Method for producing iodine-containing compound and iodine-containing compound

Abstract

This method for producing an iodine-containing compound comprises a process wherein a halogen-containing organic iodide compound and a compound having a reactive carbon-carbon double bond are caused to react with each other in the presence of a compound that is represented by formula (21) or formula (22). In formula (21), R21 represents a hydrogen atom, an iodine atom, or an organic group having from 1 to 20 carbon atoms; R22 represents a hydrogen atom, an iodine atom, an organic group having from 1 to 20 carbon atoms, or a boron-containing group; and A1 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom. In formula (22), each of R23 and R24 represents a hydrogen atom, an iodine atom, or an organic group having from 1 to 20 carbon atoms; R25 represents a hydrogen atom, an iodine atom, an organic group having from 1 to 20 carbon atoms, or a silicon-containing group; and A2 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom.

Description

[Technical Field]

[0001] The present disclosure relates to a method for producing an iodine-containing compound and an iodine-containing compound. [Background technology]

[0002] Radical polymerization is widely used industrially because it is versatile and can be easily performed in polar media such as water. However, the molecular weight control of conventional radical polymerization methods is limited, and the molecular weight distribution of the resulting polymers tends to be broad.

[0003] On the other hand, living radical polymerization has attracted attention as a polymerization method that can produce polymers with controlled molecular weights and narrow molecular weight distributions, and various polymerization control agents have been developed. Living radical polymerization is a polymerization method that controls the radical polymerization rate by reversibly protecting growing radicals with protecting groups that are dormant species, thereby making it possible to control the molecular weight distribution. Furthermore, living radical polymerization also makes it possible to use the resulting polymer as a polymerization initiator or chain transfer agent to add different compounds via radical reactions.

[0004] Patent Document 1 describes a living radical 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 called TERP (organo tellurium-mediated living radical polymerization).

[0005] Patent Document 2 discloses a method for producing a polymer by emulsion polymerization of a fluorine-containing monomer using RAFT (reversible addition fragmentation chain transfer) polymerization, which is one of the living radical polymerization methods. The RAFT method enables control of molecular weight distribution by carrying out polymerization through a reversible chain transfer reaction in the presence of a specific chain transfer agent called a RAFT agent.

[0006] Iodine transfer polymerization (ITP) is another form of living radical polymerization. ITP is a polymerization method that uses an organic iodide compound as a chain transfer agent, and is useful in that it can also be applied to fluorine-based monomers. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2018 / 164147 [Patent Document 2] International Publication No. 2015 / 173193 Summary of the Invention [Problem to be solved by the invention]

[0008] When an organic iodide compound is used as a chain transfer agent or polymerization initiator, the iodine in the terminal CI bond must be abstracted in order to further promote a radical reaction starting from the organic iodide compound to obtain an elongated product. However, when a compound in which a fluorine atom or a chlorine atom is directly bonded to the carbon of the CI bond (conveniently referred to as a "halogen-containing organic iodide compound" in the present disclosure) is used, it is difficult to cause iodine abstraction at an appropriate rate. Therefore, when such a halogen-containing organic iodide compound is used, conventional methods have had the problem that it is difficult to obtain an elongated product from the halogen-containing organic iodide compound and that sufficient control is difficult to achieve.

[0009] In view of the above circumstances, an object of the present disclosure is to provide a method for producing an iodine-containing compound, which is capable of elongating a halogen-containing organic iodide compound containing a fluorine atom or a chlorine atom to obtain an elongated product having a controlled molecular weight distribution, and an iodine-containing compound having a controlled molecular weight distribution. [Means for solving the problem]

[0010] The embodiments of the present disclosure include the following. <1> In the presence of at least one compound selected from the group consisting of a compound represented by the following formula (21) and a compound represented by the following formula (22), The method comprises reacting a compound (10) having a partial structure represented by the following formula (1) with a compound represented by the following formula (3): Method for producing iodine-containing compounds.

[0011] [ka]

[0012] (In formula (1), * represents a bond bonded to an organic group. X represents a fluorine atom or a chlorine atom. X 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or -CX 5 X 6 X 7 represents X 5 ~X 7 each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

[0013] [ka]

[0014] (In formula (21), R 21 represents a hydrogen atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms; R 22represents a hydrogen atom, an iodine atom, a substituted or unsubstituted organic group having 1 to 20 carbon atoms, or a boron-containing group, and the boron atom in the boron-containing group is bonded to the boron atom in formula (21). 21 and R 22 may be linked to form a cyclic structure. 1 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom. The boron atom in formula (21) may further be coordinated with a ligand. (In formula (22), R 23 and R 24 each independently represents a hydrogen atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms; R 25 represents a hydrogen atom, an iodine atom, a substituted or unsubstituted organic group having 1 to 20 carbon atoms, or a silicon-containing group, and the silicon atom in the silicon-containing group is bonded to the silicon atom in formula (22). 23 ~R 25 Except when all of R are hydrogen atoms. 23 , R 24 , and R 25 Two or more of these may be linked to form a cyclic structure. 2 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom.

[0015] [ka]

[0016] (In formula (3), R 1 ~R 4 R each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 40 carbon atoms. 1 and R 4 , or R 2 and R 3 may be linked to form a cyclic structure. <2> In the formula (3), R 1 ~R 4each independently represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 40 carbon atoms and having at least one reactive carbon-carbon double bond; R 1 and R 4 , or R 2 and R 3 may be linked to form a cyclic structure, and the formula (3) has at least two reactive carbon-carbon double bonds. <1> The manufacturing method described in <3> The compound represented by formula (3) includes a compound represented by formula (5): <1> The manufacturing method described in

[0017] [ka]

[0018] (wherein X represents a fluorine atom or a chlorine atom, X 2 ~X 4 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or -CX 5 X 6 X 7 represents X 5 ~X 7 each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom. <4> the obtained iodine-containing compound is a copolymer obtained by copolymerizing the first compound represented by the formula (5) with a compound represented by the formula (3) that is different from the first compound. <3> The manufacturing method described in <5> The copolymerization is a block copolymerization. <4> The manufacturing method described in <6> The copolymerization is random copolymerization or alternating copolymerization. <4> The manufacturing method described in <7> The compound represented by formula (3) that is different from the first compound is at least one selected from the group consisting of ethylene, propylene, isobutylene, alkyl vinyl ether, hexafluoropropylene, perfluoro(alkyl vinyl ether), triallyl isocyanurate, 1,4-divinyloctafluorobutane, 1,6-divinyldodecafluorohexane, vinyl acetate, styrene, butyl acrylate, and divinylbenzene. <4> ~ <6> The manufacturing method according to any one of the above. <8> the compound represented by formula (5) is at least one selected from the group consisting of 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, vinyl chloride, and vinylidene chloride; <3> ~ <7> The manufacturing method according to any one of the above. <9> The compound (10) is a compound represented by the following formula (11) or a compound represented by the following formula (12): <1> ~ <8> The manufacturing method according to any one of the above.

[0019] [ka]

[0020] (In the formula, R 11 represents a perfluoroalkyl group having 1 to 4 carbon atoms. 12 represents a perfluoroalkylene group having 1 to 4 carbon atoms. Each X independently represents a fluorine atom or a chlorine atom. X 21 ~X 23are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or -CX 24 X 25 X 26 represents X 24 ~X 26 each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom. <10> The compound (10) is a compound containing a plurality of units represented by the following formula (4): <1> ~ <9> The manufacturing method according to any one of the above.

[0021] [ka]

[0022] (In the formula, X 31 ~X 34 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or -CX 35 X 36 X 37 represents X 35 ~X 37 each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom. <11> The fluorine content of the compound (10) is 50% by mass or more. <10> The manufacturing method described in <12> The obtained iodine-containing compound is a polymer, and the polydispersity of the polymer is 2.0 or less. <1> ~ <11> The manufacturing method according to any one of the above. <13> In formula (21), A 1 is a hydrogen atom and the boron atom has a ligand, or A 1 is an iodine atom, <1> ~ <12> The manufacturing method according to any one of the above. <14> In formula (22), R 23 , R 24 , and R 25 At least one of the above contains an aromatic ring, <1> ~ <12> The manufacturing method according to any one of the above. <15> An iodine-containing compound, which is a polymer containing a structure derived from an azo-based radical initiator or a peroxide-based radical initiator, wherein the ratio of the structure derived from the azo-based radical initiator or the peroxide-based radical initiator to the terminals of the polymer is 40 mol % or less. [Effects of the Invention]

[0023] According to the present disclosure, there are provided a method for producing an iodine-containing compound, which is capable of elongating a halogen-containing organic iodide compound containing a fluorine atom or a chlorine atom to obtain an elongated product having a controlled molecular weight distribution, and an iodine-containing compound having a controlled molecular weight distribution. DETAILED DESCRIPTION OF THE INVENTION

[0024] Hereinafter, embodiments of the present disclosure will be described in detail, but the embodiments of the present disclosure are not limited to the following embodiments. In the present disclosure, the term "process" includes not only a process that is independent of other processes, but also a process that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the present disclosure, each component may contain multiple substances corresponding to the component. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, unless otherwise specified, organic groups or hydrocarbon groups may or may not have a substituent. In the present disclosure, the number of carbon atoms in a chemical structure means the total number of carbon atoms contained in the entire chemical structure, and when the chemical structure does not have a substituent, it represents the number of carbon atoms forming the skeleton of the chemical structure, and when the chemical structure has a substituent, it represents the total number obtained by adding the number of carbon atoms forming the skeleton of the chemical structure to the number of carbon atoms in the substituent. The term "aryl group" refers to a monovalent group equivalent to the residue obtained by removing one hydrogen atom bonded to any one of the carbon atoms forming an aromatic ring in an aromatic compound, and is used as a general term that includes both homoaryl groups derived from carbocyclic compounds and heteroaryl groups derived from heterocyclic compounds. An arylene group refers to a divalent group corresponding to a residue obtained by removing one hydrogen atom bonded to any one of the carbon atoms of an aryl group. In the present disclosure, a reactive carbon-carbon double bond means a carbon-carbon double bond that can undergo various reactions as an olefin, and does not include aromatic double bonds. In the present disclosure, (meth)acrylic acid is a general term for acrylic acid and methacrylic acid, (meth)acrylate is a general term for acrylate and methacrylate, and (meth)acrylamide is a general term for acrylamide and methacrylamide. In the present disclosure, a "polymer" is a compound formed by polymerizing monomers, i.e., a "polymer" has a plurality of structural units. In this disclosure, unless otherwise specified, the expression "polymerizing compound A" encompasses both the case where only compound A is polymerized and the case where compound A is polymerized with another compound. Furthermore, the expression "polymerizing compound A and compound B" encompasses 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 this disclosure that has a carbon-carbon double bond in the molecule. Furthermore, unless otherwise specified, the polymer described in this disclosure may be a homopolymer of one type of compound or a copolymer of two or more types of compounds.

[0025] Hereinafter, 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.

