Method for producing iodine-containing compound and polymer

Abstract

This method for producing an iodine–containing compound comprises reacting a compound (10) having a partial structure represented by formula (1), and a compound represented by formula (3), in the presence of at least one compound selected from the group consisting of compounds represented by formulae (20)-(22).

Description

[Technical field]

[0001] The present disclosure relates to methods for producing iodine-containing compounds and polymers. [Background technology]

[0002] Radical polymerization is widely used industrially because it has excellent monomer versatility and can be easily carried out in polar media such as water. However, the molecular weight control by general radical polymerization methods is limited, and the molecular weight distribution of the obtained polymer tends to be broad.

[0003] On the other hand, the living radical polymerization method has attracted attention as a polymerization method that can obtain a polymer with a controlled molecular weight and a narrow molecular weight distribution, and various polymerization control agents have been developed. The living radical polymerization method is a polymerization method that controls the radical polymerization rate by reversibly protecting the growing radical with a protecting group that is a dormant species, thereby making it possible to control the molecular weight distribution. In addition, according to the living radical polymerization method, it is also possible to add a different compound by a radical reaction by using the obtained polymer as a polymerization initiator or chain transfer agent.

[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 the RAFT (reversible addition fragmentation chain transfer) method, 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] ITP (iodine transfer polymerization) 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 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, in order to proceed with further radical reaction starting from this organic iodide compound to obtain an elongated product, it is necessary to abstract iodine from the terminal CI bond. However, when a fluorine-containing organic iodide compound in which a fluorine atom is directly bonded to the carbon of the CI bond is used, it is difficult to cause iodine abstraction at an appropriate ratio. Therefore, when such a fluorine-containing organic iodide compound is used, there is a problem that it is difficult to obtain an elongated product from the fluorine-containing organic iodide compound and it is difficult to obtain sufficient controllability by the conventional method.

[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 fluorine-containing organic iodide compound to obtain an elongated product having a controlled molecular weight distribution, and a polymer having a controlled molecular weight distribution. [Means for solving the problem]

[0010] The embodiments of the present disclosure include the following embodiments. <1> In the presence of at least one compound selected from the group consisting of compounds represented by the following formulas (20) to (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): A method for producing an iodine-containing compound.

[0011] [ka]

[0012] (In formula (1), * represents a bond bonded to an organic group. 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 (20), R 21 and R 22 each independently represents a substituted or unsubstituted organic group having 1 to 20 carbon atoms; R 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. (In formula (21), R 23and R 24 A each independently represents a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms. 2 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom. (In formula (22), R 25 and R 26 Each of A independently represents a substituted or unsubstituted organic group having 1 to 20 carbon atoms. 3 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 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. <1> The manufacturing method described in <3> The compound represented by the formula (3) includes a compound represented by the following formula (5): <1> The manufacturing method described in

[0017] [ka]

[0018] (In the formula, X 2 ~X 4 each independently represents 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 a first compound represented by the formula (5) and 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 the 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, perfluoro(alkyl vinyl ether), triallyl isocyanurate, 1,4-divinyl octafluorobutane, 1,6-divinyl dodecafluorohexane, vinyl acetate, styrene, butyl acrylate, and divinyl benzene. <4> ~ <6> The method for producing a product according to any one of claims 1 to 5. <8> The compound represented by the 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; <3> ~ <7> The method for producing a product according to any one of claims 1 to 5. <9> The compound (10) is at least one selected from the group consisting of a compound represented by the following formula (11) and a compound represented by the following formula (12): <1> ~ <8> The method for producing a product according to any one of claims 1 to 5.

[0019] [ka]

[0020] (In the formula, R 11 R represents a perfluoroalkyl group having 1 to 4 carbon atoms. 12 represents a perfluoroalkylene group having 1 to 4 carbon atoms. 21 ~X 23 each independently represents 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 method for producing a product according to any one of claims 1 to 5.

[0021] [ka]

[0022] (In the formula, X 31 ~X 34 each independently represents 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 method for producing a product according to any one of claims 1 to 5. <13> In the formula (21), R 23 and R 24 each independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or -OR, where R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; <1> ~ <12> The method for producing a product according to any one of claims 1 to 5. <14> In the formula (22), R 25 and R 26 each independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or -OR, where R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; <1> ~ <13> The method for producing a product according to any one of claims 1 to 5. <15> 1. 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 a proportion of the structure derived from the azo-based radical initiator or the peroxide-based radical initiator at a terminal of the polymer is 40 mol % or less. Effect of the Invention

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

[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 "step" includes not only a step that is independent of other steps, but also a step that cannot be clearly distinguished from other steps as long as the purpose of the step is achieved. In the present disclosure, a numerical range indicated using "~" includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the present disclosure, each component may contain multiple types of the corresponding substance. 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, the number of carbon atoms means the total number of carbon atoms contained in an entire group, and when the group does not have a substituent, it represents the number of carbon atoms forming the skeleton of the group, and when the group has a substituent, it represents the total number obtained by adding the number of carbon atoms forming the skeleton of the group 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 constituting 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. The term "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 this 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 polymerization of monomers, i.e., a "polymer" has a plurality of structural units. In this disclosure, unless otherwise specified, the description "polymerizing compound A" includes both the case where only compound A is polymerized and the case where compound A is polymerized with another compound. In addition, the description "polymerizing compound A and compound B" includes 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 having a reactive carbon-carbon double bond in the molecule. In addition, 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] <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 compound selected from the group consisting of compounds represented by the following formulas (20) to (22).

