01 mol or more, more preferably 0.05 mol or more, and even more preferably 0.1 mol or more, from the viewpoint of improving the polymerization rate. Furthermore, from the viewpoints of achieving a high molecular weight, a narrow molecular weight distribution, and facilitating heat removal, 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 control agent (1) 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.

[0062] Examples of peroxide radical initiators include diisopropyl peroxydicarbonate, tert-butyl peroxypivalate, and benzoyl peroxide.

[0063] 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.

[0064] 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.

[0065] Examples of aqueous solvents include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol.

[0066] 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.

[0067] [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.

[0068] The molecular weight of the polymer can be adjusted by the amount of the control agent (1) and the radical initiator used if necessary, 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. According to the polymer production method of the present disclosure, from the viewpoint of enabling the polymer to have a high molecular weight, the Mn of the polymer may be 15,000 or more, 20,000 or more, 30,000 or more, 40,000 or more, or 50,000 or more. Furthermore, 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. According to the method for producing a polymer of the present disclosure, from the viewpoint that a polymer having a high molecular weight can be obtained, the Mw of the polymer may be 15,000 or more, 20,000 or more, 30,000 or more, 40,000 or more, 50,000 or more, 60,000 or more, or 70,000 or more. 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.

[0069] By using the polymer production method of the present disclosure, it is preferable to control the polydispersity of the obtained polymer to, for example, 2.5 or less. It is more preferable to use the production method of the present disclosure to control the polydispersity to 2.1 or less, 2.0 or less, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, or 1.3 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 by the following formula: PD = Mw (weight average molecular weight) / Mn (number average molecular weight)

[0070] The resulting polymer preferably has a structure derived from the leaving group of the control agent (1) in a part thereof. For example, the polymer may have a Z(CXY-)ｎ The ratio of the number of moles of the structure derived from the leaving group of the control agent (1) to the total number of moles of the polymer is preferably 10 to 100 mol %, more preferably 25 to 100 mol %. The ratio can be measured by NMR.

[0071] [Polymerization Method] A specific example of the polymerization method in the polymer production method of the present disclosure is described below. The control agent (1) and the polymerizable monomer are mixed in a container purged with an inert gas or a container under vacuum pressure. Examples of the inert gas 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 promote polymerization. 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.

[0072] 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 30 to 150°C for 1 to 100 hours, or at 50 to 120°C for 3 to 30 hours. The reaction may be carried out at normal pressure, or under increased or reduced pressure.

[0073] 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.

[0074] A block copolymer, a random copolymer, or an alternating copolymer may be prepared using multiple types of polymerizable monomers. For example, the polymerizable monomer polymerized in the presence of the control agent (1) 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 the control agent (1), and then the product may be reacted with the second polymerizable monomer in the presence of the control agent (1). Alternatively, the first polymerizable monomer may be polymerized in the presence of the control agent (1), and then the product may be reacted with the second polymerizable monomer without the use of the control agent (1) (i.e., by a method different from the polymer production method of the present disclosure). In one embodiment, the polymerizable monomer polymerized in the presence of the control agent (1) 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.

[0075] 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.

[0076] 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 17 are examples, and Examples 18 to 21 are comparative examples.

[0077] In the following examples, nuclear magnetic resonance spectra (NMR) were measured by Fourier transform NMR. １ H-NMR was measured at 400 MHz using tetramethylsilane as the reference with a chemical shift value of 0 ppm. １９F-NMR was measured at 376 MHz using 1,4-bis(trifluoromethyl)benzene as the reference with a chemical shift value of -63.5 ppm. The abbreviations used in the text have the following meanings: s: singlet, d: doublet, t: triplet, m: multiplet, Hz: Hertz. CDCl ３ : deuterated chloroform １ H-NMR: proton nuclear magnetic resonance １９ F-NMR: fluorine-19 nuclear magnetic resonance

[0078] 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).

[0079] 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.