[0026] <Method for producing iodine-containing compound> The method for producing an iodine-containing compound of the present disclosure (hereinafter also referred to as the production method of the present disclosure) includes reacting a compound (10) having a partial structure represented by the following formula (1) with a compound represented by the following formula (3) in the presence of at least one selected from the group consisting of a compound represented by the following formula (21) and a compound represented by the following formula (22).

[0027] [ka]

[0028] (In formula (1), * represents a bond bonded to an organic group. X represents a fluorine atom or a chlorine atom. X 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or -CX 5 X 6 X 7 represents X 5 ~X 7 each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

[0029] [ka]

[0030] In formula (21), R 21 represents a hydrogen atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms; R 22 represents a hydrogen atom, an iodine atom, a substituted or unsubstituted organic group having 1 to 20 carbon atoms, or a boron-containing group, and the boron atom in the boron-containing group is bonded to the boron atom in formula (21). 21 and R 22 may be linked to form a cyclic structure. 1 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom. The boron atom in formula (21) may further be coordinated with a ligand.

[0031] In formula (22), R 23 and R 24each independently represents a hydrogen atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms; R 25 represents a hydrogen atom, an iodine atom, a substituted or unsubstituted organic group having 1 to 20 carbon atoms, or a silicon-containing group, and the silicon atom in the silicon-containing group is bonded to the silicon atom in formula (22). 23 ~R 25 Except when all of R are hydrogen atoms. 23 , R 24 , and R 25 Two or more of these may be linked to form a cyclic structure. 2 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom.

[0032] [ka]

[0033] (In formula (3), R 1 ~R 4 R each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 40 carbon atoms. 1 and R 4 , or R 2 and R 3 may be linked to form a cyclic structure.

[0034] According to the production method of the present disclosure, it has been found that by using as a catalyst at least one selected from the group consisting of compounds represented by formula (21) and compounds represented by formula (22), a halogen-containing organic iodide compound containing fluorine or chlorine atoms can be elongated to obtain an elongated product with a controlled molecular weight distribution. The production method of the present disclosure is based on a living radical polymerization method known as reversible chain transfer catalyzed living radical polymerization (RTCP), and proceeds according to the mechanism shown in the diagram below.

[0035] [ka]

[0036] W·: Radical species (W is any structure) AY: catalyst (at least one of a compound represented by formula (21) and a compound represented by formula (22); in the case of formula (21), A is A 1 , Y is A 1 In the case of formula (22), A represents a structure other than A 2 , Y is A 2 Represents a structure other than ZI: Iodide (I is an iodine atom, Z is any structure (alkyl iodide, iodine terminal of a polymer, IY, etc.)) X and X 1 : X and X in formula (1) 1 Synonymous with R 1 ~R 4 : R in Equation (3) 1 ~R 4 Synonymous with

[0037] First, the radical species (W·) present in the reaction system reacts with the catalyst (AY) to generate the Y radical (Y·). This Y radical (Y·) can then selectively remove the iodine from the halogen-containing organic iodide compound. This removes the iodine protecting group, and the radical reaction from the halogen-containing organic iodide compound proceeds to produce the elongation product. When the radical at the elongation terminal reacts with iodide (ZI), the elongation terminal is reprotected.

[0038] In the conventional method, a halogen-containing organic iodide compound in which a fluorine atom or a chlorine atom is directly bonded to the carbon of a CI bond, i.e., -CXX 1Abstraction of iodine from compounds having the partial structure I (X is a fluorine atom or a chlorine atom) is difficult, and it has been difficult to advance the elongation of such halogen-containing organic iodide compounds to obtain elongated products with controlled molecular weights. This is thought to be due in part to the instability of the radical on the carbon atom in the C—X bond. However, it has been found that the use of a specific compound selected from the group consisting of compounds represented by formula (21) and compounds represented by formula (22) as the catalyst (AY) facilitates abstraction of iodine from halogen-containing organic iodide compounds, enabling highly controllable elongation reactions. Therefore, for example, by polymerizing a halogen-containing monomer using the production method of the present disclosure, it becomes possible to produce a fluorine-containing polymer or a chlorine-containing polymer having a controlled molecular weight distribution. In addition, by using the production method of the present disclosure to cause a reaction between a fluorine-containing polymer or a chlorine-containing polymer and a crosslinking agent, it becomes possible to apply the method to the production of crosslinked rubber, etc.

[0039] First, the compounds used in the production method of the present disclosure will be described.

[0040] <Compound represented by formula (21) and compound represented by formula (22)> The compound represented by the following formula (21) functions as a catalyst for mediating the abstraction of iodine from a halogen-containing organic iodide compound.

[0041] (Compound represented by formula (21))

[0042] [ka]

[0043] In formula (21), R 21 represents a hydrogen atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms; R 22 represents a hydrogen atom, an iodine atom, a substituted or unsubstituted organic group having 1 to 20 carbon atoms, or a boron-containing group, and the boron atom in the boron-containing group is bonded to the boron atom in formula (21). 21and R 22 may be linked to form a cyclic structure. 1 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom. The boron atom in formula (21) may further be coordinated with a ligand.

[0044] In the reaction system, the compound represented by formula (21) is converted to A 1 The radical generated on the atom by the abstraction abstracts iodine from the halogen-containing organic iodide compound.

[0045] R 21 and R 22 Each of the substituted or unsubstituted organic groups having 1 to 20 carbon atoms represented by the formula (I) is preferably a substituted or unsubstituted organic group having 1 to 15 carbon atoms, and more preferably a substituted or unsubstituted organic group having 1 to 10 carbon atoms. Examples of such organic groups include saturated or unsaturated hydrocarbon groups, and -OR (R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, and more preferably a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms). R 21 and R 22 The substituted or unsubstituted organic group having 1 to 20 carbon atoms represented by the formula (I) is preferably an organic group having a carbon atom bonded to a boron atom. Furthermore, the carbon atom is preferably an sp3 carbon atom. This facilitates the generation of boron radicals and enhances the iodine abstraction ability of the radicals. From this perspective, R 21 and R 22 The substituted or unsubstituted organic group having 1 to 20 carbon atoms represented by the formula (I) is preferably a substituted or unsubstituted alkyl group.

[0046] R 21 or R 22When the substituted or unsubstituted organic group having 1 to 20 carbon atoms represented by the formula (2) has a substituent, the substituent may be, for example, a group containing a boron atom. An example of the group containing a boron atom is -BY2, where each Y is independently a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms, and two Ys may be linked to each other to form a cyclic structure. The cyclic structure formed may be a bicyclo structure. A ligand may further be coordinated to the boron atom in the substituent. Details of the ligand are the same as those of the ligand of the boron atom shown in formula (21) described below.

[0047] R 22 When R is a boron-containing group, the boron atom in the boron-containing group is bonded to the boron atom in formula (21). 22 Examples of the boron-containing group represented by the formula (2) include -BZ2, where each Z is independently a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms, and two Zs may be linked to each other to form a cyclic structure. A ligand may be further coordinated to the boron atom in the boron-containing group. Details of the ligand are the same as those of the ligand of the boron atom shown in formula (21) described below.

[0048] A 1 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a hydrogen atom, a bromine atom, or an iodine atom, more preferably a hydrogen atom or an iodine atom, and even more preferably a hydrogen atom. The boron atom in formula (21) may further have a ligand attached. In other words, in addition to the three covalent bonds to the boron atom shown in formula (21), there may be a ligand attached to the boron atom by a coordinate bond. For example, in complexes such as the borane-tetrahydrofuran complex described below, the BH3 is stabilized by the ligand, which tends to improve handling. In addition, the presence of a ligand facilitates the generation of boron radicals. Examples of the ligand include a ligand having a nitrogen atom or an oxygen atom at the coordination site, and a hydrogen atom or a substituted or unsubstituted organic group having 1 to 20 carbon atoms bonded to each of the bonds of the nitrogen atom or oxygen atom independently. When a plurality of the substituted or unsubstituted organic groups having 1 to 20 carbon atoms are present, they may be linked to form a ring structure. Examples of the ligand include tetrahydrofuran, pyridine, trimethylamine, triethylamine, and tetramethylethylenediamine.

[0049] A from boron atom 1 In view of the extraction speed and handling properties, a preferred embodiment of the compound represented by formula (21) is 1 is a hydrogen atom and the boron atom has a ligand, or 1 is an iodine atom.

[0050] In one embodiment, formula (21) may be a compound represented by the following formula (21a):

[0051] [ka]

[0052] In formula (21a), A 1 and R 21 is A in equation (21) 1 and R 21 are synonymous with R. 26 represents a substituted or unsubstituted divalent organic group, R 27 and R 28 each independently represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group; R 26 ~R 28 The total number of carbon atoms is 1 to 20. The two boron atoms shown in formula (21a) may each independently be further coordinated with a ligand.

[0053] In formula (21a), R 26is preferably a substituted or unsubstituted divalent organic group having 1 to 10 carbon atoms, and more preferably a substituted or unsubstituted divalent organic group having 1 to 6 carbon atoms. 27 and R 28 are each independently preferably a hydrogen atom or a substituted or unsubstituted organic group having 1 to 15 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted organic group having 1 to 10 carbon atoms. Details of the ligand are the same as those of the ligand of the boron atom shown in formula (21).

[0054] In a further embodiment, formula (21) may be a compound represented by the following formula (21b):

[0055] [ka]

[0056] In formula (21b), A 1 and R 21 is A in equation (21) 1 and R 21 are synonymous with R 29 and R 30 each independently represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group; R 29 and R 30 The total number of carbon atoms in the formula (21b) is 1 to 20. The two boron atoms in the formula (21b) may each independently be further coordinated with a ligand.

[0057] In formula (21b), R 29 and R 30 are each independently preferably a hydrogen atom or a substituted or unsubstituted organic group having 1 to 15 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted organic group having 1 to 10 carbon atoms. Details of the ligand are the same as those of the ligand of the boron atom shown in formula (21).

[0058] In one embodiment, a plurality of compounds represented by formula (21) may be aggregated to form a multimer, for example, a dimer.

[0059] Examples of compounds represented by formula (21) include 9-borabicyclo[3.3.1]nonane, 9-iodo-9-borabicyclo[3.3.1]nonane, borane-tetrahydrofuran complex, borane-pyridine complex, borane-trimethylamine complex, borane-triethylamine complex, pinacolborane, catecholborane, isopinocampheylborane-tetramethylethylenediamine complex, and boron triiodide. Among these, at least one compound selected from the group consisting of 9-borabicyclo[3.3.1]nonane, 9-iodo-9-borabicyclo[3.3.1]nonane, and boron triiodide is preferred. Compounds represented by formula (21) may be used singly or in combination.

[0060] (Compound represented by formula (22))

[0061] [ka]

[0062] In formula (22), R 23 and R 24 each independently represents a hydrogen atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms; R 25 represents a hydrogen atom, an iodine atom, a substituted or unsubstituted organic group having 1 to 20 carbon atoms, or a silicon-containing group, and the silicon atom in the silicon-containing group is bonded to the silicon atom in formula (22). 23 ~R 25 Except when all of R are hydrogen atoms. 23 , R 24 , and R 25 Two or more of these may be linked to form a cyclic structure. 2 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom.

