Tellurium-containing compounds, polymers and methods of making polymers

Abstract

A tellurium-containing compound represented by formula (M1), a polymer of a tellurium-containing compound represented by any one of formulas (M1) to (M3), and a method for producing the polymer. X 1 ~ X 3 , Y 1 ~ Y 3 and Z 1 ~ Z 3 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X 1 , Y 1 and Z 1 at least one of X 2 , Y 2 and Z 2 represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group; and R 1 ~ R 3 represent an organic group having 1 to 20 carbon atoms.

Description

Technical Field

[0001] This disclosure relates to tellurium-containing compounds, polymers, and methods for manufacturing 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, the control of molecular weight through conventional free radical polymerization is limited, and the resulting polymer's molecular weight distribution tends to be broadened. On the other hand, living radical polymerization has attracted much attention as a polymerization method that can yield controlled molecular structures, and various polymerization control agents have been developed. Living radical polymerization is a polymerization method that controls the rate of free radical polymerization by reversibly protecting the growing free radicals using a protecting group that acts as a dormant species, thereby enabling control over the molecular weight distribution.

[0003] Patent document 1 describes a living radical polymerization method that uses specific halogenated olefins to undergo free radical polymerization in the presence of a specific organotellurium compound to produce halogenated olefin polymers or copolymers. This method is based on a process called TEP (organotellurium mediated living radical polymerization).

[0004] However, in recent years, the development of polymers with intramolecular branching structures has become increasingly important. Branched polymers possess various properties that differ from linear polymers. For example, due to the presence of multiple terminal groups, branched polymers can increase the crosslinking density of molded articles and thus improve curability when used as molding materials. Furthermore, branched polymers are known to have lower intrinsic viscosity and lower glass transition temperature compared to linear polymers. Thus, branched polymers possess unique properties that distinguish them from linear polymers, making them highly useful in industry.

[0005] Non-patent document 1 discloses the following controlled polymerization method: based on the TEP method, vinyl telluride is copolymerized with acrylic monomer in the presence of a tellurium compound as a chain transfer agent, thereby producing a highly branched polymer.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2018 / 164147

[0009] Non-patent literature

[0010] Non-patent document 1: Yangtian Lu et al., Synthesis of structurally controlled hyperbranched polymers using a monomer having hierarchical reactivity. Nature Communications 2017, 8(1) Summary of the Invention

[0011] However, current insights into techniques for producing polymers with branched structures through controlled polymerization are limited.

[0012] The first embodiment of this disclosure relates to providing a novel tellurium-containing compound capable of being used to produce polymers having a controlled molecular structure and a branched structure, and polymers produced using the tellurium-containing compound.

[0013] The second embodiment of this disclosure relates to providing a novel polymer having a controlled molecular structure and a branched structure.

[0014] The third embodiment of this disclosure relates to providing a polymer having a controlled molecular structure and a branched structure, which is polymerized from fluorinated monomers.

[0015] The fourth embodiment of this disclosure relates to a method for manufacturing a polymer having a controlled molecular structure and a branched structure.

[0016] The fifth embodiment of this disclosure relates to a method for manufacturing a novel polymer having a controlled molecular structure and a branched structure.

[0017] The sixth embodiment of this disclosure relates to a method for manufacturing a polymer having a controlled molecular structure and a branched structure by polymerizing fluorinated monomers.

[0018] The methods used to solve the above problems include the following approaches.

[0019] <1> A tellurium-containing compound, represented by the following formula (M1),

[0020]

[0021] In formula (M1),

[0022] X 1 Y 1 and Z 1 Each of the following independently represents an organic group having 1 to 20 carbon atoms: hydrogen, fluorine, chlorine, bromine, iodine, or hydrogen atoms. 1 Y 1and Z 1 At least one of them represents a fluorine atom.

[0023] R 1 Organic groups that represent 1 to 20 carbon atoms.

[0024] <2> According to the tellurium-containing compound described in <1>, wherein, in the above formula (M1), R 1 It is an alkyl group with 1 to 20 carbon atoms that is substituted or unsubstituted, an alkoxy group with 1 to 20 carbon atoms that is substituted or unsubstituted, a monovalent hydrocarbon group with 1 to 20 carbon atoms that is substituted or unsubstituted and has an oxoalkylene structure, or an aryl group with 3 to 20 carbon atoms that is substituted or unsubstituted.

[0025] <3> According to <1> or <2>, in the above formula (M1), X 1 Y 1 and Z 1 Each of the following is independently a hydrogen atom, a fluorine atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms with an oxoalkylene structure, or a substituted or unsubstituted aryl group having 3 to 20 carbon atoms.

[0026] <4> A polymer is formed by polymerizing at least any one of <1> to <3> containing a tellurium compound.

[0027] <5> The polymer according to <4> is formed by polymerizing the above-mentioned tellurium-containing compound with a polymerizable compound, wherein the polymerizable compound is different from the above-mentioned tellurium-containing compound and has carbon-carbon double bonds in its molecule.

[0028] <6> The polymer according to <5>, wherein the polymeric compound is a compound represented by the following formula (M11).

[0029]

[0030] In formula (M11), 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.

[0031] <7> A polymer is formed by polymerizing at least a tellurium-containing compound represented by the following formula (M2).

[0032]

[0033] In formula (M2),

[0034] X 2 Y 2 and Z 2 Each of the following independently represents an organic group having 1 to 20 carbon atoms: hydrogen, fluorine, chlorine, bromine, iodine, or hydrogen atoms. 2 Y 2 and Z 2 At least one of them represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxygen-perfluoroalkylene structure, or a phenyl group.

[0035] R 2 Organic groups that represent 1 to 20 carbon atoms.

[0036] <8> The polymer described in <7> is formed by polymerizing the above-mentioned tellurium-containing compound with a polymerizable compound, wherein the polymerizable compound is different from the above-mentioned tellurium-containing compound and has carbon-carbon double bonds in its molecule.

[0037] <9> The polymer according to <8>, wherein the polymeric compound is a compound represented by the following formula (M11).

[0038]

[0039] In formula (M11), 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.

[0040] <10> A polymer is formed by polymerizing at least a tellurium-containing compound represented by the following formula (M3) with a compound represented by the following formula (M11).

[0041]

[0042] In formula (M3),

[0043] X 3 Y 3 and Z 3 Each can independently represent an organic group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or 1 to 20 carbon atoms.

[0044] R 3 Organic groups that represent 1 to 20 carbon atoms.

[0045]

[0046] In formula (M11), 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.

[0047] <11> A method for manufacturing a polymer, comprising: polymerizing at least one of the tellurium-containing compounds selected from the compounds represented by the following formula (T1) and the compounds represented by the following formula (T2).

[0048]

[0049] In equation (T1), R 6 R represents an alkyl group having 1 to 8 carbon atoms, either substituted or unsubstituted, or an aryl group having 3 to 16 carbon atoms, either substituted or unsubstituted. 7 and R 8 Each of the following independently represents a hydrogen atom, or an alkyl group having 1 to 8 substituted or unsubstituted carbon atoms. R 9 The group represents a hydrogen atom, an alkyl group with 1 to 8 substituted or unsubstituted carbon atoms, an aryl group with 3 to 16 substituted or unsubstituted carbon atoms, an acyl group with 2 to 8 carbon atoms, an amide group with 2 to 8 carbon atoms, a group containing an oxygen carbonyl group, or a cyano group.

[0050] (R 10 Te)2 (T2)

[0051] In equation (T2), R 10 It refers to an alkyl group having 1 to 8 carbon atoms, either substituted or unsubstituted, or an aryl group having 3 to 16 carbon atoms, either substituted or unsubstituted.

[0052] <12> The method for manufacturing the polymer according to <11> includes: polymerizing the tellurium-containing compound described in any one of <1> to <3> with a polymerizable compound, wherein the polymerizable compound is different from the tellurium-containing compound and has carbon-carbon double bonds in its molecule.

[0053] <13> The method for manufacturing the polymer according to <12>, wherein the polymeric compound is a compound represented by the following formula (M11).

[0054]

[0055] In formula (M11), X 11 ~X 14Each 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.

[0056] <14> A method for manufacturing a polymer, comprising: polymerizing at least one tellurium-containing compound represented by formula (M2) in the presence of at least one compound selected from compounds represented by formula (T1) and compounds represented by formula (T2).

[0057]

[0058] In equation (T1), R 6 R represents an alkyl group having 1 to 8 carbon atoms, either substituted or unsubstituted, or an aryl group having 3 to 16 carbon atoms, either substituted or unsubstituted. 7 and R 8 Each of the following independently represents a hydrogen atom, or an alkyl group having 1 to 8 substituted or unsubstituted carbon atoms. R 9 The group represents a hydrogen atom, an alkyl group with 1 to 8 substituted or unsubstituted carbon atoms, an aryl group with 3 to 16 substituted or unsubstituted carbon atoms, an acyl group with 2 to 8 carbon atoms, an amide group with 2 to 8 carbon atoms, a group containing an oxygen carbonyl group, or a cyano group.

