Process for producing tellurium-containing compounds and polymers

Abstract

A tellurium-containing compound represented by any one of formulas (1) to (4): R 1 represents an unsubstituted alkyl group having 2 to 6 carbon atoms, R 2 and R 3 each independently represents a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, Ar represents a substituted or unsubstituted aryl group having 5 to 18 atoms constituting an aromatic ring, R f represents a perfluoroalkyl group having 1 to 12 carbon atoms, A represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 5 to 18 atoms constituting an aromatic ring, X represents a hydrogen atom, a fluorine atom, a CF2-Z group or a CHF-Z group, Y represents a CF2-Z group or a CHF-Z group, and Z represents a fluorine atom or an organic group having 1 to 12 carbon atoms.

Description

Technical Field

[0001] This invention relates to a method for manufacturing tellurium-containing compounds and polymers. Background Technology

[0002] Free radical polymerization is widely used in industry due to the excellent versatility of monomers and its ease of operation even in polar media such as water. However, in conventional free radical polymerization, the molecular weight distribution of the resulting polymer tends to broaden. On the other hand, controlled polymerization has attracted much attention as a polymerization method that can obtain controlled molecular structures, and various polymerization control agents have been developed. Controlled polymerization is a polymerization method in which the growth free radical is reversibly protected by a protecting group acting as a dormant species, thereby controlling the free radical polymerization rate and thus the molecular weight distribution.

[0003] Patent document 1 describes a controlled polymerization method in which specific haloolefins are subjected to free radical polymerization in the presence of specific organotellurium compounds to produce haloolefin polymers or copolymers. This method is based on a process known as TEP (organotellurium mediated living radical polymerization).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2018 / 164147 Summary of the Invention

[0007] On the other hand, even when using controlled polymerization based on the TEP method, conventional methods have room for improvement due to insufficient control over molecular weight distribution caused by different monomer species. In view of this, this disclosure relates to a novel tellurium-containing compound for controlled polymerization with excellent control over molecular weight distribution, and a method for manufacturing polymers using the tellurium-containing compound.

[0008] The means to solve the above problems include the following methods.

[0009] <1> A tellurium-containing compound, represented by any one of the following formulas (1) to (4).

[0010]

[0011] In equations (1) to (4),

[0012] R 1 This refers to an unsubstituted alkyl group having 2 to 6 carbon atoms.

[0013] R2 and R 3 Each of the following independently represents a hydrogen atom, or an alkyl group having 1 to 6 substituted or unsubstituted carbon atoms.

[0014] Ar represents a substituted or unsubstituted aryl group consisting of 5 to 18 atoms forming the aromatic ring.

[0015] R f Perfluoroalkyl groups representing 1 to 12 carbon atoms

[0016] A represents an alkyl group with 1 to 12 carbon atoms, either substituted or unsubstituted, or an aryl group with 5 to 18 atoms forming an aromatic ring, either substituted or unsubstituted.

[0017] X represents a hydrogen atom, a fluorine atom, a CF2-Z group, or a CHF-Z group.

[0018] Y represents CF2-Z group or CHF-Z group.

[0019] Z represents a fluorine atom or an organic group having 1 to 12 carbon atoms.

[0020] In equations (2) and (3), Y and R f They may connect to form a ring structure, or they may not form a ring structure.

[0021] <2> According to the tellurium-containing compound described in <1>, wherein, in the above formulas (1) to (4),

[0022] Ar represents substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl groups.

[0023] A represents an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; an unsubstituted alkyl group having 1 to 4 hydrogen atoms each independently substituted by a fluorine atom, chlorine atom, hydroxyl group, alkoxy group, fluoroalkoxy group, amino group, cyano group, carbonyl group, or sulfonyl group; or a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group.

[0024] Z represents a fluorine atom; an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; an unsubstituted alkyl group having 1 to 4 hydrogen atoms each independently substituted by a fluorine atom, chlorine atom, hydroxyl group, alkoxy group, fluoroalkoxy group, amino group, cyano group, carbonyl group, or sulfonyl group; a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group; or -OZ 1 Base, here, Z 1The term refers to an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; an unsubstituted alkyl group having 1 to 4 hydrogen atoms each independently replaced by a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl group, or a sulfonyl group; or a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group.

[0025] <3> A method for manufacturing a polymer, wherein a compound having a carbon-carbon double bond is polymerized in the presence of at least one compound selected from the compounds represented by the following formulas (1) to (4).

[0026]

[0027] In equations (1) to (4),

[0028] R 1 This refers to an unsubstituted alkyl group having 2 to 6 carbon atoms.

[0029] R 2 and R 3 Each of the following independently represents a hydrogen atom, or an alkyl group having 1 to 6 substituted or unsubstituted carbon atoms.

[0030] Ar represents a substituted or unsubstituted aryl group consisting of 5 to 18 atoms forming the aromatic ring.

[0031] R f Perfluoroalkyl groups representing 1 to 12 carbon atoms

[0032] A represents an alkyl group with 1 to 12 carbon atoms, either substituted or unsubstituted, or an aryl group with 5 to 18 atoms forming an aromatic ring, either substituted or unsubstituted.

[0033] X represents a hydrogen atom, a fluorine atom, a CF2-Z group, or a CHF-Z group.

[0034] Y represents CF2-Z group or CHF-Z group.

[0035] Z represents a fluorine atom or an organic group having 1 to 12 carbon atoms.

[0036] In equations (2) and (3), Y and R f They may connect to form a ring structure, or they may not form a ring structure.

[0037] <4> The method for manufacturing the polymer according to <3>, wherein, in the above formulas (1) to (4),

[0038] Ar represents substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl groups.

[0039] A represents an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; an unsubstituted alkyl group having 1 to 4 hydrogen atoms each independently substituted by a fluorine atom, chlorine atom, hydroxyl group, alkoxy group, fluoroalkoxy group, amino group, cyano group, carbonyl group, or sulfonyl group; or a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group.

[0040] Z represents a fluorine atom; an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; an unsubstituted alkyl group having 1 to 4 hydrogen atoms each independently substituted by a fluorine atom, chlorine atom, hydroxyl group, alkoxy group, fluoroalkoxy group, amino group, cyano group, carbonyl group, or sulfonyl group; a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group; or -OZ 1 Base, here, Z 1 The term refers to an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; an unsubstituted alkyl group having 1 to 4 hydrogen atoms each independently replaced by a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl group, or a sulfonyl group; or a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group.

[0041] <5> The method for manufacturing the polymer according to <3> or <4>, wherein at least one compound selected from the compounds represented by formulas (1) to (4) above is a compound represented by formula (1), and the above-mentioned compound having a carbon-carbon double bond includes a compound represented by formula (5) below.

[0042]

[0043] In equation (5), A 1 and A 2 Each of these groups independently represents an organic group consisting of 1 to 20 hydrogen, fluorine, chlorine, bromine, iodine, or carbon atoms.

[0044] <6> The method for manufacturing the polymer according to <5>, wherein, in the above formula (5), A 1 and A 2 Each of the following can be independently represented: hydrogen atom; fluorine atom; chlorine atom; bromine atom; iodine atom; alkyl group having 1 to 12 carbon atoms (substituted or unsubstituted); alkoxy group having 1 to 12 carbon atoms (substituted or unsubstituted); or phenyl, naphthyl, pyridyl or imidazolyl group (substituted or unsubstituted).

[0045] <7> The method for manufacturing the polymer according to <3> or <4>, wherein at least one compound selected from the compounds represented by formulas (1) to (4) above is a compound represented by formula (2), and the above-mentioned compound having a carbon-carbon double bond includes a compound represented by formula (6) below.

[0046]

[0047] In equation (6), A 1 and A 2 Each of the following can independently represent an organic group having 1 to 20 carbon atoms: hydrogen, fluorine, chlorine, bromine, iodine, or hydrogen atoms. f It refers to perfluoroalkyl groups with 1 to 12 carbon atoms.

[0048] <8> The method for manufacturing the polymer according to <7>, wherein, in the above formula (6), A 1 and A 2 Each of the following can be independently represented: hydrogen atom; fluorine atom; chlorine atom; bromine atom; iodine atom; alkyl group having 1 to 12 carbon atoms (substituted or unsubstituted); alkoxy group having 1 to 12 carbon atoms (substituted or unsubstituted); or phenyl, naphthyl, pyridyl or imidazolyl group (substituted or unsubstituted).

[0049] <9> The method for manufacturing the polymer according to <3> or <4>, wherein at least one compound selected from the compounds represented by formulas (1) to (4) above is a compound represented by formula (3), and the above-mentioned compound having a carbon-carbon double bond includes a compound represented by formula (7) below.

[0050]

[0051] In equation (7), A 1 and A 2 Each of the following can independently represent an organic group having 1 to 20 carbon atoms: hydrogen, fluorine, chlorine, bromine, iodine, or hydrogen atoms. f It refers to perfluoroalkyl groups with 1 to 12 carbon atoms.

[0052] <10> The method for manufacturing the polymer according to <9>, wherein, in the above formula (7), A 1 and A 2 Each of the following can be independently represented: hydrogen atom; fluorine atom; chlorine atom; bromine atom; iodine atom; alkyl group having 1 to 12 carbon atoms (substituted or unsubstituted); alkoxy group having 1 to 12 carbon atoms (substituted or unsubstituted); or phenyl, naphthyl, pyridyl or imidazolyl group (substituted or unsubstituted).

[0053] <11> The method for manufacturing the polymer according to <3> or <4>, wherein at least one compound selected from the compounds represented by formulas (1) to (4) above is a compound represented by formula (4), and the above-mentioned compound having a carbon-carbon double bond includes a compound represented by formula (8) below.

[0054]

[0055] In equation (8), A 1 and A 2 Each of these groups independently represents an organic group consisting of 1 to 20 hydrogen, fluorine, chlorine, bromine, iodine, or carbon atoms.

[0056] <12> According to the polymer manufacturing method described in <11>, wherein, in the above formula (8), A 1 and A 2 Each of the following can be independently represented: hydrogen atom; fluorine atom; chlorine atom; bromine atom; iodine atom; alkyl group having 1 to 12 carbon atoms (substituted or unsubstituted); alkoxy group having 1 to 12 carbon atoms (substituted or unsubstituted); or phenyl, naphthyl, pyridyl or imidazolyl group (substituted or unsubstituted).

[0057] <13> The method for manufacturing the polymer according to <3> or <4>, wherein the compound having carbon-carbon double bonds comprises at least one selected from vinyl fluoride, vinylidene fluoride, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, perfluoro(methyl vinyl ether), vinylidene chloride, vinyl chloride, perfluoro(n-propyl vinyl ether), perfluoro(3-butenyl vinyl ether), (perfluoro-n-butyl)ethylene, (perfluoro-n-hexyl)ethylene, 1,4-divinylperfluorobutane, 1,6-divinylperfluorohexane, ethylene, and propylene.

[0058] <14> A method for manufacturing a polymer according to any one of <3> to <13>, wherein the process is carried out in the presence of an azo radical initiator.

[0059] <15> The method for manufacturing the polymer according to <14>, wherein 0.01 to 100 mol of the above-described azo radical initiator is used relative to a total of 1 mol of at least one compound selected from the compounds represented by formulas (1) to (4) above.

[0060] <16> A method for manufacturing a polymer according to any one of <3> to <15>, wherein, relative to a total of 1 mol of the compounds having carbon-carbon double bonds described above, a total of 0.001 to 1 mol of the compounds represented by the above formulas (1) to (4) is used.

[0061] <17> A method for manufacturing a polymer according to any one of <3> to <16>, wherein the weight-average molecular weight of the obtained polymer is 1,000 to 500,000.

[0062] <18> A method for manufacturing a polymer according to any one of <3> to <17>, wherein the polydispersity of the obtained polymer is 2.0 or less.

[0063] <19> A method for manufacturing a polymer according to any one of <3> to <18>, wherein the compound having carbon-carbon double bonds comprises a first compound having carbon-carbon double bonds, and the first compound having carbon-carbon double bonds is block copolymerized with a second compound having carbon-carbon double bonds that is different from the first compound having carbon-carbon double bonds.