[0080] (Example 1) 1,4-di(n-butyltellanyl)-n-octafluorobutane ((n-BuTe)-C ４ F ８ Synthesis of n-BuTe ２ + IC ４ F ８ I → (n-BuTe)-C ４ F ８-(n-BuTe) In a nitrogen-purged glove box, a magnetic rotor, 3.7 g (10 mmol) of di-n-butyl ditelluride, and 35 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, 1.3 g (35 mmol) of sodium borohydride was added to the flask, and the mixture was stirred at room temperature for 15 minutes. The flask was cooled to -73°C while stirring under a nitrogen atmosphere. Under a nitrogen atmosphere, a solution of 5.0 g (11 mmol) of pre-degassed 1,4-diiodo-n-octafluorobutane dissolved in 60 mL of pre-degassed ethanol was added to the flask at a rate that did not cause the mixture to exceed -50°C. The flask was stirred at room temperature for 21 hours under a nitrogen atmosphere. Under a nitrogen atmosphere, 100 mL of saturated saline solution, previously degassed under reduced pressure, and 200 mL of hexane, previously degassed, 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 hexane, previously degassed, and combined with the organic phase. The organic phase was washed with previously degassed ion-exchanged water. In a nitrogen-substituted 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 under a nitrogen atmosphere, and the residue was distilled under reduced pressure under a nitrogen atmosphere to obtain 1.9 g of the title compound. １ H NMR (400 MHz, CDCl ３ ) δ0.94 (6H, t), δ1.34 to 1.43 (4H, m), δ1.86 to 1.94 (4H, m), δ3.13 (4H, t) １９ F NMR (376 MHz, CDCl ３ ) δ-114.6 (4F, m), δ-84.2 (4F, t) MS (EI+): [M+] 573.9

[0081] The following Examples 2 to 7 are examples that are expected to be synthesizable based on the findings of the present disclosure and known techniques.

[0082] (Example 2) 1,4-di(methyltellanyl)-n-octafluorobutane (MeTeC ４ F ８ Synthesis of TeMe) (MeTe)２ + IC ４ F ８ I → MeTeC ４ F ８ TeMe The title compound is obtained in the same manner as in Example 1, except that di-n-butyl ditelluride in Example 1 is changed to dimethyl ditelluride.

[0083] (Example 3) 1,4-di(phenyltellanyl)-n-octafluorobutane (PhTeC ４ F ８ Synthesis of (PhTe) ２ + IC ４ F ８ I → PhTeC ４ F ８ TePh The title compound is obtained in the same manner as in Example 1, except that di-n-butyl ditelluride is replaced with diphenyl ditelluride.

[0084] Example 4: 1,6-di(n-butyltellanyl)-n-dodecafluorohexane ((n-BuTe)-C ６ F １２ Synthesis of n-BuTe ２ + IC ６ F １２ I → (n-BuTe)-C ６ F １２ -(n-BuTe) The title compound is obtained in the same manner as in Example 1, except that 1,4-diiodooctafluorobutane in Example 1 is changed to 1,6-diiodododecafluorohexane.

[0085] Example 5: Synthesis of 1,4-di(n-butyltellanyl)-perfluoromonoglyme (n-BuTe) ２ + ICF ２ O.C. ２ F ４ OCF ２ I → (n-BuTe)-CF ２ O.C. ２ F ４ OCF ２ -(n-BuTe) The title compound is obtained in the same manner as in Example 1, except that 1,4-diiodoperfluoromonoglyme is used instead of 1,4-diiodooctafluorobutane.

[0086] Example 6: Synthesis of 1,6-di(n-butyltellanyl)-perfluorodiglyme (n-BuTe) ２ + ICF ２ O.C. ２ F ４ O.C. ２ F ４ OCF ２ I → (n-BuTe)-CF ２ O.C. ２ F ４ O.C. ２ F ４ OCF ２ -(n-BuTe) The title compound is obtained in the same manner as in Example 1, except that 1,4-diiodooctafluorobutane is replaced with 1,6-diiodoperfluorodiglyme.

[0087] Example 7: Synthesis of 2,4,6-tris(1,1,2,2-tetrafluoro-2-(n-butyltellanyl)ethyl)-1,3,5-triazine 3(n-BuTe) ２ + 2{2,4,6-tris(1,1,2,2-tetrafluoro-2-iodoethyl)-1,3,5-triazine} → 2{2,4,6-tris(1,1,2,2-tetrafluoro-2-(n-butyltellanyl)ethyl)-1,3,5-triazine} The title compound is obtained in the same manner as in Example 1, except that 1,4-diiodooctafluorobutane in Example 1 is changed to 2,4,6-tris(1,1,2,2-tetrafluoro-2-iodoethyl)-1,3,5-triazine.

