Method for producing tellurium-compound-containing composition and method for producing polymer

Abstract

Provided is a method for producing a tellurium-compound-containing composition in which a raw material containing a tellurium compound represented by formula (10): R4Te-TeR5 is reacted to obtain a crude product containing at least one tellurium compound represented by any of formulas (1)-(4), which are reaction products, and the crude product is purified. In the tellurium-compound-containing composition, the content of the tellurium compound represented by formula (10) is 20 mol% or less relative to the total content of the at least one tellurium compound represented by any of formulas (1)-(4) and the tellurium compound represented by formula (10). Also provided is a method for producing a polymer using the tellurium-compound-containing composition.

Description

Method for producing a tellurium compound-containing composition and method for producing a polymer

[0001] The present disclosure relates to methods for producing tellurium compound-containing compositions and methods for producing 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] 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. The inventors have investigated controlled polymerization methods with excellent controllability of molecular weight distribution and found that using a specific control agent described below as a control agent can improve the controllability of molecular weight distribution. On the other hand, it has also been found that when controlled polymerization is performed using a specific control agent, the induction period until the reaction starts is relatively long, and productivity may be insufficient. In view of the above circumstances, the present disclosure relates to a method for producing a tellurium compound-containing composition and a method for producing a polymer, which can shorten the induction period in controlled polymerization.

[0006] Means for solving the above problems include the following aspects: <1> A method for producing a tellurium compound-containing composition, comprising reacting a raw material containing a tellurium compound represented by the following formula (10), obtaining a reaction product, a crude product containing at least one tellurium compound represented by any one of the following formulas (1) to (4), and purifying the crude product, in which the content of the tellurium compound represented by the following formula (10) in the tellurium compound-containing composition is 20 mol % or less based on the total content of the at least one tellurium compound represented by any one of the formulas (1) to (4) and the tellurium compound represented by the formula (10). R ４ Te-TeR ５ ... (10) In the formulas (1) to (4) and (10), 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; R ４ and R ５ each independently represents a monovalent organic group having 1 to 18 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 a monovalent 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 to form a cyclic structure.<2> A method for producing a polymer, comprising polymerizing a compound having a carbon-carbon double bond in the presence of the tellurium compound-containing composition obtained by the method described in <1>.<3> A method for producing a polymer according to <2>, 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.<4> A method for producing a polymer according to <2> or <3>, wherein the method is carried out in the presence of an azo-based radical initiator. <5> The method for producing a polymer according to <4>, wherein 0.01 to 100 mol of the azo-based radical initiator is used per 1 mol in total of at least one tellurium compound represented by any one of formulas (1) to (4). <6> The method for producing a polymer according to any one of <2> to <5>, wherein the polydispersity of the resulting polymer is 2.0 or less. <7> The method for producing a polymer according to any one of <2> 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. <8> The method for producing a polymer according to any one of <2> 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.

[0007] According to the present disclosure, there are provided a method for producing a tellurium compound-containing composition and a method for producing a polymer, which can shorten the induction period in controlled polymerization.

[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] <Method for Producing a Tellurium Compound-Containing Composition> In one embodiment of the present disclosure, there is provided a method for producing a tellurium compound-containing composition, comprising reacting a raw material containing a tellurium compound represented by the following formula (10), obtaining a reaction product, a crude product containing at least one tellurium compound represented by any one of the following formulas (1) to (4), and purifying the crude product, wherein the content of the tellurium compound represented by the following formula (10) in the tellurium compound-containing composition is 20 mol % or less based on the total content of the at least one tellurium compound represented by any one of the formulas (1) to (4) and the tellurium compound represented by the formula (10) (hereinafter also referred to as the "method for producing a tellurium compound-containing composition of the present disclosure"): R ４ Te-TeR ５ ... (10) In the formulas (1) to (4) and (10), 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; R ４ and R ５ each independently represents a monovalent organic group having 1 to 18 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 a monovalent organic group having 1 to 12 carbon atoms, and in formula (2) and formula (3), Y and Rｆ may or may not be linked to form a ring structure.

[0011] The tellurium compounds represented by formulas (1) to (4) can function as control agents in controlled polymerization. Hereinafter, the tellurium compounds represented by formulas (1) to (4) are collectively referred to as "specific control agents." The tellurium compounds represented by formulas (1) to (4) are also referred to as "specific control agent (1)," "specific control agent (2)," "specific control agent (3)," and "specific control agent (4)," respectively. The tellurium compound represented by formula (10) is a compound that serves as a raw material for specific control agents (1) to (4). Hereinafter, the tellurium compound represented by formula (10) is also referred to as "compound (10)." In the method for producing a tellurium compound-containing composition of the present disclosure, the step of reacting a raw material containing compound (10) to obtain a crude product containing at least one of the specific control agents (1) to (4) as a reaction product is also referred to as the "reaction step." The step of purifying the crude product is also referred to as the "purification step."

