Tellurium-containing compounds, polymers, and methods for producing polymers

Abstract

Provided are novel tellurium-containing compounds that have a controlled molecular structure and can be used to prepare polymers having a branched structure, and polymers prepared using the tellurium-containing compounds. The present invention provides 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 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 X represents a fluorine atom; 2 , Y 2 , and Z 2 At least one of R represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group; 1 ~R 3 represents an organic group having 1 to 20 carbon atoms. JPEG2026043011000054.jpg25159

Description

[Technical Field]

[0001] The present disclosure relates to tellurium-containing compounds, polymers, and methods for making polymers. [Background technology]

[0002] Radical polymerization reactions are widely used industrially because of their excellent monomer versatility and their ease of use in polar media such as water. However, conventional radical polymerization methods offer limited control over molecular weight, and the resulting polymers tend to have broad molecular weight distributions. Living radical polymerization, on the other hand, has attracted attention as a polymerization method that can produce 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 propagating radicals with dormant protecting groups, thereby enabling control of molecular weight distribution.

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

[0004] In recent years, the development of polymers with branched structures within their molecules has become increasingly important. Branched polymers have various properties that differ from those of linear polymers. For example, because branched polymers have many terminal groups, when used as molding materials, they can increase the crosslink density of molded articles and improve curability. Furthermore, branched polymers are known to have lower intrinsic viscosities and lower glass transition temperatures than linear polymers. Thus, branched polymers have unique properties that differ from those of linear polymers, making them highly useful in industry.

[0005] Non-Patent Document 1 discloses a controlled polymerization method based on the TERP method, in which a highly branched polymer is prepared by copolymerizing vinyl telluride and an acrylic acid monomer in the presence of a tellurium compound as a chain transfer agent. [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) Summary of the Invention [Problem to be solved by the invention]

[0008] However, currently, there is limited knowledge regarding techniques for producing polymers with branched structures by controlled polymerization.

[0009] A first embodiment of the present disclosure relates to providing a novel tellurium-containing compound that can be used to prepare a polymer having a controlled molecular structure and a branched structure, and a polymer prepared using the tellurium-containing compound.

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

[0011] A third embodiment of the present disclosure relates to providing a polymer having a controlled molecular structure and a branched structure, which is obtained by polymerizing a fluorine-containing monomer.

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

[0013] A fifth embodiment of the present 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 the present disclosure relates to providing a method for producing a polymer having a controlled molecular structure and a branched structure, which is obtained by polymerizing a fluorine-containing monomer. [Means for solving the problem]

[0015] Means for solving the above problems include the following aspects. <1> A tellurium-containing compound represented by the following formula (M1):

[0016] [ka]

[0017] 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; X 1 , Y 1 , and Z 1 at least one of represents a fluorine atom, R 1 represents an organic group having 1 to 20 carbon atoms. <2> In the formula (M1), R 1is 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 substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms and an oxyalkylene structure, or a substituted or unsubstituted aryl group having 3 to 20 carbon atoms, <1> The tellurium-containing compound according to claim 1. <3> In the formula (M1), X 1 , Y 1 , and Z 1 each independently represents 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 and an oxyalkylene structure, or a substituted or unsubstituted aryl group having 3 to 20 carbon atoms; <1> or <2> The tellurium-containing compound according to claim 1. <4> at least <1> ~ <3> 1. A polymer obtained by polymerizing the tellurium-containing compound according to any one of claims 1 to 9. <5> The polymerizable compound is obtained by polymerizing the tellurium-containing compound and a polymerizable compound having a carbon-carbon double bond in the molecule, different from the tellurium-containing compound. <4> The polymer according to claim 1. <6> The polymerizable compound is a compound represented by the following formula (M11): <5> A polymer according to claim 1,

[0018] [ka]

[0019] In 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; X 11 ~X 14 At least one of 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] [ka]

[0021] In formula (M2), X 2 , Y 2 , and Z 2 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; X 2 , Y 2 , and Z 2 at least one of represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group; R 2 represents an organic group having 1 to 20 carbon atoms. <8> The polymerizable compound is obtained by polymerizing the tellurium-containing compound and a polymerizable compound having a carbon-carbon double bond in the molecule, different from the tellurium-containing compound. <7> The polymer according to claim 1. <9> The polymerizable compound is a compound represented by the following formula (M11): <8> A polymer according to claim 1,

[0022] [ka]

[0023] In 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; X 11 ~X 14 At least one of 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 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 represents an organic group having 1 to 20 carbon atoms.