[0064] <20> A method for manufacturing a polymer according to any one of <3> to <18>, wherein the compound having carbon-carbon double bonds comprises a first compound having carbon-carbon double bonds and a second compound having carbon-carbon double bonds, different from the first compound having carbon-carbon double bonds, and the first compound having carbon-carbon double bonds and the second compound having carbon-carbon double bonds are randomly copolymerized.

[0065] According to this disclosure, a novel tellurium-containing compound is provided for controlled polymerization with excellent control over molecular weight distribution, and a method for manufacturing polymers using the tellurium-containing compound is also provided. Detailed Implementation

[0066] The following describes in detail the methods for implementing the present disclosure. However, the embodiments of the present disclosure are not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not essential unless specifically stated otherwise. The same applies to numerical values ​​and their ranges; they do not limit the embodiments of the present disclosure.

[0067] In this disclosure, the term "process" is used not only to include processes that are independent of other processes, but also to include processes that achieve their purpose, even if they cannot be clearly distinguished from other processes.

[0068] In this disclosure, the numerical range represented by “~” includes the minimum and maximum values ​​recorded before and after “~”, respectively.

[0069] In this disclosure, each component may comprise multiple corresponding substances. In the presence of multiple substances corresponding to each component in a composition or system, unless otherwise specified, the content or percentage of each component refers to the total content or percentage of the multiple substances present in the composition or system.

[0070] In the numerical ranges described in this disclosure in stages, the upper or lower limit of one numerical range can be replaced by the upper or lower limit of another numerical range described in stages. Furthermore, the upper or lower limit of the numerical ranges described in this disclosure can be replaced by the values ​​shown in the embodiments.

[0071] In this disclosure, unless otherwise specified, organic groups or hydrocarbon groups may or may not have substituents.

[0072] The number of carbon atoms in the compounds or constituent parts of this disclosure, when the compound or constituent part has substituents, refers to the number of carbon atoms containing the substituents.

[0073] In this disclosure, carbon-carbon double bonds refer to carbon-carbon double bonds that can undergo various reactions as alkenes, excluding aromatic double bonds.

[0074] In this disclosure, (meth)acrylic acid is a collective term for acrylic acid and methacrylic acid. (meth)acrylate is a collective term for acrylate and methacrylate. (meth)acrylamide is a collective term for acrylamide and methacrylamide.

[0075] In this disclosure, "polymer" or "aggregate" refers to a compound formed by the polymerization of monomers. That is, it has multiple structural units.

[0076] In this disclosure, unless otherwise specified, the descriptions of "polymerizing compound A" and "polymerizing at least compound A" include both the case of polymerizing only compound A and the case of polymerizing compound A with other compounds. Similarly, the descriptions of "polymerizing compound A with compound B" and "polymerizing at least compound A with compound B" include both the case of polymerizing only compound A and compound B, and the case of polymerizing compound A, compound B, and other compounds. Here, compound A and compound B refer to any compound described in this disclosure that has a carbon-carbon double bond in its molecule. Furthermore, unless otherwise specified, the polymer described in this disclosure can be a homopolymer of a single compound or a copolymer of two or more compounds. In this disclosure, the terms "polymer" or "polymerized body" do not exclude mixtures of raw materials (monomers, catalysts), byproducts, impurities, etc., in addition to polymers.

[0077] <Tellulose-containing compounds>

[0078] In one embodiment of this disclosure, the tellurium-containing compound is a compound represented by any of the following formulas (1) to (4).

[0079]

[0080] In equations (1) to (4),

[0081] R 1 This refers to an unsubstituted alkyl group having 2 to 6 carbon atoms.

[0082] R 2 and R 3 Each of the following independently represents a hydrogen atom, or an alkyl group having 1 to 6 substituted or unsubstituted carbon atoms.

[0083] Ar represents a substituted or unsubstituted aryl group consisting of 5 to 18 atoms forming the aromatic ring.

[0084] R f Perfluoroalkyl groups representing 1 to 12 carbon atoms

[0085] A represents an alkyl group with 1 to 12 carbon atoms, either substituted or unsubstituted, or an aryl group with 5 to 18 atoms forming an aromatic ring, either substituted or unsubstituted.

[0086] X represents a hydrogen atom, a fluorine atom, a CF2-Z group, or a CHF-Z group.

[0087] Y represents CF2-Z group or CHF-Z group.

[0088] Z represents a fluorine atom or an organic group having 1 to 12 carbon atoms.

[0089] In equations (2) and (3), Y and R f They may connect to form a ring structure, or they may not form a ring structure.

[0090] The compounds represented by formulas (1) to (4) can function as control agents in controlling polymerization. Hereinafter, the compounds represented by formulas (1) to (4) will also be collectively referred to as "specific control agents". In addition, the compounds represented by formulas (1) to (4) will be referred to as "specific control agent (1)", "specific control agent (2)", "specific control agent (3)" and "specific control agent (4)" respectively.

[0091] The inventors discovered that in controlled polymerization based on the TEP method, the molecular weight distribution can be appropriately controlled by using a specific control agent instead of a conventional one. The mechanism is not yet fully understood, but is hypothesized as follows.

[0092] In controlled polymerization based on the TEP method, if the growth free radicals are close to the control agent (R... a -Te-X a Here, R a X is a non-leaving group. a (Leaving group), leaving group (X) a ) detaches from the control agent, the remaining part (R) a -Te) binds to the terminus of the growth radical as a protecting group. Leaving group (X)a The free radical reacts with the monomer to become the initiation terminator. The protection of the growing free radical using a protecting group is reversible, and deprotection occurs through reactions with other free radicals. Through this mechanism, deprotection, growth (monomer addition), and protection are repeatedly performed, thereby achieving rate-controlled polymerization. Here, if a specific control agent is used, compared to conventional control agents, it is necessary to sufficiently retain the non-leaving group (R) a While protecting the polymer ends of the polymer, the leaving group (X) is utilized. a The re-initiation rate is faster. If the protection rate at the polymer ends is high, bimolecular termination can be suppressed. In addition, if the re-initiation rate is high, the timing deviation of polymer generation is smaller. Therefore, it is believed that polymers with a narrow molecular weight distribution can be formed compared with previous methods.

[0093] In a specific control agent (1), -CF2X becomes a leaving group, and in a specific control agent (2), -CFR f Y becomes a leaving group, and in a specific control agent (3), -CHR f Y becomes a leaving group, and in a specific control agent (4), -CHFCR 2 R 3 X becomes the leaving group. It is speculated that through the structure of these leaving groups, the ease of free radical generation and the stability of the free radical are within an appropriate range, and the re-initiation rate of the leaving group and the monomer is accelerated. If the re-initiation rate relative to the reaction rate of the free radical with the monomer from the free radical initiator is above a certain value, then there is a tendency for the induction period until polymerization initiation to be shortened, thus shortening the reaction time.

[0094] It should be noted that the embodiments of this disclosure are not subject to any of the above-described speculative mechanisms.

[0095] In equation (1), R 1 This refers to an unsubstituted alkyl group having 2 to 6 carbon atoms. Examples of unsubstituted alkyl groups having 2 to 6 carbon atoms include linear, branched, or cyclic alkyl groups such as ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, and cyclohexyl. In one embodiment, as R... 1 Preferably, it is a straight-chain alkyl group, more preferably n-butyl.

[0096] In equation (4), R 2 and R 3 Each of these independently represents a hydrogen atom, or an alkyl group having 1 to 6 substituted or unsubstituted carbon atoms. In one embodiment, as R 2 and R 3 Each of them is preferably a hydrogen atom, and more preferably all of them are hydrogen atoms.

[0097] Examples of unsubstituted alkyl groups having 1 to 6 carbon atoms include straight-chain, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, and cyclohexyl.

[0098] As the substituted alkyl group having 1 to 6 carbon atoms, examples include alkyl groups in which any hydrogen atom bonded to the unsubstituted alkyl group having 1 to 6 carbon atoms is replaced by a substituent such as a fluorine atom, chlorine atom, alkoxy group, or fluoroalkoxy group. There is no particular limitation on the number of substituents; it can be 1 to 4, 1 to 3, 1 to 2, or even just 1.

[0099] In one embodiment, the substituted alkyl group having 1 to 6 carbon atoms is preferably a fluoroalkyl group having 1 to 6 carbon atoms. Examples of fluoroalkyl groups having 1 to 6 carbon atoms include those in which some or all of the hydrogen atoms bonded to the unsubstituted alkyl group having 1 to 6 carbon atoms are replaced by fluorine atoms. Here, "fluoroalkyl group" refers to an alkyl group consisting only of C, F, and H (where present).

[0100] In formula (2), Ar represents a substituted or unsubstituted aryl group that constitutes the aromatic ring with 5 to 18 atoms. Preferably, Ar is a substituted or unsubstituted aryl group that constitutes the aromatic ring with 5 to 12 atoms. Here, "number of atoms constituting the aromatic ring" refers to the number of atoms in the ring itself that constitutes the aromatic ring, excluding hydrogen atoms or substituents.

[0101] Examples of unsubstituted aryl groups comprising 5 to 18 atoms in the aromatic ring include high aryl groups such as phenyl and naphthyl; and heteroaryl groups such as pyridyl, imidazolyl, pyrrolel, furanyl, and thiophene. Among these, homoaryl is preferred, and phenyl is more preferred.

[0102] Examples of substituted aryl groups comprising 5 to 18 atoms in the aromatic ring include aryl groups in which any hydrogen atom bonded to the aromatic ring of the unsubstituted aryl group is replaced by a halogen atom, hydroxyl group, alkoxy group, amino group, nitro group, cyano group, carbonyl group, sulfonyl group, trifluoromethyl group, or other substituents. The number of substituents is not particularly limited and can be 1 to 4, 1 to 3, 1 to 2, or even just 1.

[0103] In one manner, Ar is preferably substituted or unsubstituted phenyl, naphthyl, pyridyl or imidazole.

[0104] In equations (2) and (3), R f This refers to perfluoroalkyl groups with 1 to 12 carbon atoms. As R fPreferably, it is a perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of perfluoroalkyl groups having 1 to 12 carbon atoms include perfluoromethyl, perfluoroethyl, perfluoron-propyl, perfluoroisopropyl, perfluoron-butyl, perfluorosec-butyl, perfluorotert-butyl, perfluoron-pentyl, perfluoron-hexyl, perfluoron-heptyl, and perfluoron-octyl. In one embodiment, as R... f Preferably, it is perfluoromethyl.

[0105] In formulas (3) and (4), A represents an alkyl group with 1 to 12 carbon atoms that is substituted or unsubstituted, or an aryl group with 5 to 18 atoms that constitutes an aromatic ring that is substituted or unsubstituted.

[0106] The unsubstituted alkyl group having 1 to 12 carbon atoms is preferably an unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of unsubstituted alkyl groups having 1 to 12 carbon atoms include straight-chain, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, and n-octyl. Among these, methyl, ethyl, or n-butyl are preferred.

[0107] Examples of alkyl groups with 1 to 12 carbon atoms that are substituted include alkyl groups in which any hydrogen atom bonded to the unsubstituted alkyl group with 1 to 12 carbon atoms is replaced by a fluorine atom, chlorine atom, hydroxyl group, alkoxy group, fluoroalkoxy group, amino group, cyano group, carbonyl group, sulfonyl group, etc. Examples of carbonyl groups include acyl group, formyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, carbamoyl group, amide group, etc. Examples of sulfonyl groups include sulfonyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfonyloxy group, aminosulfonyl group, sulfonylamide group, etc. The number of substituents is not particularly limited and can be 1 to 4, 1 to 3, 1 to 2, or even 1.

[0108] Examples of unsubstituted aryl groups comprising 5 to 18 atoms in the aromatic ring include high aryl groups such as phenyl and naphthyl; and heteroaryl groups such as pyridyl, imidazolyl, pyrrolel, furanyl, and thiophene. Among these, high aryl groups are preferred, and phenyl is more preferred.

[0109] Examples of substituted aryl groups comprising 5 to 18 atoms in the aromatic ring include aryl groups in which any hydrogen atom bonded to the aromatic ring of the unsubstituted aryl group is replaced by a halogen atom, hydroxyl group, alkoxy group, amino group, nitro group, cyano group, carbonyl group, sulfonyl group, trifluoromethyl group, or other substituents. The number of substituents is not particularly limited and can be 1 to 4, 1 to 3, 1 to 2, or even just 1.