[0012] The inventors have found that in controlled polymerization based on the TERP method, the molecular weight distribution can be suitably controlled by using a specific control agent instead of a conventional control agent. The mechanism behind this is not clear, but is presumed to be as follows. In controlled polymerization based on the TERP method, the 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 ａThe 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.

[0013] 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 ３ Each X is 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 reinitiation rate. Furthermore, a fast reinitiation rate tends to shorten the induction period until polymerization begins, thereby shortening the reaction time.

[0014] On the other hand, even when specific control agents (1) to (4) are used, the relatively long induction period required until the reaction begins can sometimes result in insufficient productivity. In response to this, the inventors have discovered that the induction period can be shortened by the method for producing a tellurium compound-containing composition disclosed herein. In the method for producing a tellurium compound-containing composition disclosed herein, a crude product containing at least one of the specific control agents (1) to (4) is obtained by reacting a raw material containing compound (10), and the crude product is then purified to produce a tellurium compound-containing composition. In the obtained tellurium compound-containing composition, the content of compound (10) is 20 mol % or less relative to the total content of the specific control agents (1) to (4) and compound (10). The inventors have discovered that the induction period can be shortened by producing a tellurium compound-containing composition so that the content of compound (10) satisfies the above-mentioned ratio, and then performing controlled polymerization using the tellurium compound-containing composition as a control agent. One of the reasons for this is presumably that by reducing the proportion of compound (10) in the reaction system, the inhibitory effect of compound (10) on the initiation of polymerization can be suppressed.

[0015] [Specific Control Agents (1) to (4)] The specific control agents (1) to (4) are tellurium compounds represented by formulas (1) to (4), respectively.

[0016] 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, from the viewpoint of synthesizability (that is, ease of synthesis) and chain transfer reactivity, a linear alkyl group is preferred, and an n-butyl group is more preferred.

[0017] 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 ３From the viewpoint of the balance between the chain transfer reaction rate and the reinitiation rate, each independently is preferably a hydrogen atom, and more preferably both 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, from the viewpoint of the balance between the chain transfer reaction rate and the reinitiation rate, 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).

[0018] In formula (2), Ar represents a substituted or unsubstituted aryl group having 5 to 18 atoms constituting the aromatic ring. From the viewpoints of synthesis and chain transfer reactivity, 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 groups and naphthyl groups; and heteroaryl groups such as pyridyl groups, pyrrole groups, furyl groups, and thienyl groups. Among these, from the viewpoint of synthesis, 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 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 or 2, or 1.

[0019] In formulas (2) and (3), R ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms. ｆ From the viewpoint of synthesizing property and the balance between the chain transfer reaction rate and the reinitiation rate, a perfluoroalkyl group having 1 to 6 carbon atoms is preferred, and a perfluoroalkyl group having 1 to 3 carbon atoms is more preferred. 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.

[0020] 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 from the viewpoints of synthesis and chain transfer reactivity. 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, 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 or 2, or 1.

[0021] In formulas (1) and (4), X represents a hydrogen atom, a fluorine atom, or CF ２The monovalent organic group having 1 to 12 carbon atoms represented by Z is 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 from the viewpoints of synthesis and chain transfer reactivity. 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. Among these, from the viewpoint of suppressing chain transfer of carbon-hydrogen bonds, which is a side reaction during polymerization, 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 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 12 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 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. 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 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 In one embodiment, X is CF ２ The group -Z is preferred.

[0022] In formulas (2) and (3), Y is CF ２ -Z group or CHF-Z group, where Z represents a fluorine atom or a monovalent 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.

[0023] 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.

[0024] [Compound (10)] Compound (10) is a compound that serves as a raw material for the specific control agents (1) to (4).

[0025] In formula (10), R ４ and R ５ R each independently represents a monovalent organic group having 1 to 18 carbon atoms. ４ and R ５may be the same or different, and are preferably the same from the viewpoint of efficiently producing the specific control agent. The number of carbon atoms in the monovalent organic group having 1 to 18 carbon atoms may be 1 to 12 or 1 to 6. R ４ and R ５ can be selected depending on the specific regulators (1) to (4) that are the target products.