[0088] (Example 8) (n-BuTe)-C ４ F ８ Polymerization of tetrafluoroethylene using -(n-BuTe) In 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.), 0.052 g (0.092 mmol) of the (n-BuTe)-C synthesized in Example 1, and ４ F ８-(n-BuTe), and 25 g of 1H-perfluorohexane were charged. 3.7 g (37 mmol) of tetrafluoroethylene was injected, and then 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. The autoclave was cooled in an ice-water bath, and then unreacted tetrafluoroethylene was purged. The resulting polymer solution was dried in vacuum, yielding 0.5 g of a solid.

[0089] (Example 9) (n-BuTe)-C ４ F ８ Copolymerization of ethylene and tetrafluoroethylene using -(n-BuTe) In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.039 g (0.17 mmol) of an azo radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.047 g (0.083 mmol) of the (n-BuTe)-C synthesized in Example 1, and ４ F ８ -(n-BuTe), and 25 g of 1H-perfluorohexane were charged. 0.42 g (15 mmol) of ethylene and 1.8 g (18 mmol) of tetrafluoroethylene were then injected, and stirring was initiated while raising the liquid temperature to 70°C. Stirring was continued at 200 rpm for 5 hours while maintaining the liquid temperature. The autoclave was cooled in an ice-water bath, and unreacted ethylene and tetrafluoroethylene were purged. The resulting polymer solution was dried under vacuum to obtain 1.1 g of a solid. The resulting solid was measured by size exclusion chromatography, revealing Mn = 26,000 and Mw = 34,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.3, indicating that this radical polymerization is characteristic of living radical polymerization.

[0090] (Example 10) (n-BuTe)-C ４ F ８Copolymerization of tetrafluoroethylene and perfluoro(n-propyl vinyl ether) using -(n-BuTe) In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 2.1 g (7.9 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 0.057 g (0.10 mmol) of the (n-BuTe)-C synthesized in Example 1. ４ F ８ -(n-BuTe), and 25 g of 1H-perfluorohexane were charged. After 3.0 g (30 mmol) of tetrafluoroethylene was injected, stirring was initiated while raising the liquid temperature to 80°C. Stirring was carried out at 200 rpm for 4 hours while maintaining the liquid temperature. After cooling the autoclave in an ice-water bath, unreacted tetrafluoroethylene was purged. The obtained polymer solution was dried in vacuum to obtain 1.8 g of a solid.

[0091] (Example 11) (n-BuTe)-C ４ F ８ Polymerization of trifluoroethylene using -(n-BuTe) In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.035 g (0.15 mmol) of an azo radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.042 g (0.073 mmol) of the (n-BuTe)-C synthesized in Example 1, and ４ F ８ -(n-BuTe), and 12 g of acetonitrile were charged. 2.4 g (29 mmol) of trifluoroethylene was injected, and then stirring was initiated while raising the liquid temperature to 80°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 unreacted trifluoroethylene was purged. The resulting polymer solution was dried under vacuum, yielding 0.7 g of a solid. The resulting solid was measured by size exclusion chromatography, revealing Mn = 16,000 and Mw = 21,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.3, indicating that this radical polymerization is characteristic of living radical polymerization.

[0092] Example 12 Block Copolymerization of Polytrifluoroethylene and Styrene In a nitrogen-purged glove box, a 30 mL glass Schlenk tube was charged with a magnetic rotor, 0.53 g of the fluoropolymer synthesized in Example 11, 0.012 g (0.050 mmol) of azo-based radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.), 1.0 g (10 mmol) of styrene, and 12 g of acetonitrile. The Schlenk tube was attached to a water bath at 80°C, and stirring was initiated. Stirring was continued at 400 rpm for 2 hours while maintaining the water bath temperature. The Schlenk tube was cooled in the water bath. The resulting polymer solution was added to 50 mL of pre-degassed methanol to precipitate a solid. The resulting solid was filtered and washed with 10 mL of pre-degassed methanol. The resulting solid was dried in vacuo to obtain 0.7 g of solid. The solid obtained was measured by size exclusion chromatography, which showed that Mn was 19,000 and Mw was 26,000, with a single peak. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.4. The formation of a block copolymer was confirmed from Mn, Mw, polydispersity, and the single peak.

[0093] (Example 13) (n-BuTe)-C ４ F ８ Polymerization of chlorotrifluoroethylene using -(n-BuTe) 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.), 0.068 g (0.12 mmol) of the (n-BuTe)-C synthesized in Example 1, and ４ F ８-(n-BuTe), and 18 g of benzotrifluoride were charged. 14 g (120 mmol) of chlorotrifluoroethylene was injected, and stirring was initiated while raising the liquid temperature to 80°C. Stirring was carried out at 200 rpm for 4 hours while maintaining the liquid temperature. The autoclave was cooled in an ice-water bath, and unreacted chlorotrifluoroethylene was purged. The resulting polymer solution was dried under vacuum to obtain 4.2 g of a solid. The resulting solid was measured by size exclusion chromatography, revealing Mn = 38,000 and Mw = 51,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.3, indicating that this radical polymerization is characteristic of living radical polymerization.