[0110] In one embodiment, A is preferably an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; a substituted alkyl group having 1 to 12 carbon atoms in which 1 to 4 hydrogen atoms in the unsubstituted alkyl group are each independently substituted by a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl group, or a sulfonyl group; or a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group.

[0111] In formulas (1) and (4), X represents a hydrogen atom, a fluorine atom, a CF2-Z group or a CHF-Z group, where Z represents a fluorine atom or an organic group with 1 to 12 carbon atoms.

[0112] Examples of organic groups with 1 to 12 carbon atoms represented by Z include substituted or unsubstituted alkyl groups with 1 to 12 carbon atoms, substituted or unsubstituted aryl groups with 5 to 12 atoms forming an aromatic ring, substituted or unsubstituted alkoxy groups with 1 to 12 carbon atoms, and -(OX) groups with 1 to 12 carbon atoms. 1 ) n1 -OR represents a group (here, X 1 Each of these can be independently represented as an alkylene group having 1 to 11 substituted or unsubstituted carbon atoms, where R represents a hydrogen atom, or an alkyl group having 1 to 11 substituted or unsubstituted carbon atoms, and n1 represents an integer from 1 to 11.

[0113] The unsubstituted alkyl group having 1 to 12 carbon atoms is preferably an unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of unsubstituted alkyl groups having 1 to 12 carbon atoms include straight-chain, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, and n-octyl. Among these, methyl, ethyl, or n-butyl are preferred.

[0114] Examples of alkyl groups with 1 to 12 carbon atoms that are substituted include alkyl groups in which any hydrogen atom bonded to the unsubstituted alkyl group with 1 to 12 carbon atoms is replaced by a fluorine atom, chlorine atom, hydroxyl group, alkoxy group, fluoroalkoxy group, amino group, cyano group, carbonyl group, or sulfonyl group. Examples of carbonyl groups include acyl group, formyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, carbamoyl group, and amide group. Examples of sulfonyl groups include sulfonyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfonyloxy group, aminosulfonyl group, and sulfonylamide group. There is no particular limitation on the number of substituents; it can be 1 to 4, 1 to 3, 1 to 2, or even just 1.

[0115] Examples of unsubstituted aryl groups comprising 5 to 12 atoms in the aromatic ring include high aryl groups such as phenyl and naphthyl; and heteroaryl groups such as pyridyl, imidazolyl, pyrrolel, furanyl, and thiophene. Among these, homoaryl is preferred, and phenyl is more preferred.

[0116] Examples of substituted aryl groups comprising 5 to 12 atoms in the aromatic ring include aryl groups in which any hydrogen atom bonded to the aromatic ring of the unsubstituted aryl group is replaced by a halogen atom, hydroxyl group, alkoxy group, amino group, nitro group, cyano group, carbonyl group, sulfonyl group, trifluoromethyl group, or other substituents. The number of substituents is not particularly limited and can be 1 to 4, 1 to 3, 1 to 2, or even just 1.

[0117] Examples of unsubstituted alkoxy groups with 1 to 12 carbon atoms include -OR u The group indicated. Here, R u The group that represents an unsubstituted alkyl group having 1 to 12 carbon atoms can be exemplified by the aforementioned groups representing an unsubstituted alkyl group having 1 to 12 carbon atoms as Z.

[0118] As a substituted alkoxy group with 1 to 12 carbon atoms, examples include alkoxy groups in which any hydrogen atom bonded to the unsubstituted alkoxy group with 1 to 12 carbon atoms is replaced by a substituent such as a fluorine atom, chlorine atom, alkoxy group, or fluoroalkoxy group. There is no particular limitation on the number of substituents; it can be 1 to 4, 1 to 3, 1 to 2, or even just 1.

[0119] In the group with 1 to 12 carbon atoms - (OX) 1 ) n1 In the group represented by -OR, X 1 When R and / or R have substituents, examples of substituents include fluorine atoms, chlorine atoms, alkoxy groups, and fluoroalkoxy groups. The number of substituents is not particularly limited; they can be 1 to 4, 1 to 3, 1 to 2, or even just one. As X 1 Preferably, it is an unsubstituted alkylene group having 1 to 3 carbon atoms. As R, it is preferably an unsubstituted alkyl group having 1 to 3 carbon atoms. As a -(OX) group having 1 to 12 carbon atoms... 1 ) n1 Examples of groups represented by -OR include -OCH2OCH3 and -OCH2CH2OCH3.

[0120] In one embodiment, Z is preferably a fluorine atom; an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; an unsubstituted alkyl group having 1 to 4 hydrogen atoms each independently substituted by a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl group, or a sulfonyl group; a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group; or -OZ 1 Base. Here, Z 1 The term refers to an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; an unsubstituted alkyl group having 1 to 4 hydrogen atoms each independently replaced by a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl group, or a sulfonyl group; or a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group.

[0121] In one approach, X is preferably CF2-Z based.

[0122] In formulas (2) and (3), Y represents a CF2-Z group or a CHF-Z group, where Z represents an organic group with 1 to 12 fluorine atoms or carbon atoms. Details of Z are as described above. In one embodiment, Y is preferably a CF2-Z group, and more preferably CF3.

[0123] Examples of specific control agents (1) include (ethyl) pentafluoroethyl tellurium, (ethyl) n-nonafluorobutyl tellurium, (ethyl) n-tetridefluorohexyl tellurium, (n-butyl) pentafluoroethyl tellurium, (n-butyl) n-nonafluorobutyl tellurium, (sec-butyl) n-nonafluorobutyl tellurium, (tert-butyl) n-nonafluorobutyl tellurium, and (n-hexyl) n-nonafluorobutyl tellurium.

[0124] Examples of specific control agents (2) include (1,1,1,2,3,3,3-heptafluoroisopropyl)phenyl tellurium, (1,1,2,2,3,3,4,4,5,5,6-undecylfluorocyclohexyl)phenyl tellurium, and (1,1,1,2,2,3,4,4,4-nonafluorobutyl)phenyl tellurium.

[0125] Examples of specific control agents (3) include (1,1,1,3,3,3-hexafluoroisopropyl)methyl tellurium, (ethyl)1,1,1,3,3,3-hexafluoroisopropyl tellurium, (n-butyl)1,1,1,3,3,3-hexafluoroisopropyl tellurium, (1,1,1,3,3,3-hexafluoroisopropyl)phenyl tellurium, and (n-butyl)1,1,1-trifluoroisopropyl tellurium.

[0126] Examples of specific control agents (4) include (1,3,3,3-tetrafluoropropyl)methyl tellurium, (n-butyl)1,3,3,3-tetrafluoropropyl tellurium, and (1,3,3,3-tetrafluoropropyl)phenyl tellurium.

[0127] In one approach, the type of specific control agent is preferably selected based on the monomers used in the polymerization.

[0128] Specific control agents (1) can, for example, be made by making compound (R) 1 The synthesis is achieved by reacting Te2 with compound CXF2I. Here, R 1 The definition of X and R in equation (1) 1 The definition is the same as that of X. Specific control agents (2) to (4) can also be synthesized based on this reaction.

[0129] <Methods for manufacturing polymers>

[0130] One embodiment of the polymer manufacturing method of this disclosure includes polymerizing a compound having carbon-carbon double bonds in the presence of a specific control agent. Hereinafter, the compound having carbon-carbon double bonds will also be referred to as a "polymerizable monomer". The polymer manufacturing method of this embodiment provides excellent control over the molecular weight of the resulting polymer, and readily yields polymers with narrow molecular weight distributions.

[0131] In the polymer manufacturing method of this embodiment, in addition to the specific control agent and polymerizable monomer, other components such as free radical initiators, solvents, emulsifiers, suspending agents, acids or bases may be further used. Hereinafter, the components used in the polymer manufacturing method of this embodiment, the polymer as a product thereof, and the polymerization method will be described in detail.

[0132] [Specific control agent]

[0133] Regarding specific control agents, as described in the section on "Tellulose-containing compounds," a specific control agent may be used alone or in combination with two or more.

[0134] The amount of the specific control agent used relative to 1 mol of the polymerizable monomer is preferably 0.001 mol or more, more preferably 0.005 mol or more, and even more preferably 0.01 mol or more. Furthermore, the above-mentioned amount is preferably 1 mol or less, more preferably 0.5 mol or less, and even more preferably 0.1 mol or less. Therefore, the above-mentioned amount is preferably 0.001 to 1 mol, more preferably 0.005 to 0.5 mol, and even more preferably 0.01 to 0.1 mol.

[0135] [Compounds containing carbon-carbon double bonds]

[0136] Compounds containing carbon-carbon double bonds (polymerizable monomers) need to contain at least one carbon-carbon double bond, but they can also have two or more, even three or more, depending on the polymer targeted for synthesis. Polymerizable monomers preferably have one or two carbon-carbon double bonds. A single polymerizable monomer can be used, or two or more monomers can be used in combination.

[0137] The polymerizable monomer can be a monomer containing fluorine atoms (fluorinated monomer) or a monomer without fluorine atoms. In one embodiment, it is preferred that the polymerizable monomer contains a fluorinated monomer. Generally speaking, from a reaction kinetics point of view, controlled polymerization of fluorinated monomers is difficult in many cases. For example, in the polymerization of fluorinated monomers, the growth reaction rate is high, while the initiation reaction rate and the chain transfer reaction rate are low, and the side reaction rate is high, which tends to be unfavorable to controlled polymerization. However, according to the polymer manufacturing method of this embodiment, controlled polymerization of fluorinated monomers can also be carried out appropriately, and polymers with narrow molecular weight distributions can be easily formed.

[0138] In one manner, the polymerizable monomer may be a compound represented by the following formula (M1).

[0139]

[0140] In formula (M1), R 11 ~R 14 Each of these groups independently represents an organic group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or 1 to 40 carbon atoms. R 11 With R 13 Or R 12 With R 14 They can be connected to form a ring structure, or they can not form a ring structure.

[0141] R 11 ~R 14 The number of carbon atoms in the organic groups with 1 to 40 carbon atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 12.

[0142] Examples of organic groups having 1 to 40 carbon atoms include alkyl, aryl, heteroaryl, aryloxy, heteroaryloxy, alkoxy, aralkyl, heteroarylalkyl, aralkoxy, heteroarylalkoxy, carboxyl, alkoxycarbonyl, carbamoyl, amide, acyloxy, cyano, and monovalent hydrocarbon groups with an oxoalkylene structure.

[0143] As an organic group with 1 to 40 carbon atoms, it can be an organic group having substituents such as fluorine atom, chlorine atom, hydroxyl group, alkoxy group, alkoxyalkyl group, amino group, carboxylic acid group, sulfonic acid group, etc. on the above-mentioned organic groups.

[0144] When the organic group having 1 to 40 carbon atoms is an alkyl, aryl, heteroaryl, aryloxy, heteroaryloxy, alkoxy, aralkyl, heteroarylalkyl, arylalkoxy, heteroarylalkoxy, alkoxycarbonyl, or a monovalent hydrocarbon group with an oxoalkylene structure, or a hydrocarbon group with or without heteroatoms, the hydrocarbon group can be any of the following: straight-chain, branched, or cyclic. In addition, it may or may not contain unsaturated bonds.

[0145] Acyl groups, which are amide or acyloxy groups, can be exemplified by groups formed by removing the hydroxyl group from carboxylic acids or sulfonic acids.

[0146] In formula (M1), R 11 With R 13 Or R 12 With R 14 They can connect to form a cyclic structure, or they can not. That is, the compound represented by formula (M1) can be a compound with a cyclic structure, such as maleic anhydride or itaconic anhydride.