[0026] When producing the specific control agent (1), R ４ and R ５ As the R of the target specific control agent (1), １ Preferred are groups corresponding to R ４ and R ５ are each independently preferably 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, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, cyclopentyl group, n-hexyl group, and cyclohexyl group. In one embodiment, R ４ and R ５ As the alkyl group, a linear alkyl group is preferred, and a methyl group, an ethyl group, or an n-butyl group is more preferred.

[0027] When producing the specific control agent (2), R ４ and R ５ is preferably a group corresponding to Ar of the target specific control agent (2). ４ and R ５are each independently preferably a substituted or unsubstituted aryl group having 5 to 18 atoms constituting the aromatic ring, and more 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, pyrrole, furyl, and thienyl. 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 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 or 2, or 1.

[0028] When producing the specific control agent (3), R ４ and R ５ is preferably a group corresponding to A in the target specific control agent (3). ４ and R ５are each independently preferably 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, or n-butyl is preferred. Examples of the substituted alkyl group having 1 to 12 carbon atoms include alkyl groups in which any hydrogen atom bonded to the 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 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, 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 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 even 1.

[0029] When producing the specific control agent (4), R ４ and R ５ is preferably a group corresponding to A in the target specific control agent (4). ４ and R ５are each independently preferably 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, or n-butyl is preferred. Examples of the substituted alkyl group having 1 to 12 carbon atoms include alkyl groups in which any hydrogen atom bonded to the 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 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, 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 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 even 1.

[0030] Examples of compound (10) include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, di-n-butyl ditelluride, di-s-butyl ditelluride, di-t-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis-(p-methoxyphenyl) ditelluride, bis-(p-aminophenyl) ditelluride, bis-(p-nitrophenyl) ditelluride, bis-(p-cyanophenyl) ditelluride, bis-(p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride, and dipyridyl ditelluride. Dimethyl ditelluride and di-n-butyl ditelluride are preferred from the viewpoints of availability and suppression of side reactions during polymerization. The reaction step and purification step are described in detail below.

[0031] [1. Reaction Step] In the reaction step, a raw material containing compound (10) is reacted to obtain a crude product containing at least one of specific control agents (1) to (4) as a reaction product. Compound (10) reacts with a compound capable of reacting with compound (10) (also referred to as a "reactant compound") to produce the specific control agents (1) to (4) as a reaction product.

[0032] The details of the compound (10) are as described above. The compound (10) may be used alone or in combination of two or more.

[0033] The reactant compound is a compound capable of reacting with compound (10) to produce specific control agents (1) to (4). One reactant compound may be used alone, or two or more reactants may be used in combination.

[0034] When producing the specific control agent (1), the reactant compound is —CF ２ X, where X is the same as in formula (1). In one embodiment, the reactant compound may have the structure of X ２ -CF ２ The compound may be a compound represented by X. Here, the definition of X is the same as that in formula (1), and X ２ represents an iodine atom or a bromine atom. In this case, the compound (10) and the reactant compound produce the specific control agent (1) by the following reaction: R ４ Te-TeR ５+ 2 (X ２ -CF ２ X) → R ４ TeCF ２ X + R ５ TeCF ２ X

[0035] When producing the specific control agent (2), the reactant compound is -CFR ｆ Y, where R ｆ The definitions of X and Y are the same as those in formula (2). ２ -CFR ｆ Y, where R ｆ and Y are defined as in formula (2), and X ２ represents an iodine atom or a bromine atom. In this case, the compound (10) and the reactant compound produce the specific control agent (2) by the following reaction: R ４ Te-TeR ５ + 2 (X ２ -CFR ｆ Y) → R ４ TeCFR ｆ Y + R ５ TeCFR ｆ Y

[0036] When producing the specific control agent (3), the reactant compound is —CHR ｆ Y, where R ｆ The definitions of X and Y are the same as those in formula (3). In one embodiment, the reactant compound is X ２ -CHR ｆ Y, where R ｆ and Y are defined as in formula (3), and X ２ represents an iodine atom or a bromine atom. In this case, the compound (10) and the reactant compound produce the specific control agent (3) by the following reaction: R ４ Te-TeR ５ + 2 (X ２ -CHR ｆ Y) → R ４ TeCHR ｆ Y + R ５ TeCHR ｆ Y