[0026] [ka]

[0027] (In formula (1), * represents a bond bonded to an organic group. 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.

[0028] [ka]

[0029] (In formula (20), R 21 and R 22 each independently represents a substituted or unsubstituted organic group having 1 to 20 carbon atoms; R 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. (In formula (21), R 23 and R 24 A each independently represents a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms. 2 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom. (In formula (22), R 25 and R 26 Each of A independently represents a substituted or unsubstituted organic group having 1 to 20 carbon atoms. 3 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom.

[0030] [ka]

[0031] (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.

[0032] According to the production method of the present disclosure, it has been found that the use of compounds represented by formulae (20) to (22) as catalysts makes it possible to elongate a fluorine-containing organic iodide compound to obtain an elongated product with 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.

[0033] [ka]

[0034] W : Radical species (W is any structure) AY: catalyst (compounds represented by formulas (20) to (22); A is A 1 ,A 2 , A 3 Y is any one of the formulas (20) to (22). 1 ,A 2 , or A 3 (Other structure) ZI: Iodide (I is an iodine atom, Z is any structure (alkyl iodide, iodine terminal of a polymer, IY, etc.)

[0035] 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 effectively extract the iodine from the fluorine-containing organic iodide compound. This extracts the iodine protecting group, and the radical reaction from the fluorine-containing organic iodide compound proceeds to obtain an extension product. When the radical at the extension end reacts with iodide (ZI), the extension end is reprotected.

[0036] In the conventional method, a fluorine-containing organic iodide compound in which a fluorine atom is directly bonded to the carbon of a CI bond, i.e. -CFX, is prepared. 1It is difficult to abstract iodine from a compound having the partial structure of I, and it has been difficult to advance the elongation of a fluorine-containing organic iodide compound to obtain an elongated product with a controlled molecular weight. This is considered to be due in part to the instability of the radical on the carbon atom in the C-F bond. On the other hand, it has been found that by using a specific compound selected from the group consisting of the compounds represented by formulas (20) to (22) as the catalyst (AY), it is possible to facilitate the abstraction of iodine from a fluorine-containing organic iodide compound and realize a highly controllable elongation reaction. Therefore, for example, by polymerizing a fluorine-containing monomer using the production method of the present disclosure, it becomes possible to produce a fluorine-containing polymer having a controlled molecular weight distribution. In addition, by reacting a fluorine-containing polymer with a crosslinking agent using the production method of the present disclosure, it becomes possible to apply the method to the production of crosslinked rubber, etc.

[0037] First, the compounds used in the production method of the present disclosure will be described.

[0038] <Compounds represented by formulas (20) to (22)> The compounds represented by the following formulas (20) to (22) function as catalysts for mediating the abstraction of iodine from a fluorine-containing organic iodide compound.

[0039] (Compound represented by formula (20))

[0040] [ka]

[0041] In formula (20), R 21 and R 22 each independently represents a substituted or unsubstituted organic group having 1 to 20 carbon atoms; R 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.

[0042] In the reaction system, the compound represented by formula (20) is converted to A1 The radical generated on the atom by the abstraction abstracts iodine from the fluorine-containing iodide compound.

[0043] R 21 and R 22 are each independently a substituted or unsubstituted organic group having 1 to 20 carbon atoms, preferably a substituted or unsubstituted organic group having 1 to 15 carbon atoms, more preferably a substituted or unsubstituted organic group having 1 to 10 carbon atoms, and even more preferably a substituted or unsubstituted organic group having 1 to 6 carbon atoms. The organic group is preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or -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, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms). The organic group or the hydrocarbon group in R may or may not contain a saturated bond.

[0044] R 21 and R 22 may or may not be linked to form a cyclic structure. The compound represented by formula (20) preferably has a cyclic imide structure. When the compound represented by formula (20) has a cyclic imide structure, R 21 and R 22 The total number of carbon atoms in the partial structure formed by is 1 to 40, preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 12.

[0045] A 1 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a hydrogen atom, a bromine atom, or an iodine atom.

[0046] The compound represented by formula (20) is preferably at least one selected from the group consisting of succinimide, N-bromosuccinimide, N-iodosuccinimide, phthalimide, N-bromophthalimide, and N-iodophthalimide. The compound represented by formula (20) may be used alone or in combination of two or more.

[0047] (Compound represented by formula (21))

[0048] [ka]

[0049] In formula (21), R 23 and R 24 A each independently represents a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms. 2 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom.

[0050] In the reaction system, the compound represented by formula (21) is converted to A 2 The radical generated on the phosphorus atom by the abstraction abstracts iodine from the fluorine-containing organic iodide compound.

[0051] R 23 and R 24 each independently represents a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms. The substituted or unsubstituted organic group having 1 to 20 carbon atoms is preferably a substituted or unsubstituted organic group having 1 to 15 carbon atoms, more preferably a substituted or unsubstituted organic group having 1 to 12 carbon atoms, and even more preferably a substituted or unsubstituted organic group having 1 to 6 carbon atoms. The organic group is preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or -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, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms). The organic group or the hydrocarbon group in R may or may not contain a saturated bond. R23 and R 24 are each independently preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms or -OR (R is the same as above), and more preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 1 to 20 carbon atoms.