[0147] Examples of polymerizable monomers include, for instance, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, lauryl methacrylate, and hydroxyethyl methacrylate; cyclohexyl methacrylate, methylcyclohexyl methacrylate, isobornyl methacrylate, and cyclododecyl methacrylate, which are cycloalkyl-containing unsaturated monomers; carboxyl-containing unsaturated monomers such as methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, maleic anhydride, and itaconic anhydride; and N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylamide, and (meth)propyl... Unsaturated monomers containing tertiary amines, such as 2-(dimethylamino)ethyl acrylate and N,N-dimethylaminopropyl methacrylate; unsaturated monomers containing quaternary ammonium salts, such as N-2-hydroxy-3-acryloyloxypropyl-N,N,N-trimethylammonium chloride and N-methacryloylaminoethyl-N,N,N-dimethylbenzylammonium chloride; unsaturated monomers containing epoxy groups, such as glycidyl methacrylate; 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, and 2-(chloromethyl)styrene. Styrene monomers such as 3-(chloromethyl)styrene, 4-styrenesulfonic acid or their alkali metal salts (sodium salt, potassium salt, etc.); heterocyclic unsaturated monomers such as 2-vinylthiophene and N-methyl-2-vinylpyrrole; vinylamides such as N-vinylformamide and N-vinylacetamide; diallylamine, triallyl isocyanurate, tris(2-methyl-allyl) isocyanurate, ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-octene, 1-decene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, trifluorochloroethylene, 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 α-olefins such as (n-1-hexene), 1H,1H,2H-perfluoro(n-1-octene), (perfluoron-butyl)ethylene, and (perfluoron-hexyl)ethylene; vinyl ester monomers such as vinyl acetate; divinylfluoroalkanes such as 1,4-divinylperfluorobutane and 1,6-divinylperfluorohexane; acrylonitrile; acrylamide monomers such as acrylamide and N,N-dimethylacrylamide; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, and hydroxybutyl vinyl ether; perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(n-propyl vinyl ether), and perfluoro(3-butenyl vinyl ether), etc.

[0148] The polymerizable monomer preferably comprises at least one selected from vinyl fluoride, vinylidene fluoride, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, perfluoro(methyl vinyl ether), vinylidene chloride, vinyl chloride, perfluoro(n-propyl vinyl ether), perfluoro(3-butenyl vinyl ether), (perfluoro-n-butyl)ethylene, (perfluoro-n-hexyl)ethylene, 1,4-divinylperfluorobutane, 1,6-divinylperfluorohexane, ethylene, and propylene.

[0149] In one manner, the polymerizable monomer may be a compound represented by the following formula (M2).

[0150]

[0151] In formula (M2), X 11 ~X 14 Each of the following independently represents an organic group having 1 to 20 carbon atoms: hydrogen, fluorine, chlorine, bromine, iodine, or hydrogen atoms. 11 ~X 14 At least one of them represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxygen-perfluoroalkylene structure.

[0152] The monomer represented by formula (M2) is a fluorinated monomer. As described above, according to the polymer manufacturing method of this embodiment, even if the monomer represented by formula (M2) is used, controlled polymerization can be carried out appropriately.

[0153] X 11 ~X 14 The number of carbon atoms in the organic groups having 1 to 20 carbon atoms is preferably 1 to 12. Examples of organic groups having 1 to 20 carbon atoms include alkyl, aryl, heteroaryl, aryloxy, heteroaryloxy, alkoxy, aralkyl, heteroarylalkyl, arylalkoxy, heteroarylalkoxy, carboxyl, alkoxycarbonyl, carbamoyl, amide, acyloxy, cyano, and monovalent hydrocarbon groups having an oxoalkylene structure.

[0154] As an organic group having 1 to 20 carbon atoms, it can also be an organic group that further has substituents such as fluorine atoms, chlorine atoms, hydroxyl groups, alkoxy groups, alkoxyalkyl groups, amino groups, carboxylic acid groups, and sulfonic acid groups on the above-mentioned organic groups.

[0155] When the organic group having 1 to 20 carbon atoms is an alkyl, aryl, heteroaryl, aryloxy, heteroaryloxy, alkoxy, aralkyl, heteroarylalkyl, arylalkoxy, heteroarylalkoxy, alkoxycarbonyl, or a monovalent hydrocarbon group with an oxoalkylene structure, which may or may not have heteroatoms, the hydrocarbon group may be straight-chain, branched, or cyclic. In addition, it may or may not contain unsaturated bonds.

[0156] Acyl groups, which are amide or acyloxy groups, can be exemplified by groups formed by removing the hydroxyl group from carboxylic acids or sulfonic acids.

[0157] Examples of perfluoroalkyl groups include perfluoromethyl, perfluoroethyl, perfluoron-propyl, perfluoroisopropyl, perfluoron-butyl, perfluorosec-butyl, perfluorotert-butyl, perfluoron-pentyl, perfluoron-hexyl, perfluoron-heptyl, and perfluoron-octyl.

[0158] As a monovalent hydrocarbon group having an oxygen perfluoroalkylene structure, a monovalent perfluoroalkyl group with an oxygen perfluoroalkylene structure having 1 to 4 carbon atoms is preferred, and -[(CF2] is even more preferred. m -O] n -CF3 represents a perfluoroalkyl group. Here, m represents the number of repetitions of the difluoromethylene group, which is preferably an integer from 0 to 4. n represents -[(CF2) m The number of repetitions of the [-O]- structure is preferably an integer from 1 to 15.

[0159] Examples of compounds represented by formula (M2) include vinyl fluoride, vinylidene fluoride, trifluoroethylene, trifluorochloroethylene, trifluorobromoethylene, trifluoroiodoethylene, 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.

[0160] From the viewpoint of polymerization reactivity when obtaining the polymer, compounds represented by formula (M2) are preferably vinylidene fluoride, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, and 2,3,3,3-tetrafluoropropylene. Additionally, compounds having two carbon-carbon double bonds, such as perfluoro(3-butenylvinyl ether), 1,4-divinyloctafluorobutane, and 1,6-divinyldodecylfluorohexane, are also preferred.

[0161] [Other arbitrary ingredients]

[0162] In the polymer manufacturing method of this embodiment, other components such as free radical initiators, solvents, emulsifiers, suspending agents, acids or bases may also be used.

[0163] -Free radical initiators-

[0164] Examples of free radical initiators include azo-based and peroxide-based free radical initiators. From the viewpoint of minimizing interference with the action of specific control agents, azo-based free radical initiators are preferred. Free radical initiators can be used alone or in combination of two or more.

[0165] Examples of azo-based free radical initiators include 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (AMBN), 2,2'-azobis(2,4-dimethylpentanonitrile) (ADVN), 1,1'-azobis(1-cyclohexanecarboxynitrile) (ACHN), dimethyl-2,2'-azobisisobutyrate (MAIB), 4,4'-azobis(4-cyanopentanoic acid) (ACVA), 1,1'-azobis(1-acetoxy-1-phenylethane), and 2,2'-azobis(2-methylbutyronitrile). Amides), 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile), 2,2'-azobis(2-methylamidinylpropane) 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-propylazocarboxamide, 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), etc.

[0166] When using an azo-based free radical initiator for polymerization, the amount of the azo-based free radical initiator used relative to 1 mol of the specific control agent is preferably 0.01 mol or more, more preferably 0.05 mol or more, and even more preferably 0.1 mol or more. Furthermore, the above-mentioned amount is preferably 100 mol or less, more preferably 50 mol or less, even more preferably 10 mol or less, and particularly preferably 5 mol or less. Therefore, relative to 1 mol of the specific control agent, the amount of the azo-based free radical initiator used is preferably 0.01 to 100 mol, more preferably 0.05 to 50 mol, even more preferably 0.1 to 10 mol, and particularly preferably 0.1 to 5 mol.

[0167] Examples of peroxide-based free radical initiators include diisopropyl peroxide dicarbonate, tert-butyl peroxypentanoate, and benzoyl peroxide.

[0168] -solvent-

[0169] Examples of solvents include organic solvents and aqueous solvents. A single solvent can be used, or two or more solvents can be used in combination.

[0170] Examples of organic solvents include benzene, toluene, xylene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), and dimethyl ethyl ketone. Alkane, 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, trifluorotoluene, chlorobenzene, acetonitrile, etc.

[0171] Alternatively, N-methyl-N-methoxymethylpyrrolidine can also be used. Tetrafluoroborate, N-methyl-N-ethoxymethyltetrafluoroborate, 1-methyl-3-methylimidazolium Tetrafluoroborate, 1-methyl-3-methylimidazolium Hexafluorophosphate, 1-methyl-3-methylimidazolium Chlorides, etc.

[0172] Examples of aqueous solvents include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol.

[0173] The amount of solvent used can be adjusted appropriately. For example, relative to 1000g of the obtained polymer, the amount of solvent is preferably 0.01L or more, more preferably 0.05L or more, and even more preferably 0.1L or more. Furthermore, relative to 1000g of the obtained polymer, the amount of solvent is preferably 50L or less, more preferably 10L or less, and even more preferably 5L or less. Therefore, relative to 1000g of the obtained polymer, the amount of solvent is preferably 0.01 to 50L, more preferably 0.05 to 10L, and even more preferably 0.1 to 5L.

[0174] 〔polymer〕

[0175] The resulting polymer can be a homopolymer formed by polymerizing one type of polymerizable monomer, or a copolymer formed by polymerizing two or more polymerizable monomers. The copolymer can be a block copolymer, a random copolymer, or an alternating copolymer. Depending on the type of polymerizable monomer, the polymer can be a fluorinated polymer or a polymer without fluorine atoms.

[0176] The molecular weight of a polymer can be adjusted by specific control agents and the amount of free radical initiators used as needed, reaction time, etc.

[0177] For example, the number average molecular weight (Mn) of the polymer can be 100–1,000,000, 1,000–500,000, or 10,000–200,000.

[0178] In addition, the weight-average molecular weight (Mw) of the polymer can be 100–1,000,000, 1,000–500,000, or 10,000–200,000.

[0179] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) in this disclosure are determined by SEC (Size Exclusion Chromatography), using polystyrene as a standard substance for molecular weight conversion.

[0180] According to the polymer manufacturing method of this embodiment, the polydispersity of the obtained polymer can be controlled to, for example, 2.5 or less. According to the manufacturing method of this disclosure, polymers with very narrow molecular weight distributions, preferably with polydispersity of 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, can also be obtained. It should be noted that the lower limit of polydispersity is defined as 1.0.

[0181] Polydispersity (PD), an indicator of molecular weight distribution, is calculated using the following formula.

[0182] PD = Mw (weight-average molecular weight) / Mn (number-average molecular weight)

[0183] The resulting polymer preferably has a leaving group derived from a specific control agent in a portion thereof. For example, when using a specific control agent (1), the polymer preferably comprises polymer molecules with a terminal structure of -CF2X, and when using a specific control agent (2), it preferably comprises polymer molecules with a terminal structure of -CFR. f When a specific control agent (3) is used, the polymer molecule of Y preferably contains a terminal structure of -CHR. f When a specific control agent (4) is used, the polymer molecule of Y preferably contains a terminal structure of -CHFCR. 2 R 3 The polymer molecule of X. The proportion of the structure of the leaving group from the specific control agent is preferably 10 to 100 mol% relative to the number of mol at the polymer end, more preferably 25 to 100 mol%. The above proportions can be determined by NMR.

[0184] [Aggregation Method]

[0185] The following describes an example of a specific polymerization method in the polymer manufacturing method of this embodiment.

[0186] In a container purged with an inert gas or a vacuum-reduced container, a specific control agent is mixed with a polymerizable monomer. Examples of inert gases include nitrogen, argon, and helium. Nitrogen or argon is preferred, and nitrogen is more preferred. To accelerate polymerization, a free radical initiator, such as an azo radical initiator, may also be used.

[0187] Although polymerization can be carried out in solvent-free conditions, it can also be carried out using organic or aqueous solvents commonly used in free radical polymerization.

[0188] Next, the mixture obtained through the above operations is stirred. The reaction temperature and reaction time can be adjusted appropriately according to the molecular weight or molecular weight distribution of the obtained polymer. Stirring can be carried out at 60–150°C for 5–100 hours, or at 80–120°C for 10–30 hours. The reaction can be carried out under normal pressure, or under pressure or reduced pressure.

[0189] After the reaction is complete, the target polymer is removed by conventional methods under reduced pressure to eliminate the solvent and residual monomers, or by reprecipitation using a solvent insoluble in the target polymer, thereby separating the target analyte. Regarding reaction treatment, any treatment method is acceptable as long as it does not interfere with the target analyte.

[0190] The above polymerization method allows for excellent control of molecular weight and molecular weight distribution under mild conditions.

[0191] A variety of polymerizable monomers can be used to make block copolymers, random copolymers, or alternating copolymers.