[0059] (R 10 Te)2 (T2)

[0060] In equation (T2), R 10 It refers to an alkyl group having 1 to 8 carbon atoms, either substituted or unsubstituted, or an aryl group having 3 to 16 carbon atoms, either substituted or unsubstituted.

[0061]

[0062] In formula (M2),

[0063] X 2 Y 2 and Z 2 Each of the following independently represents an organic group having 1 to 20 carbon atoms: hydrogen, fluorine, chlorine, bromine, iodine, or hydrogen atoms. 2 Y 2 and Z 2 At least one of them represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxygen-perfluoroalkylene structure, or a phenyl group.

[0064] R 2 Organic groups that represent 1 to 20 carbon atoms.

[0065] <15> The method for manufacturing the polymer according to <14> includes: polymerizing a tellurium-containing compound represented by the above formula (M2) with a polymerizable compound, wherein the polymerizable compound is different from the tellurium-containing compound represented by the above formula (M2) and has carbon-carbon double bonds in its molecule.

[0066] <16> The method for manufacturing the polymer according to <15>, wherein the polymeric compound is a compound represented by the following formula (M11).

[0067]

[0068] In formula (M11), 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.

[0069] <17> A method for manufacturing a polymer, comprising: polymerizing at least one of a compound selected from the compounds represented by formula (T1) and the compounds represented by formula (T2) below with a compound represented by formula (M11) below.

[0070]

[0071] In equation (T1), R 6 R represents an alkyl group having 1 to 8 carbon atoms, either substituted or unsubstituted, or an aryl group having 3 to 16 carbon atoms, either substituted or unsubstituted. 7 and R 8 Each of the following independently represents a hydrogen atom, or an alkyl group having 1 to 8 substituted or unsubstituted carbon atoms. R 9 The group represents a hydrogen atom, an alkyl group with 1 to 8 substituted or unsubstituted carbon atoms, an aryl group with 3 to 16 substituted or unsubstituted carbon atoms, an acyl group with 2 to 8 carbon atoms, an amide group with 2 to 8 carbon atoms, a group containing an oxygen carbonyl group, or a cyano group.

[0072] (R 10 Te)2 (T2)

[0073] In equation (T2), R 10 It refers to an alkyl group having 1 to 8 carbon atoms, either substituted or unsubstituted, or an aryl group having 3 to 16 carbon atoms, either substituted or unsubstituted.

[0074]

[0075] In formula (M3),

[0076] X 3 Y 3 and Z 3 Each can independently represent an organic group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or 1 to 20 carbon atoms.

[0077] R 3 Organic groups that represent 1 to 20 carbon atoms.

[0078]

[0079] In formula (M11), 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.

[0080] According to a first embodiment of this disclosure, a novel tellurium-containing compound that can be used to produce polymers having a controlled molecular structure and a branched structure, and polymers produced using the tellurium-containing compound, are provided.

[0081] According to a second embodiment of this disclosure, a novel polymer having a controlled molecular structure and a branched structure can be provided.

[0082] According to the third embodiment of this disclosure, a polymer having a controlled molecular structure and a branched structure, formed by polymerizing fluorinated monomers, can be provided.

[0083] According to the fourth embodiment of this disclosure, a method for manufacturing a polymer having a controlled molecular structure and a branched structure can be provided.

[0084] According to the fifth embodiment of this disclosure, a method for manufacturing a novel polymer having a controlled molecular structure and a branched structure can be provided.

[0085] According to the sixth embodiment of this disclosure, a method for manufacturing a polymer having a controlled molecular structure and a branched structure by polymerizing fluorinated monomers can be provided. Detailed Implementation

[0086] The embodiments of this disclosure will now be described in detail. However, the embodiments of this 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, which are not intended to limit the embodiments of this disclosure.

[0087] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that can achieve their purpose, even if they cannot be clearly distinguished from other processes.

[0088] In this disclosure, the numerical range represented by “~” includes the minimum and maximum values ​​recorded before and after “~”, respectively.

[0089] In this disclosure, each component may comprise multiple corresponding substances. When multiple substances equivalent to each component are present in the composition, the content or percentage of each component, unless otherwise specified, refers to the total content or percentage of the multiple substances present in the composition.

[0090] In this disclosure, a reactive carbon-carbon double bond refers to a carbon-carbon double bond that can undergo various reactions as an alkene, and does not include aromatic double bonds.

[0091] In this disclosure, unless otherwise specified, organic groups or hydrocarbon groups may or may not have substituents.

[0092] The number of carbon atoms in a compound or a component thereof in this disclosure refers to the number of carbon atoms containing the substituent, where the compound or component thereof has substituents.

[0093] In this disclosure, (meth)acrylic acid is a general term for acrylic acid and methacrylic acid. (meth)acrylate is a general term for acrylate and methacrylate. (meth)acrylamide is a general term for acrylamide and methacrylamide.

[0094] In this disclosure, "polymer" refers to a compound formed by the polymerization of monomers. That is, a "polymer" has multiple structural units.

[0095] In this disclosure, unless otherwise specified, the descriptions of "polymerizing compound A" and "polymerizing at least compound A" include either the polymerization of compound A alone or the polymerization of 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 either the polymerization of compound A and compound B alone or the polymerization of compound A, compound B, and other compounds. Here, compound A and compound B refer to any compound described in this disclosure that has carbon-carbon double bonds in its molecule. Furthermore, unless otherwise specified, the polymer described in this disclosure can be a homopolymer of one compound or a copolymer of two or more compounds. In this disclosure, the term "polymer" includes, in addition to being a polymer, a mixture of raw materials (monomers, catalysts), byproducts, impurities, etc.

[0096] This disclosure relates to a controlled polymerization method for producing branched polymers using tellurium-containing compounds with reactive carbon-carbon double bonds. The insights gained from this disclosure can be used to obtain polymers with controlled molecular structures and branched structures.

[0097] Furthermore, while there are no limitations on the embodiments described in this disclosure, it has been found that the tellurium-containing compounds, polymers, and methods for manufacturing polymers detailed in this disclosure are also useful for the polymerization of fluorinated monomers. Generally speaking, the controlled polymerization of fluorinated monomers is more difficult than that of hydrocarbon monomers. For example, Sk Arif et al., Progress in PolymerScience, Volume 106, July 2020, 101255, describes the ability to achieve degenerate chain transfer polymerization of acrylates and styrene in the presence of chain transfer agents such as organo-indigo and organo-bismuth, but there are no reports of using organo-tellurium compounds as chain transfer agents to polymerize fluoroolefins. In addition, U.S. Patent Application Publication No. 2013 / 225775 describes that although significant progress has been made in the controlled polymerization of common monomers such as (meth)acrylic acid and styrene, the controlled polymerization of highly reactive and gaseous fluoroolefins such as vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene is not very effective. Furthermore, no insights have been reported to date regarding methods for introducing intramolecular branching structures into polymers during the controlled polymerization of fluorinated monomers. The inventors have discovered that the tellurium compounds, polymers, and methods for manufacturing the polymers detailed in this disclosure can be suitably applied to the polymerization of fluorinated monomers.

[0098] The various embodiments of this disclosure will now be described in detail.

[0099] Implementation Method 1

[0100] <Tellulose-containing compounds>

[0101] The tellurium-containing compound of the first embodiment is a tellurium-containing compound represented by the following formula (M1).

[0102]

[0103] In formula (M1),

[0104] X 1 Y 1 and Z 1 Each of the following independently represents an organic group having 1 to 20 carbon atoms: hydrogen, fluorine, chlorine, bromine, iodine, or hydrogen atoms. 1 Y 1 and Z 1 At least one of them represents a fluorine atom.

[0105] R 1Organic groups that represent 1 to 20 carbon atoms.

[0106] The tellurium-containing compound of the first embodiment can introduce branched chains into the polymer produced by controlled polymerization, and thus can be appropriately used to produce polymers having a controlled molecular structure and a branched structure.

[0107] In formula (M1), R 1 The organic group representing 1 to 20 carbon atoms is preferably a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group with 1 to 20 carbon atoms, a substituted or unsubstituted monovalent hydrocarbon group with 1 to 20 carbon atoms having an oxoalkylene structure, or a substituted or unsubstituted aryl group with 3 to 20 carbon atoms. It should be noted that R 1 With X 1 Y 1 Z 1 None of them are connected.

[0108] As a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, it is preferred to have a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms, and more preferably to have a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.

[0109] Examples of non-substituted 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, n-hexyl, n-heptyl, and n-octyl. Among these, methyl, ethyl, or n-butyl are more preferred.

[0110] As the substituted alkyl group having 1 to 20 carbon atoms, examples include alkyl groups in which hydrogen atoms at any position of the unsubstituted alkyl group having 1 to 20 carbon atoms are substituted with substituents such as fluorine atoms, chlorine atoms, alkoxy groups, and fluoroalkoxy groups. Among these, perfluoroalkyl groups are preferred.

[0111] 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.

[0112] The monovalent hydrocarbon group having 1 to 20 carbon atoms in the substituted or unsubstituted oxoalkylene structure preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.