[0063] In the reaction system, the compound represented by formula (22) is converted to A 2 The radical generated on the phosphorus atom by the abstraction abstracts iodine from the halogen-containing organic iodide compound.

[0064] R 23 , R 24 , and R 25 Each of the substituted or unsubstituted organic groups having 1 to 20 carbon atoms represented by the formula (I) is preferably a substituted or unsubstituted organic group having 1 to 15 carbon atoms, and more preferably a substituted or unsubstituted organic group having 1 to 10 carbon atoms. Examples of such organic groups include saturated or unsaturated hydrocarbon groups, and -OR (R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, and more preferably a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms). R 23 , R 24 , and R 25 The substituted or unsubstituted organic group having 1 to 20 carbon atoms represented by the formula (I) is preferably an organic group having a carbon atom bonded to a silicon atom. Furthermore, the carbon atom is preferably an sp2 carbon atom or an sp3 carbon atom. This facilitates the generation of silicon radicals and enhances the iodine abstraction ability of the radicals. From this perspective, R 23 , R 24 , and R 25 The substituted or unsubstituted organic group having 1 to 20 carbon atoms represented by the formula (I) is preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

[0065] R 23 , R 24 , and R 25 When the substituted or unsubstituted organic group having 1 to 20 carbon atoms represented by the formula (I) has a substituent, the substituent can be, for example, a group containing a silicon atom. Examples of the group containing a silicon atom include -SiY3, where each Y is independently a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms, and multiple Ys can be linked together to form a cyclic structure.

[0066] R 25 When R is a silicon-containing group, the silicon atom in the silicon-containing group is bonded to the silicon atom in formula (22). 25Examples of the silicon-containing group represented by the formula include -SiZ3, where each Z is independently a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms, and multiple Zs may be linked together to form a cyclic structure.

[0067] In one embodiment, from the viewpoint of catalyst stability and handling, R 23 , R 24 , and R 25 Preferably, each independently has an aromatic ring. 23 , R 24 , and R 25 In a preferred embodiment, each of the groups independently represents a substituted or unsubstituted phenyl group. From the viewpoint of the polymerization reactivity of the catalyst, R 23 , R 24 , and R 25 may or may not each independently have an aromatic ring.

[0068] A 2 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and is more preferably a hydrogen atom.

[0069] In one embodiment, Si-A 2 A from Bond 2 From the viewpoint of the extraction speed and handling property, the compound represented by formula (22) is 2 is a hydrogen atom, and R 23 , R 24 , and R 25 It is preferable that the compound has an aromatic ring in at least one of the above groups.

[0070] In one embodiment, formula (22) may be a compound represented by the following formula (22a):

[0071] [ka]

[0072] In formula (22a), A2 , R 23 , and R 24 is A in equation (22) 2 , R 23 , and R 24 are synonymous with R. 31 represents a substituted or unsubstituted divalent organic group, R 32 , R 33 , and R 34 each independently represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms; R 31 ~R 34 The total number of carbon atoms is 1 to 20.

[0073] In formula (22a), R 31 is preferably a substituted or unsubstituted divalent organic group having 1 to 10 carbon atoms, and more preferably a substituted or unsubstituted divalent organic group having 1 to 6 carbon atoms. 32 , R 33 , and R 34 are each independently preferably a hydrogen atom or a substituted or unsubstituted organic group having 1 to 15 carbon atoms, and more preferably a hydrogen atom or a substituted or unsubstituted organic group having 1 to 10 carbon atoms. From the viewpoint of catalyst stability and ease of handling, R 32 , R 33 , and R 34 It is preferred that at least one, preferably two or more, and more preferably two of R 32 , R 33 , and R 34 As a preferred embodiment of R 32 and R 33 are each independently a substituted or unsubstituted phenyl group, and R 34 is a hydrogen atom.

[0074] In a further embodiment, formula (22) may be a compound represented by the following formula (22b):

[0075] [ka]

[0076] In formula (22b), A 2 , R 23 and R 24 is A in equation (22) 2 , R 23 and R 24 are synonymous with R 35 ~R 37 each independently represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group; R 35 ~R 37 The total number of carbon atoms is 1 to 20.

[0077] In formula (22b), R 35 ~R 37 are each independently preferably a hydrogen atom or a substituted or unsubstituted organic group having 1 to 15 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted organic group having 1 to 10 carbon atoms.

[0078] Examples of the compound represented by formula (22) include 1,4-bis(dimethylsilyl)benzene, 1,1,2,2-tetraphenyldisilane, phenylsilane, di-tert-butylsilane, tri-tert-butylsilane, diphenylsilane, trimethylsilane, tert-butyldimethylsilane, di-tert-butylmethylsilane, dimethylphenylsilane, diphenylmethylsilane, tert-butyldiphenylsilane, triphenylsilane, and silicon tetraiodide. 2 A from Bond 2 From the viewpoint of the extraction speed and handling properties, preferred compounds include 1,4-bis(dimethylsilyl)benzene, 1,1,2,2-tetraphenyldisilane, dimethylphenylsilane, diphenylmethylsilane, tert-butyldiphenylsilane, triphenylsilane, etc. 2 A from Bond 2 From the viewpoint of the abstraction rate, trimethylsilane, tri-tert-butylsilane, and tert-butyldimethylsilane are also included. The compound represented by formula (22) may be used alone or in combination of two or more.

[0079] The amounts of the compound represented by formula (21) and the compound represented by formula (22) added may be adjusted as appropriate. From the viewpoint of obtaining a halogen-containing polymer with a suitably controlled molecular weight distribution, it is preferable to use 0.01 mol to 100 mol, more preferably 0.1 mol to 50 mol, still more preferably 0.2 mol to 10 mol, and particularly preferably 0.3 mol to 1.0 mol of at least one selected from the group consisting of the compound represented by formula (21) and the compound represented by formula (22) per mol of compound (10).

[0080] <Compound (10)> Compound (10) is a halogen-containing organic iodide compound having a partial structure represented by the following formula (1).

[0081] [ka]

[0082] In formula (1), * represents a bond bonded to an organic group, and X represents a fluorine atom or a chlorine atom. 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or -CX 5 X 6 X 7 represents X 5 ~X 7 each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom. Hereinafter, the partial structure represented by formula (1) will also be referred to as partial structure (1).

[0083] From the viewpoint of the rate of abstraction of the iodine atom and the rate of addition reaction of the generated carbon-centered radical, X is preferably a fluorine atom.

[0084] From the viewpoint of the rate of iodine atom abstraction and the rate of addition of the resulting carbon-centered radical, X 1 is preferably a hydrogen atom or a fluorine atom.

[0085] Compound (10) is not limited to the overall structure of the compound as long as it has the partial structure (1). That is, the organic group to which * is bonded is not limited to a hydrocarbon group, but may be various functional groups such as a hydroxyl group or an amino group, a halogeno group (halogen atom), or a hydrogen atom. The organic group may also contain a heteroatom, and its valence and molecular weight are not particularly limited.

[0086] The number of partial structures (1) contained in compound (10) is not particularly limited. For example, compound (10) may be a monoiodide halogen-containing organic compound having one partial structure (1), a diiodide halogen-containing organic compound having two partial structures (1), or a polyiodide halogen-containing organic compound having three or more partial structures (1). For example, compound (10) may be a monoiodo halogen-containing organic compound in which a substituted or unsubstituted alkyl group, a halogen atom, or a hydrogen atom is bonded to *. Furthermore, compound (10) may be a diiodo-halogen-containing organic compound in which a divalent organic group such as a substituted or unsubstituted alkylene group or an ether bond and a partial structure (1) bonded to the divalent organic group are bonded to *.

[0087] (Monoiodo-containing halogen-containing organic compounds) Among the compounds (10), the monoiodo-halogen-containing organic compound may be a compound having a structure represented by the following formula: 10 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a hydrogen atom, a fluorine atom, or a chlorine atom. X represents a fluorine atom or a chlorine atom. X 20 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or -CX 5 X 6 X 7 represents X 5 ~X 7 each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

[0088] [ka]

[0089] In the above formula, X is preferably a fluorine atom.

[0090] In the above formula, X 20 is preferably a hydrogen atom or a fluorine atom.

[0091] R 10 Of these, the substituted or unsubstituted alkyl group is preferably a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 7 carbon atoms. Examples of the alkyl group having 1 to 7 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, etc. Among these, a linear or branched alkyl group having 1 to 4 carbon atoms is more preferred, and a methyl group or an ethyl group is even more preferred.

[0092] Examples of the substituted alkyl group having 1 to 7 carbon atoms include alkyl groups having a substituent such as a fluorine atom, a chlorine atom, an alkoxy group, or a fluoroalkoxy group at any position. Among these, alkyl groups having 2 to 15 fluorine atoms are more preferred, perfluoroalkyl groups are even more preferred from the viewpoint of suppressing hydrogen atom abstraction reactions by radicals, perfluoroalkyl groups having 1 to 6 carbon atoms are even more preferred, and perfluoroalkyl groups having 1 to 4 carbon atoms are particularly preferred from the viewpoint of reducing bioaccumulation. That is, R 10 When is a substituted alkyl group, compound (10) is preferably a compound represented by the following formula (11).

[0093] [ka]

[0094] In the above formula, R 11 represents a perfluoroalkyl group having 1 to 4 carbon atoms, X represents a fluorine atom or a chlorine atom, and X21 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or -CX 24 X 25 X 26 represents X 24 ~X 26 each independently represents a hydrogen atom, a fluorine atom or a chlorine atom.

[0095] In the above formula, X is preferably a fluorine atom.

[0096] In the above formula, X 21 is preferably a hydrogen atom or a fluorine atom.

[0097] R 10 Of these, the aryl group is preferably an aryl group having 6 to 12 carbon atoms and a heteroaryl group having 3 to 12 carbon atoms, and specifically, a phenyl group, a naphthyl group, a pyridyl group, a pyrrole group, a furyl group, and a thienyl group are more preferred. R 10 Of these, the arylalkyl group is preferably an arylalkyl group having 7 to 15 carbon atoms and a heteroarylalkyl group having 4 to 15 carbon atoms, and specifically, a benzyl group, a 2-pyridylmethyl group, a 3-pyridylmethyl group, and a 4-pyridylmethyl group are more preferred.

[0098] Specific examples of the monoiodine-containing halogen-containing organic compounds include difluoroiodomethane, trifluoroiodomethane, chlorodifluoroiodomethane, 1,1-difluoroethyl iodide, 1,1-difluoro-n-propyl iodide, 1,1-difluoro-n-butyl iodide, 1,1-difluoro-isobutyl iodide, 1,1-difluoro-n-pentyl iodide, sec-butyldifluoromethylene iodide, tert-butyldifluoromethylene iodide, 1,1-difluoro-n- Examples of the iodide include hexyl iodide, 1,1-difluoro-n-heptyl iodide, 1,1-difluoro-n-octyl iodide, cyclohexyldifluoromethylene iodide, C2F5I, CHF2CF2I, CF3CF2CF2I, (CF3)2CFI, CF3(CF2)3I, (CF3)2CFCF2I, CF3(CF2)4I, CF3(CF2)5I, 1,2-dichloro-1,1,2-trifluoroethyl iodide, 1-chloro-1-iodotetrafluoroethane, and chloroiodoacetic acid.