[0192] For example, if the polymerizable monomer being polymerized in the presence of a specific control agent includes a first polymerizable monomer, the first polymerizable monomer can be block copolymerized with a second polymerizable monomer different from the first polymerizable monomer. In this case, the first polymerizable monomer can be polymerized in the presence of the specific control agent, and then the second polymerizable monomer can be reacted with the product in the presence of the specific control agent. Alternatively, the first polymerizable monomer can be polymerized in the presence of the specific control agent, and then the second polymerizable monomer can be reacted with the product without using the specific control agent (i.e., by a method different from the polymer manufacturing method in this embodiment).

[0193] In another approach, the polymerizable monomers polymerized in the presence of a specific control agent include a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer, which can be used to randomly copolymerize the first polymerizable monomer and the second polymerizable monomer.

[0194] The first and second polymerizable monomers can be any polymerizable monomers, and examples of the previously exemplified polymerizable monomers can be cited independently. In one embodiment, it is preferred that at least the first polymerizable monomer is a fluorinated monomer, and it is also preferred that both the first and second polymerizable monomers are fluorinated monomers.

[0195] In one embodiment, the combination of a specific control agent and a polymerizable monomer is preferably any one of the following combinations 1 to 4.

[0196] (Group 1)

[0197] The specific control agent is the specific control agent (1), and the polymerizable monomer comprises a compound represented by the following formula (5).

[0198]

[0199] In equation (5), A 1 and A 2 Each of these groups independently represents an organic group consisting of 1 to 20 hydrogen, fluorine, chlorine, bromine, iodine, or carbon atoms.

[0200] (Group 2)

[0201] The specific control agent is the specific control agent (2), and the polymerizable monomer comprises a compound represented by the following formula (6).

[0202]

[0203] In equation (6), A 1 and A 2 Each of the following can independently represent an organic group having 1 to 20 carbon atoms: hydrogen, fluorine, chlorine, bromine, iodine, or hydrogen atoms. f It refers to perfluoroalkyl groups with 1 to 12 carbon atoms.

[0204] (Group 3)

[0205] The specific control agent is the specific control agent (3), and the polymerizable monomer comprises a compound represented by the following formula (7).

[0206]

[0207] In equation (7), A 1 and A 2 Each of the following can independently represent an organic group having 1 to 20 carbon atoms: hydrogen, fluorine, chlorine, bromine, iodine, or hydrogen atoms. f It refers to perfluoroalkyl groups with 1 to 12 carbon atoms.

[0208] (Group 4)

[0209] The specific control agent is the specific control agent (4), and the polymerizable monomer comprises a compound represented by the following formula (8).

[0210]

[0211] In equation (8), A 1 and A 2 Each of these groups independently represents an organic group consisting of 1 to 20 hydrogen, fluorine, chlorine, bromine, iodine, or carbon atoms.

[0212] For combinations 1 to 4, the carbon atom adjacent to Te and the hydrogen atom or substituent bonded thereto in the leaving group of the specific control agent (e.g., -CF2- in specific control agent (1), -CFR in specific control agent (2)). f - Specific control agent (3) is -CHR f - In the specific control agent (4), it is -CHF-) and part of the structure of the polymerizable monomer (e.g., =CF2 in formula (5), =CFR in formula (6)). f In equation (7), =CHR f In equation (8), the hydrogen atoms or substituents bonded to the carbon atoms are common. It is believed that by combining a specific control agent with a polymerizable monomer having such a similar structure, the balance between the stability of the free radical and its reactivity with the monomer becomes moderate, the re-initiation rate becomes faster, and particularly appropriate molecular weight control can be achieved.

[0213] In equations (5) to (8), A is used as... 1 Or A 2 Examples of organic groups representing 1 to 20 carbon atoms include substituted or unsubstituted alkyl groups with 1 to 20 carbon atoms, substituted or unsubstituted aryl groups with 5 to 20 atoms forming an aromatic ring, substituted or unsubstituted alkoxy groups with 1 to 12 carbon atoms, and -(OX) groups with 1 to 12 carbon atoms. 1 ) n1 -OR represents a group (here, X 1 Each of these can be used independently to represent an alkylene group with 1 to 11 substituted or unsubstituted carbon atoms, where R represents a hydrogen atom or an alkyl group with 1 to 11 substituted or unsubstituted carbon atoms, and n1 represents an integer from 1 to 11.

[0214] The unsubstituted alkyl group having 1 to 20 carbon atoms is preferably an unsubstituted alkyl group having 1 to 12 carbon atoms, and more preferably an unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of unsubstituted alkyl groups having 1 to 20 carbon atoms include straight-chain, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, and n-octyl. Among these, methyl, ethyl, or n-butyl are preferred.

[0215] As the substituted alkyl group having 1 to 20 carbon atoms, examples include alkyl groups in which any hydrogen atom bonded to the unsubstituted alkyl group having 1 to 12 carbon atoms is replaced by a substituent such as a fluorine atom, chlorine atom, alkoxy group, or fluoroalkoxy group. There is no particular limitation on the number of substituents; it can be 1 to 4, 1 to 3, 1 to 2, or even 1.

[0216] Examples of unsubstituted aryl groups comprising 5 to 20 atoms in the aromatic ring include high aryl groups such as phenyl and naphthyl; and heteroaryl groups such as pyridyl, imidazolyl, pyrroleyl, furanyl, and thiopheneyl. Among these, high aryl groups are preferred, and phenyl is more preferred.

[0217] Examples of substituted aryl groups comprising 5 to 20 atoms in the aromatic ring include aryl groups in which any hydrogen atom bonded to the aromatic ring of the unsubstituted aryl group is replaced by a halogen atom, hydroxyl group, alkoxy group, amino group, nitro group, cyano group, carbonyl group, sulfonyl group, trifluoromethyl group, or other substituents. The number of substituents is not particularly limited and can be 1 to 4, 1 to 3, 1 to 2, or even just 1.

[0218] Examples of unsubstituted alkoxy groups with 1 to 12 carbon atoms include -OR u The group indicated. Here, R u The group that represents an unsubstituted alkyl group having 1 to 12 carbon atoms can be exemplified by the aforementioned groups representing an unsubstituted alkyl group having 1 to 12 carbon atoms as Z.

[0219] As a substituted alkoxy group with 1 to 12 carbon atoms, examples include alkoxy groups in which any hydrogen atom bonded to the unsubstituted alkoxy group with 1 to 12 carbon atoms is replaced by a substituent such as a fluorine atom, chlorine atom, alkoxy group, or fluoroalkoxy group. There is no particular limitation on the number of substituents; it can be 1 to 4, 1 to 3, 1 to 2, or even just 1.

[0220] In the group with 1 to 12 carbon atoms - (OX) 1 ) n1 In the group represented by -OR, X 1 When R and / or R have substituents, examples of substituents include fluorine atoms, chlorine atoms, alkoxy groups, and fluoroalkoxy groups. The number of substituents is not particularly limited; they can be 1 to 4, 1 to 3, 1 to 2, or even just one. As X 1 Preferably, it is an unsubstituted alkylene group having 1 to 3 carbon atoms. As R, it is preferably an unsubstituted alkyl group having 1 to 3 carbon atoms. As a -(OX) group having 1 to 12 carbon atoms... 1 ) n1Examples of groups represented by -OR include -OCH2OCH3 and -OCH2CH2OCH3.

[0221] In one way, as A 1 and A 2 Each of the following is preferably a hydrogen atom; a fluorine atom; a chlorine atom; a bromine atom; an iodine atom; a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms; or a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group.

[0222] A 1 and A 2 The combination can be any of the above combinations. For example, preferred combinations are those consisting entirely of hydrogen atoms, those consisting entirely of fluorine atoms, those consisting of hydrogen atoms and fluorine atoms, those consisting of fluorine atoms and chlorine atoms, those consisting of hydrogen atoms and organic groups having 1 to 20 carbon atoms, and those consisting of fluorine atoms and organic groups having 1 to 20 carbon atoms.

[0223] In equations (5) to (8), R f This refers to perfluoroalkyl groups with 1 to 12 carbon atoms. As R f Preferably, it is a perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of perfluoroalkyl groups having 1 to 12 carbon atoms include perfluoromethyl, perfluoroethyl, perfluoron-propyl, perfluoroisopropyl, perfluoron-butyl, perfluorosec-butyl, perfluorotert-butyl, perfluoron-pentyl, perfluoron-hexyl, perfluoron-heptyl, and perfluoron-octyl. In one embodiment, as R... f Preferably, it is perfluoromethyl. In one embodiment, R f Preferably, R is used in combination with a specific control agent. f Same structure.

[0224] Example

[0225] Next, embodiments will be described in detail, but the embodiments of this disclosure are not limited to these embodiments. In the following examples, Examples 1 to 26 are embodiments, and Examples 27 to 30 are comparative examples.

[0226] In the following examples, nuclear magnetic resonance (NMR) spectroscopy was performed using Fourier transform NMR. 1 H-NMR was performed at 300 MHz with tetramethylsilane as the reference for a chemical shift of 0 ppm. 19 F-NMR was performed at 282 MHz using 1,4-bis(trifluoromethyl)benzene as a reference with a chemical shift of -63.9 ppm. The abbreviations used in this text have the following meanings.

[0227] s: singlet

[0228] d: doublet

[0229] t: triplet

[0230] m: multiplet (multiplet)

[0231] br: broad

[0232] Hz: Hertz

[0233] CDCl3: Deuterated chloroform

[0234] 1 H-NMR: Proton Nuclear Magnetic Resonance

[0235] 19 F-NMR: Fluorine-19 NMR

[0236] In the following examples, MS (mass spectrometry) was performed using GC / MS (gas chromatography-mass spectrometry). EI (electron ionization) was used as the ionization method. Positive ionization mode (EI+) was used. Found data were recorded.

[0237] In the following examples, the number-average molecular weight (Mn) and weight-average molecular weight (Mw) were determined by SEC (Size Exclusion Chromatography), using polystyrene as a standard for molecular weight conversion.

[0238] (Example 1)

[0239] Synthesis of (n-butyl)-n-nonafluorobutyltellurium (n-BuTeC4F9)

[0240] (n-BuTe)2+n-C4F9I→2n-BuTeC4F9

[0241] In a nitrogen-purged glove box, a magnetic rotor, 3.7 g (10 mmol) of di-n-butylditellurium, and 67 mL of pre-degassed ethanol were added to a 200 mL glass three-necked flask. The flask was then sealed with a three-way stopcock, diaphragm, and flat stopper. The flask was removed from the glove box and stirred at room temperature. The diaphragm was removed while nitrogen was circulating through the flask. Under nitrogen atmosphere, 9.5 g (25 mmol) of sodium borohydride was added to the flask, and the mixture was stirred at room temperature for 15 minutes. Under nitrogen atmosphere, the flask was cooled to -73 °C while stirring. Under nitrogen atmosphere, 17 g (50 mmol) of pre-degassed n-nonafluorobutyl iodine was added to the flask at a rate not exceeding -50 °C. Under nitrogen atmosphere, the flask was stirred at room temperature for 12 hours. Under nitrogen atmosphere, 100 mL of pre-degassed saturated saline solution and 200 mL of pre-degassed hexane were added to the flask and stirred for 10 minutes. The organic and aqueous phases were separated. The aqueous phase was extracted with 100 mL of pre-degassed hexane and combined with the extract. The organic phase was washed with pre-degassed water. In a nitrogen-purged glove box, 100 g of magnesium sulfate was added to the organic phase, and the mixture was allowed to stand for 1 hour. The mixture was then filtered, and the filtrate was recovered. The solvent in the filtrate was removed by distillation under reduced pressure. The residue was purified by distillation under reduced pressure to obtain the title compound in 2.4 g liquid form.