[0026] [ka]

[0027] In 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; X 11 ~X 14 At least one of 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 compounds represented by the following formula (T1) and compounds represented by the following formula (T2), <1> ~ <3> A method for producing a polymer, comprising polymerizing the tellurium-containing compound according to any one of claims 1 to 4:

[0028] [ka]

[0029] In formula (T1), R 6 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 R each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 9represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, an amido group having 2 to 8 carbon atoms, an oxycarbonyl-containing group, or a cyano group.

[0030] [ka]

[0031] In formula (T2), R 10 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. <12> <1> ~ <3> and a polymerizable compound having a carbon-carbon double bond in the molecule, different from the tellurium-containing compound. <11> A method for producing the polymer described in <13> The polymerizable compound is a compound represented by the following formula (M11): <12> 2. A method for producing the polymer according to claim 1,

[0032] [ka]

[0033] In 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; X 11 ~X 14 At least one of 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 at least a tellurium-containing compound represented by 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 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 R each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 9 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, an amido group having 2 to 8 carbon atoms, an oxycarbonyl-containing group, or a cyano group.

[0036] [ka]

[0037] In formula (T2), R 10 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.

[0038] [ka]

[0039] In formula (M2), X 2 , Y 2 , and Z 2 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; X 2 , Y 2 , and Z 2 at least one of represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group; R 2 represents an organic group having 1 to 20 carbon atoms. <15> The method includes polymerizing the tellurium-containing compound represented by formula (M2) with a polymerizable compound that has a carbon-carbon double bond in the molecule, different from the tellurium-containing compound represented by formula (M2). <14> A method for producing the polymer described in <16> The polymerizable compound is a compound represented by the following formula (M11): <15> 2. A method for producing the polymer according to claim 1,

[0040] [ka]

[0041] In 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; X 11 ~X 14 At least one of 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 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 R each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 9represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, an amido group having 2 to 8 carbon atoms, an oxycarbonyl-containing group, or a cyano group.

[0044] [ka]

[0045] In formula (T2), R 10 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.

[0046] [ka]

[0047] In formula (M3), X 3 , Y 3 , and Z 3 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, R 3 represents an organic group having 1 to 20 carbon atoms.

[0048] [ka]

[0049] In 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; X 11 ~X 14 At least one of 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 the present disclosure, there are provided a novel tellurium-containing compound that can be used to prepare a polymer having a controlled molecular structure and a branched structure, and a polymer prepared using the tellurium-containing compound.

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

[0052] According to a third embodiment of the present disclosure, there is provided a polymer having a controlled molecular structure and a branched structure, which is obtained by polymerizing a fluorine-containing monomer.

[0053] According to a fourth embodiment of the present disclosure, there is provided a method for producing a polymer having a controlled molecular structure and a branched structure.

[0054] According to a fifth embodiment of the present disclosure, there is provided a method for producing a novel polymer having a controlled molecular structure and a branched structure.

[0055] According to a sixth embodiment of the present disclosure, there is provided a method for producing a polymer having a controlled molecular structure and a branched structure, which is obtained by polymerizing a fluorine-containing monomer. DETAILED DESCRIPTION OF THE INVENTION

