Method for producing polymer

Abstract

This method for producing a polymer comprises polymerization of a compound having a carbon-carbon double bond in the presence of at least one compound selected from the group consisting of compounds represented by formula (1) and formula (2). The symbols in formula (1) and formula (2) are as defined in the description.

Description

Polymer manufacturing method

[0001] The present disclosure relates to methods for making 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. In this context, controlled polymerization has attracted attention as a polymerization method that can produce controlled molecular structures, and various polymerization control agents 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 method for producing a fluoropolymer by solution polymerization or dispersion polymerization, which comprises (i) a step of homopolymerizing tetrafluoroethylene, or (ii) a step of randomly copolymerizing tetrafluoroethylene with a monomer represented by general formula (1) and / or a monomer represented by general formula (2) in the presence of an initiator, a chain transfer agent, and a solvent, wherein the chain transfer agent is at least one selected from the group consisting of dithioester compounds, dithiocarbamate compounds, trithiocarbonate compounds, and xanthate compounds, and the fluoropolymer contains 50 to 100 mol% of polymerized units based on tetrafluoroethylene.

[0004] International Publication No. 2020 / 226178

[0005] In conventional methods, there is room for improvement, for example, insufficient control of molecular weight distribution depending on the type of monomer. In view of this situation, an object of the present disclosure is to provide a method for producing a polymer with excellent controllability of molecular weight distribution.

[0006] Means for solving the above problems include the following aspects: <1> A method for producing a polymer, comprising polymerizing a compound having a carbon-carbon double bond in the presence of at least one compound selected from the group consisting of compounds represented by the following formula (1) and formula (2): In formula (1) and formula (2), RＦ is -CF(X １ )-X ２ represents a group, １ and X ２ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a fluoroalkyl group having 1 to 12 carbon atoms, a fluoropolyether group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 5 to 18 atoms constituting an aromatic ring; R １ , R ２ , and R ３ each independently represents an organic group having 1 to 12 carbon atoms; ２ and R ３ may be linked to each other to form a ring. Ｆ <3> The method for producing a polymer according to <1>, wherein in formula (1) and formula (2), R has a substitution rate of fluorine atoms of 30 mol % or more. Ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms, -CHF ２ , -CF ２ CF ２ H, CH ２ F, CCl ２ F, or -CClF ２ <4> The method for producing a polymer according to <1> or <2>, wherein in formula (1) and formula (2), R １ , R ２ , and R ３are each independently an unsubstituted alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 12 carbon atoms. <5> The method for producing a polymer according to any one of <1> to <4>, wherein the compound having a carbon-carbon double bond is a fluorine-containing compound containing a fluorine atom. <6> The method for producing a polymer according to <5>, wherein the fluorine-containing compound includes at least one selected from the group consisting of vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, perfluoro(methyl vinyl ether), perfluoro(n-propyl vinyl ether), perfluoro(3-butenyl vinyl ether), (perfluoro-n-butyl)ethylene, (perfluoro-n-hexyl)ethylene, 1,4-divinylperfluorobutane, perfluoro(2,2-dimethyl-1,3-dioxole), and 1,6-divinylperfluorohexane. <7> The method for producing a polymer according to any one of <1> to <4>, wherein the compound having a carbon-carbon double bond is a non-fluorine compound containing no fluorine atoms. <8> The method for producing a polymer according to <7>, wherein the non-fluorine compound contains at least one selected from the group consisting of vinylidene chloride, vinyl chloride, ethylene, propylene, and vinyl acetate. <9> The method for producing a polymer according to any one of <1> to <8>, wherein polymerization is carried out in a fluorine-containing solvent containing fluorine atoms.

[0007] According to the present disclosure, a method for producing a polymer with excellent controllability of molecular weight distribution is provided.

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

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

[0010] <Method for Producing Polymer> The method for producing a polymer according to the present disclosure includes polymerizing a compound having a carbon-carbon double bond in the presence of at least one compound selected from the group consisting of compounds represented by the following formula (1) and formula (2):

[0011]

[0012] In formula (1) and formula (2), R Ｆ is -CF(X １ )-X ２ represents a group, １ and X ２ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a fluoroalkyl group having 1 to 12 carbon atoms, a fluoropolyether group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 5 to 18 atoms constituting an aromatic ring; R １ , R ２ , and R ３ each independently represents an organic group having 1 to 12 carbon atoms; R ２ and R ３ may be linked to each other to form a ring. ２ and R ３ are linked to each other to form a ring or do not form a ring.

[0013] The compounds represented by formula (1) and formula (2) can function as control agents in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. Hereinafter, the compounds represented by formula (1) and formula (2) will be collectively referred to as "specific control agents." The compounds represented by formula (1) and formula (2) will also be referred to as "specific control agent (1)" and "specific control agent (2)," respectively. The present inventors have discovered that using a specific control agent instead of a conventional control agent in RAFT polymerization can favorably control the molecular weight distribution. The mechanism behind this is unclear, but is presumed to be as follows. In RAFT polymerization, when a growing radical comes into contact with the control agent, a leaving group is released from the control agent, and the remaining portion binds to the terminal of the growing radical as a protecting group. The leaving group reacts with a monomer as a radical to become an initiating terminal. The protection of the growing radical by the protecting group is reversible, and the radical is deprotected by reaction with another radical. Through this mechanism, polymerization proceeds with a controlled reaction rate by repeating deprotection, growth (monomer addition), and protection. When a specific control agent is used as a control agent, the rate of protection of the polymer end by the protecting group is maintained as necessary and sufficient, and the rate of reinitiation by the leaving group is increased, compared with conventional control agents. A high rate of protection of the polymer end can suppress bimolecular termination, and a high rate of reinitiation reduces the variability in the timing of polymer generation. These factors are believed to enable the formation of polymers with a narrower molecular weight distribution than conventional methods.

[0014] Specific control agent is R Ｆ is the leaving group. It is presumed that the specific structure of the leaving group brings the ease of radical generation and radical stability into an appropriate range, thereby accelerating the reinitiation rate. Furthermore, a fast reinitiation rate tends to shorten the induction period until polymerization starts, thereby shortening the reaction time. Note that the embodiments of the present disclosure are not bound by the above-mentioned presumed mechanism.

[0015] In the method for producing a polymer according to the present disclosure, in addition to the specific control agent and the compound having a carbon-carbon double bond (hereinafter also referred to as a "polymerizable monomer"), other components such as a radical initiator, a solvent, an emulsifier, a suspending aid, an acid or an alkali may be further used. Hereinafter, each component used in the method for producing a polymer according to the present disclosure, the polymer produced therefrom, and the polymerization method will be described in detail.

[0016] <Specific Control Agent> In the method for producing a polymer according to the present disclosure, at least one compound selected from the group consisting of compounds represented by formula (1) and formula (2) is used as the specific control agent. The specific control agent may be used alone or in combination of two or more.

[0017] [R Ｆ In formula (1) and formula (2), R Ｆ is -CF(X １ )-X ２ Represents a group.

[0018] X １ and X ２ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a fluoroalkyl group having 1 to 12 carbon atoms, a fluoropolyether group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 5 to 18 atoms constituting an aromatic ring.

[0019] Examples of fluoroalkyl groups having 1 to 12 carbon atoms include fluoroalkyl groups in which some or all of the hydrogen atoms bonded to an alkyl group having 1 to 12 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).