[0094] (Example 14) (n-BuTe)-C ４ F ８ Polymerization of perfluoro(3-butenyl vinyl ether) using -(n-BuTe) In a nitrogen-substituted glove box, a 30 mL glass Schlenk tube was charged with a magnetic rotor, 5.8 g (10 mmol) of perfluoro(3-butenyl vinyl ether), 0.012 g (0.050 mmol) of an azo radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.), and 0.006 g (0.01 mmol) of the (n-BuTe)-C synthesized in Example 1. ４ F ８ -(n-BuTe) was charged. The Schlenk tube was attached to a water bath with a water temperature of 80°C, and stirring was initiated. Stirring was carried out at 400 rpm for 3 hours while maintaining the water bath temperature. The Schlenk tube was cooled in the water bath. The obtained polymer solution was added to 20 mL of pre-degassed n-hexane to precipitate a solid. The resulting mixture was centrifuged and the supernatant was discarded to obtain a solid. The obtained solid was dried in vacuum to obtain 0.4 g of a solid. Measurement of the obtained solid by size exclusion chromatography revealed that Mn = 31,000 and Mw = 38,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.2, indicating that this radical polymerization is characteristic of living radical polymerization.

[0095] (Example 15) (n-BuTe)-C ４ F ８Polymerization of perfluoro(3-butenyl vinyl ether) using -(n-BuTe)-2 0.8 g of a solid was obtained in the same manner as in Example 14, except that the heating and stirring time in Example 14 was changed from 3 hours to 6 hours. When the obtained solid was measured by size exclusion chromatography, it was found to have Mn = 58,000 and Mw = 72,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.2, and Mn also increased with an increase in the monomer conversion compared to Example 14, indicating that this radical polymerization exhibited the characteristics of living radical polymerization.

[0096] (Example 16) (n-BuTe)-C ４ F ８ Copolymerization of vinylidene fluoride and trifluoroethylene using (n-BuTe)-(n-BuTe) In a nitrogen-purged glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.042 g (0.18 mmol) of an azo radical initiator “V-601” (FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.052 g (0.091 mmol) of the (n-BuTe)-C synthesized in Example 1, and ４ F ８ -(n-BuTe), and 12 g of acetonitrile were charged. 1.2 g (19 mmol) of vinylidene fluoride and 1.4 g (17 mmol) of trifluoroethylene were then injected, and stirring was initiated while raising the liquid temperature to 65°C. Stirring was continued at 200 rpm for 5 hours while maintaining the liquid temperature. The autoclave was cooled in an ice-water bath, and unreacted vinylidene fluoride and trifluoroethylene were purged. 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 = 19,000 and Mw = 23,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.2, indicating that this radical polymerization is characteristic of living radical polymerization.

[0097] (Example 17) (n-BuTe)-C ４ F ８Polymerization of vinyl chloride using -(n-BuTe) In a nitrogen-purged glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.12 g (0.52 mmol) of an azo radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.14 g (0.25 mmol) of the (n-BuTe)-C synthesized in Example 1, and ４ F ８ -(n-BuTe), 1.0 g of toluene, and 14 g of ion-exchanged water were charged. 6.3 g (100 mmol) of vinyl chloride was injected, and then stirring was initiated while raising the liquid temperature to 65°C. Stirring was continued at 200 rpm for 4 hours while maintaining the liquid temperature. The autoclave was cooled in an ice-water bath, and unreacted vinyl chloride was purged. The resulting polymer solution was dried under vacuum, yielding 2.3 g of a solid.