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

[0057] In the present disclosure, the term "process" includes not only a process that is independent of other processes, but also a process that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the present disclosure, each component may contain multiple substances corresponding to the component. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, a reactive carbon-carbon double bond means a carbon-carbon double bond that can undergo various reactions as an olefin, and does not include aromatic double bonds. In the present disclosure, unless otherwise specified, organic groups or hydrocarbon groups may or may not have a substituent. In the present disclosure, the number of carbon atoms in a compound or a constituent part thereof means the number including the number of carbon atoms in the substituent when the compound or constituent part has a substituent. In the present disclosure, (meth)acrylic acid is a general term for acrylic acid and methacrylic acid, (meth)acrylate is a general term for acrylate and methacrylate, and (meth)acrylamide is a general term for acrylamide and methacrylamide. In the present disclosure, a "polymer" is a compound formed by polymerizing monomers, i.e., a "polymer" has a plurality of structural units. In this disclosure, unless otherwise specified, the terms "polymerizing compound A" and "polymerizing at least compound A" encompass both polymerizing compound A alone and polymerizing compound A with another compound. Furthermore, the terms "polymerizing compound A and compound B" and "polymerizing at least compound A and compound B" encompass both polymerizing compound A and compound B alone and polymerizing compound A, compound B, and another compound. Here, compound A and compound B represent any compound described in this disclosure that has a carbon-carbon double bond in the molecule. Furthermore, unless otherwise specified, the polymer described in this disclosure may be a homopolymer of one type of compound or a copolymer of two or more types of compounds. In this disclosure, the term "polymer" does not exclude a mixture containing raw materials (monomers, catalysts), by-products, impurities, etc., in addition to the polymer.

[0058] The present disclosure relates to controlled polymerization of tellurium-containing compounds with reactive carbon-carbon double bonds to produce branched polymers. The findings of the present disclosure can be used to obtain branched polymers with controlled molecular architectures. Furthermore, while not limiting the embodiments of the present disclosure, the tellurium-containing compounds, polymers, and polymer production methods described in detail herein have also been found to be useful for the polymerization of fluorine-containing monomers. 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, pp. 101255, discloses that while degenerative chain transfer polymerization of acrylates and styrene was possible in the presence of chain transfer agents such as organostilbenes and organobismuths, there have been no reports of polymerization of fluoroalkenes using organotellurium compounds as chain transfer agents. Furthermore, U.S. Patent Application Publication No. 2013 / 225775 discloses that while controlled polymerization methods have made great progress in the polymerization of common monomers such as (meth)acrylic acid and styrene, they are still ineffective for the polymerization of highly reactive, gaseous fluoroalkenes such as vinylidene fluoride, hexafluoropropene, and tetrafluoroethylene. Furthermore, no findings have been reported so far regarding a method for introducing a branched structure into a polymer molecule in the controlled polymerization of a fluorine-containing monomer. The inventors have found that the tellurium-containing compound, polymer, and method for producing the polymer described in detail in the present disclosure are suitably applicable to the polymerization of a fluorine-containing monomer.

[0059] Each embodiment of the present disclosure will be 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 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 represents a fluorine atom, R 1 represents an organic group having 1 to 20 carbon atoms.

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

[0064] In formula (M1), R 1 represents an organic group having 1 to 20 carbon atoms, and is 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 and a substituted or unsubstituted oxyalkylene structure, or a substituted or unsubstituted aryl group having 3 to 20 carbon atoms. 1 is 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 the unsubstituted alkyl group having 1 to 20 carbon atoms 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. Of these, methyl, ethyl, and n-butyl groups are more preferred. Examples of the substituted alkyl group having 1 to 20 carbon atoms include alkyl groups in which a hydrogen atom at any position in the above-mentioned unsubstituted alkyl group having 1 to 20 carbon atoms is substituted with a substituent such as a fluorine atom, a chlorine atom, an alkoxy group, or a fluoroalkoxy group. Of these, perfluoroalkyl groups are preferred.

[0066] Examples of perfluoroalkyl groups include perfluoromethyl, perfluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-n-butyl, perfluoro-sec-butyl, perfluoro-tert-butyl, perfluoro-n-pentyl, perfluoro-n-hexyl, perfluoro-n-heptyl, and perfluoro-n-octyl groups.