[0052] A 2 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a hydrogen atom or an iodine atom, and more preferably a hydrogen atom.

[0053] The compound represented by formula (21) is preferably a dialkylphosphine, a diarylphosphine, an arylalkylphosphine, or an iodide thereof. More specifically, the compound represented by formula (21) may be di-tert-butylphosphine, diphenylphosphine, or the like. The compound represented by formula (21) may be used alone or in combination of two or more.

[0054] (Compound represented by formula (22))

[0055] [ka]

[0056] In formula (22), R 25 and R 26 Each of A independently represents a substituted or unsubstituted organic group having 1 to 20 carbon atoms. 3 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom.

[0057] In the reaction system, the compound represented by formula (22) is converted to A 3 The radical generated by the extraction abstracts iodine from the fluorine-containing organic iodide compound.

[0058] R 25 and R 26are each independently a substituted or unsubstituted organic group having 1 to 20 carbon atoms, preferably a substituted or unsubstituted organic group having 1 to 15 carbon atoms, more preferably a substituted or unsubstituted organic group having 1 to 10 carbon atoms, and even more preferably a substituted or unsubstituted organic group having 1 to 6 carbon atoms. The organic group is preferably a substituted or unsubstituted hydrocarbon group or -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, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and even more preferably a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms). The organic group or the hydrocarbon group in R may or may not contain a saturated bond.

[0059] A 3 represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a hydrogen atom.

[0060] The compound represented by formula (22) is preferably at least one selected from the group consisting of diphosphite, arylphosphine ester, dialkylphosphine oxide, and diarylphosphine oxide, and more preferably at least one selected from the group consisting of diethyl phosphite, dibutyl phosphite, di-tert-butyl phosphite, diphenyl phosphite, ethyl phenylphosphine, diethylphosphine oxide, dibutylphosphine oxide, di-tert-butylphosphine oxide, and diphenylphosphine oxide. The compound represented by formula (22) may be used alone or in combination of two or more.

[0061] The amount of the compound represented by formulae (20) to (22) to be added may be appropriately adjusted. From the viewpoint of obtaining a fluoropolymer having a suitably controlled molecular weight distribution, the compound represented by formulae (20) to (22) is preferably used in an amount of 0.01 mol to 100 mol, more preferably 0.1 mol to 50 mol, further preferably 0.2 mol to 10 mol, particularly preferably 0.3 mol to 1.0 mol, per mol of compound (10).

[0062] <Compound (10)> Compound (10) is a fluorine-containing organic iodide compound having a partial structure represented by the following formula (1).

[0063] [ka]

[0064] In formula (1), * represents a bond bonded to an organic group. 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. Hereinafter, the partial structure represented by formula (1) will also be referred to as partial structure (1).

[0065] Compound (10) may have the partial structure (1) above, and the structure of the entire compound is not limited in any way. That is, the organic group to which * is bonded is not limited to a hydrocarbon group, and may be various functional groups such as a hydroxyl group or an amino group, a halogeno group (a halogen atom), or a hydrogen atom. In addition, the organic group may contain a heteroatom, and the valence and molecular weight of the organic group are not particularly limited.

[0066] The number of partial structures (1) contained in compound (10) is not particularly limited. For example, compound (10) may be a monoiodine-containing fluorine-containing organic compound having one partial structure (1), a diiodine-containing fluorine-containing organic compound having two partial structures (1), or a polyiodide-containing fluorine-containing organic compound having three or more partial structures (1). For example, compound (10) may be a monoiodo fluorine-containing organic compound in which a substituted or unsubstituted alkyl group, a halogen atom or a hydrogen atom is bonded to *. In addition, compound (10) may be a diiodo fluorine-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 *.

[0067] (Monoiodo-containing fluorine-containing organic compounds) Among the compounds (10), the monoiodo fluorine-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. 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.

[0068] [ka]

[0069] R 10 Of these, the substituted or unsubstituted alkyl group is preferably a substituted or unsubstituted straight-chain, branched-chain, 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.

[0070] 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, an alkyl group having 2 to 15 fluorine atoms is more preferable, a perfluoroalkyl group is even more preferable from the viewpoint of suppressing hydrogen atom abstraction reaction by radicals, a perfluoroalkyl group having 1 to 6 carbon atoms is even more preferable, and a perfluoroalkyl group having 1 to 4 carbon atoms is particularly preferable 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).

[0071] [ka]

[0072] In the above formula, R 11 represents a perfluoroalkyl group having 1 to 4 carbon atoms, and X 21 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.

[0073] 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.

[0074] Specific examples of the monoiodo fluorine-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- Examples of such iodides include butyl difluoromethylene iodide, 1,1-difluoro-n-hexyl iodide, 1,1-difluoro-n-heptyl iodide, 1,1-difluoro-n-octyl iodide, cyclohexyl difluoromethylene iodide, C2F5I, CHF2CF2I, CF3CF2CF2I, (CF3)2CFI, CF3(CF2)3I, (CF3)2CFCF2I, CF3(CF2)4I, and CF3(CF2)5I.

