Tellurium-containing compound, polymer, and method for producing the polymer

Abstract

Provided are: a tellurium-containing compound represented by formula (M1); a polymer of a tellurium-containing compound represented by any one of formulae (M1) to (M3); and a method for producing the polymer. X1 to X3, Y1 to Y3 and Z1 to Z3 each independently denote a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or an organic group having 1-20 carbon atoms. At least one of X1, Y1 and Z1 is a fluorine atom. At least one of X2, Y2 and Z2 is a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group. R1 to R3 each denote an organic group having 1-20 carbon atoms.

Description

[Technical Field]

[0001] This disclosure relates to tellurium-containing compounds, polymers, and methods for producing polymers. [Background technology]

[0002] Radical polymerization reactions are widely used industrially due to their excellent monomer versatility and ease of operation even in polar media such as water. However, molecular weight control by general radical polymerization methods is limited, and the molecular weight distribution of the resulting polymers tends to be broad. On the other hand, living radical polymerization has attracted attention as a polymerization method that can obtain controlled molecular structures, and various polymerization control agents have been developed. Living radical polymerization is a polymerization method that controls the radical polymerization rate by reversibly protecting the growing radicals with a dormant species protecting group, thereby enabling control of the molecular weight distribution.

[0003] Patent Document 1 describes a living radical polymerization method for producing a haloolefin polymer or copolymer by radical polymerization of a specific haloolefin in the presence of a specific organotellurium compound. This method is based on a method called TERP (organotellurium-mediated living radical polymerization).

[0004] In recent years, the importance of developing polymers with branched structures within their molecules has been increasing. Branched polymers possess various properties that differ from linear polymers. For example, because branched polymers have numerous end groups, when used as molding materials, they can increase the crosslinking density of the molded product and improve its curability. Furthermore, branched polymers are known to have lower intrinsic viscosity and lower glass transition temperatures compared to linear polymers. Thus, branched polymers have unique properties that differ from linear polymers, and their industrial utility is high.

[0005] Non-patent document 1 discloses a controlled polymerization method for producing highly branched polymers by copolymerizing vinyl telluride and acrylic acid monomer in the presence of a tellurium compound, which is a chain transfer agent, based on the TERP method. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2018 / 164147 [Non-patent literature]

[0007] [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) [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] However, currently, knowledge regarding techniques for producing branched polymers through controlled polymerization is limited.

[0009] A first embodiment of this disclosure relates to a novel tellurium-containing compound that can be used to produce polymers having a controlled molecular structure and a branched structure, and a polymer produced using the tellurium-containing compound.

[0010] A second embodiment of this disclosure relates to providing a novel polymer having a controlled molecular structure and a branched structure.

[0011] A third embodiment of this disclosure relates to providing a polymer obtained by polymerizing fluorine-containing monomers having a controlled molecular structure and a branched structure.

[0012] A fourth embodiment of this disclosure relates to a method for producing a polymer having a controlled molecular structure and a branched structure.

[0013] A fifth embodiment of this disclosure relates to providing a method for producing a novel polymer having a controlled molecular structure and a branched structure.

[0014] A sixth embodiment of this disclosure relates to a method for producing a polymer having a controlled molecular structure and a branched structure by polymerizing fluorine-containing monomers. [Means for solving the problem]

[0015] The means for solving the above problems include the following embodiments. <1> Tellurium-containing compounds represented by the following formula (M1):

[0016] [ka]

[0017] In formula (M1), X 1 , Y 1 , and Z 1 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X 1 , Y 1 , and Z 1 At least one of them represents a fluorine atom, R 1 This represents an organic group with 1 to 20 carbon atoms. <2> In the above formula (M1), R 1is a tellurium-containing compound according to <1>, which is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a monovalent hydrocarbon group having 1 to 20 carbon atoms and having a substituted or unsubstituted oxyalkylene structure, or a substituted or unsubstituted aryl group having 3 to 20 carbon atoms. <3> In the formula (M1), X 1 , Y 1 , and Z 1 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a monovalent hydrocarbon group having 1 to 20 carbon atoms and having a substituted or unsubstituted oxyalkylene structure, or a substituted or unsubstituted aryl group having 3 to 20 carbon atoms, which is a tellurium-containing compound according to <1> or <2>. <4> A polymer obtained by polymerizing at least the tellurium-containing compound according to any one of <1> to <3>. <5> A polymer according to <4>, which is obtained by polymerizing the tellurium-containing compound and a polymerizable compound having a carbon-carbon double bond in the molecule, which is different from the tellurium-containing compound. <6> The polymer according to <5>, wherein the polymerizable compound is a compound represented by the following formula (M11):

[0018]

Chemical formula

[0019] In the formula (M11), X 11 ~X 14 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and at least one of X 11 ~X 14 represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure. <7> A polymer obtained by polymerizing at least a tellurium-containing compound represented by the following formula (M2):

[0020]

Chemical formula

[0021] In formula (M2), X 2 , Y 2 , and Z 2 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X 2 , Y 2 , and Z 2 At least one of them represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group. R 2 This represents an organic group with 1 to 20 carbon atoms. <8> A polymerizable compound obtained by polymerizing the tellurium-containing compound and a polymerizable compound that, unlike the tellurium-containing compound, has a carbon-carbon double bond in its molecule, <7> The polymer described above. <9> The polymerizable compound is a compound represented by the following formula (M11): <8> Polymers described:

[0022] [ka]

[0023] In formula (M11), X 11 ~X 14 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X 11 ~X 14 At least one of these represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure. <10> A polymer obtained by polymerizing at least a tellurium-containing compound represented by the following formula (M3) and a compound represented by the following formula (M11):

[0024] [ka]

[0025] In formula (M3), X 3 , Y 3 , and Z 3 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms. R 3 This represents an organic group with 1 to 20 carbon atoms.

[0026] [ka]

[0027] In formula (M11), X 11 ~X 14 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X 11 ~X 14 At least one of these represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure. <11> In the presence of at least one compound selected from the group consisting of the compound represented by the following formula (T1) and the compound represented by the following formula (T2), <1> ~ <3> A method for producing a polymer, comprising polymerizing a tellurium-containing compound as described in any one of the following items:

[0028] [ka]

[0029] In formula (T1), R 6 R represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms. 7 and R 8 Each of these independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 9This represents a hydrogen atom, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C16 aryl group, a C2-C8 acyl group, a C2-C8 amide group, an oxycarbonyl-containing group, or a cyano group.

[0030] [ka]

[0031] In formula (T2), R 10 This represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or an substituted or unsubstituted aryl group having 3 to 16 carbon atoms. <12> <1> ~ <3> The process involves polymerizing a tellurium-containing compound described in any one of the items and a polymerizable compound that, unlike the tellurium-containing compound, has a carbon-carbon double bond in its molecule. <11> A method for producing the polymer described above. <13> The polymerizable compound is a compound represented by the following formula (M11): <12> Method for producing the polymer described:

[0032] [ka]

[0033] In formula (M11), X 11 ~X 14 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X 11 ~X 14 At least one of these represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure. <14> A method for producing a polymer, comprising polymerizing a tellurium-containing compound represented by at least the following formula (M2) in the presence of at least one compound selected from the group consisting of a compound represented by the following formula (T1) and a compound represented by the following formula (T2):

[0034] [ka]

[0035] In formula (T1), R 6 R represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms. 7 and R 8 Each of these independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 9 This represents a hydrogen atom, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C16 aryl group, a C2-C8 acyl group, a C2-C8 amide group, an oxycarbonyl-containing group, or a cyano group.

[0036] [ka]

[0037] In formula (T2), R 10 This represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or an substituted or unsubstituted aryl group having 3 to 16 carbon atoms.

[0038] [ka]

[0039] In formula (M2), X 2 , Y 2 , and Z 2 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X 2 , Y 2 , and Z 2 At least one of them represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group. R 2 This represents an organic group with 1 to 20 carbon atoms. <15> The process involves polymerizing a tellurium-containing compound represented by formula (M2) and a polymerizable compound that, unlike the tellurium-containing compound represented by formula (M2), has a carbon-carbon double bond in its molecule. <14> A method for producing the polymer described above. <16> The polymerizable compound is a compound represented by the following formula (M11): <15> Method for producing the polymer described:

[0040] [ka]

[0041] In formula (M11), X 11 ~X 14 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X 11 ~X 14 At least one of these represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure. <17> A method for producing a polymer, comprising polymerizing at least a tellurium-containing compound represented by the following formula (M3) and a compound represented by the following formula (M11) in the presence of at least one compound selected from the group consisting of a compound represented by the following formula (T1) and a compound represented by the following formula (T2):

[0042] [ka]

[0043] In formula (T1), R 6 R represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms. 7 and R 8 Each of these independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 9This represents a hydrogen atom, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C16 aryl group, a C2-C8 acyl group, a C2-C8 amide group, an oxycarbonyl-containing group, or a cyano group.