[0020] The fluoroalkyl group having 1 to 12 carbon atoms is preferably a perfluoroalkyl group having 1 to 12 carbon atoms, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and even more preferably a perfluoroalkyl group having 1 to 3 carbon atoms.

[0021] The fluoroalkyl group having 1 to 12 carbon atoms may be linear, branched, or cyclic, and is preferably linear or branched. Examples of the perfluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl 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.

[0022] The fluoropolyether group having 1 to 12 carbon atoms is preferably represented by the following formula (F1): ｆ０ O-(R ｆ１ O) ｃ１ (R ｆ１ ) ｃ２ -...Formula (F1)

[0023] In formula (F1), R ｆ０ is a fluoroalkyl group having 1 to 6 carbon atoms, and R ｆ１ is a fluoroalkylene group having 1 to 6 carbon atoms, and R ｆ１ When there are multiple R ｆ１ may be the same or different. c1 is an integer of 1 to 6, preferably an integer of 1 to 4. c2 is 0 or 1.

[0024] As a substituted or unsubstituted aryl group having 5 to 18 atoms constituting the aromatic ring, a substituted or unsubstituted aryl group having 5 to 12 atoms constituting the aromatic ring is preferred. 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, as an unsubstituted aryl group having 5 to 18 atoms constituting the aromatic ring, a homoaryl group is preferred, and a phenyl group is 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.

[0025] R Ｆ The substitution rate of fluorine atoms is preferably 30 mol % or more.

[0026] In the present disclosure, the "substitution ratio of fluorine atoms" means "the ratio of fluorine atoms to the total number of moles of hydrogen atoms and halogen atoms directly bonded to carbon atoms." When the substitution ratio of fluorine atoms is 30 mol% or more, the reaction rate is improved. From the viewpoint of further improving the reaction rate, the substitution ratio of fluorine atoms is preferably 40 mol% or more, and more preferably 60 mol% or more. The upper limit of the substitution ratio of fluorine atoms is 100 mol%.

[0027] Specifically, from the viewpoint of excellent controllability of molecular weight distribution, R Ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms, -CHF ２ , -CF ２ CF ２ H, CH ２ F, CCl ２ F, or -CClF ２is preferred, a perfluoroalkyl group having 1 to 12 carbon atoms is more preferred, a perfluoroalkyl group having 1 to 6 carbon atoms is even more preferred, and a perfluoroalkyl group having 1 to 4 carbon atoms is particularly preferred.

[0028] [R １ , R ２ , and R ３ In formula (1) and formula (2), R １ , R ２ , and R ３ R each independently represents an organic group having 1 to 12 carbon atoms. ２ and R ３ may be linked to each other to form a ring.

[0029] Examples of the organic group having 1 to 12 carbon atoms include 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, and a -(R Ａ O) ｎ１ -R Ｂ (wherein R Ａ each independently represents a substituted or unsubstituted alkylene group having 1 to 11 carbon atoms; R Ｂ 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). ２ and R ３ When R are linked to each other to form a ring, for example, a cyclic amide is obtained. ２ and R ３ Examples of the alkylene group include (oxa)alkylene groups having 4 to 12 carbon atoms.

[0030] 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, the unsubstituted alkyl group having 1 to 12 carbon atoms is preferably a methyl, ethyl, or n-butyl group.

[0031] 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, a fluoroalkoxy group, or an aromatic group. The number of substituents is not particularly limited, and may be 1 to 4, 1 to 3, 1 to 2, or 1. Among these, the substituted alkyl group having 1 to 12 carbon atoms is preferably an alkyl group having 7 to 12 carbon atoms substituted with an aromatic group (i.e., an arylalkyl group having 7 to 12 carbon atoms), and more preferably a benzyl group or a phenylethyl group.

[0032] Examples of the unsubstituted aryl group having 5 to 12 atoms constituting the aromatic ring include homoaryl groups such as a phenyl group and a naphthyl group, and heteroaryl groups such as a pyridyl group, a pyrrole group, a furyl group and a thienyl group. Of these, the unsubstituted aryl group having 5 to 12 atoms constituting the aromatic ring is preferably a homoaryl group, and more preferably a phenyl group.

[0033] Examples of the substituted aryl group 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, a trifluoromethyl group, etc. The number of substituents is not particularly limited and may be 1 to 4, 1 to 3, 1 to 2, or even 1.

[0034] -(R Ａ O) ｎ１ -R Ｂ In the group represented by Ａ and R Ｂ When at least one of 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 substituents is not particularly limited, and may be 1 to 4, 1 to 3, 1 to 2, or 1, independently. Ａis preferably an unsubstituted alkylene group having 1 to 3 carbon atoms. Ｂ is preferably an unsubstituted alkyl group having 1 to 3 carbon atoms. Ａ O) ｎ１ -R Ｂ Examples of the group represented by the formula include —CH ２ CH ２ OCH ３ , -CH ２ CH ２ OCH ２ CH ３ etc.

[0035] Examples of the (oxa)alkylene group having 4 to 12 carbon atoms include butane-1,4-diyl, pentane-1,5-diyl, and 3-oxapentane-1,5-diyl.

[0036] From the viewpoint of excellent controllability of molecular weight distribution, R １ , R ２ , and R ３ are each preferably independently an unsubstituted alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 12 carbon atoms.