[0242] 1 H NMR (300MHz, CDCl3) δ0.95 (3H, t), δ1.37~1.46 (2H, m), δ1.86~1.94 (2H, m), δ3.15 (2H, t)

[0243] 19 F NMR (282MHz, CDCl3) δ-125.4~-125.5 (2F, m), δ-116.1~-116.2 (2F, m), δ-85.1~-85.2 (2F, br), δ-81.2 (3F, t)

[0244] MS (EI+): [M+] 406.0

[0245] (Example 2)

[0246] Synthesis of (1,1,1,2,3,3,3-heptafluoroisopropyl)phenyltellurium (PhTeCF(CF3)2)

[0247] (PhTe)2+CF3CFICF3→2PhTeCF (CF3)2

[0248] The 3.7 g (10 mmol) of di-n-butylditellurium in Example 1 was replaced with 4.1 g (10 mmol) of diphenylditellurium, and the 17 g (50 mmol) of n-nonafluorobutyliodide was replaced with 15 g (50 mmol) of 1,1,1,2,3,3,3-heptafluoroisopropyliodide. Otherwise, the procedure was carried out in the same manner as in Example 1, and the title compound was obtained in 2.8 g liquid form.

[0249] 1 H NMR (300MHz, CDCl3) δ7.30~7.46 (3H, m), δ7.75~7.78 (2H, m)

[0250] 19 F NMR (282MHz, CDCl3) δ-176.9~-177.1 (1F, m), δ-73.5 (6F, d)

[0251] MS (EI+): [M+] 375.9

[0252] (Example 3)

[0253] Synthesis of (1,1,1,3,3,3-hexafluoroisopropyl)phenyltellurium (PhTeCH(CF3)2)

[0254] (PhTe)2+CF3CHICF3→2PhTeCH(CF3)2

[0255] The 15 g (50 mmol) of 1,1,1,2,3,3,3-heptafluoroisopropyl iodide in Example 2 was replaced with 14 g (50 mmol) of 1,1,1,3,3,3-hexafluoroisopropyl iodide, and otherwise the same procedure was performed as in Example 2, yielding the title compound in 1.5 g liquid form.

[0256] 1 H NMR (300MHz, CDCl3) δ4.0~4.5 (1H, m), δ7.26~7.45 (3H, m), δ7.72~7.75 (2H, m)

[0257] 19 F NMR (282MHz, CDCl3) δ-61.7 (6F, d)

[0258] MS (EI+): [M+] 357.9

[0259] (Example 4)

[0260] Synthesis of (n-butyl)1,3,3,3-tetrafluoropropyltellurium (n-BuTeCHFCH2CF3)

[0261] (n-BuTe)2+n-CF3CH2CHFI→2n-BuTeCHFCH2CF3

[0262] The 17 g (50 mmol) of n-nonafluorobutyl iodide in Example 1 was replaced with 12 g (50 mmol) of 1,3,3,3-tetrafluoropropyl iodide, otherwise the procedure was the same as in Example 1, and the title compound was obtained in 0.8 g liquid form.

[0263] 1 H NMR (300MHz, CDCl3) δ0.91 (3H, t), δ1.35~1.44 (2H, m), δ1.72~1.80 (2H, m), δ2.44~2.54 (2H, m), δ3.12 (2H, t), δ6.12.44~2.54 (2H, m)

[0264] 19 F NMR (282MHz, CDCl3) δ-184.0 (1F, br), δ-65.6 (3F, m)

[0265] MS (EI+): [M+] 302.0

[0266] Examples 5-9 below are embodiments that are expected to be synthesized based on the insights and known methods of this disclosure.

[0267] (Example 5)

[0268] (Ethyl)-n-Tetrofluorohexyl tellurium (EtTeC6F) 13 Synthesis of )

[0269] (EtTe)2+C6F 13 I→2EtTeC6F 13

[0270] The di-n-butylditellurium in Example 1 was replaced with diethylditellurium, and the n-nonafluorobutyliodine was replaced with n-tetrafluorohexyliodine. Otherwise, the procedure was carried out in the same manner as in Example 1, and the title compound was obtained in liquid form.

[0271] (Example 6)

[0272] (1,1,2,2,3,3,4,4,5,5,6-undecylfluorocyclohexyl)phenyltellurium (PhTeC6F) 11 Synthesis of )

[0273] (PhTe)2+C6F 11 I→2PhTeC6F 11

[0274] The 1,1,1,2,3,3,3-heptafluoroisopropyl iodide in Example 2 was replaced with 1,1,2,2,3,3,4,4,5,5,6-undecanofluorohexyl iodide, and otherwise the same procedure was performed as in Example 2 to obtain the title compound in liquid form.

[0275] (Example 7)

[0276] Synthesis of (1,1,1,3,3,3-hexafluoroisopropyl)methyltellurium (MeTeCH(CF3)2)

[0277] (MeTe)2+CF3CHICF3→2MeTeCH(CF3)2

[0278] The diphenylditellurium in Example 3 was replaced with dimethylditellurium, and otherwise the same procedure was followed as in Example 3 to obtain the title compound in liquid form.

[0279] (Example 8)

[0280] Synthesis of (n-butyl)1,1,1,3,3,3-hexafluoroisopropyltellurium (n-BuTeCH(CF3)2)

[0281] (n-BuTe)2+CF3CHICF3→2n-BuTeCH(CF3)2

[0282] The diphenylditellurium in Example 3 was replaced with di-n-butylditellurium, and otherwise the same procedure was followed as in Example 3 to obtain the title compound in liquid form.

[0283] (Example 9)

[0284] Synthesis of (1,3,3,3-tetrafluoropropyl)phenyltellurium (PhTeCHFCH2CF3)

[0285] (PhTe)2+CF3CH2CHFI→PhTeCHFCH2CF3

[0286] The di-n-butylditellurium in Example 4 was replaced with diphenylditellurium, and otherwise the same procedure was followed as in Example 4 to obtain the title compound in liquid form.

[0287] (Example 10)

[0288] Polymerization of tetrafluoroethylene using n-BuTeC4F9

[0289] In a nitrogen-purged glove box, 0.046 g (0.18 mmol) of the azo radical initiator "V-65" (Fujifilm and Koh Genuine Chemicals Co., Ltd.), 0.074 g (0.18 mmol) of n-BuTeC4F9 synthesized in Example 1, and 25 g of 1H-perfluorohexane were added to a 30 mL stainless steel autoclave equipped with a stirrer.

[0290] After adding 3.7 g (37 mmol) of tetrafluoroethylene, the liquid temperature was raised to 65 °C while stirring was started. While maintaining the liquid temperature, the mixture was stirred at 200 rpm for 5 hours.

[0291] After cooling the autoclave in an ice-water bath, purge any unreacted tetrafluoroethylene.

[0292] The obtained polymer solution was dried under vacuum to obtain 0.4 g of solid.

[0293] (Example 11)

[0294] Copolymerization of ethylene with tetrafluoroethylene using n-BuTeC4F9

[0295] In a nitrogen-purged glove box, 0.036 g (0.16 mmol) of the azo radical initiator "V-601" (Fujifilm and Koh Genuine Chemicals Co., Ltd.), 0.063 g (0.16 mmol) of n-BuTeC4F9 synthesized in Example 1, and 25 g of 1H-perfluorohexane were added to a 30 mL stainless steel autoclave equipped with a stirrer.

[0296] After adding 0.41 g (15 mmol) of ethylene and 1.7 g (17 mmol) of tetrafluoroethylene, the liquid temperature was raised to 70 °C while stirring was started. The liquid temperature was maintained and the mixture was stirred at 200 rpm for 5 hours.

[0297] After cooling the autoclave in an ice-water bath, purge any unreacted ethylene and tetrafluoroethylene.

[0298] The obtained polymer solution was dried under vacuum to obtain 1.2 g of solid.

[0299] The obtained solid was determined by size exclusion chromatography, and the results were Mn = 14000 and Mw = 18000.

[0300] The polydispersity (Mw / Mn) of the fluoropolymer was calculated to be 1.3, and the free radical polymerization exhibited the characteristics of living free radical polymerization.

[0301] (Example 12)

[0302] Copolymerization of tetrafluoroethylene with n-BuTeC4F9 and perfluorinated (n-propyl vinyl ether)

[0303] In a nitrogen-purged glove box, 2.1 g (8.0 mmol) of perfluoro(n-propyl vinyl ether), 0.046 g (0.20 mmol) of azo radical initiator "V-601" (Fujifilm and Koh Genuine Chemicals Co., Ltd.), 0.080 g (0.20 mmol) of n-BuTeC4F9 synthesized in Example 1 and 25 g of 1H-perfluorohexane were added to a 30 mL stainless steel autoclave equipped with a stirrer.

[0304] After adding 3.0 g (30 mmol) of tetrafluoroethylene, the liquid temperature was raised to 80 °C while stirring was started. The liquid temperature was maintained while stirring at 200 rpm for 4 hours.

[0305] After cooling the autoclave in an ice-water bath, purge any unreacted tetrafluoroethylene.

[0306] The obtained polymer solution was dried under vacuum to obtain 1.9 g of solid.

[0307] (Example 13)

[0308] Polymerization of vinylidene fluoride using n-BuTeC4F9

[0309] In a nitrogen-purged glove box, 0.025 g (0.10 mmol) of the azo radical initiator "VR-110" (Fujifilm and Koh Genuine Chemicals Co., Ltd.), 0.040 g (0.10 mmol) of n-BuTeC4F9 synthesized in Example 1, and 12 g of acetonitrile were added to a 30 mL stainless steel autoclave equipped with a stirrer.

[0310] After adding 1.3 g (20 mmol) of vinylidene fluoride, the liquid temperature was raised to 110 °C while stirring was started. The liquid temperature was maintained while stirring at 200 rpm for 5 hours.

[0311] After cooling the autoclave in an ice-water bath, purge any unreacted vinylidene fluoride.

[0312] The obtained polymer solution was dried under vacuum to obtain 0.3 g of solid.

[0313] (Example 14)

[0314] Polymerization of trifluoroethylene using n-BuTeC4F9

[0315] In a nitrogen-purged glove box, 0.034 g (0.15 mmol) of the azo radical initiator "V-601" (Fujifilm and Koh Genuine Chemicals Co., Ltd.), 0.059 g (0.15 mmol) of n-BuTeC4F9 synthesized in Example 1, and 12 g of acetonitrile were added to a 30 mL stainless steel autoclave equipped with a stirrer.

[0316] After adding 2.4 g (29 mmol) of trifluoroethylene, the liquid temperature was raised to 80 °C while stirring was started. The liquid temperature was maintained while stirring at 200 rpm for 5 hours.

[0317] After cooling the autoclave in an ice-water bath, purge any unreacted trifluoroethylene.

[0318] The obtained polymer solution was dried under vacuum to obtain 0.9 g of solid.

[0319] The obtained solid was determined by size exclusion chromatography, and the results were Mn = 9000 and Mw = 11000.

[0320] The polydispersity (Mw / Mn) of the fluoropolymer was calculated to be 1.2, and the free radical polymerization exhibited the characteristics of living free radical polymerization.

[0321] (Example 15)

[0322] Block copolymer of polytrifluoroethylene and styrene

[0323] A magnetic rotor, 0.52 g of the fluoropolymer synthesized in Example 14, 0.012 g (0.050 mmol) of the azo radical initiator "V-601" (Fujifilm and Koh Genuine Chemicals Co., Ltd.), 1.0 g (10 mmol) of styrene and 12 g of acetonitrile were loaded into a 30 mL glass Schlenk tube.

[0324] While raising the water bath temperature to 80°C, start stirring. While maintaining the water bath temperature, stir at 400 rpm for 2 hours.

[0325] Cool the Schlenk tube in a water bath.

[0326] The obtained polymer solution was added to 50 mL of pre-degassed methanol to precipitate the solid.

[0327] The obtained solid was separated by filtration and washed with 10 mL of pre-degassed methanol.

[0328] The obtained solid was dried under vacuum to obtain 0.7 g of solid.

[0329] The obtained solid was determined by size exclusion chromatography, and the results were Mn = 11000, Mw = 14000, and the peaks were unimodal.

[0330] The polydispersity (Mw / Mn) of the fluoropolymer was calculated to be 1.3.

[0331] The formation of the block copolymer was confirmed based on Mn, Mw, polydispersity, and the unimodality of the peaks.

[0332] (Example 16)

[0333] Polymerization of trifluorochloroethylene using n-BuTeC4F9

[0334] In a nitrogen-purged glove box, 0.14 g (0.60 mmol) of the azo radical initiator "V-601" (Fujifilm and Koh Genuine Chemicals Co., Ltd.), 0.097 g (0.24 mmol) of n-BuTeC4F9 synthesized in Example 1, and 18 g of trifluorotoluene were added to a 30 mL stainless steel autoclave equipped with a stirrer.