[0098] (Example 18) n-BuTeC ４ F ９ Copolymerization of ethylene and tetrafluoroethylene using 0.047 g (0.083 mmol) of (n-BuTe)-C synthesized in Example 1 in Example 9 ４ F ８ -(n-BuTe) was mixed with 0.063 g (0.16 mmol) of n-BuTeC ４ F ９ The same procedure as in Example 9 was carried out except for changing the solid to (n-BuTe)-C. 1.2 g of solid was obtained. The obtained solid was measured by size exclusion chromatography, and Mn was 14,000 and Mw was 18,000. Since Mn relative to the solid yield was smaller than in Example 9, (n-BuTe)-C ４ F ８ -(n-BuTe) is n-BuTeC ４ F ９ It has a higher ability to produce high molecular weight compared to

[0099] (Example 19) n-BuTeC ４ F ９ In Example 11, 0.042 g (0.073 mmol) of (n-BuTe)-C synthesized in Example 1 was used. ４ F ８ -(n-BuTe) was mixed with 0.059 g (0.15 mmol) of n-BuTeC４ F ９ The same procedure as in Example 11 was carried out except for changing the solid to (n-BuTe)-C. 0.9 g of a solid was obtained. The obtained solid was measured by size exclusion chromatography, and the Mn was 9,000 and the Mw was 11,000. Since the Mn relative to the solid yield was smaller than in Example 11, it was determined that (n-BuTe)-C ４ F ８ -(n-BuTe) is n-BuTeC ４ F ９ It has a higher ability to produce high molecular weight compared to

[0100] (Example 20) n-BuTeC ４ F ９ In Example 13, 0.068 g (0.12 mmol) of (n-BuTe)-C synthesized in Example 1 was used. ４ F ８ -(n-BuTe) was mixed with 0.097 g (0.24 mmol) of n-BuTeC ４ F ９ The procedure of Example 13 was repeated except for changing the temperature to (n-BuTe)-C to obtain 4.5 g of a solid. The obtained solid was measured by size exclusion chromatography, and the Mn was 22,000 and the Mw was 27,000. Since the Mn relative to the solid yield was smaller than that of Example 13, it was determined that (n-BuTe)-C ４ F ８ -(n-BuTe) is n-BuTeC ４ F ９ It has a higher ability to produce high molecular weight compared to

[0101] (Example 21) n-BuTeC ４ F ９ In Example 15, 0.006 g (0.01 mmol) of the (n-BuTe)-C synthesized in Example 1 was used to polymerize perfluoro(3-butenyl vinyl ether). ４ F ８ -(n-BuTe) was mixed with 0.008 g (0.02 mmol) of n-BuTeC ４ F ９The same procedure as in Example 15 was carried out except for changing the solid to (n-BuTe)-C. 0.9 g of a solid was obtained. The obtained solid was measured by size exclusion chromatography, and the Mn was 30,000 and the Mw was 36,000. Since the Mn relative to the solid yield was smaller than in Example 15, it was determined that (n-BuTe)-C ４ F ８ -(n-BuTe) is n-BuTeC ４ F ９ It has a higher ability to produce high molecular weight compared to

[0102] The disclosure of Japanese Patent Application No. 2024-065988, filed on April 16, 2024, 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 the following formula (1): (R-Te-CXY) ｎ Z ... (1) In formula (1), n ​​represents an integer of 2 to 4; each R independently 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; each X independently represents a fluorine atom or CF ２ A and Y each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or an organic group having 1 to 12 carbon atoms; Z represents a single bond or an n-valent group; and X and Y each independently bond to each other to form a cyclic structure or not.

2. The tellurium-containing compound according to claim 1, wherein Z in formula (1) is a single bond, an oxygen atom, or a fluoroalkylene group having 1 to 12 carbon atoms and which may or may not contain an oxygen atom.

3. A method for producing a polymer, comprising polymerizing a compound having a carbon-carbon double bond in the presence of the tellurium-containing compound according to claim 1.

4. The method for producing a polymer according to claim 3, 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), perfluoro(n-propyl vinyl ether), perfluoro(3-butenyl vinyl ether), (perfluoro-n-butyl)ethylene, (perfluoro-n-hexyl)ethylene, 1,4-divinylperfluorobutane, perfluoro(2,2-dimethyl-1,3-dioxole), and 1,6-divinylperfluorohexane.

5. A method for producing the polymer according to claim 3, which is carried out in the presence of an azo radical initiator.

6. The method for producing a polymer according to claim 5, wherein 0.01 to 100 mol of the azo radical initiator is used per 1 mol of the compound represented by formula (1).

7. The method for producing a polymer according to any one of claims 3 to 6, wherein the polydispersity of the resulting polymer is 2.0 or less.

8. The method for producing a polymer according to any one of claims 3 to 6, 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 is block copolymerized with a compound having a second carbon-carbon double bond different from the compound having the first carbon-carbon double bond.

9. The method for producing a polymer according to any one of claims 3 to 6, 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.

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