[0037] The specific control agent (1) is, for example, CF ３ SC(=S)OMe,C ２ F ５ SC(=S)OMe,C ３ F ７ SC(=S)OMe, (CF ３ ) ２ CFSC(=S)OMe,C ４ F ９ SC(=S)OMe,C ５ F １１ SC(=S)OMe,C ３ F ７ OCF (CF ３ )SC(=S)OMe,CF ３ SC(=S)OEt,C ２ F ５ SC(=S)OEt,C ３ F ７ SC(=S)OEt, (CF ３ ) ２ CFSC(=S)OEt,C ４ F９ SC(=S)OEt、C ５ F １１ SC(=S)OEt、C ３ F ７ OCF(CF ３ )SC(=S)OEt、CF ３ SC(=S)OC ３ H ７ 、C ２ F ５ SC(=S)OC ３ H ７ 、C ３ F ７ SC(=S)OC ３ H ７ 、(CF ３ ) ２ CFSC(=S)OC ３ H ７ 、C ４ F ９ SC(=S)OC ３ H ７ 、C ５ F １１ SC(=S)OC ３ H ７ 、C ３ F ７ OCF(CF ３ )SC(=S)OC ３ H ７ 、CF ３ SC(=S)OCHMe ２ 、C ２ F ５ SC(=S)OCHMe ２ 、C ３ F ７ SC(=S)OCHMe ２ 、(CF ３ ) ２ CFSC(=S)OCHMe ２ 、C ４ F ９ SC(=S)OCHMe ２ 、C ５ F １１ SC(=S)OCHMe ２ 、C ３ F ７ OCF(CF ３ )SC(=S)OCHMe ２ 、CF ３ SC(=S)OC ４ H９ 、C ２ F ５ SC(=S)OC ４ H ９ 、C ３ F ７ SC(=S)OC ４ H ９ 、(CF ３ ) ２ CFSC(=S)OC ４ H ９ 、C ４ F ９ SC(=S)OC ４ H ９ 、C ５ F １１ SC(=S)OC ４ H ９ 、C ３ F ７ OCF(CF ３ )SC(=S)OC ４ H ９ 、CF ３ SC(=S)OC ５ H １１ 、C ２ F ５ SC(=S)OC ５ H １１ 、C ３ F ７ SC(=S)OC ５ H １１ 、(CF ３ ) ２ CFSC(=S)OC ５ H １１ 、C ４ F ９ SC(=S)OC ５ H １１ 、C ５ F １１ SC(=S)OC ５ H １１ 、C ３ F ７ OCF(CF ３ )SC(=S)OC ５ H １１ 、CF ３ SC(=S)OC ６ H １３ 、C ２ F ５ SC(=S)OC ６ H １３ 、C３ F ７ SC(=S)OC ６ H １３ 、(CF ３ ) ２ CFSC(=S)OC ６ H １３ 、C ４ F ９ SC(=S)OC ６ H １３ 、C ５ F １１ SC(=S)OC ６ H １３ 、C ３ F ７ OCF(CF ３ )SC(=S)OC ６ H １３ 、CF ３ SC(=S)OC ８ H １７ 、C ２ F ５ SC(=S)OC ８ H １７ 、C ３ F ７ SC(=S)OC ８ H １７ 、(CF ３ ) ２ CFSC(=S)OC ８ H １７ 、C ４ F ９ SC(=S)OC ８ H １７ 、C ５ F １１ SC(=S)OC ８ H １７ 、C ３ F ７ OCF(CF ３ )SC(=S)OC ８ H １７ 、CF ３ SC(=S)OCH ２ Ph、C ２ F ５ SC(=S)OCH ２ Ph、C ３ F ７ SC(=S)OCH ２ Ph、(CF ３ ) ２ CFSC(=S)OCH ２Ph、C ４ F ９ SC(=S)OCH ２ Ph、C ５ F １１ SC(=S)OCH ２ Ph、C ３ F ７ OCF(CF ３ )SC(=S)OCH ２ Ph、CF ３ SC(=S)OCH ２ CH ２ Ph、C ２ F ５ SC(=S)OCH ２ CH ２ Ph、C ３ F ７ SC(=S)OCH ２ CH ２ Ph、(CF ３ ) ２ CFSC(=S)OCH ２ CH ２ Ph、C ４ F ９ SC(=S)OCH ２ CH ２ Ph、C ５ F １１ SC(=S)OCH ２ CH ２ Ph、C ３ F ７ OCF(CF ３ )SC(=S)OCH ２ CH ２ Ph、CF ３ SC(=S)OCH ２ CH ２ OM%、C ２ F ５ SC(=S)OCH ２ CH ２ OM%、C ３ F ７ SC(=S)OCH ２ CH ２ Oｭe, (CF ３ ) ２ CFSC(=S)OCH ２ CH ２ OM%、C ４ F ９ SC(=S)OCH ２ CH ２OMe, C ５ F １１ SC(=S)OCH ２ CH ２ OMe, and C ３ F ７ OCF (CF ３ )SC(=S)OCH ２ CH ２ In addition, Me means a methyl group, Et means an ethyl group, and Ph means a phenyl group.

[0038] The specific control agent (2) is, for example, CF ３ SC(=S)NMe ２ , C ２ F ５ SC(=S)NMe ２ , C ３ F ７ SC(=S)NMe ２ , (CF ３ ) ２ CFSC(=S)NMe ２ , C ４ F ９ SC(=S)NMe ２ , C ５ F １１ SC(=S)NMe ２ , C ３ F ７ OCF (CF ３ )SC(=S)NMe ２ , C.F. ３ SC(=S)NEt ２ , C ２ F ５ SC(=S)NEt ２ , C ３ F ７ SC(=S)NEt ２ , (CF ３ ) ２ CFSC(=S)NET ２ , C ４ F ９ SC(=S)NEt ２ , C ５ F １１ SC(=S)NEt ２ , C ３ F ７ OCF (CF ３ )SC(=S)NEt ２ , C.F.３ SC(=S)N(C ３ H ７ ) ２ 、C ２ F ５ SC(=S)N(C ３ H ７ ) ２ 、C ３ F ７ SC(=S)N(C ３ H ７ ) ２ 、(CF ３ ) ２ CFSC(=S)N(C ３ H ７ ) ２ 、C ４ F ９ SC(=S)N(C ３ H ７ ) ２ 、C ５ F １１ SC(=S)N(C ３ H ７ ) ２ 、C ３ F ７ OCF(CF ３ )SC(=S)N(C ３ H ７ ) ２ 、CF ３ SC(=S)N(CH ２ Ph) ２ 、C ２ F ５ SC(=S)N(CH ２ Ph) ２ 、C ３ F ７ SC(=S)N(CH ２ Ph) ２ 、(CF ３ ) ２ CFSC(=S)N(CH ２ Ph) ２ 、C ４ F ９ SC(=S)N(CH ２ Ph) ２ 、C ５ F １１ SC(=S)N(CH ２ Ph) ２ 、C ３ F ７ OCF(CF３ )SC(=S)N(CH ２ Ph) ２ 、CF ３ SC(=S)(pyrrolidin-1-yl)、C ２ F ５ SC(=S)(pyrrolidin-1-yl)、C ３ F ７ SC(=S)(pyrrolidin-1-yl)、(CF ３ ) ２ CFSC(=S)(pyrrolidin-1-yl)、C ４ F ９ SC(=S)(pyrrolidin-1-yl)、C ５ F １１ SC(=S)(pyrrolidin-1-yl)、C ３ F ７ OCF(CF ３ )SC(=S)(pyrrolidin-1-yl)、CF ３ SC(=S)(piperidin-1-yl)、C ２ F ５ SC(=S)(piperidin-1-yl)、C ３ F ７ SC(=S)(piperidin-1-yl)、(CF ３ ) ２ CFSC(=S)(piperidin-1-yl)、C ４ F ９ SC(=S)(piperidin-1-yl)、C ５ F １１ SC(=S)(piperidin-1-yl)、C ３ F ７ OCF(CF ３ )SC(=S)(piperidin-1-yl)、CF ３ SC(=S)(morpholin-4-yl)、C ２ F ５ SC(=S)(morpholin-4-yl)、C ３ F ７ SC(=S)(morpholin-4-yl)、(CF ３ ) ２ CFSC(=S)(morpholin-4-yl)、C４ F ９ SC (=S) (morpholin-4-yl), C ５ F １１ SC(=S) (morpholin-4-yl), and C ３ F ７ OCF (CF ３ ) SC(=S) (morpholin-4-yl).

[0039] The amount of the specific control agent used per 1 mol of polymerizable monomer is preferably 0.0001 mol or more, more preferably 0.001 mol or more, and even more preferably 0.01 mol or more. Furthermore, the amount used is preferably 10 mol or less, more preferably 1 mol or less, and even more preferably 0.1 mol or less. Therefore, the amount used is preferably 0.0001 to 10 mol, more preferably 0.001 to 1 mol, and even more preferably 0.01 to 0.1 mol.

[0040] <Compound Having a Carbon-Carbon Double Bond> The compound having a carbon-carbon double bond (polymerizable monomer) may contain at least one carbon-carbon double bond, or may contain two or more, or may contain three or more, and may be selected depending on the polymer to be synthesized. The polymerizable monomer preferably has one or two carbon-carbon double bonds. One type of polymerizable monomer may be used alone, or two or more types may be used in combination.