[0335] After adding 14 g (120 mmol) of trifluorochloroethylene, the liquid temperature was raised to 80 °C while stirring was started. The liquid temperature was maintained while stirring at 200 rpm for 4 hours.

[0336] After cooling the autoclave in an ice-water bath, purge any unreacted trifluorochloroethylene.

[0337] The obtained polymer solution was dried under vacuum to obtain 4.5 g of solid.

[0338] The obtained solids were determined by size exclusion chromatography, and the results were Mn = 22000 and Mw = 27000.

[0339] The polydispersity (Mw / Mn) of the fluoropolymer was calculated to be 1.2, and the free radical polymerization exhibited the characteristics of living free radical polymerization.

[0340] (Example 17)

[0341] Copolymerization of trifluorochloroethylene with ethyl vinyl ether using n-BuTeC4F9

[0342] In a nitrogen-purged glove box, 2.9 g (40 mmol) of ethyl vinyl ether, 0.099 g (0.40 mmol) of azo radical initiator "V-65" (Fujifilm and Koh Genuine Chemicals Co., Ltd.), 0.16 g (0.40 mmol) of n-BuTeC4F9 synthesized in Example 1, and 13 g of o-xylene were added to a 30 mL stainless steel autoclave equipped with a stirrer.

[0343] After adding 4.7 g (60 mmol) of trifluorochloroethylene, the liquid temperature was raised to 65 °C while stirring was started. The liquid temperature was maintained while stirring at 200 rpm for 3 hours.

[0344] After cooling the autoclave in an ice-water bath, purge any unreacted trifluorochloroethylene.

[0345] The obtained polymer solution was dried under vacuum to obtain 4.7 g of solid.

[0346] The obtained solid was determined by size exclusion chromatography, and the results were Mn = 14000 and Mw = 18000.

[0347] The polydispersity (Mw / Mn) of the fluoropolymer was calculated to be 1.3, and the free radical polymerization exhibited the characteristics of living free radical polymerization.

[0348] (Example 18)

[0349] Polymerization of perfluorinated (3-butenyl vinyl ether) using n-BuTeC4F9

[0350] A magnetic rotor, 5.6 g (20 mmol) of perfluorinated (3-butenyl vinyl ether), 0.023 g (0.10 mmol) of azo radical initiator "V-601" (Fujifilm and Koh Genuine Chemicals Co., Ltd.), 0.040 g (0.10 mmol) of n-BuTeC4F9 synthesized in Example 1, and 25 g of 1H-perfluorohexane were loaded into a 30 mL glass Schlenk tube.

[0351] While raising the water bath temperature to 80°C, start stirring. While maintaining the water bath temperature, stir at 400 rpm for 4 hours.

[0352] Cool the Schlenk tube in a water bath.

[0353] The obtained polymer solution was dried under vacuum to obtain 0.8 g of solid.

[0354] (Example 19)

[0355] Copolymerization of vinylidene fluoride and trifluoroethylene using n-BuTeC4F9

[0356] In a nitrogen-purged glove box, 0.042 g (0.18 mmol) of the azo radical initiator "V-601" (Fujifilm and Koh Genuine Chemicals Co., Ltd.), 0.073 g (0.18 mmol) of n-BuTeC4F9 synthesized in Example 1, and 12 g of acetonitrile were added to a 30 mL stainless steel autoclave equipped with a stirrer.

[0357] After adding 1.2 g (18 mmol) of vinylidene fluoride and 1.4 g (17 mmol) of trifluoroethylene, the liquid temperature was raised to 65 °C while stirring was started. The liquid temperature was maintained and the mixture was stirred at 200 rpm for 5 hours.

[0358] After cooling the autoclave in an ice-water bath, unreacted vinylidene fluoride and trifluoroethylene are purged.

[0359] The obtained polymer solution was dried under vacuum to obtain 1.0 g of solid.

[0360] The obtained solid was determined by size exclusion chromatography, and the results were Mn = 9000 and Mw = 13000.

[0361] The polydispersity (Mw / Mn) of the fluoropolymer was calculated to be 1.4, and the free radical polymerization exhibited the characteristics of living free radical polymerization.

[0362] (Example 20)

[0363] Copolymerization of vinylidene fluoride and hexafluoropropylene using PhTeCF(CF3)2

[0364] In a nitrogen-purged glove box, 0.043 g (0.19 mmol) of the azo radical initiator "V-601" (Fujifilm and Koh Genuine Chemicals Co., Ltd.), 0.070 g (0.19 mmol) of PhTeCF(CF3)2 synthesized in Example 2, and 12 g of acetonitrile were added to a 30 mL stainless steel autoclave equipped with a stirrer.

[0365] After adding 2.3 g (16 mmol) of hexafluoropropylene and 1.2 g (19 mmol) of vinylidene fluoride, the liquid temperature was raised to 80 °C while stirring was started. The liquid temperature was maintained and the mixture was stirred at 200 rpm for 3 hours.

[0366] After cooling the autoclave in an ice-water bath, purge any unreacted vinylidene fluoride and hexafluoropropylene.

[0367] The obtained polymer solution was dried under vacuum to obtain 0.9 g of solid.

[0368] The obtained solid was determined by size exclusion chromatography, and the results were Mn = 7000 and Mw = 10000.

[0369] The polydispersity (Mw / Mn) of the fluoropolymer was calculated to be 1.4, and the free radical polymerization exhibited the characteristics of living free radical polymerization.

[0370] (Example 21)

[0371] Copolymerization of PhTeCF(CF3)2 with vinylidene fluoride and 2,3,3,3-tetrafluoropropylene

[0372] In a nitrogen-purged glove box, 0.043 g (0.19 mmol) of the azo radical initiator "V-601" (Fujifilm and Koh Genuine Chemicals Co., Ltd.), 0.070 g (0.19 mmol) of PhTeCF(CF3)2 synthesized in Example 2, and 12 g of acetonitrile were added to a 30 mL stainless steel autoclave equipped with a stirrer.

[0373] After adding 2.0 g (18 mmol) of 2,3,3,3-tetrafluoropropylene and 1.2 g (19 mmol) of vinylidene fluoride, the liquid temperature was raised to 80 °C while stirring was started. The liquid temperature was maintained and the mixture was stirred at 200 rpm for 5 hours.

[0374] After cooling the autoclave in an ice-water bath, unreacted vinylidene fluoride and 2,3,3,3-tetrafluoropropylene were purged.

[0375] The obtained polymer solution was dried under vacuum to obtain 0.9 g of solid.

[0376] The obtained solid was determined by size exclusion chromatography, and the results were Mn = 8000 and Mw = 11000.

[0377] The polydispersity (Mw / Mn) of the fluoropolymer was calculated to be 1.4, and the free radical polymerization exhibited the characteristics of living free radical polymerization.

[0378] (Example 22)

[0379] Polymerization of 1,4-divinyloctafluorobutane using PhTeCH(CF3)2

[0380] A magnetic rotor, 13 g (50 mmol) of 1,4-divinyloctafluorobutane, 0.064 g (0.25 mmol) of the azo radical initiator "VR-110" (Fujifilm and Koh Pure Chemical Industries Co., Ltd.), 0.089 g (0.25 mmol) of PhTeCH(CF3)2 synthesized in Example 3 and 25 g of 1H-perfluorohexane were loaded into a 30 mL glass Schlenk tube.

[0381] While heating the oil bath to 110°C, begin stirring. Maintain the oil bath temperature and stir at 400 rpm for 8 hours.

[0382] Cool the Schlenk tube in a water bath.

[0383] The obtained polymer solution was dried under vacuum to obtain 2.7 g of liquid.

[0384] The obtained liquid was determined by size exclusion chromatography, and the results were Mn = 4000 and Mw = 6000.

[0385] The polydispersity (Mw / Mn) of the fluoropolymer was calculated to be 1.5, and the free radical polymerization exhibited the characteristics of living free radical polymerization.

[0386] (Example 23)

[0387] Copolymerization of (perfluoro-n-hexyl)ethylene with vinyl acetate using PhTeCH(CF3)2

[0388] A magnetic rotor, 5.2 g (15 mmol) of (perfluoro-n-hexyl)ethylene, 1.3 g (15 mmol) of vinyl acetate, 0.035 g (0.15 mmol) of azo radical initiator "V-601" (Fujifilm and Kohden Chemical Co., Ltd.), 0.053 g (0.15 mmol) of PhTeCH(CF3)2 synthesized in Example 3, and 12 g of acetonitrile were loaded into a 30 mL glass Schlenk tube.

[0389] While raising the water bath temperature to 80°C, start stirring. While maintaining the water bath temperature, stir at 400 rpm for 4 hours.

[0390] Cool the Schlenk tube in a water bath.

[0391] The obtained polymer solution was dried under vacuum to obtain 3.1 g of liquid.

[0392] The obtained liquid was determined by size exclusion chromatography, and the results were Mn = 12000 and Mw = 16000.

[0393] The polydispersity (Mw / Mn) of the fluoropolymer was calculated to be 1.3, and the free radical polymerization exhibited the characteristics of living free radical polymerization.

[0394] (Example 24)

[0395] Polymerization of trifluoroethylene using n-BuTeCHFCH2CF3

[0396] The 0.040 g (0.10 mmol) of n-BuTeC4F9 synthesized in Example 1 in Example 14 was replaced with 0.044 g (0.10 mmol) of n-BuTeCHFCH2CF3 synthesized in Example 4. Otherwise, the procedure was the same as in Example 14, yielding 0.7 g of solid.

[0397] The obtained solid was determined by size exclusion chromatography, and the results were Mn = 10000 and Mw = 13000.

[0398] The polydispersity (Mw / Mn) of the fluoropolymer was calculated to be 1.3, and the free radical polymerization exhibited the characteristics of living free radical polymerization.

[0399] (Example 25)

[0400] Polymerization of vinyl chloride using PhTeCH(CF3)2

[0401] In a nitrogen-purged glove box, 0.12 g (0.50 mmol) of azo radical initiator "V-601" (Fujifilm and Koh Genuine Chemicals Co., Ltd.), 0.18 g (0.50 mmol) of PhTeCH(CF3)2 synthesized in Example 3, 1.0 g of toluene, and 14 g of deionized water were added to a 30 mL stainless steel autoclave equipped with a stirrer.

[0402] After adding 6.3 g (100 mmol) of vinyl chloride, the liquid temperature was raised to 65 °C while stirring was started. The liquid temperature was maintained while stirring at 200 rpm for 4 hours.

[0403] After cooling the autoclave in an ice-water bath, purge any unreacted vinyl chloride.

[0404] The obtained polymer solution was dried under vacuum to obtain 1.2 g of solid.

[0405] The obtained solid was determined by size exclusion chromatography, and the result was Mn = 10000.

[0406] (Example 26)

[0407] Polymerization of vinyl chloride using PhTeCH(CF3)2-2

[0408] The heating and stirring time in Example 25 was changed from 4 hours to 8 hours, but otherwise the same procedure was followed as in Example 25, yielding 2.3 g of solid.

[0409] The obtained solid was determined by size exclusion chromatography, and the result was Mn = 17000.

[0410] Compared to Example 25, Mn increases with increasing monomer conversion, thus this radical polymerization exhibits characteristics of living radical polymerization.

[0411] (Example 27)

[0412] Polymerization of tetrafluoroethylene using (n-BuTe)2

[0413] In Example 10, the 0.074 g (0.18 mmol) of n-BuTeC4F9 synthesized in Example 1 was replaced with 0.034 g (0.092 mmol) of (n-BuTe)2. Otherwise, the procedure was the same as in Example 10, and no solid was obtained.

[0414] (Example 28)

[0415] Polymerization of tetrafluoroethylene using (n-BuTe)2

[0416] The 0.046 g (0.18 mmol) of azo radical initiator "V-65" (Fujifilm and Wakamitsu Chemical Co., Ltd.) in Example 27 was replaced with 0.042 g (0.18 mmol) of azo radical initiator "V-601" (Fujifilm and Wakamitsu Chemical Co., Ltd.), and the polymerization time was extended. As a result, the pressure began to decrease 18 hours after the heating was completed.