[0113] As a non-substituted monovalent hydrocarbon group having an oxoalkylene structure, examples include hydrocarbon groups whose constituent units are oxoalkylene structures having 1 to 4 carbon atoms; more specifically, examples include -((CH2). m -O) n-CH3 represents the group. Here, m represents the number of repeats of the methylene group, which is preferably an integer from 0 to 4. n represents the number of repeats of the -((CH2)m-O)- structure, which is preferably an integer from 1 to 15.

[0114] As substituted monovalent hydrocarbon groups with an oxoalkylene structure, examples include those unsubstituted monovalent hydrocarbon groups with an oxoalkylene structure in which hydrogen atoms at any position of the oxoalkylene structure are replaced by substituents such as fluorine atoms, chlorine atoms, alkoxy groups, or fluoroalkoxy groups. For example, monovalent hydrocarbon groups with an oxoperfluoroalkylene structure are preferred; from the viewpoint of ease of synthesis, monovalent perfluoroalkyl hydrocarbon groups with an oxoperfluoroalkylene structure having 1 to 4 carbon atoms are more 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 one or more -((CF2) groups. m The number of repetitions of the -O)- structure is preferably an integer from 1 to 15.

[0115] It should be noted that in this disclosure, when a "monovalent hydrocarbon group having an oxygen perfluoroalkylene structure" is described, the hydrogen atom of the hydrocarbon group may be replaced by a fluorine atom or the like.

[0116] As a substituted or unsubstituted aryl group with 3 to 20 carbon atoms, a substituted or unsubstituted aryl group with 3 to 16 carbon atoms is preferred, and a substituted or unsubstituted aryl group with 3 to 12 carbon atoms is more preferred.

[0117] Examples of non-substituted aryl groups with 3 to 20 carbon atoms include phenyl, naphthyl, and other isoaryl groups; and heteroaryl groups such as pyridyl, pyrroleyl, furanyl, and thiopheneyl. Among these, isoaryl groups are preferred, and phenyl groups are more preferred.

[0118] As substituted aryl groups with 3 to 20 carbon atoms, examples include aryl groups with 3 to 20 carbon atoms in which any hydrogen atom bonded to the aromatic ring 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. 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 formula (M1), X 1 Y 1 and Z 1 Each of the following independently represents an organic group having 1 to 20 carbon atoms: hydrogen, fluorine, chlorine, bromine, iodine, or hydrogen atoms. 1 Y 1 and Z 1 At least one of them represents a fluorine atom. X1 Y 1 and Z 1 Each of the following is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms with an oxoalkylene structure, or a substituted or unsubstituted aryl group having 3 to 20 carbon atoms.

[0120] Examples of substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted monovalent hydrocarbon groups having an oxoalkylene structure having 1 to 20 carbon atoms, and substituted or unsubstituted aryl groups having 3 to 20 carbon atoms, can be cited as R 1 The examples mentioned above are substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms with an oxoalkylene structure, and substituted or unsubstituted aryl groups having 3 to 20 carbon atoms.

[0121] Examples of compounds represented by formula (M1) include phenyl (trifluorovinyl) telluride, (2,2-difluorovinyl)phenyl telluride, (1-chlorodifluorovinyl)phenyl telluride, butyl (trifluorovinyl) telluride, and methyl (trifluorovinyl) telluride.

[0122] [Method for manufacturing tellurium-containing compounds represented by formula (M1)]

[0123] There are no particular limitations on the method for manufacturing the tellurium-containing compound represented by formula (M1). For example, the tellurium-containing compound represented by formula (M1) can be prepared by CX. 1 Y 1 =CZ 1 Li represents vinyl lithium and R 1 TeBr is obtained by reacting the two. Here, X 1 Y 1 Z 1 and R 1 respectively with X in equation (M1) 1 Y 1 Z 1 and R 1 same.

[0124] The following are examples of specific synthesis schemes.

[0125]

[0126] <Polymer>

[0127] The polymer of the first embodiment is formed by polymerizing at least the tellurium-containing compound of the first embodiment described above. The polymer can be a homopolymer of the tellurium-containing compound of the first embodiment described above, or it can be a copolymer. The copolymer can be a block copolymer, a random copolymer, or an alternating copolymer.

[0128] In one embodiment, the polymer can be a copolymer formed by polymerizing a tellurium-containing compound represented by formula (M1) with a polymerizable compound (hereinafter also referred to as "first comonomer"), wherein the polymerizable compound is different from the tellurium-containing compound represented by formula (M1) and has carbon-carbon double bonds in its molecule. The first comonomer can be used alone or in combination of two or more.

[0129] There are no particular restrictions on the first comonomer. In one embodiment, the first comonomer may be a compound represented by the following formula (M12).

[0130]

[0131] In formula (M12), 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 a substituted or unsubstituted carbon atom with 1 to 40 carbon atoms. R 1 With R 4 Or R 2 With R 3 They can be connected to form a ring structure.

[0132] R 11 ~R 14 The number of carbon atoms in the substituted or unsubstituted 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.

[0133] Examples of organic groups having 1 to 40 carbon atoms that are either substituted or unsubstituted include alkyl, aryl, heteroaryl, aryloxy, heteroaryloxy, alkoxy, arylalkyl, heteroarylalkyl, arylalkoxy, heteroarylalkoxy, carboxyl, alkoxycarbonyl, carbamoyl, acylamino, acyloxy, cyano, and monovalent hydrocarbon groups having an oxoalkylene structure.

[0134] When the substituted or unsubstituted organic group having 1 to 40 carbon atoms is an alkyl, aryl, heteroaryl, aryloxy, heteroaryloxy, alkoxy, arylalkyl, heteroarylalkyl, arylalkoxy, heteroarylalkoxy, or a monovalent hydrocarbon group having an oxoalkylene structure, and may have heteroatoms, the hydrocarbon group may be any of straight-chain, branched, or cyclic. In addition, it may or may not contain unsaturated bonds.

[0135] Acyl groups, which are acylamino or acyloxy groups, can be exemplified by groups obtained by removing the hydroxyl group from carboxylic acids or sulfonic acids.

[0136] Examples of substituents in organic groups having 1 to 40 carbon atoms include fluorine atoms, chlorine atoms, hydroxyl groups, alkoxy groups, alkoxyalkyl groups, amino groups, carboxylic acid groups, sulfonic acid groups, and 1,3,5-triazine trione skeletons.

[0137] In formula (M12), R 11 With R 13 Or R 12 With R 14 They can be linked to form a cyclic structure. That is, the compound represented by formula (M12) can be a compound with a cyclic structure, such as maleic anhydride or itaconic anhydride.

[0138] Examples of first comonomers 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 unsaturated monomers containing cycloalkyl groups; methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, which are unsaturated monomers containing carboxyl groups; and N,N-dimethylaminopropyl (meth)acrylamide and N,N-dimethylaminoethyl (meth)acrylamide. Unsaturated monomers containing tertiary amines, such as amides, 2-(dimethylamino)ethyl(meth)acrylate, and N,N-dimethylaminopropyl(meth)acrylate; unsaturated monomers containing quaternary ammonium groups, 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 (meth)acrylate; styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 2-chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 1-vinylnaphthalene, divinylbenzene, 4 Styrene monomers such as chloromethyl)styrene, 2-(chloromethyl)styrene, 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 α-olefins such as 1,2-dichloro-1,2-difluoroethylene, 1H,1H,2H-perfluoro(n-1-hexene), and 1H,1H,2H-perfluoro(n-1-octene); vinyl ester monomers such as vinyl acetate; divinylfluoroalkanes such as 1,4-divinyloctafluorobutane and 1,6-divinyldodecylfluorohexane; 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; perfluorinated (methyl vinyl ether), perfluorinated (ethyl vinyl ether), and perfluorinated (n-propyl vinyl ether), etc.

[0139] In one embodiment, the first comonomer may be a compound represented by the following formula (M11).

[0140]

[0141] In formula (M11), 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.

[0142] The compound represented by formula (M1) can introduce branches into fluoropolymers by copolymerizing with the fluorinated monomer represented by the compound represented by formula (M11).

[0143] In formula (M11), X is... 11 ~X 14 Examples of organic groups with 1 to 20 carbon atoms include substituted or unsubstituted alkyl groups with 1 to 20 carbon atoms, and substituted or unsubstituted aryl groups with 1 to 20 carbon atoms.

[0144] Examples of substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms include alkyl, aryl, heteroaryl, aryloxy, heteroaryloxy, alkoxy, arylalkyl, heteroarylalkyl, arylalkoxy, heteroarylalkoxy, carboxyl, alkoxycarbonyl, carbamoyl, acylamino, acyloxy, cyano, etc.

[0145] When the substituted or unsubstituted organic group having 1 to 20 carbon atoms is an alkyl, aryl, heteroaryl, aryloxy, heteroaryloxy, alkoxy, arylalkyl, heteroarylalkyl, arylalkoxy, or heteroarylalkoxy hydrocarbon group that may have heteroatoms, the hydrocarbon group may be any of straight-chain, branched, or cyclic. In addition, it may or may not contain unsaturated bonds.

[0146] Acyl groups, which are acylamino or acyloxy groups, can be exemplified by groups obtained by removing the hydroxyl group from carboxylic acids or sulfonic acids.