[0041] The polymerizable monomer may be a fluorine-containing compound (fluorine-containing monomer) containing a fluorine atom, or a non-fluorine compound containing no fluorine atom. In one embodiment, the polymerizable monomer preferably contains a fluorine-containing monomer. In general, controlled polymerization of a fluorine-containing monomer is often difficult from the viewpoint of reaction kinetics. For example, polymerization of a fluorine-containing monomer tends to be disadvantageous for controlled polymerization because of a high propagation reaction rate, a low initiation reaction rate and a low exchange chain transfer reaction rate, and a high side reaction rate. However, according to the method for producing a polymer of the present disclosure, the controlled polymerization of a fluorine-containing monomer can also be favorably carried out, and a polymer with a narrow molecular weight distribution can easily be formed.

[0042] In one embodiment, the polymerizable monomer may be a compound represented by the following formula (M1):

[0043]

[0044] 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 １２ , or R １１ and R １３ may be linked to form a cyclic structure. １１ and R １２ , or R １１ and R １３ are linked together to form a cyclic structure, or do not form a cyclic structure.

[0045] 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.

[0046] 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.

[0047] When the organic group having 1 to 40 carbon atoms is a hydrocarbon group which may have a heteroatom, such as an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkoxy group, an arylalkyl group, a heteroarylalkyl group, an arylalkoxy group, a heteroarylalkoxy group, an alkoxycarbonyl group, or a monovalent hydrocarbon group having an oxyalkylene structure, the hydrocarbon group may be linear, branched, or cyclic, and may or may not contain an unsaturated bond.

[0048] 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.

[0049] In formula (M1), R １１ and R １２ , or R １１ and R １３ 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.

[0050] 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 ester monomers such as 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); perfluoro(2,2-dimethyl-1,3-dioxole);

[0051] In one embodiment, the polymerizable monomer may be a compound represented by the following formula (M2):

[0052]

[0053] 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 １４At least one of X represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure. １１ and X １２ , X １１ and X １３ may be bonded to each other to form a ring. １１ and X １２ , X １１ and X １３ are bonded to each other to form a ring or do not form a ring.

[0054] 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).

[0055] In general, in radical polymerization reactions, the propagation reaction rate and chain transfer reaction rate are greatly affected by the electronic state around the radical. Fluorine atoms have an extremely strong electron-withdrawing inductive effect and a moderate electron-donating resonance effect. Furthermore, perfluoroalkyl groups have a strong electron-withdrawing inductive effect. Therefore, the reactivity of fluorine-containing monomers tends to be significantly different from the reactivity of non-fluorine-containing monomers. Therefore, when a fluorine-containing monomer is used as a polymerizable monomer, it is difficult to predict the reactivity. In the past, it has been difficult to appropriately control the balance between the propagation reaction rate and the chain transfer reaction rate in controlled polymerization, particularly for fluorine-containing monomers. It was not predicted from the prior art that controlled polymerization can be favorably carried out even for fluorine-containing monomers by using a specific control agent.

[0056] 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.

[0057] When the organic group having 1 to 20 carbon atoms is a hydrocarbon group which may have a heteroatom, such as an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkoxy group, an arylalkyl group, a heteroarylalkyl group, an arylalkoxy group, a heteroarylalkoxy group, an alkoxycarbonyl group, or a monovalent hydrocarbon group having an oxyalkylene structure, the hydrocarbon group may be linear, branched, or cyclic, and may or may not contain an unsaturated bond.

[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] Examples of perfluoroalkyl groups include a trifluoromethyl group, a pentafluoroethyl 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.

[0060] 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 —[OCF２ CF (CF ３ )] ｍ -O-(CF ２ ) ｎ CF ３ More preferred is a perfluorohydrocarbon group represented by the following formula: m is preferably an integer of 0 to 4, and n is preferably an integer of 1 to 15.

[0061] 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, perfluoro(methyl vinyl ether), perfluoro(n-propyl vinyl ether), perfluoro(3-butenyl vinyl ether), 1,4-divinyloctafluorobutane, and 1,6-divinyldodecyl ether. perfluorohexane, (perfluoro-n-butyl)ethylene, (perfluoro-n-hexyl)ethylene, 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, 1,2-difluoro-1,2-diiodoethylene, perfluoro(2,2-dimethyl-1,3-dioxole), and the like.

[0062] 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.

[0063] When the polymerizable monomer is a fluorine-containing compound, the polymerizable monomer preferably contains at least one selected from the group consisting of vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, perfluoro(methyl vinyl ether), perfluoro(n-propyl vinyl ether), perfluoro(3-butenyl vinyl ether), (perfluoro-n-butyl)ethylene, (perfluoro-n-hexyl)ethylene, 1,4-divinylperfluorobutane, perfluoro(2,2-dimethyl-1,3-dioxole), and 1,6-divinylperfluorohexane.

[0064] When the polymerizable monomer is a non-fluorine compound, the polymerizable monomer preferably includes at least one selected from the group consisting of vinylidene chloride, vinyl chloride, ethylene, propylene, and vinyl acetate.

[0065] <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.

[0066] - 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.

[0067] 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.

[0068] When a polymerization reaction is carried out using an azo radical initiator, the amount of the azo radical initiator used per 1 mol of the specific control agent is preferably 0.01 mol or more, more preferably 0.05 mol or more, and even more preferably 0.1 mol or more. Furthermore, the amount used is preferably 100 mol or less, more preferably 50 mol or less, even more preferably 10 mol or less, and particularly preferably 5 mol or less. Therefore, the amount of the azo radical initiator used per 1 mol of the specific control agent is preferably 0.01 to 100 mol, more preferably 0.05 to 50 mol, even more preferably 0.1 to 10 mol, and particularly preferably 0.1 to 5 mol.

[0069] Examples of peroxide radical initiators include diisopropyl peroxydicarbonate, tert-butyl peroxypivalate, and benzoyl peroxide.

[0070] 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.

[0071] Examples of the organic solvent 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, and acetonitrile.

[0072] Furthermore, 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.

[0073] Also, CF ３ CFHCF ２ CF ２ CF ３ , C.F. ３ (CF ２ ) ４ H, C.F. ３ CF ２ CFHCF ２ CF ３ , C.F. ３ CFHCFHCF ２ CF ３ , C.F. ２ HCFHCF ２ CF ２ CF ３ , C.F. ３ (CF ２ ) ５ H, C.F. ３ CH (CF ３ )CF ２ CF ２ CF３ 、CF ３ CF(CF ３ )CFHCF ２ CF ３ 、CF ３ CH (CF ３ )CFHCF ２ CF ３ 、CF ３ CF ２ CH ２ CH ３ 、CF ３ (CF ２ ) ３ CH ２ CH ３ 、1、1、2、2-テトラフルオロシクロブタン、CF ３ CFHCFHCF ３ 、CF ３ CF(CF ３ )CFHCFHCF ３ 、CF ３ CH ２ CF ２ CH ３ 、CF ２ CCCFCO ２ 、CF ３ CCFCFCCCF ３ 、CF ３ CH ２ OCF ２ CF ２ H、CF ３ (CF ３ )CFCF ２ OCH ３ 、CF ３ (CF ２ ) ３ OCH ３ 、CF ３ (CF ２ ) ３ OC ２ H ５、 CF ３ (CF ２ ) ２ C ３ F ７ OCH ３ 、 (CF ３ ) ２ CFOCH ３, 1,1,2,2,3-pentafluoropropane, 3-chloro-1,1,2,2-tetrafluoropropane, 1-chloro-2,3,3-trifluoropropene, 1,2-dichloro-3,3-difluoropropene, 1,3-dichloro-2,3-difluoropropene, 2,3-dichloro-1,3-difluoropropene, 1,2,3-trichloro-3-fluoropropene, 2,3,3-trichloro-1-fluoropropene, 1,3,3-trichloro-2-fluoropropene, 1,2,3,3-tetrachloropropene, chlorotrifluoropropene, dichlorotrifluoropropene, 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene, 2,3,3,3-tetrafluoropropene, dichloropentafluoropropane, and the like may also be used.