[0099] The monoiodo-halogen-containing organic compound can be produced by a conventionally known method, for example, by the following method: 10 It can also be produced by reacting a radical generator such as CF2C(=O)O)2 with I2.

[0100] (Diiodo-containing halogen-containing organic compounds) Among the compounds (10), the diiodo-halogen-containing organic compound may be a compound having a structure represented by the following formula: 10 "'" represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted arylene alkylene group, or a substituted or unsubstituted alkylene arylene alkylene group. X represents a fluorine atom or a chlorine atom. X 20 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or -CX 5 X 6 X 7 represents X 5 ~X 7 each independently represents a hydrogen atom, a fluorine atom or a chlorine atom.

[0101] [ka]

[0102] From the viewpoint of the rate of abstraction of the iodine atom and the rate of addition reaction of the generated carbon-centered radical, X is preferably a fluorine atom.

[0103] From the viewpoint of the rate of iodine atom abstraction and the rate of addition of the resulting carbon-centered radical, X 20 are preferably each independently a hydrogen atom or a fluorine atom.

[0104] R 10 Of the above, the substituted or unsubstituted alkylene group is preferably a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 6 carbon atoms. Examples of alkylene groups having 1 to 6 carbon atoms include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, n-hexylene, 1,4-cyclohexylene, etc. Among these, linear or branched alkylene groups having 1 to 4 carbon atoms are more preferred, and ethylene is even more preferred.

[0105] Examples of the substituted alkylene group having 1 to 6 carbon atoms include alkylene groups having a substituent such as a fluorine atom, a chlorine atom, an alkoxy group, or a fluoroalkoxy group at any position. Among these, an alkylene group having 2 to 12 fluorine atoms is more preferred, a perfluoroalkylene group is even more preferred from the viewpoint of suppressing hydrogen atom abstraction reactions by radicals, a perfluoroalkylene group having 1 to 4 carbon atoms is even more preferred, and a perfluoroalkylene group having 2 to 4 carbon atoms is particularly preferred. That is, compound (10) is R 10 When ' is a perfluoroalkylene group having 1 to 4 carbon atoms, the compound is represented by the following formula (12).

[0106] [ka]

[0107] In the above formula, R 12 represents a perfluoroalkylene group having 1 to 4 carbon atoms. X represents a fluorine atom or a chlorine atom. X 22 and X 23 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or -CX 24 X 25 X 26 represents X 24 ~X 26 each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

[0108] In the above formula, it is preferable that each X is independently a fluorine atom.

[0109] In the above formula, X 22 and X 23 are preferably each independently a hydrogen atom or a fluorine atom.

[0110] R 10 Among these, the arylene group is preferably an arylene group having 6 to 12 carbon atoms and a heteroarylene group having 3 to 12 carbon atoms. Specifically, a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 4,4'-biphenylene group, a 2,2'-biphenylene group, a 2,6-naphthylene group, a 2,7-naphthylene group, a 2,4-pyridylene group, a 2,5-pyridylene group, a 2,6-pyridylene group, a pyrrolene group, a furylene group, a thienylene group, and a 1,5-furandiyl group are more preferred. R 10 Of these, the arylene alkylene group is preferably an arylene alkylene group having 7 to 15 carbon atoms and a heteroarylene alkylene group having 4 to 15 carbon atoms. Specifically, a benzylene group, a 2-pyridylene methylene group, a 3-pyridylene methylene group, and a 4-pyridylene methylene group are more preferred.

[0111] R 10Among these, the alkylenearylenealkylene group is preferably an alkylenearylenealkylene group having 8 to 18 carbon atoms, and an alkyleneheteroarylenealkylene group having 5 to 18 carbon atoms. Specifically, a 1,2-dimethylenephenylene group, a 1,3-dimethylenephenylene group, a 1,4-dimethylenephenylene group, a 2,2'-dimethylenebiphenylene group, a 2,4-dimethylenepyridylene group, a 2,5-dimethylenepyridylene group, a 2,6-dimethylenepyridylene group, and a 1,5-dimethylfurandiyl group are more preferred.

[0112] Specific examples of the diiodo-halogen-containing organic compound include 1,2-diiodotetrafluoroethane, 1,4-diiodooctafluorobutane, and 1,6-diiodododecafluorohexane. Among these, 1,4-diiodooctafluorobutane is preferred from the viewpoint of being an easy-to-handle, low-volatility liquid.

[0113] The method for producing the diiodo-containing halogen-containing organic compound is not particularly limited, and the compound can be obtained by a conventionally known method.

[0114] (Polyiodide halogen-containing organic compounds) Among compounds (10), the polyiodide halogen-containing organic compound has three or more partial structures (1). Among compounds (10), the polyiodide halogen-containing organic compound may be one in which the organic group bonded to * in partial structure (1) contains a partial structure of a fluorine-containing polymer such as an unvulcanized fluoroelastomer or a partial structure of a polysiloxane, and compound (10) has three or more partial structures (1). "The organic group bonded to * in partial structure (1) contains a partial structure of a polysiloxane" refers to, for example, a case in which partial structure (1) is bonded to a polysiloxane via a divalent bonding group such as a substituted or unsubstituted alkylene group or an ether bond. The polysiloxane may be silicone or a product produced by a condensation reaction of a silane coupling agent. The polyiodide halogen-containing organic compound can be produced by a conventionally known method.

[0115] Compound (10) may be a compound containing a plurality of units represented by the following formula (4). When compound (10) contains a plurality of units represented by the following formula (4), the fluorine content of compound (10) is preferably 50% by mass or more, more preferably 60% by mass or more, from the viewpoints of heat resistance and flame retardancy. The fluorine content of the compound is determined by combustion ion chromatography.

[0116] [ka]

[0117] In the above formula, X 31 ~X 34 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or -CX 35 X 36 X 37 represents X 35 ~X 37 each independently represents a hydrogen atom, a fluorine atom or a chlorine atom.

[0118] The amount of compound (10) used in the production method of the present disclosure is not particularly limited. In one embodiment, compound (10) is used in an amount of preferably 0.0001 mol to 3 mol, more preferably 0.001 mol to 2 mol, and even more preferably 0.002 mol to 1 mol, per mol of the compound represented by formula (3).

[0119] Compound (10) is preferably at least one selected from the group consisting of monoiodine-containing halogen-containing organic compounds and diiodine-containing halogen-containing organic compounds, and is preferably at least one selected from the group consisting of compounds represented by formula (11) and compounds represented by formula (12).

[0120] When a monoiodo-halogen-containing organic compound and a diiodo-halogen-containing organic compound are used in combination as compound (10), the diiodo-halogen-containing organic compound is used in an amount of preferably 0.01 mol or more, more preferably 0.05 mol or more, and even more preferably 0.1 mol or more per mol of the monoiodo-halogen-containing organic compound. The diiodo-halogen-containing organic compound is used in an amount of preferably 100 mol or less, more preferably 10 mol or less, and even more preferably 5 mol or less per mol of the monoiodo-halogen-containing organic compound.

[0121] <Compound represented by formula (3)> The compound represented by formula (3) is a compound that is added to compound (10) having a partial structure represented by formula (1) by the production method of the present disclosure.

[0122] [ka]

[0123] In formula (3), R 1 ~R 4 R each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 40 carbon atoms. 1 and R 4 , or R 2 and R 3 may be linked to form a cyclic structure.

[0124] R 1 ~R 4 The number of carbon atoms in the substituted or unsubstituted organic group having 1 to 40 carbon atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 12. The organic group may be linear, branched, or cyclic, and may or may not contain an unsaturated bond. The organic group may or may not contain a heteroatom, and the substituent main chain may contain a heteroatom.

[0125] Examples of the substituted or unsubstituted 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, and a cyano group.

[0126] When the substituted or unsubstituted 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, or a heteroarylalkoxy group, the hydrocarbon group may be linear, branched, or cyclic, and may or may not contain an unsaturated bond.

[0127] 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.

[0128] Examples of the substituted organic group having 1 to 40 carbon atoms include a substituted alkyl group, a substituted alkoxy group, a substituted alkoxycarbonyl group, an N-substituted carbamoyl group, etc. The number of substituents may be one or more. Examples of the substituent of the substituted alkyl group include a fluorine atom, a chlorine atom, a hydroxy group, an alkoxy group, an amino group, a carboxylic acid group, a sulfonic acid group, and a 1,3,5-triazinetrione skeleton. Examples of the substituent of the substituted alkoxy group include a fluorine atom, a hydroxy group, and an amino group. Examples of the substituent of the substituted alkoxycarbonyl group include a fluorine atom, a hydroxy group, and an amino group. Examples of the substituent of the N-substituted carbamoyl group include an alkyl group and an alkoxyalkyl group.

[0129] In equation (3), R 1 and R 4 , or R2 and R 3 may be linked to form a cyclic structure. That is, the compound represented by formula (3) may be a compound having a cyclic structure such as maleic anhydride or itaconic anhydride.

[0130] From the viewpoint of reducing steric hindrance in the elongation reaction and facilitating the reaction, the compound represented by formula (3) is 1 ~R 4 At least two of the above are preferably compounds selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, and a methyl group.

[0131] The compound represented by formula (3) may be a compound having one reactive carbon-carbon double bond or a compound having multiple reactive carbon-carbon double bonds. Thus, the compound represented by formula (3) may be a diallyl compound such as diallylamine, a triallyl compound such as triallyl isocyanurate, or the like.

[0132] Examples of the compound represented by formula (3) 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-hydroxypropyl (meth)acrylate; 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-based 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 its alkali metal salts (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-methylallyl) 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, 1,2-dichloro-1,2-difluoroethylene, 1H,1H,2H-perfluoro(n-1-hexene), 1H,1H,2H-perfluoro(n-1-octene); vinyl esters such as vinyl acetate; Examples of suitable compounds include ester monomers; divinylfluoroalkanes such as 1,4-divinyloctafluorobutane and 1,6-divinyldodecafluorohexane; acrylonitrile; acrylamide monomers such as acrylamide and N,N-dimethylacrylamide; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, and hydroxybutyl vinyl ether; and perfluoro(alkyl vinyl ethers) such as perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), and perfluoro(n-propyl vinyl ether). The compounds represented by formula (3) may be used singly or in combination of two or more.

[0133] In a preferred embodiment, in formula (3), R 1 ~R 4 each independently represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 40 carbon atoms and having at least one reactive carbon-carbon double bond; R 1 and R 4 , or R 2 and R 3may be linked to form a cyclic structure, and an embodiment of the formula (3) is one in which the formula (3) has at least two reactive carbon-carbon double bonds. In this case, the compound represented by formula (3) is also referred to as a "compound represented by formula (3) having at least two reactive carbon-carbon double bonds." For example, by reacting a compound represented by formula (3) having at least two reactive carbon-carbon double bonds with a fluorine-containing polymer having a CI bond, or a chlorine-containing polymer having a CI bond, a crosslinked structure can be introduced into the fluorine-containing polymer or chlorine-containing polymer.