[0044] [ka]

[0045] In formula (T2), R 10 This represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or an substituted or unsubstituted aryl group having 3 to 16 carbon atoms.

[0046] [ka]

[0047] In formula (M3), X 3 , Y 3 , and Z 3 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms. R 3 This represents an organic group with 1 to 20 carbon atoms.

[0048] [ka]

[0049] In formula (M11), X 11 ~X 14 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X 11 ~X 14 At least one of these represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure. [Effects of the Invention]

[0050] According to a first embodiment of this disclosure, a novel tellurium-containing compound is provided that can be used to produce polymers having a controlled molecular structure and a branched structure, and a polymer produced using the tellurium-containing compound is provided.

[0051] According to a second embodiment of the present disclosure, a novel polymer having a controlled molecular structure and a branched structure is provided.

[0052] A third embodiment of the present disclosure provides a polymer obtained by polymerizing fluorine-containing monomers having a controlled molecular structure and a branched structure.

[0053] A fourth embodiment of the present disclosure provides a method for producing a polymer having a controlled molecular structure and a branched structure.

[0054] A fifth embodiment of this disclosure provides a method for producing a novel polymer having a controlled molecular structure and a branched structure.

[0055] A sixth embodiment of the present disclosure provides a method for producing a polymer obtained by polymerizing fluorine-containing monomers having a controlled molecular structure and a branched structure. [Modes for carrying out the invention]

[0056] The embodiments of this disclosure will be described in detail below. However, the embodiments of this disclosure are not limited to the embodiments described below. In the embodiments described below, the components (including elemental steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the embodiments of this disclosure.

[0057] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, provided that the purpose of such process is achieved. In this disclosure, the numerical range indicated using "~" includes the numbers before and after "~" as the minimum and maximum values, respectively. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. In this disclosure, the term "reactive carbon-carbon double bond" refers to a carbon-carbon double bond that can react in various ways as an olefin, and does not include aromatic double bonds. In this disclosure, unless otherwise specified, organic groups or hydrocarbon groups may have substituents or not. In this disclosure, the number of carbon atoms in a compound or its component means the number of carbon atoms in the substituent if the compound or component has substituents. In this disclosure, (meth)acrylic acid is a general term for acrylic acid and methacrylic acid. (Meth)acrylate is a general term for acrylate and methacrylate. (Meth)acrylamide is a general term for acrylamide and methacrylamide. In this disclosure, "polymer" refers to a compound formed by the polymerization of monomers. That is, a "polymer" has multiple structural units. In this disclosure, unless otherwise specified, the phrases "polymerize compound A" and "polymerize at least compound A" encompass both cases of polymerizing compound A alone and cases of polymerizing compound A with other compounds. Similarly, the phrases "polymerize compound A and compound B" and "polymerize at least compound A and compound B" encompass both cases of polymerizing compound A and compound B alone, and cases of polymerizing compound A, compound B, and other compounds. Here, compound A and compound B represent any compound described in this disclosure that has a carbon-carbon double bond in its molecule. Unless otherwise specified, the polymers described in this disclosure may be homopolymers of one compound or copolymers of two or more compounds. In this disclosure, the term "polymer" does not exclude mixtures containing raw materials (monomers, catalysts), by-products, impurities, etc., in addition to polymers.

[0058] This disclosure relates to controlled polymerization for producing branched polymers using tellurium-containing compounds having reactive carbon-carbon double bonds. The findings of this disclosure can be used to obtain polymers having a controlled molecular structure and a branched structure. Furthermore, without limiting the embodiments of this disclosure, the tellurium-containing compounds, polymers, and methods for producing polymers detailed in this disclosure have been found to be useful for the polymerization of fluorine-containing monomers as well. Generally, controlled polymerization of fluorine-containing monomers is more difficult than controlled polymerization of hydrocarbon monomers. For example, Sk Arif et al., Progress in Polymer Science, Volume 106, July 2020, 101255, states that while degenerative chain transfer polymerization of acrylates and styrene was possible in the presence of chain transfer agents such as organo-stilbene and organo-bismuth, there are no reports of polymerization of fluoroalkenes using organo-tellurium compounds as chain transfer agents. Also, U.S. Patent Application Publication No. 2013 / 225775 states that although controlled polymerization methods have made great progress in the polymerization of common monomers such as (meth)acrylic acid and styrene, controlled polymerization methods are not yet efficient for the polymerization of highly reactive gaseous fluoroalkenes such as vinylidene fluoride, hexafluoropropene, and tetrafluoroethylene. Furthermore, no knowledge has been reported to date regarding methods for introducing branched structures into the polymer molecule during the controlled polymerization of fluorine-containing monomers. The inventors have found that the tellurium-containing compound, polymer, and method for producing the polymer described in detail in this disclosure are suitably applicable to the polymerization of fluorine-containing monomers.

[0059] The embodiments of this disclosure are described in detail below.

[0060] ≪First Embodiment≫ <Tellurium-containing compounds> The tellurium-containing compound according to the first embodiment is a tellurium-containing compound represented by the following formula (M1).

[0061] [ka]

[0062] In formula (M1), X 1 , Y 1 , and Z 1Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X 1 , Y 1 , and Z 1 At least one of them represents a fluorine atom, R 1 This represents an organic group with 1 to 20 carbon atoms.

[0063] The tellurium-containing compound according to the first embodiment can be suitably used to produce polymers having a controlled molecular structure and a branched structure, because branched chains can be introduced into the polymer produced by controlled polymerization.

[0064] In equation (M1), R 1 R represents an organic group having 1 to 20 carbon atoms, preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a monovalent hydrocarbon group having 1 to 20 carbon atoms having a substituted or unsubstituted oxyalkylene structure, or a substituted or unsubstituted aryl group having 3 to 20 carbon atoms. 1 X 1 , Y 1 , Z 1 It is not connected to any of the above.

[0065] As the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 14 carbon atoms is preferred, and a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms is more preferred. Examples of unsubstituted C1-C20 alkyl groups include linear, 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 groups. Among these, methyl, ethyl, or n-butyl groups are more preferred. Examples of substituted C1-C20 alkyl groups include alkyl groups in which a hydrogen atom at any position of the above-mentioned unsubstituted C1-C20 alkyl group is substituted with a substituent such as a fluorine atom, a chlorine atom, an alkoxy group, or a fluoroalkoxy group. Among these, perfluoroalkyl groups are preferred.

[0066] Examples of perfluoroalkyl groups include perfluoromethyl group, perfluoroethyl group, perfluoron-propyl group, perfluoroisopropyl group, perfluoron-butyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoron-pentyl group, perfluoron-hexyl group, perfluoron-heptyl group, and perfluoron-octyl group.

[0067] The number of carbon atoms in the substituted or unsubstituted oxyalkylene monovalent hydrocarbon group having 1 to 20 carbon atoms is preferably 1 to 12, and more preferably 1 to 6. Examples of monovalent hydrocarbon groups having an unsubstituted oxyalkylene structure include hydrocarbon groups whose constituent units are oxyalkylene structures with 1 to 4 carbon atoms, and more specifically, -((CH2) m -O) n A group represented by -CH3 is an example. Here, m represents the number of repeating methylene groups, and each is preferably an integer between 0 and 4. n is 1 or greater -((CH2) m -O)- Represents the number of repetitions of the structure, and is preferably an integer between 1 and 15. Examples of monovalent hydrocarbon groups having a substituted oxyalkylene structure include groups in which a hydrogen atom at any position in the oxyalkylene structure of the above-mentioned unsubstituted monovalent hydrocarbon group having an oxyalkylene structure is substituted with substituents such as a fluorine atom, a chlorine atom, an alkoxy group, or a fluoroalkoxy group. For example, monovalent hydrocarbon groups having an oxyperfluoroalkylene structure are preferred, and from the viewpoint of ease of synthesis, monovalent perfluorohydrocarbon groups having an oxyperfluoroalkylene structure with 1 to 4 carbon atoms as the unit are more preferred, and -((CF2) m -O) nA perfluorohydrocarbon group represented by -CF3 is more preferable. Here, m represents the number of repeating units of the difluoromethylene group, and each is preferably an integer of 0 to 4 independently. n represents the number of repeating units of the -((CF2) m -O)- structure, and is preferably an integer of 1 to 15. In the present disclosure, when describing "a monovalent hydrocarbon group having an oxyperfluoroalkylene structure", the hydrogen atom of the hydrocarbon group may be substituted with a fluorine atom or the like.