[0147] Examples of substituents in organic groups having 1 to 20 carbon atoms include fluorine atoms, chlorine atoms, hydroxyl groups, alkoxy groups, alkoxyalkyl groups, amino groups, carboxylic acid groups, and sulfonic acid groups.

[0148] 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.

[0149] 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 more 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.

[0150] Examples of compounds represented by formula (M11) 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.

[0151] As the compound represented by formula (M11), from the perspective of polymerization reactivity when the polymer is obtained, vinylidene fluoride, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene and 2,3,3,3-tetrafluoropropylene are preferred.

[0152] The polymer of the first embodiment can be obtained, for example, by the polymerization method of the polymer of the fourth embodiment described later.

[0153] Implementation Method 2

[0154] <Polymer>

[0155] The polymer of the second embodiment is formed by polymerizing at least a tellurium-containing compound represented by the following formula (M2).

[0156]

[0157] In formula (M2),

[0158] X 2 Y 2 and Z 2 Each of the following independently represents an organic group having 1 to 20 carbon atoms: hydrogen, fluorine, chlorine, bromine, iodine, or hydrogen atoms. 2 Y 2 and Z 2 At least one of them represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxygen-perfluoroalkylene structure, or a phenyl group.

[0159] R 2Organic groups that represent 1 to 20 carbon atoms.

[0160] R in formula (M2) 2 The details are the same as R in the above formula (M1). 1 The details are the same.

[0161] In formula (M2) X 2 Y 2 and Z 2 At least one of them is a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group to replace X in formula (M1). 1 Y 1 and Z 1 At least one of them is a fluorine atom, and in addition, X in formula (M2) is a fluorine atom. 2 Y 2 and Z 2 The details are the same as X in equation (M1). 1 Y 1 and Z 1 The details are the same.

[0162] 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.

[0163] As a monovalent hydrocarbon group having an oxygen perfluoroalkylene structure, for example, perfluoroalkyl groups with an oxygen perfluoroalkylene structure having 1 to 4 carbon atoms as the constituent unit can be cited.

[0164] The phenyl group may or may not have substituents, but is preferably unsubstituents. Examples of substituents include substituted or unsubstituted alkyl groups, substituted or unsubstituted monovalent hydrocarbon groups with an oxoalkylene structure, halogen atoms, hydroxyl groups, alkoxy groups, amino groups, nitro groups, cyano groups, carbonyl groups, sulfonyl groups, trifluoromethyl groups, etc., with unsubstituted alkyl groups, perfluoroalkyl groups, unsubstituted monovalent hydrocarbon groups with an oxoalkylene structure and monovalent hydrocarbon groups with an oxoperfluoroalkylene structure being preferred.

[0165] Examples of compounds represented by formula (M2) include (1-chlorodifluorovinyl)phenyl telluride, (2-nonafluorobutylvinyl)phenyl telluride, (1-chlorovinyl)phenyl telluride, (2-chlorovinyl)phenyl telluride, and (1-phenylvinyl)phenyl telluride.

[0166] There are no particular limitations on the method for manufacturing the tellurium-containing compound represented by formula (M2). For example, the compound represented by formula (M2) can be prepared by CX. 2 Y 2 =CZ 2Li represents vinyl lithium and R 2 TeBr is obtained by reacting the two. Here, X 2 Y 2 Z 2 and R 2 respectively with X in equation (M2) 2 Y 2 Z 2 and R 2 The same. Specific examples of synthetic schemes are based on examples of methods for manufacturing tellurium-containing compounds represented by formula (M1) in the first embodiment.

[0167] The polymer in the second embodiment can be a homopolymer of a tellurium-containing compound represented by formula (M2) or a copolymer. The copolymer can be a block copolymer, a random copolymer, or an alternating copolymer.

[0168] In one embodiment, the polymer can be a copolymer formed by polymerizing a tellurium-containing compound represented by formula (M2) with a polymerizable compound (hereinafter also referred to as "second comonomer"), wherein the polymerizable compound is different from the tellurium-containing compound represented by formula (M2) and has carbon-carbon double bonds in its molecule. The second comonomer can be used alone or in combination of two or more.

[0169] There are no particular restrictions on the second comonomer. The details of the second comonomer are the same as those of the first comonomer, except that it is a polymerizable compound different from the tellurium-containing compound represented by formula (M2) instead of the tellurium-containing compound represented by formula (M1).

[0170] In one embodiment, the second comonomer may be a compound represented by formula (M11) above. The compound represented by formula (M2) can introduce branches into the fluoropolymer by copolymerization with a fluorinated monomer represented by the compound represented by formula (M11).

[0171] The polymer of the second embodiment can be obtained, for example, by the manufacturing method of the polymer of the fifth embodiment described later.

[0172] Third Implementation Method

[0173] <Polymer>

[0174] The polymer of the third embodiment is formed by polymerizing at least the tellurium-containing compound represented by the following formula (M3) with the compound represented by the following formula (M11).

[0175]

[0176] In formula (M3),

[0177] X 3 Y3 and Z 3 Each can independently represent an organic group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or 1 to 20 carbon atoms.

[0178] R 3 Organic groups that represent 1 to 20 carbon atoms.

[0179]

[0180] In formula (M11), 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.

[0181] R in formula (M3) 3 The details are the same as R in equation (M1). 1 The details are the same.

[0182] In the substitution formula (M1), X 1 Y 1 and Z 1 At least one of them is a fluorine atom, but the above restrictions do not apply to formula (M3). Otherwise, X in formula (M3) is... 3 Y 3 and Z 3 The details are the same as X in equation (M1). 1 Y 1 and Z 1 The details are the same.

[0183] There are no particular limitations on the method for manufacturing tellurium-containing compounds represented by formula (M3). For example, compounds represented by formula (M3) can be prepared by CX. 3 Y 3 =CZ 3 Li represents vinyl lithium and R 3 TeBr is obtained by reacting the two. Here, X 3 Y 3 Z 3 and R 3 respectively with X in equation (M3) 3 Y 3 Z 3 and R 3 The same. Specific examples of synthetic schemes are based on examples of methods for manufacturing tellurium-containing compounds represented by formula (M1) in the first embodiment.

[0184] The details of the compound represented by formula (M11) are as described above.

[0185] The polymer of the third embodiment can be obtained, for example, by the manufacturing method of the polymer of the sixth embodiment described later.

[0186] Implementation Method 4

[0187] <Methods for manufacturing polymers>

[0188] The method for manufacturing the polymer according to the fourth embodiment includes: polymerizing at least one of the compounds selected from the compounds represented by the following formula (T1) and the compounds represented by the following formula (T2), namely the tellurium-containing compound of the first embodiment, i.e., the tellurium-containing compound represented by formula (M1).

[0189]

[0190] In equation (T1), R 6 R represents an alkyl group having 1 to 8 carbon atoms, either substituted or unsubstituted, or an aryl group having 3 to 16 carbon atoms, either substituted or unsubstituted. 7 and R 8 Each of the following independently represents a hydrogen atom, or an alkyl group having 1 to 8 substituted or unsubstituted carbon atoms. R 9 The group represents a hydrogen atom, an alkyl group with 1 to 8 substituted or unsubstituted carbon atoms, an aryl group with 3 to 16 substituted or unsubstituted carbon atoms, an acyl group with 2 to 8 carbon atoms, an amide group with 2 to 8 carbon atoms, a group containing an oxygen carbonyl group, or a cyano group.

[0191] (R 10 Te)2 (T2)

[0192] In equation (T2), R 10 It refers to an alkyl group having 1 to 8 carbon atoms, either substituted or unsubstituted, or an aryl group having 3 to 16 carbon atoms, either substituted or unsubstituted.

[0193] The polymer manufacturing method of the fourth embodiment is as follows: based on the TEP method, at least one compound selected from the compounds represented by formula (T1) and formula (T2) is used as a chain transfer agent to polymerize at least the tellurium-containing compound of the first embodiment. According to this manufacturing method, a polymer having a controlled molecular structure and a branched structure can be obtained.

[0194] (The compound represented by formula (T1))

[0195] In equation (T1), R 6 The specific groups represented are as follows.

[0196] Examples of non-substituted alkyl groups with 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl alkyl groups that are straight-chain, branched, or cyclic with 1 to 8 carbon atoms. Among these, straight-chain or branched alkyl groups with 1 to 4 carbon atoms are preferred, and methyl, ethyl, or n-butyl are more preferred.

[0197] Examples of substituted alkyl groups having 1 to 8 carbon atoms include alkyl groups having substituents such as fluorine atoms, chlorine atoms, alkoxy groups, or fluoroalkoxy groups at any position. Among these, alkyl groups having 2 to 13 fluorine atoms are preferred, and from the viewpoint of using free radicals to suppress hydrogen abstraction reactions, (perfluoroalkyl)ethyl groups having 3 to 8 carbon atoms are more preferred.

[0198] Examples of non-substituted aryl groups with 3 to 16 carbon atoms include phenyl, naphthyl, and other isoaryl groups; and heteroaryl groups such as pyridyl, pyrroleyl, furanyl, and thiopheneyl. Among these, isoaryl groups are preferred, and phenyl groups are more preferred.