[0074] Examples of aqueous solvents include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol.

[0075] 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.

[0076] <Polymer> The obtained 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. The polymer may be a fluorine-containing polymer or a polymer not containing fluorine atoms, depending on the type of polymerizable monomer.

[0077] The molecular weight of the polymer can be adjusted by the amount of specific control agent and optionally radical initiator, 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 polymethyl methacrylate is used as a standard substance for molecular weight conversion.

[0078] According to the method for producing a polymer of the present disclosure, it is possible to control the polydispersity of the resulting polymer to, for example, 2.5 or less. According to the method for producing a polymer of the present disclosure, it is also possible to obtain a polymer having a very narrow molecular weight distribution, such as a polydispersity of preferably 2.1 or less, 2.0 or less, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, or 1.5 or less. The lower limit of the polydispersity is 1.0 by definition. The 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)

[0079] In general, in free radical polymerization, the lifetime of active species is extremely short compared to the polymerization time. From the perspective of polymerization time, the time from radical generation to the termination of propagation is instantaneous. Therefore, if the polymerization temperature, the concentration of each component involved in the polymerization, and the viscosity of the polymerization solution are constant, the Mn of the resulting polymer is approximately the same regardless of the polymerization time. On the other hand, in RAFT polymerization, a specific control agent reacts with the propagating radical, which is the active species, to temporarily form a dormant species. If not only the propagating radical but also the dormant species are included in the active species, the polymerization time and the lifetime of the active species can be considered to be approximately the same, and therefore, as the polymerization time increases, the Mn of the resulting polymer tends to increase monotonically.

[0080] In general, whether or not the reaction mechanism of controlled polymerization is manifested in radical polymerization can be determined by whether Mn increases linearly with monomer conversion or whether PD is less than 1.5. It can also be determined by whether PD is smaller than that in free radical polymerization where the polymerization temperature and the concentrations of the components involved in the polymerization are the same.

[0081] [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.

[0082] 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.

[0083] 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.

[0084] 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 the 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 the 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.

[0085] 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.

[0086] 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, Example 1 is a synthesis example, Examples 2 to 20 are working examples, and Examples 21 to 25 are comparative examples.

[0087] 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. １９F-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

[0088] 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).

[0089] 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 polymethyl methacrylate was used as a standard substance for molecular weight conversion.

[0090] (Example 1) O-ethyl-S-heptafluoropropyl dithiocarbonate (C ３ F ７ Synthesis of SC(=S)OEt

[0091]

[0092] In a nitrogen-purged glove box, a 100 mL four-neck flask was charged with a magnetic stirrer, 6.72 g (28.5 mmol) of heptafluorobutyryl chloride (C ３ F ７ COCl) and 50 mL of 1,2-dichloroethane were added, and stirring was started while the flask was immersed in an ice-water bath. ２ H ５) was added and stirred overnight at room temperature (25°C; the same applies hereinafter). The resulting mixture was pressure filtered to obtain a filtrate. The filtrate was irradiated with blue light from an LED lamp (wavelength 450 nm, 40 W x 2) for 4 hours while stirring at room temperature (25°C) to obtain a crude reaction solution. The crude reaction solution contained 5.48 g (18.9 mmol) of C ３ F ７ SC(=S)OEt was included.

[0093] The crude reaction solution was concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (developing solvent: hexane) and vacuum distillation (boiling point: 58-60°C at 25 mmHg) to obtain 4.14 g (14.3 mmol) of C ３ F ７ SC(=S)OEt was isolated in 57 mol% yield.

[0094] １ H NMR (300 MHz, CDCl ３ ) δ1.48 (t, J=7.1Hz, 3H), δ4.72 (q, J=7.1Hz, 2H) １９ F NMR (282 MHz, CDCl ３ ) δ-80.62 (t, J = 9.0 Hz, 3F), δ-89.43 (tq, J = 2.8, 9.0 Hz, 2F), -124.23 (m, 2F) IR absorption peak wave number [cm －１ ]: 2994, 1304, 1284, 1231, 1211, 1118, 1032, 909, 841, 741

[0095] (Example 2) C ３ F ７ Polymerization of Tetrafluoroethylene Using SC(═S)OEt In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.48 g (0.12 mmol) of a peroxide radical initiator “Perloyl IPP” (trade name, manufactured by NOF Corporation) dissolved in a fluorine-based solvent “Asahiklin AE-3000” (trade name, manufactured by AGC Inc.) to give a 5 mass % solution, 0.17 g (0.59 mmol) of the C synthesized in Example 1, and 0.17 g (0.59 mmol) of the C synthesized in Example 1. ３ F ７SC(═S)OEt and 25 g of 1H-perfluorohexane were charged. After 5.8 g (58 mmol) of tetrafluoroethylene was injected, stirring was initiated while raising the liquid temperature to 50°C. After the liquid temperature reached 50°C, the gas phase pressure began to decrease within 5 minutes. While maintaining the liquid temperature, stirring was carried out at 200 rpm (200 revolutions per minute) for 4 hours. After the autoclave was cooled in an ice-water bath, unreacted tetrafluoroethylene was purged.

[0096] The resulting polymer solution was dried in vacuo to give 1.9 g of a solid.

[0097] (Example 3) C ３ F ７ Copolymerization of tetrafluoroethylene and perfluoro(n-propyl vinyl ether) using SC(=S)OEt In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 2.7 g (10 mmol) of perfluoro(n-propyl vinyl ether), 0.48 g (0.12 mmol) of a peroxide radical initiator "Perloyl IPP" (trade name, manufactured by NOF Corporation) in a fluorine-based solvent "Asahiklin AE-3000" (trade name, manufactured by AGC Inc.) to a concentration of 5% by mass, 0.17 g (59 mmol) of the C synthesized in Example 1, and 0.17 g (59 mmol) of the C synthesized in Example 1. ３ F ７ SC(═S)OEt and 25 g of 1H-perfluorohexane were charged. 4.7 g (47 mol) of tetrafluoroethylene was injected, and then stirring was initiated while the liquid temperature was raised to 50°C. Stirring was continued at 200 rpm for 6 hours while maintaining the liquid temperature. The autoclave was cooled in an ice-water bath, and then unreacted tetrafluoroethylene was purged.

[0098] The resulting polymer solution was dried in vacuo to give 1.9 g of a solid.

[0099] (Example 4) C ３ F ７Polymerization of vinylidene fluoride using SC(═S)OEt In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.42 g (0.12 mmol) of a peroxide radical initiator “Perbutyl PV” (trade name, manufactured by NOF Corporation) dissolved in a fluorine-based solvent “Asahiklin AE-3000” (trade name, manufactured by AGC Inc.) to give a 5 mass % solution, 0.088 g (0.30 mmol) of the C synthesized in Example 1, and 0.088 g (0.30 mmol) of the C synthesized in Example 1. ３ F ７ SC(═S)OEt and 12 g of acetonitrile were charged. After 3.9 g (61 mmol) of vinylidene fluoride was injected, stirring was initiated while the liquid temperature was raised to 65°C. After the liquid temperature reached 65°C, the gas phase pressure began to decrease within 15 minutes. While maintaining the liquid temperature, stirring was carried out at 200 rpm for 6 hours. After the autoclave was cooled in an ice-water bath, unreacted vinylidene fluoride was purged.