[0068] As the substituted or unsubstituted aryl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms is preferable, and a substituted or unsubstituted aryl group having 3 to 12 carbon atoms is more preferable. Examples of the unsubstituted aryl group having 3 to 20 carbon atoms include homoaryl groups such as phenyl group and naphthyl group; heteroaryl groups such as pyridyl group, pyrrole group, furyl group, and thienyl group. Among them, homoaryl group is preferable, and phenyl group is more preferable. Examples of the substituted aryl group having 3 to 20 carbon atoms include aryl groups in which any hydrogen atom bonded to the aromatic ring of the above unsubstituted aryl group having 3 to 20 carbon atoms is substituted with a substituent such as a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, a carbonyl-containing group, a sulfonyl group, or a trifluoromethyl group. The number of substituents is not particularly limited, and may be 1 to 4, may be 1 to 3, may be 1 to 2, or may be 1.

[0069] In formula (M1), X 1 , Y 1 , and Z 1 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, and at least one of X 1 , Y 1 , and Z 1 represents a fluorine atom. At least one of X 1 , Y 1 , and Z 1Preferably, each of these is independently a hydrogen atom, a fluorine atom, a chlorine atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 monovalent hydrocarbon group having an oxyalkylene structure, or a substituted or unsubstituted C3-C20 aryl group.

[0070] Examples of substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C1-C20 monovalent hydrocarbon groups having an oxyalkylene structure, and substituted or unsubstituted C3-C20 aryl groups include R 1 Examples of substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C1-C20 monovalent hydrocarbon groups having an oxyalkylene structure, and substituted or unsubstituted C3-C20 aryl groups are given above.

[0071] Compounds represented by formula (M1) include phenyl(trifluorovinyl) tellurides, (2,2-difluorovinyl)phenyl tellurides, (1-chlorodifluorovinyl)phenyl tellurides, butyl(trifluorovinyl) tellurides, and methyl(trifluorovinyl) tellurides.

[0072] [Method for producing a tellurium-containing compound represented by formula (M1)] The method for producing the tellurium-containing compound represented by formula (M1) is not particularly limited. For example, the tellurium-containing compound represented by formula (M1) is CX 1 Y 1 =CZ 1 Li represents vinyl lithium and R 1 It is obtained by preparing TeBr and reacting the two. Here, X 1 , Y 1 , Z 1 , and R 1 These are X in equation (M1), respectively. 1 , Y 1 , Z 1 , and R 1 It is the same as this.

[0073] An example of a specific synthesis scheme is shown below.

[0074] [ka]

[0075] [ka]

[0076] <polymer> The polymer according to the first embodiment is obtained by polymerizing at least the tellurium-containing compound according to the first embodiment. The polymer may be a homopolymer or copolymer of the tellurium-containing compound according to the first embodiment. The copolymer may be a block copolymer, a random copolymer, or an alternating copolymer.

[0077] In one embodiment, the polymer may be a copolymer obtained by polymerizing a tellurium-containing compound represented by formula (M1) and a polymerizable compound that, unlike the tellurium-containing compound represented by formula (M1), has a carbon-carbon double bond in its molecule (hereinafter also referred to as the "first copolymer monomer"). The first copolymer monomer may be used alone or in combination of two or more types.

[0078] The first copolymer monomer is not particularly limited. In one embodiment, the first copolymer monomer may be a compound represented by the following formula (M12).

[0079] [ka]

[0080] In formula (M12), R 11 ~R 14 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted or unsubstituted organic group having 1 to 40 carbon atoms. 1 and R 4 , or R 2 and R 3They may be connected to form a ring structure.

[0081] R 11 ~R 14 The number of carbon atoms in the substituted or unsubstituted organic group having 1 to 40 carbon atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 12.

[0082] Examples of substituted or unsubstituted organic groups having 1 to 40 carbon atoms include alkyl groups, aryl groups, heteroaryl groups, aryloxy groups, heteroaryloxy groups, alkoxy groups, arylalkyl groups, heteroarylalkyl groups, arylalkoxy groups, heteroarylalkoxy groups, carboxyl groups, alkoxycarbonyl groups, carbamoyl groups, acylamino groups, acyloxy groups, cyano groups, and monovalent hydrocarbon groups having an oxyalkylene structure.

[0083] If the substituted or unsubstituted C1-C40 organic group is a hydrocarbon group that may have heteroatoms, such as an alkyl group, aryl group, heteroaryl group, aryloxy group, heteroaryloxy group, alkoxy group, arylalkyl group, heteroarylalkyl group, arylalkoxy group, heteroarylalkoxy group, or monovalent hydrocarbon group having an oxyalkylene structure, then the hydrocarbon group may be linear, branched, or cyclic, and may or may not contain unsaturated bonds.

[0084] Examples of acyl groups in acylamino or acyloxy groups include groups obtained by removing a hydroxyl group from a carboxylic acid or sulfonic acid.

[0085] Examples of substituents in C1-C40 organic groups include fluorine atoms, chlorine atoms, hydroxyl groups, alkoxy groups, alkoxyalkyl groups, amino groups, carboxylic acid groups, sulfonic acid groups, and 1,3,5-triazinetrione skeletons.

[0086] In equation (M12), R 11 and R 13 , or R12 and R 14 These may be linked together to form a cyclic structure. That is, the compound represented by formula (M12) may be a compound having a cyclic structure, such as maleic anhydride or itaconic anhydride.

[0087] Examples of the first copolymer monomers include (meth)acrylic acid ester monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, and hydroxyethyl methacrylate; cycloalkyl group-containing unsaturated monomers such as cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and cyclododecyl (meth)acrylate; carboxyl group-containing unsaturated monomers such as (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, maleic anhydride, and itaconic anhydride; tertiary amine-containing unsaturated monomers such as N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylamide, 2-(dimethylamino)ethyl (meth)acrylate, and N,N-dimethylaminopropyl (meth)acrylate; and N-2-hydroxy Unsaturated monomers containing quaternary ammonium bases such as -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 monomers such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 2-chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 1-vinylnaphthalene, divinylbenzene, 4-(chloromethyl)styrene, 2-(chloromethyl)styrene, 3-(chloromethyl)styrene, 4-styrenesulfonic acid or its alkali metal salts (sodium salt, potassium salt, etc.); unsaturated monomers containing heterocyclic compounds such as 2-vinylthiophene and N-methyl-2-vinylpyrrole; vinylamides such as N-vinylformamide and N-vinylacetamide;Diallylamine, triallyl isocyanurate, tri(2-methyl-allyl) isocyanurate, ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-octene, 1-decene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, vinylidene chloride, vinyl chloride, 1-chloro-1-fluoroethylene, or 1,2-dichloro-1,2-difluoroethylene, α-olefins such as 1H,1H,2H-perfluoro(n-1-hexene), 1H,1H,2H-perfluoro(n-1-octene); vinyl acetate and other vinyl acetates. Examples include thermonomers; divinylfluoroalkanes such as 1,4-divinyloctafluorobutane and 1,6-divindodecafluorohexane; acrylonitriles; 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; and perfluoro(alkyl vinyl ethers) such as perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), and perfluoro(n-propyl vinyl ether).

[0088] In one embodiment, the first copolymer monomer may be a compound represented by the following formula (M11).

[0089] [ka]

[0090] In formula (M11), X 11 ~X 14 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X 11 ~X 14At least one of these represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.

[0091] The compound represented by formula (M1) can introduce branched chains into fluorine-containing polymers by copolymerizing it with a fluorine-containing monomer, such as the compound represented by formula (M11).

[0092] In equation (M11), X 11 ~X 14 Examples of organic groups having 1 to 20 carbon atoms represented by this formula include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 1 to 20 carbon atoms, and the like.