[0199] Examples of substituted aryl groups having 3 to 16 carbon atoms include those having 1 to 4, preferably 1 to 3, more preferably 1 halogen atom at any position, preferably at the para or ortho position, hydroxyl, alkoxy, amino, nitro, cyano, or -COR groups. a This indicates an aryl group containing substituents such as a carbonyl group, sulfonyl group, or trifluoromethyl group. The above R... a The alkyl group having 1 to 8 carbon atoms, preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 8 carbon atoms, preferably a straight-chain or branched alkoxy group having 1 to 4 carbon atoms; an aryl group; or an aryloxy group.

[0200] R 7 and R 8 The specific groups represented are as follows.

[0201] Examples of substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms include those related to the above-mentioned R. 6 The same substituted or unsubstituted alkyl group represents a carbon number of 1 to 8. As R 7 and R 8 Preferably, it is an alkyl group having 1 to 4 hydrogen atoms or carbon atoms.

[0202] R 9 The specific groups represented are as follows.

[0203] Examples of substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms and substituted or unsubstituted aryl groups having 3 to 16 carbon atoms, related to the above-mentioned R, can be cited. 6 The groups represented are the same groups.

[0204] Examples of acyl groups with 2 to 8 carbon atoms include acetyl and benzoyl.

[0205] Examples of amide groups containing 2 to 8 carbon atoms include carbamoylmethyl, dicarbamoylmethyl, 4-carbamoylphenyl, etc.; thiocarbamoylmethyl, 4-thiocarbamoylphenyl, etc.; and N-substituted carbamoyl groups such as dimethylcarbamoylmethyl.

[0206] Examples of groups containing an oxygen carbonyl group include -COOR. b The group indicated. Here, R b The following can be represented as a hydrogen atom; an alkyl group having 1 to 8 carbon atoms, preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms; an alkenyl group having 2 to 8 carbon atoms, preferably a straight-chain or branched alkenyl group having 2 to 4 carbon atoms; an alkynyl group having 2 to 8 carbon atoms, preferably a straight-chain or branched alkynyl group having 2 to 4 carbon atoms; or an aryl group having 3 to 12 carbon atoms.

[0207] R b The alkyl group with 1 to 8 carbon atoms, the alkenyl group with 2 to 8 carbon atoms, the alkynyl group with 2 to 8 carbon atoms, and the aryl group with 3 to 12 carbon atoms may have 1 to 4, preferably 1 to 3, more preferably 1 halogen atom, hydroxyl group, alkoxy group, trialkylsilyl ether group, trialkylsilyl group, amino group, nitro group, cyano group, sulfonyl group, trifluoromethyl group, etc., at any position, or may not have substituents.

[0208] Examples of groups containing an oxygen carbonyl group include carboxyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentoxycarbonyl, and phenoxycarbonyl. Among these, methoxycarbonyl or ethoxycarbonyl are preferred.

[0209] Among these, as R 9 Preferably, it is an aryl, alkoxycarbonyl, or cyano group with 5 to 12 carbon atoms.

[0210] In a preferred embodiment, the compound represented by formula (T1) can be R. 6 Represented by alkyl or phenyl groups having 1 to 4 carbon atoms, R 7 and R 8 Each is independently represented by a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 9 Compounds represented by aryl or alkoxycarbonyl groups having 5 to 12 carbon atoms.

[0211] In a particularly preferred embodiment, the compound represented by formula (T1) can be R. 6 Represented by alkyl or phenyl groups having 1 to 4 carbon atoms, R 7 and R 8Each is independently represented by a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 9 Compounds represented by phenyl, methoxycarbonyl, or ethoxycarbonyl groups.

[0212] Specifically, examples of compounds represented by formula (T1) include (methyltellurylmethyl)benzene, (methyltellurylmethyl)naphthalene, ethyl-2-methyl-2-methyltelluryl-propionate, ethyl-2-methyl-2-n-butyltelluryl-propionate, (2-trimethylsilyloxyethyl)-2-methyl-2-methyltelluryl-propionate, (2-hydroxyethyl)-2-methyl-2-methyltelluryl-propionate, and (3-trimethylsilylpropynyl)-2-methyl-2-methyltelluryl-propionate, as described in International Publications Nos. 2004 / 014848 and 2004 / 014962. Furthermore, examples include compounds described in publication number 2D03 of Polymer Preprints, Japan Vol.65, No.1 (2016), such as ethyl-2-methyl-2-1H,1H,2H,2H-heptadecyltellurylpropionate, methyl-2-methyl-2-1H,1H,2H,2H-heptadecyltellurylpropionate, and N,N-diethyl-2-methyl-2-1H,1H,2H,2H-heptadecyltellurylpropionamide. Compounds represented by formula (T1) can be used alone or in combination of two or more.

[0213] The method of manufacturing the compound represented by formula (T1) is not particularly limited and can be manufactured by known methods described in International Publication Nos. 2004 / 014848, 2004 / 014962 and 2018 / 164147.

[0214] (The compound represented by formula (T2))

[0215] In equation (T2), R 10 The details are independently related to R in the above equation (T1). 6 The details are the same.

[0216] In a preferred embodiment, the compound represented by formula (T2) can be R. 10 Compounds that are independently represented by alkyl or phenyl groups having 1 to 4 carbon atoms.

[0217] Specifically, compounds represented by formula (T2) include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, di-n-butyl ditelluride, di-sec-butyl ditelluride, di-tert-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis-(p-methoxyphenyl) ditelluride, bis-(p-aminophenyl) ditelluride, bis-(p-nitrophenyl) ditelluride, bis-(p-cyanophenyl) ditelluride, bis-(p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride, and dipyridyl ditelluride. A single compound represented by formula (T2) may be used alone, or in combination of two or more.

[0218] Among them, dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, di-n-butyl ditelluride or diphenyl ditelluride are preferred.

[0219] (Other arbitrary ingredients)

[0220] In the polymer manufacturing method of the fourth embodiment, other components such as free radical initiators, solvents, emulsifiers, suspending agents, acids or bases may be further used.

[0221] - Free radical initiators -

[0222] Examples of free radical initiators include azo-based free radical initiators and peroxide-based free radical initiators. Free radical initiators can be used alone or in combination of two or more.

[0223] Examples of azo 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-methylbutyl) Amides), 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile), 2,2'-azobis(2-methylamidinylpropane) dihydrochloride, 2,2'-azobis[2-(2-imidazoline-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.

[0224] Examples of peroxide-based free radical initiators include diisopropyl peroxide dicarbonate, tert-butyl peroxypentanoate, and benzoyl peroxide.

[0225] - Solvent -

[0226] Examples of solvents include organic solvents and aqueous solvents. A single solvent can be used alone, or two or more solvents can be used in combination.

[0227] Examples of organic solvents include benzene, toluene, 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, etc.

[0228] Alternatively, ionic liquids such as N-methyl-N-methoxymethylpyrrolomium tetrafluoroborate, N-methyl-N-ethoxymethyl tetrafluoroborate, 1-methyl-3-methylimidazolium tetrafluoroborate, 1-methyl-3-methylimidazolium hexafluorophosphate, and 1-methyl-3-methylimidazolium chloride can also be used.

[0229] Examples of aqueous solvents include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol.

[0230] In one embodiment, the method for manufacturing the polymer of the fourth embodiment includes: polymerizing the tellurium-containing compound of the first embodiment (i.e., the tellurium-containing compound represented by formula (M1)) with a polymerizable compound (i.e., the first comonomer of the first embodiment), wherein the polymerizable compound is different from the tellurium-containing compound of the first embodiment (i.e., the tellurium-containing compound represented by formula (M1)) and has carbon-carbon double bonds in its molecule. Details of the first comonomer are as described above.

[0231] [Aggregation Method]

[0232] The following describes an example of a specific polymerization method in the polymer manufacturing method of the fourth embodiment.

[0233] In a container purged with an inert gas or a vacuum-reduced container, at least one compound selected from the compounds represented by formula (T1) and the compounds represented by formula (T2) below is mixed with a tellurium-containing compound represented by formula (M1). Examples of inert gases include nitrogen, argon, and helium. Among these, nitrogen or argon is preferred, and nitrogen is more preferred. For the purpose of accelerating polymerization, a free radical initiator such as an azo polymerization initiator may also be used.

[0234] The amount of compound represented by formula (T1) or more, more preferably 0.005 mol or more, and even more preferably 0.01 mol or more, relative to 1 mol of the compound having reactive carbon-carbon double bonds (i.e., the total of the tellurium-containing compound represented by formula (M1) and the first comonomer used as needed).

[0235] When using an azo polymer initiator, the amount of azo polymer initiator used is preferably 0.01 mol or more, more preferably 0.05 mol or more, and even more preferably 0.1 mol or more, relative to 1 mol of the compound represented by formula (T1) or the compound represented by formula (T2) (or the total of both when using the compound represented by formula (T1) and the compound represented by formula (T2)). Furthermore, this amount is preferably 50 mol or less, more preferably 10 mol or less, and even more preferably 5 mol or less.