[0037] When producing the specific control agent (4), the reactant compound is -CHFCR ２ R ３ X, where R ２ , R ３ and X are defined as in formula (4). In one embodiment, the reactant compound is X ２ -CHFCR ２ R ３ X, where R ２ , R ３ , and X are defined as in formula (4), and X ２ represents an iodine atom or a bromine atom. In this case, the compound (10) and the reactant compound produce the specific control agent (4) by the following reaction: R ４ Te-TeR ５ + 2 (X ２ -CHFCR ２ R ３ X) → R ４ TeCHFCR ２ R ３ X + R ５ TeCHFCR ２ R ３ X

[0038] The reaction temperature when reacting raw materials containing compound (10) is preferably −100 to −20° C., more preferably −100 to −50° C., from the viewpoint of suppressing side reactions. The reaction time is preferably 2 to 24 hours, more preferably 4 to 18 hours, from the viewpoint of balancing the raw material conversion rate and selectivity. From the viewpoint of suppressing side reactions, the reaction is preferably carried out under an inert atmosphere such as nitrogen gas, argon gas, or helium gas.

[0039] The molar ratio of compound (10) to the reactant compound added in the reaction is preferably 1:2 to 1:10, more preferably 1:2.5 to 1:8, and even more preferably 1:3 to 1:6, from the viewpoint of a balance between promoting the target reaction and suppressing side reactions.

[0040] An organic solvent can be used as the reaction solvent. One type of organic solvent may be used alone, or two or more types may be used in combination. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, tert-butyl alcohol, ethylene glycol, and propylene glycol, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), diethyl ether, tert-butyl methyl ether, tetrahydrofuran (THF), 1,4-dioxane, ethyl acetate, acetonitrile, dichloromethane, chloroform, benzene, toluene, xylene, 1H-perfluorohexane, 1H,1H,1H,2H,2H-perfluorooctane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, and benzotrifluoride.

[0041] To promote the reaction between compound (10) and the reactant, a reducing agent may be added to the reaction. Examples of the reducing agent include borohydride compounds such as sodium borohydride and lithium borohydride; and aluminum hydride compounds such as lithium aluminum hydride and diisobutylaluminum hydride.

[0042] [2. Purification Step] In the purification step, the crude product obtained in the reaction step is purified. As a result, the content of compound (10) is adjusted to 20 mol% or less based on the total content of specific control agents (1) to (4) and compound (10). Purification methods include extraction, distillation, sublimation, and column chromatography. One type of purification method may be used, or two or more types of purification methods may be combined.

[0043] From the viewpoint of balancing recovery rate and operational simplicity, solvent extraction is preferred for extraction, and solvent extraction using water or an aqueous solution and an organic solvent is more preferred. Examples of aqueous solutions include aqueous sodium chloride, aqueous ammonium chloride, aqueous sodium bicarbonate, and aqueous sodium carbonate. Examples of organic solvents include pentane, hexane, diethyl ether, tert-butyl methyl ether, dichloromethane, chloroform, ethyl acetate, 1H-perfluorohexane, and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether. From the viewpoint of preventing deterioration of the target product, water, aqueous solutions, and organic solvents may be degassed before the extraction. From the viewpoint of preventing deterioration of the target product, extraction may be performed under an inert atmosphere such as nitrogen gas, argon gas, or helium gas.

[0044] The distillation may be simple distillation or continuous distillation (including flash distillation). The distillation may be atmospheric distillation, reduced pressure distillation (including vacuum distillation), or pressurized distillation. From the viewpoint of suppressing deterioration of the target product, the distillation is preferably carried out under an inert atmosphere such as nitrogen gas, argon gas, or helium gas.

[0045] In one embodiment, the crude product is preferably purified by solvent extraction followed by distillation.

[0046] In the tellurium compound-containing composition obtained through the purification step, the content of compound (10) is 20 mol% or less relative to the total content of specific control agents (1) to (4) and compound (10). Here, the "total content of specific control agents (1) to (4) and compound (10)" is synonymous with the "total content of at least one tellurium compound represented by any one of formulas (1) to (4) and the tellurium compound represented by formula (10)." For example, if specific control agent (1) and compound (10) are present in the tellurium compound-containing composition but specific control agents (2) to (4) are not present, the "total content" refers to the total content of specific control agent (1) and compound (10). If specific control agent (1), specific control agent (2), and compound (10) are present in the tellurium compound-containing composition but specific control agent (3) and specific control agent (4) are not present, the "total content" refers to the total content of specific control agent (1), specific control agent (2), and compound (10). From the viewpoint of shortening the induction period in controlled polymerization, the content of the compound (10) is preferably 15 mol % or less, more preferably 10 mol % or less, even more preferably 5 mol % or less, particularly preferably 1 mol % or less, and extremely preferably substantially 0 mol %. Here, "substantially 0 mol %" means that the compound (10) is not detected. In the present disclosure, the "tellurium compound-containing composition" intends a composition containing at least one of the specific control agents (1) to (4) and other impurities, but even if the composition does not contain impurities, it is conveniently included in the term "tellurium compound-containing composition." The content of the compound (10) in the tellurium compound-containing composition is １ This is confirmed from the ratio of the peak area of ​​the compound (10) to the peak area of ​​the specific control agents (1) to (4) in H-NMR. １ For H-NMR measurement, the tellurium compound-containing composition may be dissolved in an organic solvent, such as deuterated chloroform, acetonitrile-d3, acetone-d6, dimethyl sulfoxide-d6, or tetrahydrofuran-d8.