[0093] Examples of substituted or unsubstituted C1-C20 alkyl groups include alkyl groups, aryl groups, heteroaryl groups, aryloxy groups, heteroaryloxy groups, alkoxy groups, arylalkyl groups, heteroarylalkyl groups, arylalkoxy groups, heteroarylalkoxy groups, carboxyl groups, alkoxycarbonyl groups, carbamoyl groups, acylamino groups, acyloxy groups, and cyano groups.

[0094] If the substituted or unsubstituted C1-C20 organic group is a hydrocarbon group which may have heteroatoms, such as an alkyl group, aryl group, heteroaryl group, aryloxy group, heteroaryloxy group, alkoxy group, arylalkyl group, heteroarylalkyl group, arylalkoxy group, or heteroarylalkoxy group, then the hydrocarbon group may be linear, branched, or cyclic, and may or may not contain unsaturated bonds.

[0095] Examples of acyl groups in acylamino or acyloxy groups include groups obtained by removing a hydroxyl group from a carboxylic acid or sulfonic acid.

[0096] Examples of substituents in C1-C20 organic groups include fluorine atoms, chlorine atoms, hydroxyl groups, alkoxy groups, alkoxyalkyl groups, amino groups, carboxylic acid groups, and sulfonic acid groups.

[0097] Examples of perfluoroalkyl groups include perfluoromethyl group, perfluoroethyl group, perfluoron-propyl group, perfluoroisopropyl group, perfluoron-butyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoron-pentyl group, perfluoron-hexyl group, perfluoron-heptyl group, and perfluoron-octyl group.

[0098] As a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, a monovalent perfluorohydrocarbon group having an oxyperfluoroalkylene structure with 1 to 4 carbon atoms as the unit is more preferably -((CF2) m -O) n A perfluorohydrocarbon group represented by -CF3 is even more preferred. Here, m represents the number of repeating difluoromethylene groups, and each is preferably an integer from 0 to 4. n is -((CF2) m -O)- Represents the number of repetitions of the structure, and is preferably an integer between 1 and 15.

[0099] Compounds represented by formula (M11) include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 1,3,3,3-tetrafluoropropylene, 2,3,3,3-tetrafluoropropylene, 1-chloro-1-fluoroethylene, 1-bromo-1-fluoroethylene, 1-iodo-1-fluoroethylene, 1,1-dibromo-2,2-difluoroethylene, 1,1-difluoro-2,2-diiodoethylene, 1,2-dichloro-1,2-difluoroethylene, 1,2-dibromo-1,2-difluoroethylene, and 1,2-difluoro-1,2-diiodoethylene.

[0100] From the viewpoint of polymerization reactivity when obtaining polymers, the compounds represented by formula (M11) are preferably vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and 2,3,3,3-tetrafluoropropylene.

[0101] The polymer according to the first embodiment can be obtained, for example, by the polymerization method for the polymer according to the fourth embodiment, which will be described later.

[0102] ≪Second Embodiment≫ <polymer> The polymer according to the second embodiment is obtained by polymerizing at least a tellurium-containing compound represented by the following formula (M2).

[0103] [ka]

[0104] In formula (M2), X 2 , Y 2 , and Z 2 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X 2 , Y 2 , and Z 2 At least one of them represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group. R 2 This represents an organic group with 1 to 20 carbon atoms.

[0105] R in equation (M2) 2 For details, see R in equation (M1) above. 1 The details are the same as above.

[0106] In equation (M1), X 1 , Y 1 , and Z 1 Instead of at least one of being a fluorine atom, in formula (M2) X 2, Y 2 , and Z 2 Except that at least one of them is a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group, X in formula (M2) 2 , Y 2 , and Z 2 For details, see X in equation (M1). 1 , Y 1 , and Z 1 The details are the same as above.

[0107] Examples of perfluoroalkyl groups include perfluoromethyl group, perfluoroethyl group, perfluoron-propyl group, perfluoroisopropyl group, perfluoron-butyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoron-pentyl group, perfluoron-hexyl group, perfluoron-heptyl group, and perfluoron-octyl group.

[0108] Examples of monovalent hydrocarbon groups having an oxyperfluoroalkylene structure include perfluorohydrocarbon groups whose constituent units are oxyperfluoroalkylene structures having 1 to 4 carbon atoms.

[0109] The phenyl group may or may not have substituents, but it is preferable that it is unsubstituted. Examples of substituents include substituted or unsubstituted alkyl groups, substituted or unsubstituted monovalent hydrocarbon groups having an oxyalkylene structure, halogen atoms, hydroxyl groups, alkoxy groups, amino groups, nitro groups, cyano groups, carbonyl-containing groups, sulfonyl groups, and trifluoromethyl groups, with unsubstituted alkyl groups, perfluoroalkyl groups, unsubstituted monovalent hydrocarbon groups having an oxyalkylene structure, and monovalent hydrocarbon groups having an oxyperfluoroalkylene structure being preferred.

[0110] Compounds represented by formula (M2) include (1-chlorodifluorovinyl)phenylterlide, (2-nonafluorobutylvinyl)phenylterlide, (1-chlorovinyl)phenylterlide, (2-chlorovinyl)phenylterlide, and (1-phenylvinyl)phenylterlide.

[0111] The method for producing the tellurium-containing compound represented by formula (M2) is not particularly limited. For example, the compound represented by formula (M2) is CX 2 Y 2 =CZ 2 Li represents vinyl lithium and R 2 It is obtained by preparing TeBr and reacting the two. Here, X 2 , Y 2 , Z 2 , and R 2 These are X in equation (M2), respectively. 2 , Y 2 , Z 2 , and R 2 It is the same as above. An example of a specific synthesis scheme is similar to the example of a method for producing the tellurium-containing compound represented by formula (M1) in the first embodiment.

[0112] The polymer according to the second embodiment may be a homopolymer or copolymer of a tellurium-containing compound represented by formula (M2). The copolymer may be a block copolymer, a random copolymer, or an alternating copolymer.

[0113] In one embodiment, the polymer may be a copolymer obtained by polymerizing a tellurium-containing compound represented by formula (M2) and a polymerizable compound that, unlike the tellurium-containing compound represented by formula (M2), has a carbon-carbon double bond in its molecule (hereinafter also referred to as the "second copolymer monomer"). The second copolymer monomer may be used alone or in combination of two or more types.

[0114] The second copolymer monomer is not particularly limited. The details of the second copolymer monomer are the same as those of the first copolymer monomer, 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).

[0115] In one embodiment, the second copolymer monomer may be a compound represented by formula (M11) described above. The compound represented by formula (M2) can introduce branched chains into a fluorine-containing polymer by copolymerizing it with a fluorine-containing monomer, such as the compound represented by formula (M11).

[0116] The polymer according to the second embodiment can be obtained, for example, by the polymer manufacturing method according to the fifth embodiment described later.

[0117] ≪Third Embodiment≫ <polymer> The polymer according to the third embodiment is obtained by polymerizing at least a tellurium-containing compound represented by the following formula (M3) and a compound represented by the following formula (M11).

[0118] [ka]

[0119] In formula (M3), X 3 , Y 3 , and Z 3 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms. R 3 This represents an organic group with 1 to 20 carbon atoms.

[0120] [ka]

[0121] In formula (M11), X 11 ~X 14Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X 11 ~X 14 At least one of these represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.

[0122] R in equation (M3) 3 For details, see R in equation (M1). 1 The details are the same as above.

[0123] In equation (M1), X 1 , Y 1 , and Z 1 In addition to the fact that at least one of the atoms is a fluorine atom, the X in equation (M3) is not subject to such restrictions. 3 , Y 3 , and Z 3 For details, see X in equation (M1). 1 , Y 1 , and Z 1 The details are the same as above.

[0124] The method for producing the tellurium-containing compound represented by formula (M3) is not particularly limited. For example, the compound represented by formula (M3) is CX 3 Y 3 =CZ 3 Li represents vinyl lithium and R 3 It is obtained by preparing TeBr and reacting the two. Here, X 3 , Y 3 , Z 3 , and R 3 These are X in equation (M3), respectively. 3 , Y 3 , Z 3 , and R 3 It is the same as above. An example of a specific synthesis scheme is similar to the example of a method for producing the tellurium-containing compound represented by formula (M1) in the first embodiment.