[0100] The resulting polymer solution was dried in vacuo to give 0.7 g of a solid.

[0101] (Example 5) C ３ F ７ Polymerization of trifluoroethylene using SC(═S)OEt In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.48 g (0.14 mmol) of a peroxide radical initiator “Perbutyl PV” (trade name, manufactured by NOF Corporation) dissolved in a fluorine-based solvent “Asahiklin AE-3000” (trade name, manufactured by AGC Inc.) to give a 5 mass % solution, 0.10 g (0.34 mmol) of the C synthesized in Example 1, and 0.10 g (0.34 mmol) of the C synthesized in Example 1. ３ F ７ SC(=S)OEt and 12 g of acetonitrile were charged. 5.7 g (69 mmol) of trifluoroethylene was injected, and then stirring was initiated while the liquid temperature was raised to 65°C. Stirring was continued at 200 rpm for 6 hours while maintaining the liquid temperature. The autoclave was cooled in an ice-water bath, and then unreacted trifluoroethylene was purged.

[0102] The resulting polymer solution was dried under vacuum to obtain 1.3 g of a solid. The resulting solid was measured by size exclusion chromatography, and found to have Mn = 3,400 and Mw = 4,800. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.4, indicating that this radical polymerization is characteristic of living radical polymerization.

[0103] (Example 6) C ３ F ７ Copolymerization of vinylidene fluoride and trifluoroethylene using SC(═S)OEt In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.58 g (0.14 mmol) of a peroxide radical initiator “Perloyl IPP” (trade name, manufactured by NOF Corporation) dissolved in a fluorine-based solvent “Asahiklin AE-3000” (trade name, manufactured by AGC Inc.) to give a 5 mass % solution, 0.21 g (0.71 mmol) of the C synthesized in Example 1, and 0.58 g (0.14 mmol) of the peroxide radical initiator “Perloyl IPP” (trade name, manufactured by NOF Corporation) dissolved in a fluorine-based solvent “Asahiklin AE-3000” (trade name, manufactured by AGC Inc.) to give a 5 mass % solution, and 0.21 g (0.71 mmol) of the C synthesized in Example 1 were charged. ３ F ７ SC(=S)OEt and 12 g of acetonitrile were charged. 2.8 g (34 mmol) of trifluoroethylene and 2.3 g (36 mmol) of vinylidene fluoride were then injected, and stirring was initiated while the liquid temperature was raised to 50°C. Stirring was continued at 200 rpm for 4 hours while maintaining the liquid temperature. The autoclave was cooled in an ice-water bath, and unreacted vinylidene fluoride and trifluoroethylene were then purged.

[0104] The resulting polymer solution was dried under vacuum to obtain 2.1 g of a solid. The resulting solid was measured by size exclusion chromatography, and found to have Mn=9,700 and Mw=12,500. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.3, indicating that this radical polymerization is characteristic of living radical polymerization.

[0105] (Example 7) C ３ F ７Polymerization of chlorotrifluoroethylene using SC(═S)OEt In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 1.0 g (12 mmol) of a peroxide radical initiator “Perbutyl PV” (trade name, manufactured by NOF Corporation) dissolved in a fluorine-based solvent “Asahiklin AE-3000” (trade name, manufactured by AGC Inc.) to give a 20 mass % solution, 0.35 g (1.2 mmol) of the C synthesized in Example 1, and 0.5 g (1.2 mmol) of the C synthesized in Example 2. ３ F ７ SC(=S)OEt and 7 g of benzotrifluoride were charged. 14 g (120 mmol) of chlorotrifluoroethylene was injected, and then stirring was initiated while raising the liquid temperature to 65°C. After the liquid temperature reached 65°C, the gas phase pressure began to decrease within 10 minutes. While maintaining the liquid temperature, stirring was carried out at 200 rpm for 6 hours. The autoclave was cooled in an ice-water bath, and then unreacted chlorotrifluoroethylene was purged.

[0106] The resulting polymer solution was dried under vacuum to obtain 2.8 g of a solid. The resulting solid was measured by size exclusion chromatography to find that Mn was 8,500 and Mw was 13,500. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.6.

[0107] (Example 8) C ３ F ７ Polymerization of perfluoro(3-butenyl vinyl ether) using SC(═S)OEt In a nitrogen-substituted glove box, a 50 mL Schlenk tube was charged with a magnetic rotor, 10 g (36 mmol) of perfluoro(3-butenyl vinyl ether), 0.37 g (0.090 mmol) of a peroxide-based radical initiator “Perloyl IPP” (trade name, manufactured by NOF Corporation) dissolved in a fluorine-based solvent “Asahiklin AE-3000” (trade name, manufactured by AGC Inc.) to a concentration of 5% by mass, and 0.10 g (0.36 mmol) of the C synthesized in Example 1. ３ F ７SC(=S)OEt was charged. The reaction solution was freeze-degassed, and then nitrogen was added until the gas phase reached atmospheric pressure. The Schlenk flask was immersed in a 40°C water bath, and stirring was initiated. Stirring was carried out at 400 rpm for 8 hours while maintaining the temperature of the water bath. The Schlenk flask was then placed in a room temperature water bath to cool.

[0108] 20 mL of 1H-perfluorohexane was added to the reaction solution, and the mixture was stirred for 5 minutes. The reaction solution was concentrated under reduced pressure to precipitate a solid. The mixture was suction filtered to separate the solid, which was then washed twice with 5 mL of hexane. The resulting solid was dried under vacuum to obtain 2.0 g of a solid. Measurement of the resulting solid by size exclusion chromatography revealed that Mn = 5,700 and Mw = 6,200. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.1, indicating that this radical polymerization is characteristic of living radical polymerization.

[0109] (Example 9) C ３ F ７ Polymerization of perfluoro(3-butenyl vinyl ether) using SC(=S)OEt 3.9 g of a solid was obtained in the same manner as in Example 8, except that the 8-hour heating and stirring time in Example 8 was changed to 16 hours.

[0110] The obtained solid was measured by size exclusion chromatography, and it was found that Mn was 9,600 and Mw was 10,500. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.1, and this radical polymerization shows the characteristics of living radical polymerization.

[0111] (Example 10) C ３ F ７ Polymerization of perfluoro(3-butenyl vinyl ether) using SC(=S)OEt 6.0 g of a solid was obtained in the same manner as in Example 8, except that the 8-hour heating and stirring time in Example 8 was changed to 24 hours.

[0112] The solid obtained was measured by size exclusion chromatography, and was found to have Mn = 13,000 and Mw = 14,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.1, and there was a positive correlation between the weight of the solid obtained in Examples 8 to 10 and Mn, indicating that this radical polymerization exhibits the characteristics of living radical polymerization.