[0067] The monovalent hydrocarbon group having 1 to 20 carbon atoms and a substituted or unsubstituted oxyalkylene structure preferably has 1 to 12 carbon atoms, and more preferably has 1 to 6 carbon atoms. Examples of monovalent hydrocarbon groups having an unsubstituted oxyalkylene structure include hydrocarbon groups having an oxyalkylene structure having 1 to 4 carbon atoms as a constituent unit, and more specifically, -((CH2) m -O) n Here, m represents the number of repeating methylene groups, and each m is preferably an integer of 0 to 4. n is 1 or more -((CH2) m It represents the number of repetitions of the —O)— structure, and is preferably an integer of 1 to 15. Examples of the monovalent hydrocarbon group having a substituted oxyalkylene structure include the above-mentioned monovalent hydrocarbon group having an unsubstituted oxyalkylene structure, in which a hydrogen atom at any position in the oxyalkylene structure is substituted with a substituent such as a fluorine atom, a chlorine atom, an alkoxy group, or a fluoroalkoxy group. For example, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure is preferred, and from the viewpoint of ease of synthesis, a monovalent perfluorohydrocarbon group having an oxyperfluoroalkylene structure unit having 1 to 4 carbon atoms is more preferred, such as -((CF2) m -O) nMore preferred is a perfluorohydrocarbon group represented by -CF3. Here, m represents the number of repeating difluoromethylene groups, and each m is preferably an integer of 0 to 4. n is 1 or more and is -((CF2) m It represents the number of repetitions of the —O)— structure, and is preferably an integer of 1 to 15. In the present disclosure, when a "monovalent hydrocarbon group having an oxyperfluoroalkylene structure" is mentioned, a 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 preferred, and a substituted or unsubstituted aryl group having 3 to 12 carbon atoms is more preferred. Examples of the unsubstituted aryl group having 3 to 20 carbon atoms include homoaryl groups such as a phenyl group and a naphthyl group, and heteroaryl groups such as a pyridyl group, a pyrrole group, a furyl group and a thienyl group. Of these, a homoaryl group is preferred, and a phenyl group is more preferred. 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-mentioned unsubstituted aryl group having 3 to 20 carbon atoms has been 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, a trifluoromethyl group, etc. The number of substituents is not particularly limited and may be 1 to 4, 1 to 3, 1 or 2, or even 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; X 1 , Y 1 , and Z 1 At least one of X represents a fluorine atom. 1 , Y 1 , and Z 1are preferably each 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 and an oxyalkylene structure, or a substituted or unsubstituted aryl group having 3 to 20 carbon atoms.

[0070] Examples of substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, monovalent hydrocarbon groups having 1 to 20 carbon atoms and a substituted or unsubstituted oxyalkylene structure, and substituted or unsubstituted aryl groups having 3 to 20 carbon atoms include R 1 Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, the substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms and an oxyalkylene structure, and the substituted or unsubstituted aryl group having 3 to 20 carbon atoms are those mentioned above.

[0071] Examples of the compound represented by formula (M1) include phenyl(trifluorovinyl) telluride, (2,2-difluorovinyl)phenyl telluride, (1-chlorodifluorovinyl)phenyl telluride, butyl(trifluorovinyl) telluride, and methyl(trifluorovinyl) telluride.

[0072] [Method for producing 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) can be produced by the method of CX 1 Y 1 =CZ 1 Vinyllithium represented by Li and R 1 TeBr and reacting them. 1 , Y 1 , Z 1 , and R 1 are the X in formula (M1), respectively. 1 , Y 1 , Z 1 , and R 1 is the same as

[0073] A specific example of the 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 a 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 (hereinafter also referred to as a "first copolymerizable monomer") that has a carbon-carbon double bond in the molecule, different from the tellurium-containing compound represented by formula (M1). The first copolymerizable monomer may be used alone or in combination of two or more.

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

[0079] [ka]

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

[0081] R 11 ~R 14 The substituted or unsubstituted organic group having 1 to 40 carbon atoms in the formula (I) preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 12 carbon atoms.

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

[0083] When the substituted or unsubstituted organic group having 1 to 40 carbon atoms is a hydrocarbon group which may have a heteroatom, such as an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkoxy group, an arylalkyl group, a heteroarylalkyl group, an arylalkoxy group, a heteroarylalkoxy group, or a monovalent hydrocarbon group having an oxyalkylene structure, the hydrocarbon group may be linear, branched, or cyclic, and may or may not contain an unsaturated bond.

[0084] The acyl group of the acylamino group or acyloxy group includes groups obtained by removing the hydroxy group from a carboxylic acid or sulfonic acid.