[0047] <Method for Producing a Polymer> In one embodiment of the present disclosure, there is provided a method for producing a polymer (hereinafter also referred to as the "method for producing a polymer of the present disclosure"), which comprises polymerizing a compound having a carbon-carbon double bond in the presence of a tellurium compound-containing composition obtained by the method for producing a tellurium compound-containing composition of the present disclosure. According to the method for producing a polymer of the present disclosure, the induction period in controlled polymerization can be shortened, and productivity can be improved. Hereinafter, a compound having a carbon-carbon double bond will also be referred to as a "polymerizable monomer."

[0048] In the method for producing a polymer according to the present disclosure, in addition to the tellurium compound-containing composition obtained by the method for producing a tellurium compound-containing composition according to the present disclosure, other components such as a radical initiator, a solvent, an emulsifier, a suspending aid, an acid or an alkali, etc. Each component used in the method for producing a polymer according to the present disclosure, the polymer produced therefrom, and the polymerization method will be described in detail below.

[0049] [Tellurium Compound-Containing Composition Containing Specific Control Agent] Details of the tellurium compound-containing composition containing a specific control agent are as described above. The amount of the specific control agent used per 1 mol of polymerizable monomer is preferably 0.001 mol or more, and more preferably 0.005 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 0.001 to 0.5 mol, and even more preferably 0.05 to 0.1 mol. One specific control agent may be used alone, or two or more specific control agents may be used in combination.

[0050] [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.

[0051] 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 rate of side reactions such as carbon-hydrogen bond chain transfer reactions. 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.

[0052] In one embodiment, the polymerizable monomer may be a compound represented by the following formula (M1):

[0053]

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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);

[0061] 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.

[0062] In one embodiment, the polymerizable monomer may be a compound represented by the following formula (M2):

[0063]

[0064] 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.

[0065] 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).

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] [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.

[0074] - Radical initiator - Examples of the radical initiator include azo-based radical initiators, peroxide-based radical initiators, etc. The radical initiators may be used alone or in combination of two or more.

[0075] 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.

[0076] 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, 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 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.

[0077] Examples of peroxide radical initiators include diisopropyl peroxydicarbonate, tert-butyl peroxypivalate, and benzoyl peroxide.

[0078] 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.

[0079] 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.

[0080] Examples of aqueous solvents include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol.

[0081] 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.

[0082] [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.

[0083] 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.

[0084] 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 polymer 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)

[0085] 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 ２ It 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.

[0086] [Polymerization Method] A specific example of the polymerization method in the polymer production method of the present disclosure 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.

[0087] 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.

[0088] 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.

[0089] Multiple types of polymerizable monomers may be used to prepare block copolymers, random copolymers, or alternating copolymers. 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 a second polymerizable monomer in the presence of a 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 a second polymerizable monomer without using a specific control agent (i.e., by a method different from the polymer production method of the present disclosure). In one embodiment, 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.

[0090] 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.

[0091] 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.

[0092] (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).

[0093]

[0094] 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.

[0095] (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).

[0096]

[0097] 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.

[0098] (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).

[0099]

[0100] 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.

[0101] (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).

[0102]

[0103] 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.

[0104] 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 In formula (8), the hydrogen atom or the substituent bonded to the carbon atom is the same. 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 favorable molecular weight control.

[0105] 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, a pyrrole 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 etc. 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.

[0106] In formulas (5) to (8), R ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms. ｆis 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

[0107] 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 9 are synthesis examples, of which Examples 1, 2, 4, 6, and 8 are working examples, and Examples 3, 5, 7, and 9 are comparative examples. Examples 10 to 21 are polymerization examples, of which Examples 10, 11, 13, 14, 16, 18, and 20 are working examples, and Examples 12, 15, 17, 19, and 21 are comparative examples.