[0113] (Example 11) C ３ F ７ Polymerization of vinyl acetate using SC(=S)OEt In a Schlenk tube with an internal volume of 50 mL, a magnetic rotor, 0.016 g (0.10 mmol) of azobisisobutyronitrile, and 0.15 g (0.52 mmol) of C synthesized in Example 1 were placed. ３ F ７ SC(=S)OEt was charged. The Schlenk tube was immersed in a dry ice / acetone bath at -78°C, and 4.3 g (50 mmol) of vinyl acetate was charged using the trap-to-trap method. The reaction solution was subjected to three cycles of freeze-degassing using liquid nitrogen. The Schlenk tube was returned to room temperature, and nitrogen was added until the gas phase reached atmospheric pressure. The Schlenk tube was immersed in a water bath at 60°C, and stirring was initiated. Stirring was carried out at 400 rpm for 45 minutes while maintaining the temperature of the water bath. The Schlenk tube was cooled in the water bath.

[0114] The reaction solution was added to 20 mL of hexane and stirred for 5 minutes to precipitate a solid. The mixture was suction filtered to separate the solid, which was then washed twice with 5 mL of hexane. The resulting solid was dried in vacuo to obtain 1.0 g of solid. The resulting solid was measured by size exclusion chromatography to find that Mn = 3,900 and Mw = 4,400. The calculated polydispersity (Mw / Mn) of the polymer was 1.1, indicating that this radical polymerization is characteristic of living radical polymerization.

[0115] (Example 12) C ３ F ７ Polymerization of Vinyl Acetate Using SC(=S)OEt 2.5 g of a solid was obtained in the same manner as in Example 11, except that the heating and stirring time in Example 11 was changed from 45 minutes to 90 minutes.

[0116] The obtained solid was measured by size exclusion chromatography, and found to have Mn = 11,500 and Mw = 14,000. The calculated polydispersity (Mw / Mn) of the polymer was 1.2, indicating that this radical polymerization is characteristic of living radical polymerization.

[0117] (Example 13) C ３ F ７ Polymerization of Vinyl Acetate Using SC(=S)OEt 3.5 g of a solid was obtained in the same manner as in Example 11, except that the heating and stirring time in Example 11 was changed from 45 minutes to 2 hours.

[0118] The solid obtained was measured by size exclusion chromatography, and was found to have an Mn of 15,500 and an Mw of 19,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.2, and there was a positive correlation between the weight of the solid obtained in Examples 11 to 13 and Mn, indicating that this radical polymerization exhibits the characteristics of living radical polymerization.

[0119] (Example 14) C ３ F ７ SC(=S)NEt ２ In Example 2, 0.17 g (0.59 mmol) of C synthesized in Example 1 was used for polymerization of tetrafluoroethylene. ３ F ７ SC(=S)OEt was synthesized according to the literature (Wessel, W.; Tyrra, W.; Naumann, D. Z. Anorg. Allg. Chem. 2001, 627, 1264.) using 0.16 g (0.59 mmol) of C ３ F ７ SC(=S)NEt ２ The procedure of Example 2 was repeated except for changing the solvent to 1.2 g of a solid.

[0120] (Example 15) C ３ F ７ SC(=S)NEt ２ Copolymerization of tetrafluoroethylene and perfluoro(n-propyl vinyl ether) using 0.17 g (59 mmol) of C synthesized in Example 1 in Example 3 ３ F ７SC(=S)OEt was synthesized according to the literature: Wessel, W.; Tyrra, W.; Naumann, D. Z. Anorg. Allg. Chem. 2001, 627, 1264. 0.16 g (0.59 mmol) of C ３ F ７ SC(=S)NEt ２ The procedure of Example 3 was repeated except for changing the solvent to 0.7 g of a solid.

[0121] (Example 16) C ３ F ７ SC(=S)NEt ２ Polymerization of chlorotrifluoroethylene using 0.35 g (1.2 mmol) of C synthesized in Example 1 in Example 7 ３ F ７ SC(=S)OEt was synthesized according to the literature: Wessel, W.; Tyrra, W.; Naumann, D. Z. Anorg. Allg. Chem. 2001, 627, 1264. 0.32 g (1.2 mmol) of C ３ F ７ SC(=S)NEt ２ The procedure of Example 7 was repeated except for changing the solvent to the following, to obtain 4.1 g of a solid.

[0122] The obtained solid was measured by size exclusion chromatography, and it was found that Mn was 11,500 and Mw was 16,000. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.4, and this radical polymerization shows the characteristics of living radical polymerization.

[0123] (Example 17) C ３ F ７ SC(=S)NEt ２Copolymerization of chlorotrifluoroethylene and ethyl vinyl ether using 3.6 g (50 mmol) of ethyl vinyl ether and 1.7 g (0.49 mmol) of a peroxide radical initiator "Perbutyl PV" (trade name, manufactured by NOF Corporation) in a fluorine-based solvent "ASAHIKLIN AE-3000" (trade name, manufactured by AGC Inc.) were placed in a 30 mL stainless steel autoclave equipped with a stirrer in a nitrogen-substituted glove box. A 5 mass % solution was prepared by dissolving 3.6 g (50 mmol) of ethyl vinyl ether and 1.7 g (0.49 mmol) of a peroxide radical initiator "Perbutyl PV" (trade name, manufactured by NOF Corporation) in a fluorine-based solvent "ASAHIKLIN AE-3000" (trade name, manufactured by AGC Inc.), and 0.27 g (1.0 mmol) of C synthesized according to the literature (Wessel, W.; Tyrra, W.; Naumann, D. Z. Anorg. Allg. Chem. 2001, 627, 1264). ３ F ７ SC(=S)NEt ２ , and 14 g of benzotrifluoride were charged. After 5.8 g (50 mmol) of chlorotrifluoroethylene was injected, stirring was started while the liquid temperature was raised to 65°C. Stirring was carried out at 200 rpm for 2 hours while maintaining the liquid temperature. After the autoclave was cooled in an ice-water bath, unreacted chlorotrifluoroethylene was purged.

[0124] The resulting polymer solution was dried under vacuum to obtain 6.3 g of a solid. The resulting solid was measured by size exclusion chromatography, and found to have Mn=4,200 and Mw=5,700. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.4, indicating that this radical polymerization is characteristic of living radical polymerization.

[0125] Example 18 Block Copolymerization of Polychlorotrifluoroethylene and Chlorotrifluoroethylene-Ethyl Vinyl Ether In a nitrogen-purged glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 1.4 g (20 mmol) of ethyl vinyl ether, 1.3 g of the fluoropolymer synthesized in Example 16, 0.28 g (0.080 mmol) of a solution of the peroxide-based radical initiator "Perbutyl PV" (trade name, manufactured by NOF Corporation) dissolved in the fluorine-based solvent "ASAHIKLIN AE-3000" (trade name, manufactured by AGC Inc.) to a concentration of 5% by mass, and 18 g of benzotrifluoride. 2.3 g (20 mmol) of chlorotrifluoroethylene was injected, and then stirring was initiated while the liquid temperature was raised to 65°C. Stirring was continued at 200 rpm for 1 hour while maintaining the liquid temperature. The autoclave was cooled in an ice-water bath, and then unreacted chlorotrifluoroethylene was purged.

[0126] The obtained polymer solution was dried under vacuum to obtain 2.1 g of a solid. When the obtained solid was measured by size exclusion chromatography, Mn = 13,500, Mw = 19,000, and the peak was monomodal. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.4. The formation of a block copolymer was confirmed from Mn, Mw, polydispersity, and the monomodal peak.