[0125] The details of the compound represented by formula (M11) are as described above.

[0126] The polymer according to the third embodiment can be obtained, for example, by the polymer manufacturing method according to the sixth embodiment described later.

[0127] ≪Fourth Embodiment≫ <Method for producing polymers> The method for producing a polymer according to the fourth embodiment includes polymerizing a tellurium-containing compound according to at least the first embodiment, i.e., a tellurium-containing compound represented by formula (M1), in the presence of at least one compound selected from the group consisting of a compound represented by the following formula (T1) and a compound represented by the following formula (T2).

[0128] [ka]

[0129] In formula (T1), R 6 R represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms. 7 and R 8 Each of these independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 9 This represents a hydrogen atom, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C16 aryl group, a C2-C8 acyl group, a C2-C8 amide group, an oxycarbonyl-containing group, or a cyano group.

[0130] [ka]

[0131] In formula (T2), R 10 This represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or an substituted or unsubstituted aryl group having 3 to 16 carbon atoms.

[0132] The polymer production method according to the fourth embodiment is a polymer production method in which at least one tellurium-containing compound according to the first embodiment is polymerized using the TERP method, with at least one compound selected from the group consisting of compounds represented by formula (T1) and compounds represented by formula (T2) as a chain transfer agent. This production method yields a polymer having a controlled molecular structure and a branched structure.

[0133] (The compound represented by formula (T1)) In equation (T1), R 6 The bases indicated by are specifically as follows: Examples of unsubstituted alkyl groups having 1 to 8 carbon atoms include linear, branched, or cyclic alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Among these, linear or branched alkyl groups having 1 to 4 carbon atoms are preferred, with methyl, ethyl, or n-butyl groups being more preferred.

[0134] Examples of substituted alkyl groups having 1 to 8 carbon atoms include alkyl groups having substituents such as fluorine atoms, chlorine atoms, alkoxy groups, and fluoroalkoxy groups at arbitrary positions. Among these, alkyl groups having 2 to 13 fluorine atoms are preferred, and (perfluoroalkyl)ethyl groups having 3 to 8 carbon atoms are more preferred from the viewpoint of suppressing hydrogen atom abstraction reactions by radicals.

[0135] Examples of unsubstituted aryl groups having 3 to 16 carbon atoms include homoaryl groups such as phenyl and naphthyl groups; and heteroaryl groups such as pyridyl, pyrrole, furyl, and thienyl groups. Among these, homoaryl groups are preferred, and phenyl groups are more preferred.

[0136] Substitutive aryl groups with 3 to 16 carbon atoms can include halogen atoms, hydroxyl groups, alkoxy groups, amino groups, nitro groups, cyano groups, and -COR groups at any position. aExamples include aryl groups having 1 to 4 substituents, preferably 1 to 3, more preferably 1, preferably at the para or ortho position, such as a carbonyl-containing group, a sulfonyl group, or a trifluoromethyl group. a This represents an alkyl group having 1 to 8 carbon atoms, preferably a linear or branched alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 8 carbon atoms, preferably a linear or branched alkoxy group having 1 to 4 carbon atoms; an aryl group; or an aryloxy group.

[0137] R 7 and R 8 Each of the groups indicated by the symbol is specifically as follows: As a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, the above R 6 Examples of substituted or unsubstituted alkyl groups similar to those shown for substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms are also included. 7 and R 8 Preferably, the element is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0138] R 9 Each of the groups indicated by the symbol is specifically as follows: As substituted or unsubstituted C1-C8 alkyl groups and substituted or unsubstituted C3-C6 aryl groups, the above R 6 Examples of the same groups as those shown are listed below.

[0139] Examples of acyl groups having 2 to 8 carbon atoms include acetyl groups and benzoyl groups.

[0140] Examples of amide groups having 2 to 8 carbon atoms include carbamoyl group-containing groups such as carbamoylmethyl group, dicarbamoylmethyl group, and 4-carbamoylphenyl group; thiocarbamoyl group-containing groups such as thiocarbamoylmethyl group and 4-thiocarbamoylphenyl group; and N-substituted carbamoyl group-containing groups such as dimethylcarbamoylmethyl group.

[0141] As for oxycarbonyl-containing groups, -COOR b The group shown is the group represented by . Here, Rb represents a hydrogen atom; an alkyl group having 1 to 8 carbon atoms, preferably a linear or branched alkyl group having 1 to 4 carbon atoms; an alkenyl group having 2 to 8 carbon atoms, preferably a linear or branched alkenyl group having 2 to 4 carbon atoms; an alkynyl group having 2 to 8 carbon atoms, preferably a linear or branched alkynyl group having 2 to 4 carbon atoms; or an aryl group having 3 to 12 carbon atoms.

[0142] R b The alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkynyl group having 2 to 8 carbon atoms, and aryl group having 3 to 12 carbon atoms represented by b may each have 1 to 4, preferably 1 to 3, more preferably 1 substituent such as a 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 have no substituent.

[0143] Examples of the oxycarbonyl-containing group include a carboxy group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentoxycarbonyl group, phenoxycarbonyl group, etc. Among them, a methoxycarbonyl group or an ethoxycarbonyl group is preferred.

[0144] Among these, R 9 is preferably an aryl group having 5 to 12 carbon atoms, an alkoxycarbonyl group, or a cyano group.

[0145] In a preferred embodiment, the compound represented by formula (T1) may be a compound in which R 6 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, R 7 and R 8 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 9 is an aryl group having 5 to 12 carbon atoms or an alkoxycarbonyl group.

[0146] In a particularly preferred embodiment, the compound represented by formula (T1) is R 6 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, R 7 and R 8 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 9 may be a compound represented by a phenyl group, a methoxycarbonyl group or an ethoxycarbonyl group.

[0147] Specific examples of the compound represented by formula (T1) include (methylteranylmethyl)benzene, (methylteranylmethyl)naphthalene, ethyl-2-methyl-2-methylteranyl-propionate, ethyl-2-methyl-2-n-butylteranyl-propionate, (2-trimethylsiloxyethyl)-2-methyl-2-methylteranyl-propinate, (2-hydroxyethyl)-2-methyl-2-methylteranyl-propinate, (3-trimethylsilylpropargyl)-2-methyl-2-methylteranyl-propinate, etc., and compounds described in International Publication No. 2004 / 014848 and International Publication No. 2004 / 014962. Further, compounds such as ethyl-2-methyl-2-1H,1H,2H,2H-heptadecafluorodecylteranyl-propionate, methyl-2-methyl-2-1H,1H,2H,2H-heptadecafluorodecylteranyl-propionate, N,N-diethyl-2-methyl-2-1H,1H,2H,2H-heptadecafluorodecylteranyl-propionamide described in the presentation number 2D03 of Polymer Preprints, Japan Vol. 65, No. 1 (2016) are included. The compound represented by formula (T1) may be used alone or in combination of two or more.

[0148] The method for producing the compound represented by formula (T1) is not particularly limited, and it can be produced by known methods described in International Publication No. 2004 / 014848, International Publication No. 2004 / 014962, and International Publication No. 2018 / 164147.

[0149] (Compound represented by formula (T2)) In formula (T2), R10 For further details, see R in equation (T1) above, independently. 6 The details are the same as above. In a preferred embodiment, the compound represented by formula (T2) is R 10 Each of these may independently be represented by an alkyl group or phenyl group having 1 to 4 carbon atoms.

[0150] Examples of compounds represented by formula (T2) include dimethyl diterlide, diethyl diterlide, di-n-propyl diterlide, diisopropyl diterlide, dicyclopropyl diterlide, di-n-butyl diterlide, di-sec-butyl diterlide, di-tert-butyl diterlide, dicyclobutyl diterlide, diphenyl diterlide, bis-(p-methoxyphenyl) diterlide, bis-(p-aminophenyl) diterlide, bis-(p-nitrophenyl) diterlide, bis-(p-cyanophenyl) diterlide, bis-(p-sulfonylphenyl) diterlide, dinaphthyl diterlide, and dipyridyl diterlide. Compounds represented by formula (T2) may be used individually or in combination of two or more.

[0151] Among these, dimethyl diterlide, diethyl diterlide, di-n-propyl diterlide, di-n-butyl diterlide, or diphenyl diterlide are preferred.

[0152] (Other optional components) In the polymer production method according to the fourth embodiment, other components such as a radical initiator, solvent, emulsifier, suspension aid, acid, or alkali may be used further.