[0236] When using compounds represented by formula (T1) and formula (T2), the amount of compound represented by formula (T2) used is preferably 0.01 mol or more, more preferably 0.05 mol or more, and even more preferably 0.1 mol or more, relative to 1 mol of compound represented by formula (T1). Furthermore, this amount is preferably 100 mol or less, more preferably 10 mol or less, and even more preferably 5 mol or less.

[0237] The above polymerization reaction can be carried out even without solvent, but it can also be carried out using organic solvents or aqueous solvents commonly used in free radical polymerization.

[0238] 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. In addition, 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.

[0239] Next, the mixture obtained in the above manner is stirred. The reaction temperature and reaction time can be appropriately adjusted according to the molecular weight or molecular weight distribution of the obtained polymer. Stirring can be carried out at 60℃ to 150℃ for 5 to 100 hours. Alternatively, it can be carried out at 80℃ to 120℃ for 10 to 30 hours. The reaction can be carried out under normal pressure, or under pressure or reduced pressure.

[0240] After the reaction is complete, the target polymer is obtained by removing the solvent and residual monomers under reduced pressure using conventional methods, or by separating the target analyte through reprecipitation using a solvent that does not dissolve the target polymer. Any treatment method can be used as long as it does not interfere with the target analyte.

[0241] Using the polymerization method described above, excellent molecular weight control and molecular weight distribution control can be achieved under very mild conditions.

[0242] Block copolymers, alternating copolymers, or random copolymers can be made using tellurium-containing compounds represented by formula (M1) and a first comonomer.

[0243] The following illustrates an example of the homopolymerization and copolymerization reaction process in Embodiment 4. In the figure below, In represents the structure from the free radical initiator, and R represents R 1 Or R 6 x, y, z, x1, x2, y1, y2, z1, z2, and n each independently represent the number of constituent units. It should be noted that when there are multiple constituent units enclosed in square brackets ([]), the arrangement of these structural units can be random.

[0244]

[0245]

[0246] When using the compound represented by (T2) instead of the compound represented by (T1) as a chain transfer agent, homopolymerization and copolymerization can also be carried out according to the above reaction process.

[0247] Fifth Implementation Method

[0248] <Methods for manufacturing polymers>

[0249] The method for manufacturing the polymer according to the fifth embodiment includes: polymerizing at least one tellurium-containing compound represented by the following formula (M2) in the presence of at least one compound selected from the compounds represented by the following formula (T1) and the compounds represented by the following formula (T2).

[0250]

[0251] In equation (T1), R 6 R represents an alkyl group having 1 to 8 carbon atoms, either substituted or unsubstituted, or an aryl group having 3 to 16 carbon atoms, either substituted or unsubstituted. 7 and R 8 Each of the following independently represents a hydrogen atom, or an alkyl group having 1 to 8 substituted or unsubstituted carbon atoms. R 9The group represents a hydrogen atom, an alkyl group with 1 to 8 substituted or unsubstituted carbon atoms, an aryl group with 3 to 16 substituted or unsubstituted carbon atoms, an acyl group with 2 to 8 carbon atoms, an amide group with 2 to 8 carbon atoms, a group containing an oxygen carbonyl group, or a cyano group.

[0252] (R 10 Te)2 (T2)

[0253] In equation (T2), R 10 It refers to an alkyl group having 1 to 8 carbon atoms, either substituted or unsubstituted, or an aryl group having 3 to 16 carbon atoms, either substituted or unsubstituted.

[0254]

[0255] In formula (M2),

[0256] X 2 Y 2 and Z 2 Each of the following independently represents an organic group having 1 to 20 carbon atoms: hydrogen, fluorine, chlorine, bromine, iodine, or hydrogen atoms. 2 Y 2 and Z 2 At least one of them represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxygen-perfluoroalkylene structure, or a phenyl group.

[0257] R 2 Organic groups that represent 1 to 20 carbon atoms.

[0258] The polymer manufacturing method of the fifth embodiment is as follows: based on the TEP method, at least one compound selected from the compounds represented by formula (T1) and formula (T2) is used as a chain transfer agent to polymerize at least the compound represented by formula (M2). By this manufacturing method, a polymer having a controlled molecular structure and a branched structure can be obtained. The obtained polymer can be the polymer of the second embodiment.

[0259] The details of the compounds represented by formula (T1), formula (T2), and formula (M2) are as described above.

[0260] In the polymer manufacturing method of the fifth embodiment, other components such as free radical initiators, solvents, emulsifiers, suspending agents, acids, or bases may be further used. Details of any component are as described above.

[0261] In one embodiment, the method for manufacturing the polymer according to the fifth embodiment includes: polymerizing a tellurium-containing compound represented by formula (M2) with a polymerizable compound (i.e., a second comonomer), wherein the polymerizable compound is different from the tellurium-containing compound represented by formula (M2) and has carbon-carbon double bonds in its molecule. Details of the second comonomer are as described above.

[0262] [Aggregation Method]

[0263] The specific polymerization method in the polymer manufacturing method of the fifth embodiment can be applied in the same way as the polymerization method described in the fourth embodiment. In this case, "tellurium-containing compound represented by formula (M1)" is replaced with "tellurium-containing compound represented by formula (M2)" and "first comonomer" is replaced with "second comonomer".

[0264] Implementation Method 6

[0265] <Methods for manufacturing polymers>

[0266] The method for manufacturing the polymer according to the sixth embodiment includes: polymerizing at least one of the compounds selected from the compounds represented by the following formula (T1) and the compounds represented by the following formula (T2) with the compound represented by the following formula (M11).

[0267]

[0268] In equation (T1), R 6 R represents an alkyl group having 1 to 8 carbon atoms, either substituted or unsubstituted, or an aryl group having 3 to 16 carbon atoms, either substituted or unsubstituted. 7 and R 8 Each of the following independently represents a hydrogen atom, or an alkyl group having 1 to 8 substituted or unsubstituted carbon atoms. R 9 The group represents a hydrogen atom, an alkyl group with 1 to 8 substituted or unsubstituted carbon atoms, an aryl group with 3 to 16 substituted or unsubstituted carbon atoms, an acyl group with 2 to 8 carbon atoms, an amide group with 2 to 8 carbon atoms, a group containing an oxygen carbonyl group, or a cyano group.

[0269] (R 10 Te)2 (T2)

[0270] In equation (T2), R 10 It refers to an alkyl group having 1 to 8 carbon atoms, either substituted or unsubstituted, or an aryl group having 3 to 16 carbon atoms, either substituted or unsubstituted.

[0271]

[0272] In formula (M3),

[0273] X3 Y 3 and Z 3 Each can independently represent an organic group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or 1 to 20 carbon atoms.

[0274] R 3 Organic groups that represent 1 to 20 carbon atoms.

[0275]

[0276] In formula (M11), 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.

[0277] The polymer manufacturing method of the sixth embodiment is as follows: based on the TEP method, at least one compound selected from the compounds represented by formula (T1) and formula (T2) is used as a chain transfer agent to copolymerize at least the tellurium-containing compound represented by formula (M3) with the compound represented by formula (M11). This manufacturing method yields a polymer having a controlled molecular structure and a branched structure, obtained by polymerizing fluorine-containing monomers. The obtained polymer can be the polymer of the third embodiment.

[0278] The details of the compounds represented by formula (T1), (T2), (M3), and (M11) are as described above.

[0279] In the polymer manufacturing method of the sixth embodiment, other components such as free radical initiators, solvents, emulsifiers, suspending agents, acids, or bases may be further used. Details of any component are as described above.

[0280] [Aggregation Method]

[0281] The specific polymerization method in the polymer manufacturing method of the sixth embodiment can be applied in the same way as the polymerization method described in the fourth embodiment. The difference is that "tellurium-containing compound represented by formula (M1)" is replaced with "tellurium-containing compound represented by formula (M3)," and "first comonomer" is replaced with "compound represented by formula (M11)." Furthermore, at least the tellurium-containing compound represented by formula (M3) is copolymerized with the compound represented by formula (M11).

[0282] Example

[0283] The following examples illustrate the implementation of this disclosure, but the implementation of this disclosure is not limited thereto.

[0284] 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 article have the following meanings.

[0285] s: singlet

[0286] d: doublet

[0287] t: triplet

[0288] m: multiplet (multiplet)

[0289] Hz: Hertz

[0290] CDCl3: Deuterated chloroform

[0291] THF-d 10 :d 10 -Tetrahydrofuran

[0292] 1 H-NMR: Proton Nuclear Magnetic Resonance

[0293] 19 F-NMR: Fluorine-19 NMR

[0294] 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. The ionization mode used was positive ion mode (EI+). Found data are recorded.

[0295] (Example 1)

[0296] Synthesis of phenyl (trifluorovinyl) telluride (CF2=CFTePh)

[0297] A magnetic rotor was added to a 300 mL glass flask, and the interior was purged with nitrogen. Under a nitrogen atmosphere, 43 g of frozen degassed diethyl ether was added, and the internal temperature was cooled to -78 °C while stirring. Under a nitrogen atmosphere, 100 mL of a 1.6 mol / L (0.16 mol) n-butyllithium / hexane solution was added, and the mixture was stirred for 30 minutes while maintaining the internal temperature at -78 °C. This solution is designated as A.