[0134] In the compound represented by formula (3) having at least two reactive carbon-carbon double bonds, the number of reactive carbon-carbon double bonds in the substituted or unsubstituted organic group having 1 to 40 carbon atoms and having at least one reactive carbon-carbon double bond is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3.

[0135] In the compound represented by formula (3) having at least two reactive carbon-carbon double bonds, the number of carbon atoms in the substituted or unsubstituted organic group having at least one reactive carbon-carbon double bond of 1 to 40 is preferably 1 to 30, more preferably 1 to 20. The organic group may be linear, branched, or cyclic, and may or may not contain an unsaturated bond. Furthermore, the organic group may or may not contain a heteroatom, and the substituent may contain a heteroatom in its main chain.

[0136] Specific examples of the compound represented by formula (3) having at least two reactive carbon-carbon double bonds include diallylamine, 1,4-divinyloctafluorobutane, 1,6-divinyldodecafluorohexane, triallyl isocyanurate, tri(2-methyl-allyl) isocyanurate, divinylbenzene, and a fluorine-containing compound having two maleimide groups.

[0137] A further preferred embodiment is one in which the compound represented by formula (3) includes a compound represented by the following formula (5).

[0138] [ka]

[0139] In formula (5), X represents a fluorine atom or a chlorine atom, and X 2 ~X 4 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or -CX 5 X 6 X 7 represents X 5 ~X 7 each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

[0140] In equation (5), X 2 ~X 4 Only one of the following is -CX 5 X 6 X 7 In this case, from the viewpoint of reactivity, X 3 or X 4 Ga-CX 5 X 6 X 7 Preferably, X 3 Ga-CX 5 X 6 X 7 It is more preferable that: Also, X 2 ~X 4 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0141] Examples of the compound represented by formula (5) 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, 1,2-difluoro-1,2-diiodoethylene, vinyl chloride, and vinylidene chloride.

[0142] As the compound represented by formula (5), vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, vinyl chloride, or vinylidene chloride is preferred from the viewpoint of polymerization reactivity when obtaining a polymer.

[0143] <Other optional ingredients> In the production method of the present disclosure, other components may be further used, such as a radical initiator other than compound (10), a solvent, an emulsifier, a suspending aid, an acid or alkali, and a reaction inhibitor other than the compound represented by formula (21) and the compound represented by formula (22).

[0144] (radical initiator) In the production method of the present disclosure, a radical initiator other than compound (10) may be used in combination. Examples of the radical initiator include an azo-based radical initiator and a peroxide-based radical initiator.

[0145] 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-methylbutyramide), 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.

[0146] It is preferable to select these azo radical initiators appropriately depending on the reaction conditions. For example, in the case of low-temperature polymerization at 40° C. or less, it is preferable to use 2,2′-azobis(2,4-dimethylvaleronitrile) (ADVN), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), or the like. In the case of medium temperature polymerization at 40 to 80°C, it is preferable to use 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (AMBN), dimethyl-2,2'-azobisisobutyrate (MAIB), 1,1'-azobis(1-acetoxy-1-phenylethane), 4,4'-azobis(4-cyanovaleric acid) (ACVA), 2,2'-azobis(2-methylbutyramide), 2,2'-azobis(2-methylamidinopropane) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], or the like. In the case of high-temperature polymerization at 80°C or higher, it is preferable to use 1,1'-azobis(1-cyclohexanecarbonitrile) (ACHN), 2-cyano-2-propylazoformamide, 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], or the like.

[0147] As the peroxide radical initiator, dialkyl peroxides, diacyl peroxides, and peroxyketals are preferred from the viewpoint of ease of β-cleavage, and diacyl peroxides are more preferred. These peroxide radical initiators rapidly generate carbon-centered radical species by β-cleavage, and therefore tend to favorably exhibit the catalytic function of the compound represented by formula (21) and the compound represented by formula (22).

[0148] Specific examples of peroxide radical initiators include dialkyl peroxides such as tert-butylcumyl peroxide, di-tert-butyl peroxide, and di-tert-hexyl peroxide; diacyl peroxides such as diisobutyryl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, disuccinic acid peroxide, benzoyl peroxide, and a mixture of dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide, and m-toluoyl peroxide; and peroxyketals such as 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, 1,1-di(tert-hexylperoxy)cyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, n-butyl 4,4-di(tert-butylperoxy)valerate, and 2,2-di(tert-butylperoxy)butane. Furthermore, the fluorine-containing peroxides described in JP-A-08-506140 can also be used.

[0149] In the reaction of compound (10) with a compound represented by formula (3) in the presence of at least one selected from the group consisting of compounds represented by formula (21) and compounds represented by formula (22), when a radical initiator other than compound (10) is used in combination, the radical initiator other than compound (10) is preferably used in an amount of 0.0001 mol to 10 mol, more preferably 0.01 mol to 5 mol, and even more preferably 0.1 mol to 2 mol, per mol of compound (10). In the reaction of compound (10) with a compound represented by formula (3) in the presence of at least one selected from the group consisting of compounds represented by formula (21) and compounds represented by formula (22), when an azo radical initiator or a peroxide radical initiator is used in combination, the azo radical initiator or the peroxide radical initiator is preferably used in an amount of 0.0001 mol to 10 mol, more preferably 0.01 mol to 5 mol, and even more preferably 0.1 mol to 2 mol, per mol of compound (10).

[0150] (solvent) The reaction in the production method of the present disclosure may be carried out using an organic solvent (including an ionic liquid) or an aqueous solvent.

[0151] Examples of organic solvents include benzene, toluene, 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. 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.

[0152] Examples of aqueous solvents include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol.

[0153] The amount of solvent used can be adjusted as appropriate. For example, it is preferable to use 0.01 L to 50 L of solvent, more preferably 0.05 L to 10 L, and even more preferably 0.1 L to 5 L, per 1000 g of the resulting iodine-containing compound.

[0154] (Reaction inhibitor) In the production method of the present disclosure, a reaction inhibitor other than the compound represented by formula (21) and the compound represented by formula (22) may be used in combination. 1 When A is a hydrogen atom, the use of a nitrogen-centered coordinating compound or an oxygen-centered coordinating compound as a reaction inhibitor in combination with the compound represented by formula (21) tends to result in particularly favorable controlled polymerization. Examples of such reaction inhibitors include ammonia, trialkylamines, pyridine, and other nitrogen-containing aromatic compounds; water, alcohols, ethers, and carbonyl-containing compounds. 1 When a compound represented by formula (21) in which is a hydrogen atom is used in combination with a nitrogen-centered coordinating compound or an oxygen-centered coordinating compound, it is preferable to use 0.1 mol to 10 mol of the coordinating compound in combination with 1 mol of the compound represented by formula (21).

[0155] <product> The resulting iodine-containing compound may be a polymer, which may be a block copolymer, a random copolymer, or an alternating copolymer.

[0156] When the obtained iodine-containing compound is a polymer, the molecular weight of the polymer can be adjusted by the reaction time, the types and amounts of the compound represented by formula (21) and the compound represented by formula (22), and the amount of compound (10). 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 this disclosure are determined by SEC (Size Exclusion Chromatography) measurement, using polystyrene as a standard substance for molecular weight conversion. The measurement conditions, excluding the apparatus and mobile phase, conform to those in the Examples of JP 2011-226846 A. The measurement is performed at 30°C using tetrahydrofuran as the mobile phase. For polymers insoluble in tetrahydrofuran at 30°C, a solvent in which the polymer is soluble is selected from isophorone, 2-chlorobenzotrifluoride, 2,6-dichlorobenzotrifluoride, 3',5'-bis(trifluoromethyl)acetophenone, and mixtures thereof, and the measurement is performed at 140°C to 200°C.

[0157] According to the production method of the present disclosure, it is possible to control the polydispersity of the obtained polymer to, for example, 2.5 or less. According to the production method of the present disclosure, it is also possible to obtain a polymer having a very narrow molecular weight distribution, such as a polydispersity of preferably 2.1 or less, 2.0 or less, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, or 1.5 or less. The lower limit of the polydispersity is 1.0 by definition. The polydispersity (PD), which is an index of molecular weight distribution, is calculated by the following formula: {PD=Mw(weight average molecular weight) / Mn(number average molecular weight)} In measuring polydispersity, the same solvent is used for measuring Mn and Mw by SEC.

[0158] When a polymer is produced using an azo-based radical initiator or a peroxide-based radical initiator in the production method of the present disclosure, the resulting iodine-containing compound contains a portion of a structure derived from the radical initiator used. However, the production method of the present disclosure can reduce the proportion of structures derived from the azo-based radical initiator or peroxide-based radical initiator used relative to the terminal end of the resulting polymer, compared to polymerization methods using general azo-based radical initiators or peroxide-based radical initiators. That is, the production method of the present disclosure allows polymerization to proceed from compound (10) rather than from an azo-based radical initiator or peroxide-based radical initiator as the initiator, thereby reducing the proportion of structures derived from the azo-based radical initiator or peroxide-based radical initiator incorporated into the polymer. The proportion of structures derived from the azo-based radical initiator or peroxide-based radical initiator relative to the number of moles of the polymer terminal is preferably 40 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, and particularly preferably 10 mol% or less. Whether the proportion of the structure derived from the azo radical initiator or peroxide radical initiator relative to the number of moles of the polymer terminals is 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less is determined by calculating the number of moles of the initiator using NMR and calculating the ratio of the number of moles of the initiator to the number of moles of the polymer terminals defined by formula X. In formula X, the average molecular weight of the repeating unit is an arithmetic average weighted by the molar fraction of the molecular weight of the repeating unit. (Formula X) (Number of moles of polymer terminals) = 2 × Mn / (average molecular weight of repeating units in polymer) Furthermore, when the radical generated by decomposition of the radical initiator has a multiple bond between a carbon atom and a heteroatom, the above-mentioned items can also be determined by IR.

[0159] [Method for producing iodine-containing compounds] As described above, the production method of the present disclosure includes reacting compound (10) with a compound represented by formula (3) in the presence of at least one selected from the group consisting of a compound represented by formula (21) and a compound represented by formula (22). In one embodiment, the production method of the present disclosure can produce a polymer of a fluorine-containing monomer or a polymer of a chlorine-containing monomer. In one embodiment, the production method of the present disclosure can produce a copolymer of a fluorine-containing monomer or a chlorine-containing monomer with another monomer. In one embodiment, the production method of the present disclosure can introduce a crosslinked structure into a fluorine-containing polymer or a chlorine-containing monomer. Hereinafter, exemplary embodiments (first to third embodiments) of the manufacturing method of the present disclosure will be described.

[0160] (1) First embodiment The method for producing an iodine-containing compound according to the first embodiment includes reacting a compound (10) having a partial structure represented by formula (1) with a compound represented by formula (5) in the presence of at least one compound selected from the group consisting of a compound represented by formula (21) and a compound represented by formula (22). Hereinafter, the method for producing an iodine-containing compound according to the first embodiment will also be referred to as the "production method according to the first embodiment."