[0153] -Radical initiator- Examples of radical initiators include azo radical initiators and peroxide radical initiators. Radical initiators may be used individually or in combination of two or more.

[0154] Examples of azo radical initiators include 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (AMBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1'-azobis(1-cyclohexanecarbonitride) (ACHN), dimethyl-2,2'-azobisisobutyrate (MAIB), 4,4'-azobis(4-cyanovaleric acid) (ACVA), 1,1'-azobis(1-acetoxy-1-phenylethane), 2,2'-azobis(2-methylbutylamide), and 2,2' Examples include -azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylamidinopropane) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2,4,4-trimethylpentane), 2-cyano-2-propylazoformamide, 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide).

[0155] Examples of peroxide-based radical initiators include diisopropyl peroxydicarbonate, tert-butyl peroxypivalate, and benzoyl peroxide.

[0156] -solvent- Examples of solvents include organic solvents and aqueous solvents. The solvent may be used alone or in combination of two or more types.

[0157] Examples of organic solvents include benzene, toluene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, hexafluoroisopropanol, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, 1H-perfluorohexane, 1H,1H,1H,2H,2H-perfluorooctane, trifluoromethylbenzene, 1,3-bis(trifluoromethyl)benzene, 1,4-bis(trifluoromethyl)benzene, benzotrifluoride, and chlorobenzene. In addition, ionic liquids such as N-methyl-N-methoxymethylpyrrolidium tetrafluoroborate, N-methyl-N-ethoxymethyl tetrafluoroborate, 1-methyl-3-methylimidazolium tetrafluoroborate, 1-methyl-3-methylimidazolium hexafluorophosphate, and 1-methyl-3-methylimidazolium chloride may be used.

[0158] Examples of aqueous solvents include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol.

[0159] In one embodiment, the method for producing the polymer according to the fourth embodiment includes polymerizing a tellurium-containing compound according to the first embodiment (i.e., a tellurium-containing compound represented by formula (M1)) and a polymerizable compound having a carbon-carbon double bond in its molecule, unlike the tellurium-containing compound according to the first embodiment (i.e., the first copolymer monomer in the first embodiment). Details of the first copolymer monomer are as described above.

[0160] [Polymerization method] A specific example of a polymerization method in the polymer manufacturing method according to the fourth embodiment is described below. In a container purged with an inert gas or under vacuum, at least one compound selected from the group consisting of the compound represented by formula (T1) and the compound 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. A radical initiator such as an azo polymerization initiator may be used in combination to accelerate the polymerization rate.

[0161] The amount of compound represented by formula (T1) or formula (T2) (the total of the compounds represented by formula (T1) and formula (T2) when used in combination) used per 1 mol of the compound having a reactive carbon-carbon double bond (i.e., the total of the tellurium-containing compound represented by formula (M1) and the first copolymer monomer used as needed) 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 amount used is preferably 1 mol or less, more preferably 0.5 mol or less, and even more preferably 0.1 mol or less.

[0162] When an azo polymerization initiator is used in combination, the amount of azo polymerization initiator used per 1 mol of the compound represented by formula (T1) or formula (T2) (or the total amount when both compounds are used in combination) is preferably 0.01 mol or more, more preferably 0.05 mol or more, and even more preferably 0.1 mol or more. Furthermore, the amount used is preferably 50 mol or less, more preferably 10 mol or less, and even more preferably 5 mol or less.

[0163] When using the compound represented by formula (T1) and the compound represented by formula (T2) in combination, the amount of the compound represented by formula (T2) used relative to 1 mol of the compound represented by formula (T1) is preferably 0.01 mol or more, more preferably 0.05 mol or more, and even more preferably 0.1 mol or more. Also, the amount is preferably 100 mol or less, more preferably 10 mol or less, and even more preferably 5 mol or less.

[0164] The above polymerization reaction can be carried out without a solvent, but can also be carried out using an organic solvent or an aqueous solvent generally used in radical polymerization.

[0165] The amount of the solvent used can be adjusted appropriately. For example, the amount of the solvent relative to 1000 g of the resulting polymer is preferably 0.01 L or more, more preferably 0.05 L or more, and even more preferably 0.1 L or more. Also, the amount of the solvent relative to 1000 g of the resulting polymer is preferably 50 L or less, more preferably 10 L or less, and even more preferably 5 L or less.

[0166] Next, the mixture obtained above is stirred. The reaction temperature and reaction time may be appropriately adjusted according to the molecular weight or molecular weight distribution of the resulting polymer, and it may be stirred at 60°C to 150°C for 5 hours to 100 hours. Or, it may be stirred at 80°C to 120°C for 10 hours to 30 hours. The reaction may be carried out at normal pressure, or under pressure or reduced pressure.

[0167] After the reaction is completed, the target polymer is taken out by removing the used solvent, residual monomer, etc. under reduced pressure by a conventional method, or the target polymer is isolated by reprecipitation treatment using a solvent in which the target polymer is insoluble. Regarding the reaction treatment, any treatment method can be used as long as there is no hindrance to the target product.

[0168] By such a polymerization method, excellent molecular weight control and molecular weight distribution control can be carried out under very mild conditions.

[0169] A block copolymer, an alternating copolymer, or a random copolymer may be prepared using a tellurium-containing compound represented by formula (M1) and the first copolymer monomer.

[0170] Examples of the reaction schemes for homopolymerization and copolymerization in the fourth embodiment are shown below. In the figure below, In represents a structure derived from the radical initiator, and R represents R 1 or R 6 This represents the number of constituent units, where x, y, z, x1, x2, y1, y2, z1, z2, and n each independently represent the number of constituent units. Note that when there are multiple constituent units enclosed in curly braces ([]), the arrangement of these constituent units may be random.

[0171] [ka]

[0172] [ka]

[0173] Even when the compound represented by (T2) is used instead of the compound represented by (T1) as a chain transfer agent, homopolymerization and copolymerization are possible using a reaction scheme similar to that described above.

[0174] ≪Fifth Embodiment≫ <Method for producing polymers> The polymer production method according to the fifth embodiment includes polymerizing a tellurium-containing compound represented by at least the following formula (M2) in the presence of at least one compound selected from the group consisting of a compound represented by the following formula (T1) and a compound represented by the following formula (T2).

[0175] [ka]

[0176] In formula (T1), R 6R represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms. 7 and R 8 Each of these independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 9 This represents a hydrogen atom, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C16 aryl group, a C2-C8 acyl group, a C2-C8 amide group, an oxycarbonyl-containing group, or a cyano group.

[0177] [ka]

[0178] In formula (T2), R 10 This represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or an substituted or unsubstituted aryl group having 3 to 16 carbon atoms.

[0179] [ka]

[0180] In formula (M2), X 2 , Y 2 , and Z 2 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X 2 , Y 2 , and Z 2 At least one of them represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group. R 2 This represents an organic group with 1 to 20 carbon atoms.

[0181] The polymer production method according to the fifth embodiment is a polymer production method that polymerizes at least one compound represented by formula (M2) using a chain transfer agent selected from the group consisting of compounds represented by formula (T1) and compounds represented by formula (T2) based on the TERP method. This production method yields a polymer having a controlled molecular structure and a branched structure. The resulting polymer may be the polymer according to the second embodiment.

[0182] Details of the compound represented by formula (T1), the compound represented by formula (T2), and the compound represented by formula (M2) are as described above.

[0183] In the polymer production method according to the fifth embodiment, other components such as radical initiators, solvents, emulsifiers, suspension aids, acids, or alkalis may be used. Details of the optional components are as described above.

[0184] In one embodiment, the method for producing a polymer according to the fifth embodiment includes polymerizing a tellurium-containing compound represented by formula (M2) with a polymerizable compound having a carbon-carbon double bond in its molecule, unlike the tellurium-containing compound represented by formula (M2) (i.e., a second copolymer monomer). Details of the second copolymer monomer are as described above.

[0185] [Polymerization method] The specific polymerization method in the polymer production method according to the fifth embodiment is the same as the polymerization method described in the fourth embodiment. However, “tellurium-containing compound represented by formula (M1)” is read as “tellurium-containing compound represented by formula (M2)” and “first copolymer monomer” is read as “second copolymer monomer”.