[0298] A magnetic rotor and 15 g (36 mmol) of diphenylditelluride were added to a 100 mL glass flask, and the interior was purged with nitrogen. Under a nitrogen atmosphere, 45 g of cryogenically degassed tetrahydrofuran was added, and the internal temperature was cooled to 0 °C while stirring. Under a nitrogen atmosphere, 5.7 mL (36 mmol) of bromine was added, and the mixture was stirred for 1 hour while maintaining the internal temperature at 0 °C. This solution is designated as solution B.

[0299] A magnetic rotor was added to a 500 mL glass flask, and the interior was purged with nitrogen. Under a nitrogen atmosphere, 128 g of frozen degassed diethyl ether was added, and the internal temperature was cooled to -78 °C while stirring. Under a nitrogen atmosphere, 41 g (400 mmol) of 1,1,1,2-tetrafluoroethane was added, and the mixture was stirred for 10 minutes while maintaining the internal temperature. Under a nitrogen atmosphere, the entire amount of A was added over 30 minutes at a constant rate, and the mixture was stirred for 2 hours while maintaining the internal temperature. Under a nitrogen atmosphere, the entire amount of B was added over 30 minutes at a constant rate, and the mixture was stirred for 30 minutes while maintaining the internal temperature at -78 °C. The internal temperature was then gradually raised to room temperature over 30 minutes while continuing to stir. The mixture was then stirred for 1 hour while maintaining the internal temperature at room temperature.

[0300] The reaction vessel was opened inside a nitrogen-purified glove box, and the reaction mixture was filtered to remove solids. The filtrate was washed three times with deionized water, and the organic phase was recovered. The solvent of the organic phase was distilled off under reduced pressure, and the residue was purified by vacuum distillation to give the title compound as 5.7 g of an oil.

[0301] 1 H NMR (300MHz, CDCl3) δ7.25-7.64 (5H, m)

[0302] 19 F NMR (282MHz, CDCl3) δ-88.3 (1F, dd), δ-105.6 (1F, dd), δ-157.7 (1F, dd)

[0303] MS(EI+): [M+] 288.0

[0304] (Example 2)

[0305] Synthesis of (2,2-difluorovinyl)phenyl telluride (CF2=CHTePh)

[0306] A magnetic rotor was added to a 100 mL glass flask, and the interior was purged with nitrogen. Under a nitrogen atmosphere, 6.7 g of frozen degassed tetrahydrofuran was added, and the internal temperature was cooled to -78 °C while stirring. Under a nitrogen atmosphere, 25 mL (1.3 mol / L, 33 mmol) of a sec-butyllithium / hexane / cyclohexane solution was added, and the mixture was stirred for 30 minutes while maintaining the internal temperature at -78 °C. This solution is designated as A.

[0307] A magnetic rotor and 5.5 g (14 mmol) of diphenylditelluride were added to a 100 mL glass flask, and the interior was purged with nitrogen. Under a nitrogen atmosphere, 45 g of cryogenically degassed tetrahydrofuran was added, and the internal temperature was cooled to 0 °C while stirring. Under a nitrogen atmosphere, 2.2 mL (14 mmol) of bromine was added, and the mixture was stirred for 1 hour while maintaining the internal temperature at 0 °C. This solution is designated as solution B.

[0308] A magnetic rotor was added to a 300 mL glass flask, and the interior was purged with nitrogen. Under a nitrogen atmosphere, 60 g of frozen degassed tetrahydrofuran was added, and the internal temperature was cooled to -108 °C while stirring. Under a nitrogen atmosphere, 2.3 g (45 mmol) of vinylidene fluoride was added at a constant rate over 1.5 hours, and the mixture was stirred for 10 minutes while maintaining the internal temperature at -108 °C. Under a nitrogen atmosphere, the entire amount of ingredient A was added at a constant rate over 30 minutes, and the mixture was stirred for 1 hour while maintaining the internal temperature at -108 °C. Under a nitrogen atmosphere, the entire amount of ingredient B was added at a constant rate over 30 minutes, and the mixture was stirred for 30 minutes while maintaining the internal temperature at -108 °C. The internal temperature was then raised to -78 °C while continuing to stir. The mixture was stirred for 30 minutes while maintaining the internal temperature at -78 °C. The internal temperature was then raised to room temperature over 30 minutes while continuing to stir. The mixture was stirred for 1 hour while maintaining the internal temperature at room temperature.

[0309] The reaction vessel was opened inside a nitrogen-purified glove box, and the reaction mixture was filtered to remove solids. The filtrate was washed three times with deionized water, and the organic phase was recovered. The solvent of the organic phase was distilled off under reduced pressure, and the residue was purified by vacuum distillation to give the title compound as 1.1 g of an oil.

[0310] 1 H NMR (300MHz, CDCl3) δ5.41 (1H, dd), δ7.20-7.32 (4H, m), δ7.68 (2H, dd),

[0311] 19F NMR (282MHz, CDCl3) δ-66.9 (1F, dd), -71.4 (1F, dd)

[0312] MS(EI+): [M+] 270.0

[0313] (Example 3)

[0314] Preparation of 1-bromo-1-chlorodifluoroethylene (structural formula: CF2=CClBr)

[0315] A magnetic rotor was added to a 50 mL glass flask, and the interior was purged with nitrogen. Under a nitrogen atmosphere, 10 g (15 wt%, 39 mmol) of degassed aqueous sodium hydroxide solution and 5 g (19 mmol) of 1,2-dibromo-2-chloro-1,1-difluoroethane were added. The mixture was stirred for 30 minutes while maintaining the internal temperature at room temperature. The organic phase was recovered, washed three times with deionized water, and dried over anhydrous sodium sulfate to give the title compound as 2.1 g of liquid. This compound was used in the next step without further purification.

[0316] MS(EI+): [M+] 176.0

[0317] Synthesis of (1-chlorodifluorovinyl)phenyl telluride (CF2=CClTePh)

[0318] A magnetic rotor was added to a 300 mL glass flask, and the interior was purged with nitrogen. Under a nitrogen atmosphere, 86 g of cryogenically degassed diethyl ether was added, and the internal temperature was cooled to -78 °C while stirring. Under a nitrogen atmosphere, 8.0 mL (1.6 mol / L, 13 mmol) of a n-butyllithium / hexane solution was added, and the mixture was stirred for 30 minutes while maintaining the internal temperature at -78 °C. This solution is designated as A.

[0319] A magnetic rotor and 2.0 g (4.8 mmol) of diphenylditelluride were added to a 50 mL glass flask, and the interior was purged with nitrogen. Under a nitrogen atmosphere, 13 g of cryogenically degassed tetrahydrofuran was added, and the internal temperature was cooled to 0 °C while stirring. Under a nitrogen atmosphere, 0.25 mL (4.8 mmol) of bromine was added, and the mixture was stirred for 1 hour while maintaining the internal temperature at 0 °C. This solution is designated as solution B.

[0320] A magnetic rotor was added to a 300 mL glass flask, and the interior was purged with nitrogen. Under a nitrogen atmosphere, 86 g of frozen degassed diethyl ether was added, and the internal temperature was cooled to -78 °C while stirring. Under a nitrogen atmosphere, 2.0 g (11 mmol) of 1-bromo-1-chlorodifluoroethylene was added, and the mixture was stirred for 10 minutes while maintaining the internal temperature. Under a nitrogen atmosphere, the entire amount of A was added over 30 minutes at a constant rate, and the mixture was stirred for 1 hour while maintaining the internal temperature. Under a nitrogen atmosphere, the entire amount of B was added over 30 minutes at a constant rate, and the mixture was stirred for 1 hour while maintaining the internal temperature. The internal temperature was gradually raised to room temperature over 30 minutes while stirring. The mixture was then stirred for 1 hour while maintaining the internal temperature at room temperature.

[0321] The reaction vessel was opened inside a nitrogen-purified glove box, and the reaction mixture was filtered to remove solids. The filtrate was washed three times with deionized water, and the organic phase was recovered. The solvent of the organic phase was distilled off under reduced pressure, and the residue was purified by vacuum distillation to give the title compound as 0.5 g of an oil.

[0322] 1 H NMR (300MHz, CDCl3) δ7.19-7.56 (5H, m)

[0323] 19 F NMR (282MHz, CDCl3) δ-83.4 (1F, dd), -84.4 (1F, d)

[0324] MS(EI+): [M+] 304.0

[0325] (Example 4)

[0326] Synthesis of butyl (trifluorovinyl) telluride (CF2=CFTeBu)

[0327] The title compound was obtained in liquid form in the same manner as in Example 1, except that the diphenylditelluride in Example 1 was replaced with dibutylditelluride.

[0328] 1 H NMR (300MHz, CDCl3) δ1.0 (1H, t)

[0329] 19 F NMR (282MHz, CDCl3) δ-86.8 (1F, dd), δ-106.1 (1F, dd), δ-156.6 (1F, dd)

[0330] MS(EI+): [M+] 268.0

[0331] Example 5 below is an example that is expected to be synthesized based on the insights and known methods of this disclosure.