[0161] In the production method according to the first embodiment, the presence of at least one compound selected from the group consisting of compounds represented by formula (21) and compounds represented by formula (22) abstracts the iodine at the terminal of compound (10), and the radical generated at the terminal causes a polymerization reaction of the compound represented by formula (5). By employing this method, a fluorine-containing polymer or chlorine-containing polymer with a highly controlled molecular weight distribution can be obtained.

[0162] Specific examples of reaction conditions are described below. In a container purged with an inert gas or a container under vacuum, at least one selected from the group consisting of compounds represented by formula (21) and compounds represented by formula (22), compound (10), and compound represented by formula (5) are mixed. Multiple compounds represented by formula (5) may be mixed. If necessary, a radical initiator other than compound (10), such as an azo-based radical initiator or a peroxide-based radical initiator, may be mixed. A reaction inhibitor other than the compound represented by formula (21) and the compound represented by formula (22) may also be used in combination. Examples of inert gases include nitrogen, argon, and helium. Among these, nitrogen or argon is preferred, and nitrogen is more preferred.

[0163] In the production method according to the first embodiment, the compound (10) is preferably used in an amount of 0.001 mol to 1 mol, more preferably 0.01 mol to 1 mol, and even more preferably 0.02 mol to 0.5 mol, relative to 1 mol of the compound represented by formula (5).

[0164] The reaction can be carried out without a solvent, but may also be carried out using an organic solvent (including an ionic liquid) or an aqueous solvent that is commonly used in general radical polymerization.

[0165] Next, the mixture obtained above is stirred. The reaction temperature and reaction time can be appropriately adjusted depending on the molecular weight, molecular weight distribution, etc. of the product. From the viewpoint of appropriately controlling the molecular weight distribution, the reaction temperature is preferably 10°C to 100°C, more preferably 20°C to 80°C, and may be 30°C to 60°C. The reaction time can be appropriately adjusted to obtain the desired molecular weight, and may be, for example, 1 hour to 24 hours, or 2 hours to 10 hours. Stirring is usually carried out at normal pressure, but may be under increased or reduced pressure.

[0166] After the reaction is completed, the target compound is isolated by removing the solvent and residual monomers under reduced pressure in a conventional manner, or by reprecipitation using a solvent in which the target compound is insoluble. Any treatment method may be used for the reaction treatment as long as it does not adversely affect the target compound.

[0167] (2) Second embodiment A method for producing an iodine-containing compound according to a second embodiment is an embodiment in which the obtained iodine-containing compound is a copolymer obtained by copolymerizing a first compound represented by formula (5) with a compound represented by formula (3) that is different from the first compound in the production method of the present disclosure. According to the method for producing an iodine-containing compound according to the second embodiment, a copolymer containing a fluorine-containing polymer or a chlorine-containing polymer represented by formula (5) can be suitably obtained. Hereinafter, the method for producing an iodine-containing compound according to the second embodiment will also be referred to as the "production method according to the second embodiment." Furthermore, hereinafter, the compound represented by formula (3) that is different from the first compound and used for copolymerization will also be referred to as a copolymerization monomer.

[0168] The details of the first compound are the same as those of the compound represented by formula (5) above.

[0169] The copolymerizable monomer may be a compound represented by formula (5) that is different from the first compound, or may be a compound represented by formula (3) other than the compound represented by formula (5). Examples of the copolymerizable monomer include (meth)acrylic acid ester monomers, styrene-based monomers, triallyl isocyanurate, ethylene, propylene, isobutylene, alkyl vinyl ether, 1H,1H,2H-perfluoro(n-1-hexene), 1H,1H,2H-perfluoro(n-1-octene), 1,4-divinyloctafluorobutane, 1,6-divinyldodecafluorohexane, and perfluoro(alkyl vinyl ether), which are different from the first compound.

[0170] Preferred (meth)acrylic acid ester monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate, with methyl (meth)acrylate or butyl (meth)acrylate being more preferred.

[0171] Preferred styrene monomers include styrene, α-methylstyrene, 2-methylstyrene, 4-methylstyrene, 4-methoxystyrene, 4-chlorostyrene, 4-(chloromethyl)styrene, divinylbenzene, and 4-styrenesulfonic acid or its alkali metal salts, with styrene, 4-methoxystyrene, 4-chlorostyrene, and 4-(chloromethyl)styrene being more preferred. Examples of the alkali metal salt include sodium salts and potassium salts.

[0172] Preferred alkyl vinyl ethers include methyl vinyl ether and ethyl vinyl ether. Preferred perfluoro(alkyl vinyl ethers) include perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), and perfluoro(n-propyl vinyl ether).

[0173] Among these, the copolymerizable monomer is preferably at least one selected from the group consisting of ethylene, propylene, isobutylene, alkyl vinyl ether, hexafluoropropylene, perfluoro(alkyl vinyl ether), triallyl isocyanurate, 1,4-divinyloctafluorobutane, 1,6-divinyldodecafluorohexane, vinyl acetate, styrene, butyl acrylate, and divinylbenzene.

[0174] The copolymerization may be block copolymerization, random copolymerization, or alternating copolymerization. Block copolymers, random copolymers, and alternating copolymers can be produced, for example, by the following method.

[0175] -Block copolymer- By using at least one selected from the group consisting of compounds represented by formula (21) and compounds represented by formula (22) and compound (10), for example, an AB diblock copolymer such as trifluoroethylene-styrene, a BAB triblock copolymer such as styrene-trifluoroethylene-styrene, etc. can be obtained.

[0176] The block copolymer may be obtained by a production method including reacting a compound (10), which is a polymer of a first compound represented by formula (5) and has a partial structure represented by formula (1), with a compound represented by formula (3) that is different from the first compound, in the presence of at least one compound selected from the group consisting of a compound represented by formula (21) and a compound represented by formula (22). The block copolymerization may be carried out using a radical initiator other than compound (10) in combination.

[0177] For example, when obtaining an AB diblock copolymer, for example, when producing a trifluoroethylene-styrene copolymer, the process is as follows. First, polytrifluoroethylene is produced by the method described in the production method according to the first embodiment. Next, styrene is mixed with the obtained polytrifluoroethylene, and a reaction is carried out by the method described in the production method according to the first embodiment, thereby obtaining a trifluoroethylene-styrene copolymer. However, in the polymerization of the copolymerization monomer, the "compound represented by formula (5)" to be polymerized in the first embodiment should be read as "copolymerization monomer."

[0178] When a BAB triblock copolymer is produced, a method can be used in which a diiodo-halogen-containing organic compound is used in place of the monoiodo-halogen-containing organic compound in the above-mentioned method for producing an AB diblock copolymer.

[0179] In the above-described method for producing a block copolymer, after one block is produced, the reaction for producing the next block may be started immediately, or the reaction may be terminated and purified before starting the reaction for the next block. The block copolymer can be isolated by a conventional method.

[0180] -Random copolymers, alternating copolymers- A random copolymer or an alternating copolymer can be obtained by reacting a first compound represented by formula (5) with a copolymerizable monomer in parallel in the presence of at least one compound selected from the group consisting of a compound represented by formula (21) and a compound represented by formula (22). The copolymerization may be carried out in combination with a radical initiator other than compound (10).

[0181] Whether the resulting copolymer is a random copolymer or an alternating copolymer is determined by the types and relative amounts of the first compound and copolymerizing monomer.

[0182] In either case of random copolymerization or alternating copolymerization, other polymerization conditions can be the same as those described in the first embodiment.

[0183] (3) Third embodiment The method for producing an iodine-containing compound according to the third embodiment comprises: 1 ~R 4 each independently represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 40 carbon atoms and having at least one reactive carbon-carbon double bond; R 1 and R 4 , or R 2 and R 3 may be linked to form a cyclic structure, and the formula (3) has at least two reactive carbon-carbon double bonds. That is, the method for producing an iodine-containing compound according to the third embodiment is an embodiment in which a compound represented by formula (3) having at least two reactive carbon-carbon double bonds is used as the compound represented by formula (3). Hereinafter, the method for producing an iodine-containing compound according to the third embodiment will also be referred to as the "production method according to the third embodiment." A crosslinked structure can be introduced into a fluorine-containing compound (10) by using a compound represented by formula (3) having at least two reactive carbon-carbon double bonds. For example, a crosslinked structure can be introduced by using a fluorine-containing polymer or a chlorine-containing polymer whose terminals are protected with iodine as compound (10) and reacting the compound represented by formula (3) having at least two reactive carbon-carbon double bonds in the presence of at least one compound selected from the group consisting of a compound represented by formula (21) and a compound represented by formula (22).

[0184] The specific reaction conditions are the same as those described in the first embodiment. However, in the first embodiment, the "compound represented by formula (5)" to be polymerized should be read as "a compound represented by formula (3) having at least two reactive carbon-carbon double bonds." Furthermore, in the third embodiment, the compound (10) is preferably used in an amount of 0.01 mol to 10 mol, more preferably 0.05 mol to 5 mol, and even more preferably 0.1 mol to 1.2 mol, per mol of the compound represented by formula (3) having at least two reactive carbon-carbon double bonds. [Example]

[0185] The following examples are provided to specifically explain the embodiments of the present disclosure, but the embodiments of the present disclosure are not limited to the following examples. Examples 1 to 12 below correspond to working examples, and Examples 13 to 15 correspond to comparative examples.

[0186] (Example 1) In a nitrogen-purged glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.024 g (0.10 mmol) of an azo radical initiator "V-40" (trade name, Fujifilm Wako Pure Chemical Industries, Ltd.), 0.012 g (0.10 mmol) of 9-borabicyclo[3.3.1]nonane, 0.016 g (0.20 mmol) of pyridine, 0.035 g (0.1 mmol) of n-nonafluorobutyl iodide, and 17.9 g of benzotrifluoride. After 3.2 g (50 mmol) of vinylidene fluoride was injected, stirring was initiated while the internal temperature was raised to 100°C. After stirring at 200 rpm (200 revolutions per minute) for 5 hours while maintaining the internal temperature, the internal pressure decreased from 1.4 MPa (gauge pressure) to 1.3 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted vinylidene fluoride.

[0187] The resulting polymer solution was dried under vacuum to obtain a solid. This solid was added to 20 mL of methanol and stirred for 30 minutes, and then the solid and the supernatant were separated using a centrifuge. The resulting solid was dried under vacuum to obtain 0.19 g of solid. The solid thus obtained was subjected to size exclusion chromatography using tetrahydrofuran as a mobile phase, and the values ​​were Mn=4,900 and Mw=9,700. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 2.0. When the 1H-NMR and 19F-NMR of the obtained solid were measured, the ratio of the number of moles of the V-40-derived structure contained in the polymer to the number of moles of the terminals of the polymer was calculated to be 5 mol% or less.

[0188] (Example 2) In a nitrogen-purged glove box, 0.024 g (0.10 mmol) of the azo radical initiator "V-40" (trade name, Fujifilm Wako Pure Chemical Industries, Ltd.), 0.012 g (0.10 mmol) of 9-borabicyclo[3.3.1]nonane, 0.016 g (0.20 mmol) of pyridine, 0.035 g (0.10 mmol) of n-nonafluorobutyl iodide, and 17.9 g of benzotrifluoride were placed in a 30 mL stainless steel autoclave equipped with a stirrer, and the contents were frozen and degassed. After 3.2 g (50 mmol) of vinylidene fluoride was injected, stirring was initiated while the internal temperature was raised to 100° C. After stirring at 200 rpm for 10 hours while maintaining the internal temperature, the internal pressure decreased from 1.4 MPa to 1.2 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted vinylidene fluoride.