[0127] (Example 19) C ３ F ７ SC(=S)NEt ２ Polymerization of perfluoro(3-butenyl vinyl ether) using the compound in Example 8 and 0.10 g (0.36 mmol) of C synthesized in Example 1 ３ F ７ SC(=S)OEt was synthesized according to the literature: Wessel, W.; Tyrra, W.; Naumann, D. Z. Anorg. Allg. Chem. 2001, 627, 1264. 0.096 g (0.36 mmol) of C ３ F ７ SC(=S)NEt ２ The procedure of Example 9 was repeated except for changing the solvent to the following, to obtain 1.6 g of a solid.

[0128] The obtained solid was measured by size exclusion chromatography, and it was found that Mn was 4,300 and Mw was 5,200. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.2, and this radical polymerization shows the characteristics of living radical polymerization.

[0129] (Example 20) C ３ F ７ SC(=S)NEt ２ Polymerization of vinyl acetate using 0.15 g (0.52 mmol) of C synthesized in Example 1 in Example 13 ３ F ７ SC(=S)OEt was synthesized according to the literature: Wessel, W.; Tyrra, W.; Naumann, D. Z. Anorg. Allg. Chem. 2001, 627, 1264. 0.13 g (0.49 mmol) of C ３ F ７ SC(=S)NEt ２ The procedure of Example 12 was repeated except for changing the solvent to the following, to obtain 3.3 g of a solid.

[0130] The obtained solid was measured by size exclusion chromatography to find that Mn = 14,500 and Mw = 18,500. The calculated polydispersity (Mw / Mn) of the polymer was 1.3, indicating that this radical polymerization is characteristic of living radical polymerization.

[0131] (Example 21) EtOC(=O)CH(CH ３ Polymerization of tetrafluoroethylene using SC(=S)OEt in Example 2: 0.17 g (0.59 mmol) of C synthesized in Example 1 ３ F ７ SC(=S)OEt was dissolved in 0.13 g (0.58 mmol) of EtOC(=O)CH(CH ３ The same procedure as in Example 2 was conducted except that the catalyst used was changed to SC(═S)OEt. The gas phase pressure began to decrease 40 minutes after the internal temperature reached 50° C., and the induction period until the start of the polymerization reaction was longer than in Example 2.

[0132] (Example 22) EtOC(=O)CH(CH ３ Polymerization of vinylidene fluoride using SC(=S)OEt in Example 4: 0.088 g (0.30 mmol) of C synthesized in Example 1３ F ７ SC(=S)OEt was dissolved in 0.067 g (0.30 mmol) of EtOC(=O)CH(CH ３ The same procedure as in Example 4 was conducted except that the catalyst used was changed to SC(═S)OEt. The gas phase pressure began to decrease 2 hours after the internal temperature reached 65° C., and the induction period until the start of the polymerization reaction was longer than in Example 4.

[0133] (Example 23) EtOC(=O)CH(CH ３ Polymerization of chlorotrifluoroethylene using SC(=S)OEt in Example 7: 0.35 g (1.2 mmol) of C synthesized in Example 1 ３ F ７ SC(=S)OEt was dissolved in 0.27 g (1.2 mmol) of EtOC(=O)CH(CH ３ The same procedure as in Example 4 was conducted except that the catalyst used was changed to SC(═S)OEt. The gas phase pressure began to decrease 45 minutes after the internal temperature reached 65° C., and the induction period until the start of the polymerization reaction was longer than in Example 7.

[0134] The resulting solid was measured by size exclusion chromatography to have Mn=6,800 and Mw=11,500. The calculated polydispersity (Mw / Mn) of the polymer was 1.7.

[0135] Example 24 Free Radical Polymerization of Perfluoro(3-butenyl vinyl ether) In Example 8, 0.10 g (0.36 mmol) of C synthesized in Example 1 was ３ F ７ The same procedure as in Example 8 was carried out except that SC(=S)OEt was not used and the heating and stirring time in Example 8 was changed from 8 hours to 3 hours, to obtain 0.9 g of a solid.

[0136] The resulting solid was measured by size exclusion chromatography to have Mn=83,000 and Mw=140,000. The calculated polydispersity (Mw / Mn) of the polymer was 1.7.

[0137] Example 25 Free Radical Polymerization of Perfluoro(3-butenyl vinyl ether) 2.5 g of a solid was obtained in the same manner as in Example 24, except that the heating and stirring time in Example 24 was changed from 3 hours to 6 hours.

[0138] The solid obtained was measured by size exclusion chromatography, and found to have an Mn of 86,000 and an Mw of 165,000. The calculated polydispersity (Mw / Mn) of the polymer was 1.9. In Examples 24 and 25, both polydispersities (Mw / Mn) were 1.5 or more, and no proportional relationship was observed between the weight of the solid obtained and Mn, indicating that this radical polymerization did not exhibit the characteristics of living radical polymerization.

[0139] From Examples 2 to 25, it was found that the polymerization method using a specific control agent can suitably carry out controlled polymerization using various polymerizable monomers, and a polymer having a narrow molecular weight distribution can be obtained.

[0140] The disclosure of Japanese Patent Application No. 2024-058074, filed on March 29, 2024, is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

Claims

1. A method for producing a polymer, comprising polymerizing a compound having a carbon-carbon double bond in the presence of at least one compound selected from the group consisting of compounds represented by the following formulas (1) and (2): In formula (1) and formula (2), R Ｆ is -CF(X １ )-X ２ represents a group, １ and X ２ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a fluoroalkyl group having 1 to 12 carbon atoms, a fluoropolyether group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 5 to 18 atoms constituting an aromatic ring; R １ , R ２ , and R ３ each independently represents an organic group having 1 to 12 carbon atoms; ２ and R ３ may be linked to each other to form a ring.

2. The above R Ｆ The method for producing a polymer according to claim 1 , wherein the substitution rate of fluorine atoms is 30 mol % or more.

3. In the formula (1) and formula (2), R Ｆ represents a perfluoroalkyl group having 1 to 12 carbon atoms, -CHF ２ , -CF ２ CF ２ H, CH ２ F, CCl ２ F, or -CClF ２ The method for producing the polymer according to claim 1 or 2, 4. In the formula (1) and formula (2), R １ , R ２ , and R ３ and each independently represent an unsubstituted alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 12 carbon atoms.

5. The method for producing a polymer according to claim 1 or 2, wherein the compound having a carbon-carbon double bond is a fluorine-containing compound containing a fluorine atom.

6. The method for producing a polymer according to claim 5, wherein the fluorine-containing compound comprises at least one selected from the group consisting of vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, perfluoro(methyl vinyl ether), perfluoro(n-propyl vinyl ether), perfluoro(3-butenyl vinyl ether), (perfluoro-n-butyl)ethylene, (perfluoro-n-hexyl)ethylene, 1,4-divinylperfluorobutane, perfluoro(2,2-dimethyl-1,3-dioxole), and 1,6-divinylperfluorohexane.

7. The method for producing a polymer according to claim 1 or 2, wherein the compound having a carbon-carbon double bond is a non-fluorine compound that does not contain a fluorine atom.

8. The method for producing a polymer according to claim 7, wherein the non-fluorine compound comprises at least one selected from the group consisting of vinylidene chloride, vinyl chloride, ethylene, propylene, and vinyl acetate.

9. A method for producing the polymer according to claim 1 or 2, wherein the polymerization is carried out in a fluorine-containing solvent containing fluorine atoms.

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