[0085] Examples of the substituent in the substituted organic group having 1 to 40 carbon atoms include a fluorine atom, a chlorine atom, a hydroxy group, an alkoxy group, an alkoxyalkyl group, an amino group, a carboxylic acid group, a sulfonic acid group, and a 1,3,5-triazinetrione skeleton.

[0086] In formula (M12), R 11 and R 13 , or R12 and R 14 may be linked 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, itaconic anhydride, etc.

[0087] Examples of the first copolymerizable monomer include (meth)acrylic acid ester monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, and hydroxyethyl methacrylate; cycloalkyl group-containing unsaturated monomers such as cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and cyclododecyl (meth)acrylate; carboxyl group-containing unsaturated monomers such as (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, maleic anhydride, and itaconic anhydride; tertiary amine-containing unsaturated monomers such as N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylamide, 2-(dimethylamino)ethyl (meth)acrylate, and N,N-dimethylaminopropyl (meth)acrylate; N-2-hydroxy quaternary ammonium base-containing unsaturated monomers such as 3-acryloyloxypropyl-N,N,N-trimethylammonium chloride and N-methacryloylaminoethyl-N,N,N-dimethylbenzylammonium chloride; epoxy group-containing unsaturated monomers such as glycidyl (meth)acrylate; styrene-based monomers such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 2-chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 1-vinylnaphthalene, divinylbenzene, 4-(chloromethyl)styrene, 2-(chloromethyl)styrene, 3-(chloromethyl)styrene, 4-styrenesulfonic acid or its alkali metal salts (sodium salt, potassium salt, etc.); heterocycle-containing unsaturated monomers such as 2-vinylthiophene and N-methyl-2-vinylpyrrole; vinylamides such as N-vinylformamide and N-vinylacetamide;α-olefins such as diallylamine, triallyl isocyanurate, tri(2-methylallyl) isocyanurate, ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-octene, 1-decene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, vinylidene chloride, vinyl chloride, 1-chloro-1-fluoroethylene, 1,2-dichloro-1,2-difluoroethylene, 1H,1H,2H-perfluoro(n-1-hexene), 1H,1H,2H-perfluoro(n-1-octene); vinyl esters such as vinyl acetate; Examples of suitable perfluoro(alkyl vinyl ethers) include termonomers; divinylfluoroalkanes such as 1,4-divinyloctafluorobutane and 1,6-divinyldodecafluorohexane; acrylonitrile; acrylamide monomers such as acrylamide and N,N-dimethylacrylamide; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, 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 copolymerizable monomer may be a compound represented by the following formula (M11):

[0089] [ka]

[0090] In 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; X 11 ~X 14At least one of 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 a branched chain into a fluorine-containing polymer by copolymerizing it with a fluorine-containing monomer, typified by the compound represented by formula (M11).

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

[0093] Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms include an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkoxy group, an arylalkyl group, a heteroarylalkyl group, an arylalkoxy group, a heteroarylalkoxy group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, an acylamino group, an acyloxy group, and a cyano group.

[0094] When the substituted or unsubstituted organic group having 1 to 20 carbon atoms is a hydrocarbon group which may have a heteroatom, such as an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkoxy group, an arylalkyl group, a heteroarylalkyl group, an arylalkoxy group, or a heteroarylalkoxy group, the hydrocarbon group may be linear, branched, or cyclic, and may or may not contain an unsaturated bond.

[0095] The acyl group of the acylamino group or acyloxy group includes groups obtained by removing the hydroxy group from a carboxylic acid or sulfonic acid.

[0096] Examples of the substituent in the substituted organic group having 1 to 20 carbon atoms include a fluorine atom, a chlorine atom, a hydroxy group, an alkoxy group, an alkoxyalkyl group, an amino group, a carboxylic acid group, and a sulfonic acid group.

[0097] Examples of perfluoroalkyl groups include perfluoromethyl, perfluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-n-butyl, perfluoro-sec-butyl, perfluoro-tert-butyl, perfluoro-n-pentyl, perfluoro-n-hexyl, perfluoro-n-heptyl, and perfluoro-n-octyl groups.