[0189] The resulting polymer solution was dried under vacuum to obtain a solid. This solid was added to 20 mL of methanol and stirred for 30 minutes, and then the solid and the supernatant were separated using a centrifuge. The resulting solid was dried under vacuum to obtain 0.32 g of solid. The solid thus obtained was analyzed by size exclusion chromatography using tetrahydrofuran as a mobile phase, and the results were Mn=6,900 and Mw=11,600. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.7. When the 1H-NMR and 19F-NMR of the obtained solid were measured, the ratio of the number of moles of the V-40-derived structure contained in the polymer to the number of moles of the terminals of the polymer was calculated to be 5 mol% or less.

[0190] (Example 3) In a nitrogen-purged glove box, 0.024 g (0.10 mmol) of the azo radical initiator "V-40" (trade name, Fujifilm Wako Pure Chemical Industries, Ltd.), 0.012 g (0.10 mmol) of 9-borabicyclo[3.3.1]nonane, 0.016 g (0.20 mmol) of pyridine, 0.035 g (0.10 mmol) of n-nonafluorobutyl iodide, and 17.9 g of benzotrifluoride were placed in a 30 mL stainless steel autoclave equipped with a stirrer, and the contents were frozen and degassed. After 0.75 g (5.0 mmol) of hexafluoropropylene and 2.9 g (45 mmol) of vinylidene fluoride were injected, stirring was initiated while the internal temperature was raised to 100° C. After stirring at 200 rpm for 10 hours while maintaining the internal temperature, the internal pressure decreased from 1.2 MPa to 1.1 MPa. After the autoclave was cooled in an ice-water bath, unreacted hexafluoropropylene and vinylidene fluoride were purged.

[0191] The resulting polymer solution was dried under vacuum to obtain a solid. This solid was added to 20 mL of methanol and stirred for 30 minutes, and then the solid and the supernatant were separated using a centrifuge. The resulting solid was dried under vacuum to obtain 0.25 g of a solid. The solid thus obtained was analyzed by size exclusion chromatography using tetrahydrofuran as the mobile phase, and the results were Mn=5,400 and Mw=10,100. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.9. When the 1H-NMR and 19F-NMR of the obtained solid were measured, the ratio of the number of moles of the V-40-derived structure contained in the polymer to the number of moles of the terminals of the polymer was calculated to be 5 mol% or less.

[0192] (Example 4) In a nitrogen-purged glove box, 0.012 g (0.050 mmol) of the azo radical initiator "V-40" (trade name, Fujifilm Wako Pure Chemical Industries, Ltd.), 0.010 g (0.050 mmol) of 1,4-bis(dimethylsilyl)benzene, 0.035 g (0.10 mmol) of n-nonafluorobutyl iodide, and 17.9 g of benzotrifluoride were placed in a 30 mL stainless steel autoclave equipped with a stirrer, and the contents were frozen and degassed. After 3.2 g (50 mmol) of vinylidene fluoride was injected, stirring was initiated while the internal temperature was raised to 100° C. After stirring at 200 rpm for 10 hours while maintaining the internal temperature, the internal pressure decreased from 1.4 MPa to 1.2 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted vinylidene fluoride.

[0193] The resulting polymer solution was dried under vacuum to obtain a solid. This solid was added to 20 mL of methanol and stirred for 30 minutes, and then the solid and the supernatant were separated using a centrifuge. The resulting solid was dried under vacuum to obtain 0.29 g of solid. The solid thus obtained was analyzed by size exclusion chromatography using tetrahydrofuran as a mobile phase, and the values ​​were Mn=17,100 and Mw=32,400. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.9. When the 1H-NMR and 19F-NMR of the obtained solid were measured, the ratio of the number of moles of the V-40-derived structure contained in the polymer to the number of moles of the terminals of the polymer was calculated to be 5 mol% or less.

[0194] (Example 5) In a nitrogen-purged glove box, 0.026 g (0.16 mmol) of 2,2'-azobis(isobutyronitrile), 0.040 g (0.16 mmol) of 9-iodo-9-borabicyclo[3.3.1]nonane, 0.025 g (0.32 mmol) of pyridine, 0.055 g (0.16 mmol) of n-nonafluorobutyl iodide, and 17.9 g of benzotrifluoride were placed in a 30 mL stainless steel autoclave equipped with a stirrer, and the mixture was freeze-degassed. After 9.3 g (80 mmol) of chlorotrifluoroethylene was injected, stirring was started while the internal temperature was raised to 75° C. After stirring at 200 rpm for 6 hours while maintaining the internal temperature, the internal pressure decreased from 0.5 MPa to 0.3 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted chlorotrifluoroethylene.

[0195] The resulting polymer solution was dried under vacuum to obtain a solid. This solid was added to 50 mL of methanol and stirred for 30 minutes, and then the solid and the supernatant were separated using a centrifuge. The resulting solid was dried under vacuum to obtain 3.9 g of solid. The solid thus obtained was analyzed by size exclusion chromatography using 3',5'-bis(trifluoromethyl)acetophenone as the mobile phase, and the values ​​were Mn=24,700 and Mw=34,800. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.4, and this radical polymerization exhibited characteristics of living radical polymerization.

[0196] (Example 6) In a nitrogen-purged glove box, 0.033 g (0.20 mmol) of 2,2'-azobis(isobutyronitrile), 0.024 g (0.20 mmol) of 9-borabicyclo[3.3.1]nonane, 0.032 g (0.40 mmol) of pyridine, 0.069 g (0.20 mmol) of n-nonafluorobutyl iodide, and 11.5 g of acetonitrile were placed in a 30 mL stainless steel autoclave equipped with a stirrer, and the mixture was freeze-degassed. After 8.2 g (100 mmol) of trifluoroethylene was injected, stirring was started while the internal temperature was raised to 75° C. After stirring at 200 rpm for 8 hours while maintaining the internal temperature, the internal pressure decreased from 1.4 MPa to 1.3 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted trifluoroethylene.

[0197] The resulting polymer solution was dried under vacuum to obtain a viscous liquid. This viscous liquid was added to 50 mL of methanol and stirred for 30 minutes. The resulting viscous liquid was then separated into a lower layer and a supernatant using a centrifuge. The resulting viscous liquid was dried under vacuum to obtain 0.57 g of a solid. The solid thus obtained was subjected to size exclusion chromatography using tetrahydrofuran as a mobile phase, and the values ​​were Mn=3,300 and Mw=6,700. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 2.0. When the 1H-NMR and 19F-NMR of the obtained solid were measured, it was calculated that the ratio of the number of moles of the structure derived from 2,2'-azobis(isobutyronitrile) contained in the polymer to the number of moles of the terminals of the polymer was 10 mol% or less.

[0198] (Example 7) In a nitrogen-purged glove box, 0.033 g (0.20 mmol) of 2,2'-azobis(isobutyronitrile), 0.024 g (0.20 mmol) of 9-borabicyclo[3.3.1]nonane, 0.032 g (0.40 mmol) of pyridine, 0.069 g (0.20 mmol) of n-nonafluorobutyl iodide, and 11.5 g of acetonitrile were placed in a 30 mL stainless steel autoclave equipped with a stirrer, and the mixture was freeze-degassed. After 6.3 g (100 mmol) of vinyl chloride was injected, stirring was initiated while the internal temperature was raised to 75° C. After stirring at 200 rpm for 4 hours while maintaining the internal temperature, the internal pressure decreased from 0.3 MPa to 0.2 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted vinyl chloride.

[0199] The resulting polymer solution was dried under vacuum to obtain a solid. This solid was added to 20 mL of methanol and stirred for 30 minutes, and then the solid and the supernatant were separated using a centrifuge. The resulting solid was dried under vacuum to obtain 0.63 g of a solid. The solid thus obtained was analyzed by size exclusion chromatography using tetrahydrofuran as a mobile phase, and the values ​​were Mn=9,800 and Mw=18,600. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.9. When the 1H-NMR and 19F-NMR of the obtained solid were measured, it was calculated that the ratio of the number of moles of the structure derived from 2,2'-azobis(isobutyronitrile) contained in the polymer to the number of moles of the terminals of the polymer was 10 mol% or less.

[0200] (Example 8) In a glove box purged with nitrogen, a 20 mL glass reactor was charged with 0.25 g of the fluorinated polymer obtained in the same manner as in Example 2, 0.0082 g (0.050 mmol) of 2,2′-azobis(isobutyronitrile), 0.024 g (0.20 mmol) of 9-borabicyclo[3.3.1]nonane, 0.032 g (0.40 mmol) of pyridine, 1.0 g (10 mmol) of styrene, 1.5 g of acetonitrile, and a magnetic stirrer. Stirring was initiated while the temperature of the oil bath was raised to 80° C. Stirring was continued at 200 rpm for 2 hours while maintaining the temperature. The reactor was allowed to cool to room temperature.

[0201] The resulting polymer solution was dried under vacuum to obtain a solid. 30 mL of toluene and 5 L of methanol were added to the solid and stirred for 30 minutes. The solid was then separated from the supernatant using a centrifuge. 0.33 g of the resulting solid was dried under vacuum. The solid thus obtained was analyzed by size exclusion chromatography using tetrahydrofuran as a mobile phase, and the values ​​were Mn=6,200, Mw=13,900, and the elution curve showed one peak. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 2.2. The 1H-NMR and 19F-NMR of the obtained solid were measured, and the molar ratio of vinylidene fluoride to styrene in the fluorine-containing copolymer was calculated to be 86:14. Size exclusion chromatography and NMR results confirmed the production of block copolymers.

[0202] (Example 9) In a glove box purged with nitrogen, 0.016 g (0.10 mmol) of 2,2′-azobis(isobutyronitrile), 0.12 g (1.0 mmol) of 9-borabicyclo[3.3.1]nonane, 0.16 g (2.0 mmol) of pyridine, 0.35 g (1.0 mmol) of n-nonafluorobutyl iodide, 1.3 g (10 mmol) of divinylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 5.5 g of chlorobenzene were charged into a glass reactor having an internal volume of 20 mL. Stirring was started while the temperature of the oil bath was raised to 80° C. Stirring was continued at 200 rpm for 2 hours while maintaining the temperature, after which the reactor was allowed to cool to room temperature.

[0203] The resulting polymer solution was centrifuged to separate the solid from the supernatant. When the 1H-NMR and 19F-NMR of the obtained supernatant were measured, the ratio of the number of moles of fluorine atoms contained in the supernatant to the number of moles of fluorine atoms contained in the charged n-nonafluorobutyl iodide was found to be 91 mol%.