[0108] 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

[0109] 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).

[0110] 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.

[0111] (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 revealed that n-BuTeC was present in the liquid. ４ F ９ and (n-BuTe) ２ When the ratio of n-BuTeC ４ F ９ is 99.5 mol% or more, (n-BuTe) ２ was 0.5 mol % or less. 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

[0112] (Example 2) (n-butyl) n-nonafluorobutyl telluride (n-BuTeC) containing a small amount of impurities ４ F ９ Synthesis of (n-BuTe) ２ + n-C ４ F ９ I → 2n-BuTeC ４ F ９ The procedure of Example 1 was repeated except that, instead of distilling off the title compound in the vacuum distillation in Example 1, the title compound was not distilled off but was recovered from the residue, to obtain 3.5 g of a liquid. １ H-NMR revealed that n-BuTeC was present in the liquid. ４ F ９ and (n-BuTe) ２ When the ratio of n-BuTeC ４ F ９ is 98 mol%, (n-BuTe) ２ was 2 mol %.

[0113] (Example 3) (n-butyl) n-nonafluorobutyl telluride (n-BuTeC) containing a large amount of impurities ４ F ９ Synthesis of (n-BuTe) ２ + n-C ４ F ９ I → 2n-BuTeC ４ F ９ The same procedure as in Example 2 was repeated except that the liquid temperature during addition of n-nonafluorobutyl iodide was maintained at 0° C. to 10° C. instead of -50° C. or lower, to obtain 2.9 g of a liquid. １ H-NMR revealed that n-BuTeC was present in the liquid. ４ F ９ and (n-BuTe) ２ When the ratio of n-BuTeC ４ F ９ is 78 mol%, (n-BuTe) ２ was 22 mol%.

[0114] (Example 4) (1,1,1,2,3,3,3-heptafluoroisopropyl)phenyl telluride (PhTeCF(CF ３ ) ２Synthesis 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 revealed that PhTeCF (CF ３ ) ２ and (PhTe) ２ When the ratio of PhTeCF (CF ３ ) ２ is 99.5 mol% or more, (PhTe) ２ was 0.5 mol % or less. 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

[0115] (Example 5) (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 procedures as in Example 4 were carried out except that the liquid temperature when adding 1,1,1,2,3,3,3-heptafluoroisopropyl iodide was kept at 0°C or higher and 10°C or lower instead of keeping it at -50°C or lower in Example 4, and the title compound was recovered from the residue without being distilled out instead of being distilled out by reduced pressure distillation, to obtain 3.4 g of a liquid. １H-NMR revealed that PhTeCF (CF ３ ) ２ and (PhTe) ２ When the ratio of PhTeCF (CF ３ ) ２ is 69 mol%, (PhTe) ２ was 31 mol%.

[0116] (Example 6) (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 4 was conducted except that 15 g (50 mmol) of 1,1,1,2,3,3,3-heptafluoroisopropyl iodide in Example 4 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 revealed that PhTeCH(CF ３ ) ２ and (PhTe) ２ When the ratio of PhTeCH(CF ３ ) ２ is 99.5 mol% or more, (PhTe) ２ was 0.5 mol % or less. 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

[0117] (Example 7) (1,1,1,3,3,3-hexafluoroisopropyl)phenyl telluride (PhTeCH(CF)) containing a large amount of impurity ３ ) ２ Synthesis of (PhTe) ２ +CF ３ CHICF３ → 2PhTeCH (CF ３ ) ２ The same procedures as in Example 6 were carried out except that the liquid temperature when adding 1,1,1,3,3,3-hexafluoroisopropyl iodide was kept at 0°C or higher and 10°C or lower instead of keeping it at -50°C or lower in Example 6, and the title compound was recovered from the residue without being distilled out instead of being distilled out by reduced pressure distillation, to obtain 2.0 g of a liquid. １ H-NMR revealed that PhTeCH(CF ３ ) ２ and (PhTe) ２ When the ratio of PhTeCH(CF ３ ) ２ is 76 mol%, (PhTe) ２ was 24 mol%.