[0075] The monoiodo fluorine-containing organic compound can be produced by a conventional method. For example, 10 It can also be prepared by reacting a radical generator such as CF2C(=O)O)2 with I2.

[0076] (Diiodo-fluorine-containing organic compounds) Among the compounds (10), the diiodo-fluorine-containing organic compound may be a compound having a structure represented by the following formula: 10 X′ 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. 20 each independently represents 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.

[0077] [ka]

[0078] R 10 Among these, 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 the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an n-pentylene group, an n-hexylene group, a 1,4-cyclohexylene group, etc. Among these, a linear or branched alkylene group having 1 to 4 carbon atoms is more preferred, and an ethylene group is even more preferred.

[0079] 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, a fluoroalkoxy group, etc. at any position. Among these, an alkylene group having 2 to 12 fluorine atoms is more preferable, a perfluoroalkylene group is even more preferable from the viewpoint of suppressing hydrogen atom abstraction reaction by radicals, a perfluoroalkylene group having 1 to 4 carbon atoms is even more preferable, and a perfluoroalkylene group having 2 to 4 carbon atoms is particularly preferable. 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).

[0080] [ka]

[0081] In the above formula, R 12 represents a perfluoroalkylene group having 1 to 4 carbon atoms. 22 and X 23 each independently represents 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.

[0082] R10 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 Among 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 preferable.

[0083] R 10 Among 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.

[0084] Specific examples of the diiodo-fluorine-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.

[0085] The method for producing the diiodo fluorine-containing organic compound is not particularly limited, and the compound can be obtained by a conventionally known method.

[0086] (Polyiodide fluorine-containing organic compounds) Among the compounds (10), the polyiodide fluorine-containing organic compound has three or more partial structures (1). Among the compounds (10), the polyiodide fluorine-containing organic compound may have an organic group bonded to * in the partial structure (1) that contains a partial structure of a fluorine-containing polymer such as an unvulcanized fluoroelastomer or a partial structure of a polysiloxane, and the compound (10) has three or more partial structures (1). "The organic group bonded to * in the partial structure (1) contains a partial structure of a polysiloxane" may, for example, be a case in which the partial structure (1) is bonded to a polysiloxane via a divalent bond 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 fluorine-containing organic compound can be produced by a conventionally known method.

[0087] 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, and 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.

[0088] [ka]

[0089] In the above formula, X 31 ~X 34 each independently represents 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.

[0090] The amount of compound (10) used in the production method of the present disclosure is not particularly limited. In one embodiment, the amount of compound (10) used is 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).

[0091] Compound (10) is preferably at least one selected from the group consisting of monoiodo-fluorine-containing organic compounds and diiodo-fluorine-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).

[0092] When a monoiodo fluorine-containing organic compound and a diiodo fluorine-containing organic compound are used in combination as compound (10), the diiodo fluorine-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 relative to 1 mol of the monoiodo fluorine-containing organic compound. Also, the diiodo fluorine-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 relative to 1 mol of the monoiodo fluorine-containing organic compound.

[0093] <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.

[0094] [ka]

[0095] 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.

[0096] R 1 ~R 4 The number of carbon atoms in the substituted or unsubstituted organic group having 1 to 40 carbon atoms in the formula (I) 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 may contain a heteroatom in the main chain of the substituent.

[0097] 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.

[0098] 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.

[0099] The acyl group of the acylamino group or acyloxy group includes groups in which a hydroxy group has been removed from a carboxylic acid or sulfonic acid.

[0100] 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 the 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.

[0101] In formula (3), R 1 and R 4 , or R 2 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, itaconic anhydride, etc.

[0102] From the viewpoint of reducing the steric hindrance in the elongation reaction and facilitating the reaction, the compound represented by formula (3) is R 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.

[0103] 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, or a triallyl compound such as triallyl isocyanurate.

[0104] 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, 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; vinyl amides such as N-vinylformamide and N-vinylacetamide;α-olefins such as diallylamine, triallyl isocyanurate, tri(2-methyl-allyl) isocyanurate, ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-octene, 1-decene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, vinylidene chloride, vinyl chloride, 1-chloro-1-fluoroethylene, or 1,2-dichloro-1,2-difluoroethylene, 1H,1H,2H-perfluoro(n-1-hexene), 1H,1H,2H-perfluoro(n-1-octene); vinyl esters such as vinyl acetate; Examples of the compounds include ester monomers, divinyl fluoroalkanes such as 1,4-divinyl octafluorobutane and 1,6-divinyl dodecafluorohexane, 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 alone or in combination of two or more.

[0105] 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". By reacting the compound represented by formula (3) having at least two reactive carbon-carbon double bonds with a fluorine-containing polymer having, for example, a CI bond, a crosslinked structure can be introduced into the fluorine-containing polymer.

[0106] In the compound represented by formula (3) having at least two 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, the number of reactive carbon-carbon double bonds is preferably 1 to 5, more preferably 1 to 4, and further preferably 1 to 3.

[0107] 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 having 1 to 40 carbon atoms 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 may contain a heteroatom in the main chain of the substituent.