[0332] (Example 5)

[0333] Synthesis of methyl (trifluorovinyl) telluride (CF2=CFTeMe)

[0334] The title compound was obtained in the same oily form as in Example 1, except that the diphenylditelluride in Example 1 was replaced with dimethylditelluride.

[0335] (Example 6)

[0336] Copolymerization of phenyl trifluorovinyl telluride and trifluorochloroethylene

[0337] In a nitrogen-purified glove box, 0.061 g (0.27 mmol) of azo radical initiator "V-601" (Fujifilm and Koh Genuine Chemicals Co., Ltd.), 0.055 g (0.13 mmol) of diphenyl ditelluride, 1.2 g (4.0 mmol) of phenyl (trifluorovinyl) telluride synthesized in Example 1, and 11 g of trifluorotoluene were added to a stainless steel autoclave with a stirrer and a volume of 30 mL.

[0338] After adding 3.3 g (28 mmol) of trifluorochloroethylene, the mixture was stirred while the internal temperature was raised to 80°C. The mixture was stirred at 200 rpm for 7 hours while maintaining the internal temperature.

[0339] After cooling the autoclave with an ice-water bath, purge any unreacted trifluorochloroethylene.

[0340] The obtained polymer solution was vacuum dried to obtain an oily substance. This oily substance was added to 40 mL of cryogenically degassed methanol in a nitrogen-purged glove box and stirred for 5 minutes. The oily substance was then separated from the supernatant using a centrifuge. The resulting oily substance was vacuum dried, yielding 0.2 g of oily substance.

[0341] Determination of the obtained oily substance 19 F-NMR analysis revealed a peak at δ = 177 ppm. Since this peak is attributed to a fluorine atom bonded to a tertiary carbon atom, it indicates that the polymer has a branched main chain backbone. Here, a tertiary carbon atom refers to a carbon atom directly bonded with three carbon atoms.

[0342] (Example 7)

[0343] Copolymerization of butyltrifluorovinyl telluride and tetrafluoroethylene

[0344] In a nitrogen-purified glove box, 0.038 g (0.17 mmol) of azo radical initiator "V-601" (Fujifilm and Koh Genuine Chemicals Co., Ltd.), 0.057 g (0.15 mmol) of dibutylditelluride, 1.3 g (4.6 mmol) of butyltrifluorovinyltelluride synthesized in Example 4, and 13 g of 1H-perfluorohexane were added to a stainless steel autoclave with a stirrer and a volume of 30 mL.

[0345] After adding 5.0 g (50 mmol) of tetrafluoroethylene, the reaction was initiated by stirring while raising the internal temperature to 72 °C. The reaction was carried out at 200 rpm for 7 hours while maintaining the internal temperature. The autoclave was then cooled in an ice-water bath, and any unreacted tetrafluoroethylene was purged.

[0346] The obtained polymer solution was vacuum dried to obtain a solid. This solid was added to 40 mL of cryogenically degassed methanol in a nitrogen-purged glove box and stirred for 5 minutes. The solid was then separated from the supernatant using a centrifuge. The obtained solid was vacuum dried to obtain 0.5 g of solid.

[0347] Examples 8-13 below are embodiments that are expected to be synthesized based on the insights and known methods of this disclosure. Since each example uses a highly reactive fluorinated monomer as a comonomer, it is considered that the copolymer can be suitably synthesized.

[0348] (Example 8)

[0349] Copolymerization of (2,2-difluorovinyl)phenyl compounds with trifluorochloroethylene

[0350] Inside a nitrogen-replaced glove box, an azo radical initiator “V-601” (Fujifilm and Koh Genuine Chemicals Co., Ltd.), diphenyl ditelluride, (2,2-difluorovinyl)phenyl telluride synthesized in Example 2, trifluorotoluene, and trifluorochloroethylene were added to a 30 mL stainless steel autoclave equipped with a stirrer. The reaction was carried out by stirring while raising the internal temperature to 80°C.

[0351] (Example 9)

[0352] Copolymerization of (1-chlorodifluorovinyl)phenyl telluride with trifluorochloroethylene

[0353] Inside a nitrogen-replaced glove box, an azo-based free radical initiator “V-601” (Fujifilm and Koh Pure Chemical Co., Ltd.), diphenyl ditelluride, (1-chlorodifluorovinyl)phenyl telluride synthesized in Example 3, trifluorotoluene, and trifluorochloroethylene were added to a 30 mL stainless steel autoclave equipped with a stirrer. The reaction was carried out by stirring while raising the internal temperature to 80°C.

[0354] (Example 10)

[0355] Copolymer of (2-nonafluorobutylvinyl)phenyl telluride and trifluorochloroethylene

[0356] Inside a nitrogen-replaced glove box, a 30 mL stainless steel autoclave equipped with a stirrer was filled with an azo radical initiator “V-601” (Fujifilm and Koh Pure Chemical Co., Ltd.), diphenyl ditelluride, (2-nonafluorobutylvinyl)phenyl telluride synthesized according to known literature, trifluorotoluene, and trifluorochloroethylene. The reaction was carried out by stirring while raising the internal temperature to 80°C.

[0357] (Example 11)

[0358] Copolymerization of (1-chlorovinyl)phenyl telluride with trifluorochloroethylene

[0359] Inside a nitrogen-replaced glove box, a 30 mL stainless steel autoclave equipped with a stirrer was filled with an azo radical initiator “V-601” (Fujifilm and Koh Pure Chemical Co., Ltd.), diphenyl ditelluride, (1-chlorovinyl)phenyl telluride synthesized according to known literature, trifluorotoluene, and trifluorochloroethylene. The reaction was carried out by stirring while raising the internal temperature to 80°C.

[0360] (Example 12)

[0361] Copolymerization of (2-chlorovinyl)phenyl telluride with trifluorochloroethylene

[0362] Inside a nitrogen-replaced glove box, a 30 mL stainless steel autoclave equipped with a stirrer was filled with an azo radical initiator “V-601” (Fujifilm and Koh Pure Chemical Co., Ltd.), diphenyl ditelluride, (2-chlorovinyl)phenyl telluride synthesized according to known literature, trifluorotoluene, and trifluorochloroethylene. The reaction was carried out by stirring while raising the internal temperature to 80°C.

[0363] (Example 13)

[0364] Copolymerization of (1-phenylvinyl)phenyl telluride with trifluorochloroethylene

[0365] Inside a nitrogen-replaced glove box, a 30 mL stainless steel autoclave equipped with a stirrer was filled with an azo radical initiator “V-601” (Fujifilm and Koh Pure Chemical Co., Ltd.), diphenyl ditelluride, (1-phenylvinyl)phenyl telluride synthesized according to known literature, trifluorotoluene, and trifluorochloroethylene. The reaction was carried out by stirring while raising the internal temperature to 80°C.

[0366] The disclosure of Japanese Patent Application No. 2020-207031, in its entirety, is incorporated herein by reference.

[0367] All documents, patent applications and technical standards described in this specification are incorporated herein by reference to the same extent that each document, patent application and technical standard is specifically and individually described and incorporated herein by reference.

Claims

1. A polymer formed by polymerizing at least one tellurium-containing compound represented by the following formula (M1) with at least one selected from trifluorochloroethylene and tetrafluoroethylene. ， In formula (M1), X 1 Y 1 and Z 1 Represents a fluorine atom. R 1 Organic groups that represent 1 to 20 carbon atoms.

2. The polymer according to claim 1, wherein, In the formula (M1), R 1 It is an alkyl group with 1 to 20 carbon atoms that is substituted or unsubstituted, an alkoxy group with 1 to 20 carbon atoms that is substituted or unsubstituted, a monovalent hydrocarbon group with 1 to 20 carbon atoms that is substituted or unsubstituted and has an oxoalkylene structure, or an aryl group with 3 to 20 carbon atoms that is substituted or unsubstituted.

3. A method for manufacturing a polymer, comprising: In the presence of at least one compound selected from compounds represented by formula (T1) and formula (T2), the tellurium-containing compound represented by formula (M1) as defined in claim 1 or 2 is polymerized with at least one compound selected from trifluorochloroethylene and tetrafluoroethylene. ， In equation (T1), R 6 R represents an alkyl group having 1 to 8 carbon atoms, either substituted or unsubstituted, or an aryl group having 3 to 16 carbon atoms, either substituted or unsubstituted. 7 and R 8 Each independently represents a hydrogen atom, or an alkyl group having 1 to 8 carbon atoms, substituted or unsubstituted; R 9 The group represents a hydrogen atom, an alkyl group with 1 to 8 substituted or unsubstituted carbon atoms, an aryl group with 3 to 16 substituted or unsubstituted carbon atoms, an acyl group with 2 to 8 carbon atoms, an amide group with 2 to 8 carbon atoms, a group containing an oxygen carbonyl group, or a cyano group. ， In equation (T2), R 10 It refers to an alkyl group having 1 to 8 carbon atoms, either substituted or unsubstituted, or an aryl group having 3 to 16 carbon atoms, either substituted or unsubstituted.

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