[0186] ≪Sixth Embodiment≫ <Method for producing polymers> The method for producing a polymer according to the sixth embodiment includes polymerizing at least a tellurium-containing compound represented by the following formula (M3) and a compound represented by the following formula (M11) in the presence of at least one compound selected from the group consisting of a compound represented by the following formula (T1) and a compound represented by the following formula (T2).

[0187] [ka]

[0188] In formula (T1), R 6 R represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms. 7 and R 8 Each of these independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 9 This represents a hydrogen atom, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C16 aryl group, a C2-C8 acyl group, a C2-C8 amide group, an oxycarbonyl-containing group, or a cyano group.

[0189] [ka]

[0190] In formula (T2), R 10 This represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or an substituted or unsubstituted aryl group having 3 to 16 carbon atoms.

[0191] [ka]

[0192] In formula (M3), X 3 , Y 3 , and Z 3 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms. R 3 This represents an organic group with 1 to 20 carbon atoms.

[0193] [ka]

[0194] In formula (M11), X 11 ~X 14 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X 11 ~X 14 At least one of these represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.

[0195] The polymer production method according to the sixth embodiment is a polymer production method based on the TERP method, in which at least one compound selected from the group consisting of compounds represented by formula (T1) and compounds represented by formula (T2) is used as a chain transfer agent to copolymerize at least a tellurium-containing compound represented by formula (M3) and a compound represented by formula (M11). This production method yields a polymer obtained by polymerizing fluorine-containing monomers having a controlled molecular structure and a branched structure. The resulting polymer may be the polymer according to the third embodiment.

[0196] Details of the compound represented by formula (T1), the compound represented by formula (T2), the compound represented by formula (M3), and the compound represented by formula (M11) are as described above.

[0197] In the polymer production method according to the sixth embodiment, other components such as radical initiators, solvents, emulsifiers, suspension aids, acids, or alkalis may be used. Details of the optional components are as described above.

[0198] [Polymerization method] The specific polymerization method in the polymer production method according to the sixth embodiment is the same as the polymerization method described in the fourth embodiment. However, “the tellurium-containing compound represented by formula (M1)” is read as “the tellurium-containing compound represented by formula (M3),” and “the first copolymer monomer” is read as “the compound represented by formula (M11).” In addition, at least the tellurium-containing compound represented by formula (M3) and the compound represented by formula (M11) are copolymerized. [Examples]

[0199] The embodiments of this disclosure will be specifically described below with reference to examples, but the embodiments of this disclosure are not limited to these examples.

[0200] In the following examples, nuclear magnetic resonance (NMR) spectra were measured using Fourier transform NMR. 1 ¹H-NMR was measured at 300 MHz, with tetramethylsilane as the reference for a chemical shift value of 0 ppm. 19 F-NMR was measured at 282 MHz using 1,4-bis(trifluoromethyl)benzene as a reference with a chemical shift value of -63.9 ppm. The abbreviations used in this text have the following meanings. s: singlet d: doublet t: Triplet m: multiplet Hz: Hertz CDCl3: Deuterated chloroform THF-d 10 : d 10 - Tetrahydrofuran 1 H-NMR: Proton Nuclear Magnetic Resonance 19 F-NMR: Fluorine-19 Nuclear Magnetic Resonance

[0201] In the following examples, mass spectra (MS) were measured using GC / MS (gas chromatograph-mass spectrometer). Electron ionization (EI) was used as the ionization method. The ionization mode used was positive mode (EI+). The data presented are the measured values ​​(found).

[0202] (Example 1) Synthesis of phenyl(trifluorovinyl) tellurides (CF2=CFTePh) 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 freeze-degassed diethyl ether was added, and the internal temperature was cooled to -78°C while stirring. Under a nitrogen atmosphere, 100 mL (1.6 mol / L, 0.1 6m A solution of n-butyllithium / hexane (1 / 4) was added and stirred for 30 minutes while maintaining the internal temperature at -78°C. This solution is denoted as A. A magnetic rotor and 15 g (36 mmol) of diphenyl diterlide were added to a 100 mL glass flask, and the interior was purged with nitrogen. Under a nitrogen atmosphere, 45 g of freeze-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 denoted as B. A magnetic rotor was added to a 500 mL glass flask, and the inside was purged with nitrogen. Under a nitrogen atmosphere, 128 g of freeze-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 at a constant rate over 30 minutes, and the mixture was stirred for 2 hours while maintaining the internal temperature. Under a nitrogen atmosphere, the entire amount of B was added at a constant rate over 30 minutes, and the mixture was stirred for 30 minutes while maintaining the internal temperature at -78°C. The internal temperature was 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. The reaction vessel was opened in a nitrogen-purged glove box, and the reaction mixture was filtered by suction 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 removed under reduced pressure, and the residue was purified by vacuum distillation to obtain the title compound as an oily substance of 5.7 g. 1 H NMR (300MHz, CDCl3) δ7.25-7.64 (5H, m) 19 F NMR (282MHz, CDCl3) δ-88.3(1F, dd), δ-105.6(1F, dd), δ-157.7(1F, dd) MS(EI+):[M+]288.0

[0203] (Example 2) Synthesis of (2,2-difluorovinyl)phenyl tellide (CF2=CHTePh) 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 freeze-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 s-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 denoted as A. A magnetic rotor and 5.5 g (14 mmol) of diphenyl diterlide were added to a 100 mL glass flask, and the interior was purged with nitrogen. Under a nitrogen atmosphere, 45 g of freeze-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 denoted as B. A magnetic rotor was added to a 300 mL glass flask, and the inside was purged with nitrogen. Under a nitrogen atmosphere, 60 g of freeze-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 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 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 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 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. The reaction vessel was opened in a nitrogen-purged glove box, and the reaction mixture was filtered by suction to remove solids. The filtrate was washed three times with deionized water to recover the organic phase. The solvent of the organic phase was removed under reduced pressure, and the residue was purified by vacuum distillation to obtain the title compound as an oily substance of 1.1 g. 1 H NMR (300MHz, CDCl3) δ5.41 (1H, dd), δ7.20-7.32 (4H, m), δ7.68 (2H, dd), 19 F NMR (282MHz, CDCl3) δ -66.9 (1F, dd), -71.4 (1F, dd) MS(EI+):[M+]270.0

[0204] (Example 3) Preparation of 1-bromo-1-chlorodifluoroethylene (structural formula: CF2=CClBr) 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 sodium hydroxide aqueous 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 obtain 2.1 g of the title compound as a liquid. This compound was not further purified and was used in the next step. MS(EI+):[M+]176.0

[0205] Synthesis of (1-chlorodifluorovinyl)phenylterlide (CF2=CClTePh) 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 freeze-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 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 denoted as A. A magnetic rotor and 2.0 g (4.8 mmol) of diphenyl diterlide were added to a 50 mL glass flask, and the interior was purged with nitrogen. Under a nitrogen atmosphere, 13 g of freeze-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 denoted as B. A magnetic rotor was added to a 300 mL glass flask, and the inside was purged with nitrogen. Under a nitrogen atmosphere, 86 g of freeze-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 at a constant rate over 30 minutes, and the mixture was stirred for 1 hour while maintaining the internal temperature. Under a nitrogen atmosphere, the entire amount of B was added at a constant rate over 30 minutes, and the mixture was stirred for 1 hour while maintaining the internal temperature. The internal temperature was 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. The reaction vessel was opened in a nitrogen-purged glove box, and the reaction mixture was filtered by suction to remove solids. The filtrate was washed three times with deionized water to recover the organic phase. The solvent of the organic phase was removed under reduced pressure, and the residue was purified by vacuum distillation to obtain the title compound as an oily substance of 0.5 g. 1 H NMR (300MHz, CDCl3) δ7.19-7.56 (5H, m) 19F NMR (282MHz, CDCl3) δ -83.4 (1F, dd), -84.4 (1F, d) MS(EI+):[M+]304.0

[0206] (Example 4) Synthesis of butyl (trifluorovinyl) telluride (CF2=CFTeBu) The title compound was obtained as a liquid in the same manner as in Example 1, except that diphenyl diterlide in Example 1 was replaced with dibutyl diterlide. 1 H NMR (300MHz, CDCl3)δ1.0(1H, t) 19 F NMR (282MHz, CDCl3) δ-86.8(1F, dd), δ-106.1(1F, dd), δ-156.6(1F, dd) MS(EI+):[M+]268.0

[0207] Example 5 below is an example that is expected to be synthesizable based on the knowledge in this disclosure and known methods.