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

[0099] Examples of the compound 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] As the compound represented by formula (M11), vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and 2,3,3,3-tetrafluoropropylene are preferred in terms of polymerization reactivity when obtaining a polymer.

[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 described below.

[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 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 represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group; R 2 represents an organic group having 1 to 20 carbon atoms.

[0105] R in formula (M2) 2 The details of R in the above formula (M1) 1 The details are the same as in

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

[0107] Examples of perfluoroalkyl groups include perfluoromethyl, perfluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-n-butyl, perfluoro-sec-butyl, perfluoro-tert-butyl, perfluoro-n-pentyl, perfluoro-n-hexyl, perfluoro-n-heptyl, and perfluoro-n-octyl groups.

[0108] Examples of the monovalent hydrocarbon group having an oxyperfluoroalkylene structure include perfluorohydrocarbon groups having an oxyperfluoroalkylene structure having 1 to 4 carbon atoms as a constituent unit.

[0109] The phenyl group may or may not have a substituent, and preferably does not have a substituent. Examples of the substituent include a substituted or unsubstituted alkyl group, a monovalent hydrocarbon group having a substituted or unsubstituted oxyalkylene structure, 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, a trifluoromethyl group, etc., and preferred are an unsubstituted alkyl group, a perfluoroalkyl group, a monovalent hydrocarbon group having an unsubstituted oxyalkylene structure, and a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.

[0110] Examples of the compound 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.

[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) can be produced by the method of 2 Y 2 =CZ 2 Vinyllithium represented by Li and R 2 TeBr and reacting them. 2 , Y 2 , Z 2 , and R 2 are the X in formula (M2), respectively. 2 , Y 2 , Z 2 , and R 2 An example of a specific synthesis scheme is similar to the example of the 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 the 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 (hereinafter also referred to as a "second copolymerizable monomer") that has a carbon-carbon double bond in the molecule, different from the tellurium-containing compound represented by formula (M2). The second copolymerizable monomer may be used alone or in combination of two or more.

[0114] The second copolymerizable monomer is not particularly limited. The details of the second copolymerizable monomer are the same as those of the first copolymerizable monomer, except that the tellurium-containing compound represented by formula (M1) is replaced with a polymerizable compound different from the tellurium-containing compound represented by formula (M2).

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

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

[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 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 represents an organic group having 1 to 20 carbon atoms.

[0120] [ka]

[0121] In formula (M11), X 11 ~X 14each 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 represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.

[0122] R in formula (M3) 3 The details of R in formula (M1) 1 The details are the same as in

[0123] In formula (M1), X 1 , Y 1 , and Z 1 is a fluorine atom, except that there is no such restriction in formula (M3). 3 , Y 3 , and Z 3 For details, see X in formula (M1). 1 , Y 1 , and Z 1 The details are the same as in

[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) can be produced by the method of 3 Y 3 =CZ 3 Vinyllithium represented by Li and R 3 TeBr and reacting them. 3 , Y 3 , Z 3 , and R 3 are the X in formula (M3), respectively. 3 , Y 3 , Z 3 , and R 3 An example of a specific synthesis scheme is similar to the example of the method for producing the tellurium-containing compound represented by formula (M1) in the first embodiment.

[0125] 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 method for producing a polymer according to the sixth embodiment described below.

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

[0128] [ka]

[0129] In formula (T1), R 6 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 R each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 9 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, an amido group having 2 to 8 carbon atoms, an oxycarbonyl-containing group, or a cyano group.

[0130] [ka]

[0131] In formula (T2), R 10 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.

[0132] The polymer production method according to the fourth embodiment is a method for producing a polymer based on the TERP method, in which at least the tellurium-containing compound according to the first embodiment is polymerized using 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 produces a polymer having a controlled molecular structure and a branched structure.

[0133] (Compound represented by formula (T1)) In formula (T1), R 6 The group represented by the formula (I) is 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. Of these, linear or branched alkyl groups having 1 to 4 carbon atoms are preferred, and methyl, ethyl, or n-butyl are more preferred.

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

[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. Of these, homoaryl groups are preferred, and phenyl groups are more preferred.