[0204] (Example 10) In a nitrogen-purged glove box, 0.026 g (0.16 mmol) of 2,2'-azobis(isobutyronitrile), 0.042 g (0.16 mmol) of triphenylsilane, 0.055 g (0.16 mmol) of n-nonafluorobutyl iodide, and 17.9 g of benzotrifluoride were placed in a 30 mL stainless steel autoclave equipped with a stirrer, and the mixture was freeze-degassed. After 9.3 g (80 mmol) of chlorotrifluoroethylene was injected, stirring was started while the internal temperature was raised to 75° C. After stirring at 200 rpm for 6 hours while maintaining the internal temperature, the internal pressure decreased from 0.5 MPa to 0.2 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted chlorotrifluoroethylene.

[0205] The resulting polymer solution was dried under vacuum to obtain a solid. This solid was added to 50 mL of methanol and stirred for 30 minutes, and then the solid and the supernatant were separated using a centrifuge. The resulting solid was dried under vacuum to obtain 5.7 g of solid. The solid thus obtained was analyzed by size exclusion chromatography using 3',5'-bis(trifluoromethyl)acetophenone as the mobile phase, and the values ​​were Mn=19,200 and Mw=37,300. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.9. When the 1H-NMR and 19F-NMR of the obtained solid were measured, it was calculated that the ratio of the number of moles of the structure derived from 2,2'-azobis(isobutyronitrile) contained in the polymer to the number of moles of the terminals of the polymer was 10 mol% or less.

[0206] (Example 11) Stirring was carried out for 6 hours in the same manner as in Example 10, except that 0.029 g (0.080 mmol) of 1,1,2,2-tetraphenyldisilane was used instead of 0.042 g (0.16 mmol) of triphenylsilane, and the internal pressure decreased from 0.5 MPa to 0.3 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted chlorotrifluoroethylene.

[0207] The resulting polymer solution was dried under vacuum to obtain a solid. This solid was added to 50 mL of methanol and stirred for 30 minutes, and then the solid and the supernatant were separated using a centrifuge. The resulting solid was dried under vacuum to obtain 5.1 g of a solid. The solid thus obtained was analyzed by size exclusion chromatography using 3',5'-bis(trifluoromethyl)acetophenone as the mobile phase, and the values ​​were Mn=18,600 and Mw=35,500. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.9. When the 1H-NMR and 19F-NMR of the obtained solid were measured, it was calculated that the ratio of the number of moles of the structure derived from 2,2'-azobis(isobutyronitrile) contained in the polymer to the number of moles of the terminals of the polymer was 10 mol% or less.

[0208] (Example 12) In a nitrogen-purged glove box, 0.033 g (0.20 mmol) of 2,2'-azobis(isobutyronitrile), 0.392 g (1.0 mmol) of boron triiodide, 0.079 g (0.32 mmol) of pyridine, 0.069 g (0.20 mmol) of n-nonafluorobutyl iodide, and 11.5 g of acetonitrile were placed in a 30 mL stainless steel autoclave equipped with a stirrer, and the contents were frozen and degassed. After 8.2 g (100 mmol) of trifluoroethylene was injected, stirring was started while the internal temperature was raised to 75° C. After stirring at 200 rpm for 8 hours while maintaining the internal temperature, the internal pressure decreased from 1.4 MPa to 1.3 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted trifluoroethylene.

[0209] The resulting polymer solution was dried under vacuum to obtain a viscous liquid. This viscous liquid was added to 50 mL of methanol and stirred for 30 minutes. The resulting viscous liquid was then separated into a lower layer and a supernatant using a centrifuge. The resulting viscous liquid was dried under vacuum to obtain 0.74 g of a solid. The solid thus obtained was subjected to size exclusion chromatography using tetrahydrofuran as a mobile phase, and the values ​​were Mn=4,200 and Mw=6,000. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.4, and this radical polymerization exhibited characteristics of living radical polymerization.

[0210] (Example 13) Stirring was carried out for 10 hours in the same manner as in Example 2, except that 9-borabicyclo[3.3.1]nonane was not used, and the internal pressure increased from 1.4 MPa to 1.5 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted vinylidene fluoride.

[0211] The resulting reaction solution was dried under vacuum to obtain a viscous liquid. This liquid was added to 20 mL of methanol and stirred for 30 minutes, and then centrifuged, but no solid was obtained.

[0212] (Example 14) Stirring was carried out for 6 hours in the same manner as in Example 5, except that 9-iodo-9-borabicyclo[3.3.1]nonane was not used, and the internal pressure decreased from 0.5 MPa to 0.2 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted chlorotrifluoroethylene.

[0213] The resulting polymer solution was dried under vacuum to obtain a solid. This solid was added to 50 mL of methanol and stirred for 30 minutes, and then the solid and the supernatant were separated using a centrifuge. The resulting solid was dried under vacuum to obtain 6.1 g of solid. The solid thus obtained was analyzed by size exclusion chromatography using 3',5'-bis(trifluoromethyl)acetophenone as the mobile phase, and the values ​​were Mn=42,200 and Mw=79,900. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.9, which revealed that the molecular weight distribution was broader than that of Example 5.

[0214] (Example 15) In a glove box purged with nitrogen, a 20 mL glass reactor was charged with 0.20 g of the fluoropolymer obtained in the same manner as in Example 2, 0.0082 g (0.050 mmol) of 2,2′-azobis(isobutyronitrile), 1.0 g (10 mmol) of styrene, 1.5 g of acetonitrile, and a magnetic stirrer. Stirring was initiated while the temperature of the oil bath was raised to 80° C. Stirring was continued at 200 rpm for 2 hours while maintaining the temperature. The reactor was allowed to cool to room temperature.

[0215] The resulting polymer solution was dried under vacuum to obtain a solid. 30 mL of toluene and 5 mL of methanol were added to the solid and stirred for 30 minutes. The solid was then centrifuged to separate the solid from the supernatant. 0.19 g of the solid was obtained by vacuum drying. The solid thus obtained was analyzed by size exclusion chromatography using tetrahydrofuran as a mobile phase, and the results were Mn=5,100, Mw=10,800, with one peak in the elution curve. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 2.1. When the obtained solid was measured by 1H-NMR, the molar ratio of vinylidene fluoride to styrene in the fluorocopolymer was calculated to be 97: 3. This shows that the fluoropolymer obtained by the method of Example 2 was hardly consumed and that synthesis of a block copolymer was more difficult than in Example 8.

[0216] The disclosure of Japanese Patent Application No. 2020-151426 is incorporated herein by reference in its entirety. All publications, patent applications, and technical standards mentioned in this specification are incorporated by reference into this specification to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. In the presence of at least one compound selected from the group consisting of a compound represented by the following formula (21) and a compound represented by the following formula (22), The method includes reacting a compound (10) having a partial structure represented by the following formula (1) with a compound represented by the following formula (3) using at least one radical initiator selected from the group consisting of an azo-based radical initiator and a peroxide-based radical initiator: Method for producing iodine-containing compounds. 【Chemistry 1】 (In formula (1), * represents a bond bonded to an organic group. X represents a fluorine atom or a chlorine atom. X １ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or -CX ５ X ６ X ７ represents. ５ ~X ７ each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom. 【Chemistry 2】 (In formula (21), R ２１ represents a hydrogen atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms; R ２２ represents a hydrogen atom, an iodine atom, a substituted or unsubstituted organic group having 1 to 20 carbon atoms, or a boron-containing group, and the boron atom in the boron-containing group is bonded to the boron atom in formula (21). ２１ and R ２２ may be linked to form a cyclic structure. １ represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom. The boron atom in formula (21) may further be coordinated with a ligand. (In formula (22), R ２３ and R ２４ each independently represents a hydrogen atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms; R ２５ represents a hydrogen atom, an iodine atom, a substituted or unsubstituted organic group having 1 to 20 carbon atoms, or a silicon-containing group, and the silicon atom in the silicon-containing group is bonded to the silicon atom in formula (22). ２３ ~R ２５ Except when all of R are hydrogen atoms. ２３ , R ２４ , and R ２５ Two or more of these may be linked to form a cyclic structure. ２ represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom. 【Transformation 3】 (In formula (3), R １ ~R ４ R each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 40 carbon atoms. １ and R ４ , or R ２ and R ３ may be linked to form a cyclic structure.)

2. The manufacturing method described in claim 1, wherein the radical initiator is an azo-based radical initiator.

3. In the formula (3), R １ ~R ４ each independently represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 40 carbon atoms and having at least one reactive carbon-carbon double bond; R １ and R ４ , or R ２ and R ３ may be linked to form a cyclic structure, and the formula (3) has at least two reactive carbon-carbon double bonds.

4. The method according to claim 1 or 2, wherein the compound represented by formula (3) includes a compound represented by the following formula (5): 【Chemistry 4】 (wherein X represents a fluorine atom or a chlorine atom, X ２ ~X ４ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or —CX ５ X ６ X ７ represents X ５ ~X ７ each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

5. 5. The method according to claim 4, wherein the obtained iodine-containing compound is a copolymer obtained by copolymerizing a first compound represented by the formula (5) and a compound represented by the formula (3) that is different from the first compound.

6. The method according to claim 5 , wherein the copolymerization is a block copolymerization.

7. The method according to claim 5 , wherein the copolymerization is random copolymerization or alternating copolymerization.

8. The compound represented by formula (3) that is different from the first compound is at least one selected from the group consisting of ethylene, propylene, isobutylene, alkyl vinyl ether, hexafluoropropylene, perfluoro(alkyl vinyl ether), triallyl isocyanurate, 1,4-divinyl octafluorobutane, 1,6-divinyl dodecafluorohexane, vinyl acetate, styrene, butyl acrylate, and divinylbenzene. The method according to any one of claims 5 to 7.

9. The compound represented by the formula (5) is 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, vinyl chloride, and at least one selected from the group consisting of vinylidene chloride, the production method according to any one of claims 4 to 8.

10. The method according to any one of claims 1 to 9, wherein the compound (10) is a compound represented by the following formula (11) or a compound represented by the following formula (12): 【Transformation 5】 (In the formula, R １１ represents a perfluoroalkyl group having 1 to 4 carbon atoms. １２ represents a perfluoroalkylene group having 1 to 4 carbon atoms. Each X independently represents a fluorine atom or a chlorine atom. X ２１ ~X ２３ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or —CX ２４ X ２５ X ２６ represents X ２４ ~X ２６ each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

11. The method according to any one of claims 1 to 10, wherein the compound (10) is a compound containing a plurality of units represented by the following formula (4): 【Transformation 6】 (In the formula, X ３１ ~X ３４ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or —CX ３５ X ３６ X ３７ represents X ３５ ~X ３７ each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

12. The method according to claim 11, wherein the compound (10) has a fluorine content of 50% by mass or more.

13. The method according to any one of claims 1 to 12, wherein the obtained iodine-containing compound is a polymer, and the polydispersity of the polymer is 2.0 or less.

14. In formula (21), A １ is a hydrogen atom and the boron atom has a ligand, or A １ is an iodine atom, The method according to any one of claims 1 to 13.

15. In formula (22), R ２３ , R ２４ , and R ２５ The method according to any one of claims 1 to 13, wherein at least one of the above formulas contains an aromatic ring.

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