[0208] (Example 5) Synthesis of methyl(trifluorovinyl)terlide (CF2=CFTeMe) The title compound is obtained as an oily substance in the same manner as in Example 1, except that diphenyl diterlide is replaced with dimethyl diterlide.

[0209] (Example 6) Copolymerization of phenyltrifluorovinyl telluride and chlorotrifluoroethylene In a nitrogen-purged glove box, a 30 mL stainless steel autoclave with a stirrer was charged with 0.061 g (0.27 mmol) of the azo radical initiator "V-601" (Fujifilm Wako Pure Chemical Corporation), 0.055 g (0.13 mmol) of diphenyl diterlide, 1.2 g (4.0 mmol) of phenyl (trifluorovinyl)terlide synthesized in Example 1, and 11 g of benzotrifluoride. After injecting 3.3 g (28 mmol) of chlorotrifluoroethylene under pressure, stirring was started while raising the internal temperature to 80°C. Stirring was continued at 200 rpm (200 revolutions per minute) for 7 hours while maintaining the internal temperature. After cooling the autoclave in an ice bath, the unreacted chlorotrifluoroethylene was purged.

[0210] The obtained polymer solution was vacuum-dried to obtain an oily substance. This oily substance was added to 40 mL of freeze-degassed methanol in a nitrogen-purged glove box and stirred for 5 minutes, after which the oily substance and supernatant were separated using a centrifuge. The obtained oily substance was vacuum-dried to obtain 0.2 g of oily substance. The oily substance obtained 19 When 1F-NMR was measured, a peak was observed at δ-177 ppm. Since this is attributed to a fluorine atom bonded to a tertiary carbon atom, it was indicated that the polymer has a branched main chain skeleton. Here, a tertiary carbon atom refers to a carbon atom directly bonded to three other carbon atoms.

[0211] (Example 7) Copolymerization of butyl trifluorovinyl telluride and tetrafluoroethylene In a nitrogen-purged glove box, a 30 mL stainless steel autoclave with a stirrer was charged with 0.038 g (0.17 mmol) of the azo radical initiator "V-601" (Fujifilm Wako Pure Chemical Corporation), 0.057 g (0.15 mmol) of dibutyl diterlide, 1.3 g (4.6 mmol) of butyl trifluorovinylterlide synthesized in Example 4, and 13 g of 1H-perfluorohexane. After injecting 5.0 g (50 mmol) of tetrafluoroethylene under pressure, the reaction was initiated by stirring while raising the internal temperature to 72°C. Stirring was continued at 200 rpm for 7 hours while maintaining the internal temperature. After cooling the autoclave in an ice bath, the unreacted tetrafluoroethylene was purged.

[0212] The obtained polymer solution was vacuum-dried to obtain a solid. This solid was added to 40 mL of freeze-degassed methanol in a nitrogen-purged glove box and stirred for 5 minutes, after which the solid and supernatant were separated using a centrifuge. The obtained solid was vacuum-dried to obtain 0.5 g of solid.

[0213] Examples 8-13 below are examples that are expected to be synthesizable based on the findings of this disclosure and known methods. Since all of these examples use highly reactive fluorine-containing monomers as copolymer monomers, it is considered that copolymers can be suitably synthesized.

[0214] (Example 8) Copolymerization of (2,2-difluorovinyl)phenylterlide and chlorotrifluoroethylene In a nitrogen-purged glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with the azo radical initiator "V-601" (Fujifilm Wako Pure Chemical Corporation), diphenyl diterlide, (2,2-difluorovinyl)phenylterlide synthesized in Example 2, benzotrifluoride, and chlorotrifluoroethylene. The reaction was then carried out by stirring while raising the internal temperature to 80°C.

[0215] (Example 9) Copolymerization of (1-chlorodifluorovinyl)phenylterlide and chlorotrifluoroethylene In a nitrogen-purged glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with the azo radical initiator "V-601" (Fujifilm Wako Pure Chemical Corporation), diphenyl diterlide, (1-chlorodifluorovinyl)phenylterlide synthesized in Example 3, benzotrifluoride, and chlorotrifluoroethylene. The reaction was then carried out by stirring while raising the internal temperature to 80°C.

[0216] (Example 10) Copolymerization of (2-nonafluorobutylvinyl)phenylterlide and chlorotrifluoroethylene In a nitrogen-purged glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with the azo radical initiator "V-601" (Fujifilm Wako Pure Chemical Corporation), diphenyl diterlide, (2-nonafluorobutylvinyl)phenylterlide synthesized according to known literature, benzotrifluoride, and chlorotrifluoroethylene. The reaction was then carried out by stirring while raising the internal temperature to 80°C.

[0217] (Example 11) Copolymerization of (1-chlorovinyl)phenylterlide and chlorotrifluoroethylene In a nitrogen-purged glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with the azo radical initiator "V-601" (Fujifilm Wako Pure Chemical Corporation), diphenyl diterlide, (1-chlorovinyl)phenylterlide synthesized according to known literature, benzotrifluoride, and chlorotrifluoroethylene. The reaction was then carried out by stirring while raising the internal temperature to 80°C.

[0218] (Example 12) Copolymerization of (2-chlorovinyl)phenylterlide and chlorotrifluoroethylene In a nitrogen-purged glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with the azo radical initiator "V-601" (Fujifilm Wako Pure Chemical Corporation), diphenyl diterlide, (2-chlorovinyl)phenylterlide synthesized according to known literature, benzotrifluoride, and chlorotrifluoroethylene. The reaction was then carried out by stirring while raising the internal temperature to 80°C.

[0219] (Example 13) Copolymerization of (1-phenylvinyl)phenylterlide and chlorotrifluoroethylene In a nitrogen-purged glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with the azo radical initiator "V-601" (Fujifilm Wako Pure Chemical Corporation), diphenyl diterlide, (1-phenylvinyl)phenylterlide synthesized according to known literature, benzotrifluoride, and chlorotrifluoroethylene. The reaction was then carried out by stirring while raising the internal temperature to 80°C.

[0220] The disclosure of Japanese Patent Application No. 2020-207031 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted as being incorporated by reference.

Claims

1. A polymer obtained by polymerizing at least a tellurium-containing compound represented by the following formula (M1) and a polymerizable compound having a carbon-carbon double bond in its molecule, unlike the tellurium-containing compound, wherein the polymerizable compound is a compound represented by the following formula (M11). 【Chemistry 1】 In formula (M1), X １ , Y １ , and Z １ Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 20 carbon atoms, X １ , Y １ , and Z １ At least one of them represents a fluorine atom, R １ This represents an organic group with 1 to 20 carbon atoms. 【Chemistry 2】 In formula (M11), X11 to X14 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, and at least one of X11 to X14 represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.

2. In the above formula (M1), R １ The polymer according to claim 1, wherein is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1-C20 monovalent hydrocarbon group having an oxyalkylene structure, or a substituted or unsubstituted C3-C20 aryl group.

3. In the formula (M1), X １ , Y １ , and Z １ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a monovalent hydrocarbon group having 1 to 20 carbon atoms and having a substituted or unsubstituted oxyalkylene structure, or a substituted or unsubstituted aryl group having 3 to 20 carbon atoms, The polymer according to claim 1 or claim 2.

4. The present invention comprises polymerizing at least one compound selected from the group consisting of a compound represented by the following formula (T1) and a compound represented by the following formula (T2), a tellurium-containing compound as defined in any one of claims 1 to 3, and a polymerizable compound that, unlike the tellurium-containing compound, has a carbon-carbon double bond in its molecule, in the presence of at least one compound selected from the group consisting of a compound represented by the following formula (T1) and a compound represented by the following formula (T2), A method for producing a polymer, wherein the polymerizable compound is a compound represented by the following formula (M11). 【Transformation 3】 In formula (T1), R ６ R represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 3 to 16 carbon atoms. ７ and R ８ Each of these independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. ９ This represents a hydrogen atom, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C16 aryl group, a C2-C8 acyl group, a C2-C8 amide group, an oxycarbonyl-containing group, or a cyano group. 【Chemistry 4】 In formula (T2), R １０ This represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or an substituted or unsubstituted aryl group having 3 to 16 carbon atoms. 【Transformation 5】 In formula (M11), X11 to X14 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, and at least one of X11 to X14 represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.

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