[0108] 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-methylallyl)isocyanurate, divinylbenzene, and fluorine-containing compounds having two maleimide groups.

[0109] A further preferred embodiment is one in which the compound represented by formula (3) includes a compound represented by the following formula (5).

[0110] [ka]

[0111] In formula (5), X 2 ~X 4 each independently represents 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.

[0112] In formula (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 It is preferable that X 3 Ga-CX 5 X 6 X 7 It is more preferable that: Also, X 2 ~X 4 are also preferably each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0113] 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, and 1,2-difluoro-1,2-diiodoethylene.

[0114] As the compound represented by formula (5), vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and 2,3,3,3-tetrafluoropropylene are more preferable from the viewpoint of polymerization reactivity when obtaining a polymer.

[0115] <Other optional ingredients> In the production method of the present disclosure, other components such as a radical initiator, a solvent, an emulsifier, a suspending aid, an acid, or an alkali other than compound (10) may be further used.

[0116] (Radical initiator) In the production method of the present disclosure, a radical initiator other than the compound (10) may be used in combination. Examples of the radical initiator include an azo-based radical initiator and a peroxide-based radical initiator.

[0117] 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.

[0118] It is preferable to appropriately select these azo radical initiators 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.

[0119] Examples of the peroxide radical initiator include diisopropyl peroxydicarbonate, t-butyl peroxypivalate, and benzoyl peroxide.

[0120] In the reaction of compound (10) with a compound represented by formula (3) in the presence of at least one compound selected from the group consisting of compounds represented by formulas (20) to (22), when a radical initiator other than compound (10) is used in combination, it is preferable to use 0.0001 mol to 10 mol, more preferably 0.01 mol to 5 mol, and even more preferably 0.1 mol to 2 mol of the radical initiator other than compound (10) 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 compound selected from the group consisting of compounds represented by formulas (20) to (22), when an azo radical initiator or a peroxide radical initiator is used in combination, it is preferable to use 0.0001 mol to 10 mol of the azo radical initiator or the peroxide radical initiator, more preferably 0.01 mol to 5 mol, and even more preferably 0.1 mol to 2 mol, per mol of compound (10).

[0121] (solvent) The reactions in the preparation methods of the present disclosure may be carried out using organic solvents (including ionic liquids) or aqueous solvents.

[0122] 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, and chlorobenzene. In addition, ionic liquids such as N-methyl-N-methoxymethylpyrrolidium tetrafluoroborate, N-methyl-N-ethoxymethyl tetrafluoroborate, 1-methyl-3-methylimidazolium tetrafluoroborate, 1-methyl-3-methylimidazolium hexafluorophosphate, and 1-methyl-3-methylimidazolium chloride may be used.

[0123] Examples of aqueous solvents include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol.

[0124] The amount of the solvent used can be appropriately adjusted. For example, it is preferable to use 0.01 L to 50 L of the solvent, more preferably 0.05 L to 10 L, and even more preferably 0.1 L to 5 L, per 1000 g of the obtained iodine-containing compound.

[0125] <product> The resulting iodine-containing compound may be a polymer, which may be a block copolymer, a random copolymer, or an alternating copolymer.

[0126] 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 compounds represented by formulas (20) to (22), and the amount of compound (10). For example, the number average molecular weight (Mn) of the polymer may be from 100 to 1,000,000, from 1,000 to 500,000, or from 10,000 to 200,000. The weight average molecular weight (Mw) of the polymer may be from 100 to 1,000,000, from 1,000 to 500,000, or from 10,000 to 200,000. The number average molecular weight (Mn) and weight average molecular weight (Mw) in the present disclosure are determined by SEC (Size Exclusion Chromatography) measurement, and polystyrene is used as a standard substance for molecular weight conversion.

[0127] According to the production method of the present disclosure, it is possible to control the polydispersity of the obtained polymer to 2.0 or less. It is also possible to obtain a polymer having a very narrow molecular weight distribution, preferably 1.5 or less, more preferably 1.4 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)}

[0128] In the manufacturing method of the present disclosure, when a polymer is manufactured by using an azo-based radical initiator or a peroxide-based radical initiator in combination, the obtained iodine-containing compound is a polymer containing a structure derived from the radical initiator used in part. However, according to the manufacturing method of the present disclosure, the ratio of the structure derived from the azo-based radical initiator or the peroxide-based radical initiator used to the obtained polymer terminal can be reduced compared to a polymerization method using a general azo-based radical initiator or a peroxide-based radical initiator. That is, according to the manufacturing method of the present disclosure, since the polymerization is not initiated by the azo-based radical initiator or the peroxide-based radical initiator but initiated by the compound (10), the ratio of the structure derived from the azo-based radical initiator or the peroxide-based radical initiator incorporated in the polymer can be reduced. The ratio of the structure derived from the azo-based radical initiator or the peroxide-based radical initiator 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, relative to the number of moles of the polymer terminal. The ratio of the number of moles of the structure derived from the radical initiator to the number of moles of the polymer terminals can be determined by NMR.