[0417] (Example 29)

[0418] Copolymerization of tetrafluoroethylene with (n-BuTe)2 and perfluorinated (n-propyl vinyl ether)

[0419] In Example 12, the 0.080 g (0.20 mmol) of n-BuTeC4F9 synthesized in Example 1 was replaced with 0.037 g (0.099 mmol) of (n-BuTe)2. Otherwise, the procedure was the same as in Example 12, and no solid was obtained.

[0420] (Example 30)

[0421] Polymerization of trifluoroethylene using (n-BuTe)2

[0422] In Example 14, the 0.059 g (0.15 mmol) of n-BuTeC4F9 synthesized in Example 1 was replaced with 0.027 g (0.073 mmol) of (n-BuTe)2. Otherwise, the procedure was the same as in Example 14, and no solid was obtained.

[0423] (Example 31)

[0424] Polymerization of trifluorochloroethylene using (n-BuTe)2

[0425] The 0.097 g (0.24 mmol) of n-BuTeC4F9 synthesized in Example 1 in Example 16 was replaced with 0.044 g (0.12 mmol) of (n-BuTe)2, and otherwise the same procedure was performed as in Example 16, yielding 3.4 g of solid.

[0426] The obtained solids were determined by size exclusion chromatography, and the results were Mn = 21000 and Mw = 31000.

[0427] The polydispersity (Mw / Mn) of the fluoropolymer was calculated to be 1.5. This free radical polymerization exhibits the characteristics of living free radical polymerization, but the polydispersity is large compared to Example 16.

[0428] Examples 10-26 demonstrate that by using a polymerization method with a specific control agent, polymerization can be appropriately controlled using various polymerizable monomers, resulting in polymers with narrow molecular weight distributions. Furthermore, when the induction period is defined as the time required from the end of the reaction liquid's heating to the decrease in gas phase pressure, the induction period in Example 28 is 18 hours. In contrast, the induction periods in Examples 10-14, 16, 17, 19-21, and 24-26 are all less than 30 minutes, indicating a short induction period until the start of polymerization.

[0429] The disclosure of Japanese Patent Application No. 2023-192418, filed on November 10, 2023, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein, and those specifically described and incorporated herein by reference, are also incorporated herein by reference to the same extent.

Claims

1. A tellurium-containing compound, represented by any one of the following formulas (1) to (4), ， In equations (1) to (4), R 1 This refers to an unsubstituted alkyl group having 2 to 6 carbon atoms. R 2 and R 3 Each of the following independently represents a hydrogen atom, or an alkyl group having 1 to 6 substituted or unsubstituted carbon atoms. Ar represents a substituted or unsubstituted aryl group consisting of 5 to 18 atoms forming the aromatic ring. R f Perfluoroalkyl groups representing 1 to 12 carbon atoms A represents an alkyl group with 1 to 12 carbon atoms, either substituted or unsubstituted, or an aryl group with 5 to 18 atoms forming an aromatic ring, either substituted or unsubstituted. X represents a hydrogen atom, a fluorine atom, a CF2-Z group, or a CHF-Z group. Y represents CF2-Z group or CHF-Z group. Z represents a fluorine atom or an organic group having 1 to 12 carbon atoms. In equations (2) and (3), Y and R f They may connect to form a ring structure, or they may not form a ring structure.

2. The tellurium-containing compound according to claim 1, wherein, In the formulas (1) to (4), Ar represents substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl groups. A represents an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; an unsubstituted alkyl group having 1 to 4 hydrogen atoms each independently substituted by a fluorine atom, chlorine atom, hydroxyl group, alkoxy group, fluoroalkoxy group, amino group, cyano group, carbonyl group, or sulfonyl group; or a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group. Z represents a fluorine atom; an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; an unsubstituted alkyl group having 1 to 4 hydrogen atoms each independently substituted by a fluorine atom, chlorine atom, hydroxyl group, alkoxy group, fluoroalkoxy group, amino group, cyano group, carbonyl group, or sulfonyl group; a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group; or -OZ 1 Base, here, Z 1 The term refers to an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; an unsubstituted alkyl group having 1 to 4 hydrogen atoms each independently replaced by a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl group, or a sulfonyl group; or a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group.

3. A method for manufacturing a polymer, comprising polymerizing a compound having carbon-carbon double bonds in the presence of at least one compound selected from those represented by formulas (1) to (4) below. ， In equations (1) to (4), R 1 This refers to an unsubstituted alkyl group having 2 to 6 carbon atoms. R 2 and R 3 Each of the following independently represents a hydrogen atom, or an alkyl group having 1 to 6 substituted or unsubstituted carbon atoms. Ar represents a substituted or unsubstituted aryl group consisting of 5 to 18 atoms forming the aromatic ring. R f Perfluoroalkyl groups representing 1 to 12 carbon atoms A represents an alkyl group with 1 to 12 carbon atoms, either substituted or unsubstituted, or an aryl group with 5 to 18 atoms forming an aromatic ring, either substituted or unsubstituted. X represents a hydrogen atom, a fluorine atom, a CF2-Z group, or a CHF-Z group. Y represents CF2-Z group or CHF-Z group. Z represents a fluorine atom or an organic group having 1 to 12 carbon atoms. In equations (2) and (3), Y and R f They may connect to form a ring structure, or they may not form a ring structure.

4. The method for manufacturing the polymer according to claim 3, wherein, In the formulas (1) to (4), Ar represents substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl groups. A represents an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; an unsubstituted alkyl group having 1 to 4 hydrogen atoms each independently substituted by a fluorine atom, chlorine atom, hydroxyl group, alkoxy group, fluoroalkoxy group, amino group, cyano group, carbonyl group, or sulfonyl group; or a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group. Z represents a fluorine atom; an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; an unsubstituted alkyl group having 1 to 4 hydrogen atoms each independently substituted by a fluorine atom, chlorine atom, hydroxyl group, alkoxy group, fluoroalkoxy group, amino group, cyano group, carbonyl group, or sulfonyl group; a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group; or -OZ 1 Base, here, Z 1 The term refers to an unsubstituted alkyl group having 1 to 12 carbon atoms; a perfluoroalkyl group having 1 to 12 carbon atoms; an unsubstituted alkyl group having 1 to 4 hydrogen atoms each independently replaced by a fluorine atom, a chlorine atom, a hydroxyl group, an alkoxy group, a fluoroalkoxy group, an amino group, a cyano group, a carbonyl group, or a sulfonyl group; or a substituted or unsubstituted phenyl, naphthyl, pyridyl, or imidazolyl group.

5. The method for manufacturing the polymer according to claim 3 or 4, wherein, At least one compound selected from the compounds represented by formulas (1) to (4) is a compound represented by formula (1), and the compound having a carbon-carbon double bond includes a compound represented by formula (5). ， In equation (5), A 1 and A 2 Each of these groups independently represents an organic group consisting of 1 to 20 hydrogen, fluorine, chlorine, bromine, iodine, or carbon atoms.

6. The method for manufacturing the polymer according to claim 5, wherein, In the above formula (5), A 1 and A 2 Each of the following can be independently represented: hydrogen atom; fluorine atom; chlorine atom; bromine atom; iodine atom; alkyl group having 1 to 12 carbon atoms (substituted or unsubstituted); alkoxy group having 1 to 12 carbon atoms (substituted or unsubstituted); or phenyl, naphthyl, pyridyl or imidazolyl group (substituted or unsubstituted).

7. The method for manufacturing the polymer according to claim 3 or 4, wherein, At least one compound selected from the compounds represented by formulas (1) to (4) is a compound represented by formula (2), and the compound having a carbon-carbon double bond includes a compound represented by formula (6). ， In equation (6), A 1 and A 2 Each of the following can independently represent an organic group having 1 to 20 carbon atoms: hydrogen, fluorine, chlorine, bromine, iodine, or hydrogen atoms. f It refers to perfluoroalkyl groups with 1 to 12 carbon atoms.

8. The method for manufacturing the polymer according to claim 7, wherein, In the above formula (6), A 1 and A 2 Each of the following can be independently represented: hydrogen atom; fluorine atom; chlorine atom; bromine atom; iodine atom; alkyl group having 1 to 12 carbon atoms (substituted or unsubstituted); alkoxy group having 1 to 12 carbon atoms (substituted or unsubstituted); or phenyl, naphthyl, pyridyl or imidazolyl group (substituted or unsubstituted).

9. The method for manufacturing the polymer according to claim 3 or 4, wherein, At least one compound selected from the compounds represented by formulas (1) to (4) is a compound represented by formula (3), and the compound having a carbon-carbon double bond includes a compound represented by formula (7). ， In equation (7), A 1 and A 2 Each of the following can independently represent an organic group having 1 to 20 carbon atoms: hydrogen, fluorine, chlorine, bromine, iodine, or hydrogen atoms. f It refers to perfluoroalkyl groups with 1 to 12 carbon atoms.

10. The method for manufacturing the polymer according to claim 9, wherein, In the above formula (7), A 1 and A 2 Each of the following can be independently represented: hydrogen atom; fluorine atom; chlorine atom; bromine atom; iodine atom; alkyl group having 1 to 12 carbon atoms (substituted or unsubstituted); alkoxy group having 1 to 12 carbon atoms (substituted or unsubstituted); or phenyl, naphthyl, pyridyl or imidazolyl group (substituted or unsubstituted).

11. The method for manufacturing the polymer according to claim 3 or 4, wherein, At least one compound selected from the compounds represented by formulas (1) to (4) is a compound represented by formula (4), and the compound having a carbon-carbon double bond includes a compound represented by formula (8). ， In equation (8), A 1 and A 2 Each of these groups independently represents an organic group consisting of 1 to 20 hydrogen, fluorine, chlorine, bromine, iodine, or carbon atoms.

12. The method for manufacturing the polymer according to claim 11, wherein, In the above formula (8), A 1 and A 2 Each of the following can be independently represented: hydrogen atom; fluorine atom; chlorine atom; bromine atom; iodine atom; alkyl group having 1 to 12 carbon atoms (substituted or unsubstituted); alkoxy group having 1 to 12 carbon atoms (substituted or unsubstituted); or phenyl, naphthyl, pyridyl or imidazolyl group (substituted or unsubstituted).

13. The method for manufacturing the polymer according to claim 3 or 4, wherein, The compound having carbon-carbon double bonds comprises at least one selected from vinyl fluoride, vinylidene fluoride, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, perfluoro(methyl vinyl ether), vinylidene chloride, vinyl chloride, perfluoro(n-propyl vinyl ether), perfluoro(3-butenyl vinyl ether), (perfluoro-n-butyl)ethylene, (perfluoro-n-hexyl)ethylene, 1,4-divinylperfluorobutane, 1,6-divinylperfluorohexane, ethylene, and propylene.

14. The method for manufacturing the polymer according to claim 3 or 4, wherein, The process is carried out in the presence of an azo radical initiator.

15. The method for manufacturing the polymer according to claim 14, wherein, 0.01 to 100 mol of the azo radical initiator is used relative to a total of 1 mol of at least one compound selected from the compounds represented by formulas (1) to (4).

16. The method for manufacturing the polymer according to claim 3 or 4, wherein, For a total of 1 mol of the compounds having carbon-carbon double bonds, use at least one compound selected from the compounds represented by formulas (1) to (4) in total of 0.001 to 1 mol.

17. The method for manufacturing the polymer according to claim 3 or 4, wherein, The weight-average molecular weight of the obtained polymers ranged from 1,000 to 500,000.

18. The method for manufacturing the polymer according to claim 3 or 4, wherein, The polydispersity of the obtained polymer is below 2.

0.

19. The method for manufacturing the polymer according to claim 3 or 4, wherein, The compound having carbon-carbon double bonds includes a first compound having carbon-carbon double bonds, and the first compound having carbon-carbon double bonds is block copolymerized with a second compound having carbon-carbon double bonds that is different from the first compound having carbon-carbon double bonds.

20. The method for manufacturing the polymer according to claim 3 or 4, wherein, The compound having carbon-carbon double bonds includes a first compound having carbon-carbon double bonds and a second compound having carbon-carbon double bonds, which is different from the first compound having carbon-carbon double bonds, and the first compound having carbon-carbon double bonds and the second compound having carbon-carbon double bonds are randomly copolymerized.

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