[0118] (Example 8) (n-butyl) 1,3,3,3-tetrafluoropropyl telluride (n-BuTeCHFCH ２ CF ３ Synthesis of (n-BuTe) ２ + n-CF ３ CH 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 revealed that n-BuTeCHFCH contained in the liquid ２ CF ３ and (n-BuTe) ２ When the ratio of n-BuTeCHFCH ２ CF ３ is 99.5 mol% or more, (n-BuTe) ２ was 0.5 mol % or less. 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

[0119] (Example 9) (n-butyl) 1,3,3,3-tetrafluoropropyl telluride (n-BuTeCHFCH) containing a large amount of impurities ２ CF ３ Synthesis of (n-BuTe) ２ + n-CF ３ CH ２ CHFI → 2n-BuTeCHFCH ２ CF ３ The same procedures as in Example 8 were carried out except that the liquid temperature when adding 1,3,3,3-tetrafluoropropyl iodide was kept at 0°C or higher and 10°C or lower instead of keeping it at -50°C or lower in Example 8, and the title compound was recovered from the residue without being distilled out instead of being distilled out by reduced pressure distillation, to obtain 2.5 g of a liquid. １ H-NMR revealed that n-BuTeCHFCH contained in the liquid ２ CF ３ and (n-BuTe) ２ When the ratio of n-BuTeCHFCH ２ CF ３ is 54 mol%, (n-BuTe) ２ was 46 mol%.

[0120] (Example 10) n-BuTeC ４ F ９ In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.046 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 started while raising the liquid temperature to 65°C. Within 5 minutes after the temperature increase was complete, the gas phase pressure began to decrease. While maintaining the liquid temperature, stirring was carried out at 200 rpm (200 revolutions per minute) for 5 hours. After the autoclave was cooled in an ice-water bath, unreacted tetrafluoroethylene was purged.

[0121] The resulting polymerization reaction solution was dried in vacuum to obtain 0.4 g of a solid.

[0122] (Example 11) n-BuTeC containing a small amount of impurities ４ F ９ Polymerization of tetrafluoroethylene using 0.074 g (0.18 mmol) of n-BuTeC synthesized in Example 1 in Example 10 ４ F ９ 0.076 g (0.18 mmol) of n-BuTeC ４ F ９ The same procedure as in Example 10 was carried out except that the liquid synthesized in Example 2 (containing 1,2-dichloro-2,4-dichloro-1,4 ...

[0123] (Example 12) n-BuTeC containing a large amount of impurities ４ F ９ Polymerization of tetrafluoroethylene using 0.074 g (0.18 mmol) of n-BuTeC synthesized in Example 1 in Example 10 ４ F ９ 0.094 g (0.18 mmol of n-BuTeC ４ F ９ The same procedure as in Example 10 was carried out except that the liquid synthesized in Example 3 (containing 2-methyl-2-propanol) was used instead. However, the gas phase pressure did not decrease within 5 hours after the completion of the temperature increase, and no solid was obtained.

[0124] (Example 13) n-BuTeC ４ F ９In 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. Within 5 minutes after the temperature increase was complete, the gas phase pressure began to decrease. While maintaining the liquid temperature, stirring was carried out at 200 rpm for 4 hours. After the autoclave was cooled in an ice-water bath, unreacted chlorotrifluoroethylene was purged.

[0125] The resulting polymerization reaction solution was dried under vacuum to obtain 4.5 g of a solid. The resulting solid was measured by size exclusion chromatography, and found to have 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.

[0126] (Example 14) n-BuTeC containing a small amount of impurities ４ F ９ Polymerization of chlorotrifluoroethylene using 0.097 g (0.24 mmol) of n-BuTeC synthesized in Example 1 in Example 13 ４ F ９ 0.099 g (0.24 mmol) of n-BuTeC ４ F ９ The same procedure as in Example 13 was carried out except that the liquid synthesized in Example 2 (containing 1,2-dichloro-2,4-dichloro-1,4 ...

[0127] The obtained solid was measured by size exclusion chromatography, and it was found that Mn was 21,000 and Mw was 27,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.3, and this radical polymerization shows the characteristics of living radical polymerization.

[0128] (Example 15) n-BuTeC containing a large amount of impurities ４ F ９ Polymerization of chlorotrifluoroethylene using 0.074 g (0.18 mmol) of n-BuTeC synthesized in Example 1 in Example 13 ４ F ９ 0.12 g (0.24 mmol) of n-BuTeC ４ F ９ The same procedure as in Example 13 was carried out except that the liquid synthesized in Example 3 (containing 1,2-dichloro-2,4 ...

[0129] The obtained solid was measured by size exclusion chromatography, and it was found that Mn was 11,000 and Mw was 14,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.3, and this radical polymerization shows the characteristics of living radical polymerization.

[0130] (Example 16) 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 4, 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.

[0131] 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.