[0129] [Method for producing iodine-containing compounds] The production method of the present disclosure, as described above, includes reacting compound (10) with a compound represented by formula (3) in the presence of at least one compound selected from the group consisting of compounds represented by formulas (20) to (22). In one embodiment, a polymer of a fluorine-containing monomer can be produced by the production method of the present disclosure. In one embodiment, a copolymer of a fluorine-containing monomer and another monomer can be produced by the production method of the present disclosure. In one embodiment, a crosslinked structure can be introduced into a fluorine-containing polymer by the production method of the present disclosure. Hereinafter, exemplary embodiments (first to third embodiments) of the manufacturing method of the present disclosure will be described.

[0130] (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 compounds represented by formulas (20) to (22). Hereinafter, the method for producing an iodine-containing compound according to the first embodiment is also referred to as the "production method according to the first embodiment."

[0131] 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 formulae (20) to (22) abstracts iodine from 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 with a highly controlled molecular weight distribution can be obtained.

[0132] Specific examples of reaction conditions are described below. In a container purged with an inert gas or a container under vacuum, at least one compound selected from the group consisting of compounds represented by formulas (20) to (22), compound (10), and compound represented by formula (5) are mixed. Multiple types of 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, is mixed. Examples of the inert gas include nitrogen, argon, and helium. Among these, nitrogen or argon is preferred, and nitrogen is more preferred.

[0133] 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).

[0134] 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.

[0135] 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 further preferably 30°C to 60°C. The reaction time can be appropriately adjusted to obtain a desired molecular weight, and may be, for example, 1 hour to 24 hours, or 2 hours to 10 hours. Stirring is usually performed at normal pressure, but may be increased or decreased.

[0136] 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 method may be used for the reaction treatment as long as it does not interfere with the target compound.

[0137] (2) Second embodiment The method for producing an iodine-containing compound according to the 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) and a compound represented by formula (3) 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 represented by formula (5) can be suitably obtained. Hereinafter, the method for producing an iodine-containing compound according to the second embodiment is also referred to as the "production method according to the second embodiment". In addition, hereinafter, the compound represented by formula (3) different from the first compound used in copolymerization is also referred to as a copolymerization monomer.

[0138] The details of the first compound are the same as those for the compound represented by formula (5) above.

[0139] The copolymerization monomer may be a compound represented by formula (5) 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 copolymerization 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.

[0140] 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.

[0141] 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, and more preferred are styrene, 4-methoxystyrene, 4-chlorostyrene, and 4-(chloromethyl)styrene. Examples of the alkali metal salts include sodium salts and potassium salts.

[0142] 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).

[0143] Among them, the copolymerization monomer is preferably at least one selected from the group consisting of ethylene, propylene, isobutylene, alkyl vinyl ether, perfluoro(alkyl vinyl ether), triallyl isocyanurate, 1,4-divinyl octafluorobutane, 1,6-divinyl dodecafluorohexane, vinyl acetate, styrene, butyl acrylate, and divinyl benzene.

[0144] 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 methods.

[0145] -Block copolymer- By using at least one compound selected from the group consisting of compounds represented by formulas (20) to (22) and compound (10), it is possible to obtain, for example, AB diblock copolymers such as trifluoroethylene-styrene, and BAB triblock copolymers such as styrene-trifluoroethylene-styrene.

[0146] 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) different from the first compound, in the presence of at least one compound selected from the group consisting of compounds represented by formulas (20) to (22). The block copolymerization may be carried out by using a radical initiator other than compound (10) in combination.

[0147] 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. Then, 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)" polymerized in the first embodiment is read as "copolymerization monomer".

[0148] When a BAB triblock copolymer is produced, a method can be mentioned in which a diiodine-containing organic compound is used in place of a monoiodine-containing organic compound in the above-mentioned method for producing an AB diblock copolymer.

[0149] In the above-mentioned 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 once and purified before starting the reaction for the next block. Isolation of the block copolymer can be carried out by a conventional method.

[0150] -Random copolymers, alternating copolymers- A random copolymer or an alternating copolymer can be obtained by reacting the 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 compounds represented by formulas (20) to (22). The copolymerization may be carried out in combination with a radical initiator other than compound (10).

[0151] Whether the resulting copolymer is a random or alternating copolymer is determined by the type and relative amounts of the first compound and comonomer.

[0152] In either case of random copolymerization or alternating copolymerization, other polymerization conditions may be the same as those described in the first embodiment.

[0153] (3) Third embodiment The method for producing an iodine-containing compound according to the third embodiment includes the steps of: 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 is also 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 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 compounds represented by formulas (20) to (22).

[0154] 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 is read as "compound represented by formula (3) having at least two reactive carbon-carbon double bonds". In the third embodiment, the compound (10) is preferably used in an amount of 0.1 mol to 10 mol, more preferably 0.5 mol to 5 mol, and even more preferably 0.8 mol to 1.2 mol, per mol of the compound represented by formula (3) having at least two reactive carbon-carbon double bonds. EXAMPLES

[0155] 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. Note that all of the following Examples 1 to 7 correspond to examples of the present disclosure.

[0156] (Example 1) In a nitrogen-substituted glove box, 0.34 g (1.1 mmol) of an azo radical initiator "V-70" (product name, Fujifilm Wako Pure Chemical Industries, Ltd.), 0.11 g (0.55 mmol) of diphenylphosphine oxide, 0.38 g (1.1 mmol) of n-nonafluorobutyl iodide, and 25.2 g of 1H-perfluorohexane were charged into a 30 mL capacity stainless steel autoclave equipped with a stirrer in a nitrogen-substituted glove box. After 18 g (220 mmol) of trifluoroethylene was injected, stirring was started while raising the internal temperature to 35° C. After stirring at 200 rpm (200 revolutions per minute) for 4 hours while maintaining the internal temperature, the internal pressure decreased from 1.9 MPa (gauge pressure) to 1.8 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted trifluoroethylene.

[0157] The obtained polymer solution was dried under vacuum to obtain a solid. The 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 obtained solid was dried under vacuum to obtain 0.78 g of a solid. The solid thus obtained had Mn=37,000 and Mw=51,000 as determined by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.4, and this radical polymerization exhibited characteristics of living radical polymerization.

[0158] (Example 2) In a nitrogen-substituted glove box, 0.34 g (1.1 mmol) of an azo radical initiator "V-70" (product name, Fujifilm Wako Pure Chemical Industries, Ltd.), 0.11 g (0.55 mmol) of diphenylphosphine oxide, 0.38 g (1.1 mmol) of n-nonafluorobutyl iodide, and 25.2 g of 1H-perfluorohexane were charged into a 30 mL capacity stainless steel autoclave equipped with a stirrer in a nitrogen-substituted glove box. After 18 g (220 mmol) of trifluoroethylene was injected, stirring was started while raising the internal temperature to 35° C. After stirring at 200 rpm for 8 hours while maintaining the internal temperature, the internal pressure decreased from 1.9 MPa (gauge pressure) to 1.7 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted trifluoroethylene.

[0159] The resulting polymer solution was dried under vacuum to obtain a solid. The solid was added to 50 mL of methanol and stirred for 30 minutes, and then the solid was separated from the supernatant using a centrifuge. The resulting solid was dried under vacuum to obtain 1.2 g of a solid. The solid thus obtained had Mn=48,000 and Mw=64,000 as determined by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.3, and this radical polymerization exhibited characteristics of living radical polymerization.

[0160] (Example 3) In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.24 g (1.1 mmol) of a peroxide radical initiator "Perloyl IPP" (trade name, manufactured by NOF Corporation) dissolved in a fluorine-based solvent "ASAHIKLIN AK-225" (trade name, manufactured by AGC Inc.) to give a 50 mass % solution, 0.076 g (0.55 mmol) of diethyl phosphite, 0.38 g (1.1 mmol) of n-nonafluorobutyl iodide, and 25.2 g of 1H-perfluorohexane. After 18 g (220 mmol) of trifluoroethylene was injected, stirring was started while raising the internal temperature to 45° C. After stirring at 200 rpm for 4 hours while maintaining the internal temperature, the internal pressure decreased from 2.2 MPa (gauge pressure) to 1.9 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted trifluoroethylene.

[0161] The obtained polymer solution was dried under vacuum to obtain a solid. The 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 obtained solid was dried under vacuum to obtain 2.2 g of a solid. The solid thus obtained had Mn=32,000 and Mw=44,000 as determined by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.4. When the 1H-NMR and 19F-NMR of the obtained solid were measured, the ratio of the number of moles of the structure derived from peroyl IPP contained in the polymer to the number of moles of the terminals of the polymer was calculated to be 5 mol % or less.

[0162] (Example 4) In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.91 g (4.4 mmol) of a peroxide radical initiator "Perloyl IPP" (trade name, manufactured by NOF Corporation) dissolved in a fluorine-based solvent "Asahiclean AK-225" (trade name, manufactured by AGC Inc.) to give a 50 mass % solution, 0.64 g (4.4 mmol) of di-tert-butylphosphine, 0.38 g (1.1 mmol) of n-nonafluorobutyl iodide, and 25.2 g of 1H-perfluorohexane. After 18 g (220 mmol) of trifluoroethylene was injected, stirring was started while raising the internal temperature to 45° C. After stirring at 200 rpm for 4 hours while maintaining the internal temperature, the internal pressure decreased from 2.2 MPa (gauge pressure) to 2.0 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted trifluoroethylene.

[0163] The obtained polymer solution was dried under vacuum to obtain a solid. The 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 obtained solid was dried under vacuum to obtain 1.6 g of a solid. The solid thus obtained had Mn=6,100 and Mw=8,900 as determined by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.5. When the 1H-NMR and 19F-NMR of the obtained solid were measured, the ratio of the number of moles of the structure derived from peroyl IPP contained in the polymer to the number of moles of the terminals of the polymer was calculated to be 10 mol % or less.

[0164] (Example 5) In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with 0.097 g (0.45 mmol) of a peroxide radical initiator "Perloyl IPP" (trade name, manufactured by NOF Corporation) dissolved in a fluorine-based solvent "ASAHIKLIN AK-225" (trade name, manufactured by AGC Inc.) to give a 50 mass % solution, 0.032 g (0.23 mmol) of diethyl phosphite, 0.16 g (0.45 mmol) of n-nonafluorobutyl iodide, and 25.2 g of 1H-perfluorohexane. After 9.0 g (90 mmol) of tetrafluoroethylene was injected, stirring was started while raising the internal temperature to 45° C. After stirring at 200 rpm for 2 hours while maintaining the internal temperature, the internal pressure decreased from 2.2 MPa (gauge pressure) to 1.4 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted tetrafluoroethylene.