[0132] (Example 17) PhTeCF(CF) containing a large amount of impurities ３ ) ２ Copolymerization of vinylidene fluoride and hexafluoropropylene using 0.070 g (0.19 mmol) of PhTeCF(CF) synthesized in Example 4 in Example 16 ３ ) ２ 0.070 g (0.19 mmol) of PhTeCF(CF ３ ) ２ The same procedure as in Example 16 was carried out except that the liquid synthesized in Example 5 (including methyl methyl acrylate) was used instead. However, the gas phase pressure did not decrease within 5 hours after the completion of the temperature increase, and no solid was obtained. In Example 16, a solid polymer was obtained in the same polymerization time, so it can be said that the induction period was longer than in Example 16.

[0133] (Example 18) PhTeCH(CF ３ ) ２ A 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 6. 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.

[0134] 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.

[0135] (Example 19) PhTeCH(CF) containing a large amount of impurities ３ ) ２ In Example 18, 0.089 g (0.25 mmol) of PhTeCH(CF) synthesized in Example 6 was used for polymerization of 1,4-divinyloctafluorobutane. ３ ) ２ 0.090 g (0.25 mmol) of PhTeCH(CF ３ ) ２ When the same procedure as in Example 18 was carried out except that the liquid synthesized in Example 7 was used instead (containing 1,000 or more), no components with an Mn of 1,000 or more were detected. In Example 18, a polymer with an Mn of 1,000 or more was obtained in the same polymerization time, which means that the induction period was longer than in Example 18.

[0136] (Example 20) n-BuTeCHFCH ２ CF ３ 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.), 0.044 g (0.10 mmol) of n-BuTeCHFCH synthesized in Example 8, ２ CF ３ , 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.

[0137] The resulting polymer solution was dried under vacuum to obtain 0.7 g of a solid. The resulting solid was measured by size exclusion chromatography, and found to have Mn=10,000 and Mw=13,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.3, indicating that this radical polymerization is characteristic of living radical polymerization.

[0138] (Example 21) n-BuTeCHFCH containing a large amount of impurities ２ CF ３ In Example 20, 0.044 g (0.10 mmol) of n-BuTeCHFCH synthesized in Example 8 was used. ２ CF ３ 0.083 g (0.10 mmol of n-BuTeCHFCH ２ CF ３ The same procedure as in Example 20 was carried out except that the liquid synthesized in Example 9 (including hydroxypropyl methylcellulose) was used instead. However, the gas phase pressure did not decrease within 5 hours after the completion of the temperature increase, and no solid was obtained. In Example 20, a solid polymer was obtained in the same polymerization time, so it can be said that the induction period was longer than in Example 20.

[0139] From Examples 10 to 21, when the induction period is defined as the time required from the completion of the temperature increase of the reaction liquid until the gas phase pressure decreases, it was found that the induction period became longer as the content of compound (10) in the tellurium compound-containing composition increased, and therefore the induction period until the initiation of polymerization was shortened when the content of compound (10) was reduced by sufficient purification of specific control agents (1) to (4).

[0140] The disclosure of Japanese Patent Application No. 2024-066059, 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 method for producing a tellurium compound-containing composition, comprising reacting a raw material containing a tellurium compound represented by the following formula (10), obtaining a crude product containing at least one tellurium compound represented by any one of the following formulae (1) to (4), which is a reaction product, and purifying the crude product, wherein the content of the tellurium compound represented by the following formula (10) in the tellurium compound-containing composition is 20 mol % or less based on the total content of the at least one tellurium compound represented by any one of the formulae (1) to (4) and the tellurium compound represented by the formula (10). R ４ Te-TeR ５ ... (10) In the formulas (1) to (4) and (10), 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; R ４ and R ５ each independently represents a monovalent organic group having 1 to 18 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 a monovalent 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.

2. A method for producing a polymer, which comprises polymerizing a compound having a carbon-carbon double bond in the presence of the tellurium compound-containing composition obtained by the method of claim 1.

3. The method for producing a polymer according to claim 2, 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.

4. The method for producing the polymer according to claim 2, which is carried out in the presence of an azo-based radical initiator.

5. The method for producing a polymer according to claim 4, wherein 0.01 to 100 mol of the azo radical initiator is used per 1 mol in total of at least one tellurium compound represented by any one of formulas (1) to (4).

6. The method for producing a polymer according to any one of claims 2 to 5, wherein the polydispersity of the resulting polymer is 2.0 or less.

7. The method for producing a polymer according to any one of claims 2 to 5, 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.

8. The method for producing a polymer according to any one of claims 2 to 5, 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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