[0165] The obtained polymer solution was dried under vacuum to obtain a solid. The 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 obtained solid was dried under vacuum to obtain 2.7 g of a solid.

[0166] (Example 6) In a nitrogen-substituted glove box, a 20 mL glass reactor was charged with 0.60 g of the fluoropolymer obtained in Example 2, 0.0051 g (0.024 mmol) of a solution of a peroxide-based radical initiator "Perloyl IPP" (trade name, manufactured by NOF Corporation) dissolved in a fluorine-based solvent "ASAHIKLIN AK-225" (trade name, manufactured by AGC Inc.) to a concentration of 50% by mass, 0.013 g (0.096 mmol) of diethyl phosphite, 1.0 g (9.6 mmol) of styrene, 6.0 g of benzotrifluoride, and a magnetic stirrer. Stirring was started while raising the temperature of the water bath to 45° C. Stirring was continued at 200 rpm for 4 hours while maintaining the temperature. The reactor was allowed to cool to room temperature.

[0167] The obtained polymer solution was dried under vacuum to obtain a solid. The solid was added to 50 mL of toluene and stirred for 30 minutes, and then the solid and the supernatant were separated using a centrifuge. The obtained solid was dried under vacuum to obtain 0.81 g of a solid. The solid thus obtained was measured by size exclusion chromatography to find that its Mn was 70,000 and its Mw was 103,000, and the elution curve showed one peak. The calculated polydispersity (Mw / Mn) of the fluoropolymer was 1.5. The 1H-NMR and 19F-NMR of the obtained solid were measured, and the molar ratio of trifluoroethylene to styrene in the fluorine-containing copolymer was calculated to be 65:35. Size exclusion chromatography and NMR results confirmed the production of block copolymers.

[0168] (Example 7) In a nitrogen-substituted glove box, a glass reactor having an internal volume of 20 mL was charged with a solution of 0.17 g (1 mmol) of a peroxide radical initiator "Perbutyl PV" (trade name, manufactured by NOF Corporation) dissolved in a fluorine-based solvent "ASAHIKLIN AK-225" (trade name, manufactured by AGC Inc.) to a concentration of 50% by mass, 1.7 g (10 mmol) of ethyl phenylphosphinate, 3.5 (10 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. Stirring was started while increasing the temperature of the oil bath 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.

[0169] 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 74 mol %.

[0170] The disclosure of Japanese Patent Application No. 2020-023636 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, and 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 compounds represented by the following formula (21) and compounds represented by the following formula (22), and at least one radical initiator selected from the group consisting of an azo-based radical initiator and a peroxide-based radical initiator, 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): A method for producing a polymeric iodine-containing compound. 【Chemistry 1】 In formula (1), * represents a bond bonded to an organic group. 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. 【Chemistry 2】 (In formula (21), R ２３ and R ２４ each independently represents a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 20 carbon atoms. ２ represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom.) (In formula (22), R ２５ and R ２６ Each of A and B independently represents a substituted or unsubstituted organic group having 1 to 20 carbon atoms. ３ represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom.) 【Chemistry 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. 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, the method according to claim 1 .

3. The method according to claim 1 , wherein the compound represented by formula (3) includes a compound represented by the following formula (5): 【Chemistry 4】 (In the formula, X ２ ~X ４ each independently represents 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 method according to claim 3, 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.

5. The method according to claim 4 , wherein the copolymerization is a block copolymerization.

6. The method according to claim 4, wherein the copolymerization is random copolymerization or alternating copolymerization.

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

8. The compound represented by the 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. The method according to any one of claims 3 to 7, wherein the compound represented by the 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, 1,2-dichloro-1,2-difluoroethylene, 1,2-dibromo-1,2-difluoroethylene, and 1,2-difluoro-1,2-diiodoethylene.

9. The method according to any one of claims 1 to 8, wherein the compound (10) is at least one selected from the group consisting of a compound represented by the following formula (11) and a compound represented by the following formula (12): 【Chemistry 5】 (In the formula, R １１ R represents a perfluoroalkyl group having 1 to 4 carbon atoms. １２ represents a perfluoroalkylene group having 1 to 4 carbon atoms. ２１ ~X ２３ each independently represents 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 method according to any one of claims 1 to 8, wherein the compound (10) is a compound containing a plurality of units represented by the following formula (4): 【Chemistry 6】 (In the formula, X ３１ ~X ３４ each independently represents 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 method according to claim 10, wherein the compound (10) has a fluorine content of 50% by mass or more.

12. The method according to any one of claims 1 to 11, wherein the polydispersity of the obtained iodine-containing compound is 2.0 or less.

13. In the formula (21), R ２３ and R ２４ each independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or -OR, where R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.

14. In the formula (22), R ２５ and R ２６ each independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or -OR, where R represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.

15. A method for producing an iodine-containing compound according to any one of claims 1 to 14, wherein the obtained iodine-containing compound is a polymer containing a structure derived from an azo-based radical initiator or a peroxide-based radical initiator, and the proportion of the structure derived from the azo-based radical initiator or the peroxide-based radical initiator at the polymer terminal is 40 mol % or less.

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