[0136] The substituted aryl group having 3 to 16 carbon atoms may include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, a -COR aExamples of the substituents include aryl groups having 1 to 4, preferably 1 to 3, and more preferably 1, substituent such as a carbonyl-containing group, sulfonyl group, or trifluoromethyl group, represented by the formula (I), preferably at the para or ortho position. a 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 The groups represented by the formula are specifically as follows. The substituted or unsubstituted alkyl group having 1 to 8 carbon atoms includes the above-mentioned R 6 Examples of the substituted or unsubstituted alkyl groups include the same substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms as those shown in R 7 and R 8 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0138] R 9 The groups represented by the formula are specifically as follows. The substituted or unsubstituted alkyl group having 1 to 8 carbon atoms and the substituted or unsubstituted aryl group having 3 to 16 carbon atoms include those listed above for R 6 Examples of the groups are the same as those shown in

[0139] Examples of the acyl group having 2 to 8 carbon atoms include an acetyl group and a benzoyl group.

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

[0141] The oxycarbonyl-containing group is -COOR b In this case, 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, the alkenyl group having 2 to 8 carbon atoms, the alkynyl group having 2 to 8 carbon atoms, and the aryl group having 3 to 12 carbon atoms, represented by the formula (I), may have 1 to 4, preferably 1 to 3, and more preferably 1, substituents such as a halogen atom, a hydroxyl group, an alkoxy group, a trialkylsilyl ether group, a trialkylsilyl group, an amino group, a nitro group, a cyano group, a sulfonyl group, or a trifluoromethyl group at any position, or may have no substituents.

[0143] Examples of the oxycarbonyl-containing group include a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an n-butoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, an n-pentoxycarbonyl group, a phenoxycarbonyl group, etc. Among these, 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 of 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, R 9 may be a compound represented by an aryl group or an alkoxycarbonyl group having 5 to 12 carbon atoms.

[0146] In one particularly preferred embodiment, the compound of 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, R 9 is a phenyl group, a methoxycarbonyl group or an ethoxycarbonyl group.

[0147] Specific examples of the compound represented by formula (T1) include (methyltellanylmethyl)benzene, (methyltellanylmethyl)naphthalene, ethyl-2-methyl-2-methyltellanylpropionate, ethyl-2-methyl-2-n-butyltellanylpropionate, (2-trimethylsiloxyethyl)-2-methyl-2-methyltellanylpropionate, (2-hydroxyethyl)-2-methyl-2-methyltellanylpropionate, and (3-trimethylsilylpropargyl)-2-methyl-2-methyltellanylpropionate, as well as the compounds described in WO 2004 / 014848 and WO 2004 / 014962. Further examples include compounds such as ethyl-2-methyl-2-1H,1H,2H,2H-heptadecafluorodecyltellanyl-propionate, methyl-2-methyl-2-1H,1H,2H,2H-heptadecafluorodecyltellanyl-propionate, and N,N-diethyl-2-methyl-2-1H,1H,2H,2H-heptadecafluorodecyltellanyl-propionamide, which are described in Polymer Preprints, Japan Vol. 65, No. 1 (2016), Publication No. 2D03. The compounds 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 the compound can be produced by known methods described in WO 2004 / 014848, WO 2004 / 014962, and WO 2018 / 164147.

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

[0150] Specific examples of the compound 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, dipyridyl ditelluride, etc. The compound represented by formula (T2) may be used alone or in combination of two or more.

[0151] Of these, dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, di-n-butyl ditelluride, or diphenyl ditelluride is preferred.

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

[0153] -Radical initiator- Examples of the radical initiator include azo-based radical initiators, peroxide-based radical initiators, etc. The radical initiators may be used alone or in combination of two or more.

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

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

[0156] -solvent- The solvent may be an organic solvent or an aqueous solvent, and one solvent may be used alone or two or more solvents may be used in combination.

[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. Furthermore, ionic liquids such as N-methyl-N-methoxymethylpyrrolidium tetrafluoroborate, N-methyl-N-ethoxymethyl tetrafluoroborate, 1-methyl-3-methylimidazolium tetrafluoroborate, 1-methyl-3-methylimidazolium hexafluorophosphate, and 1-methyl-3-methylimidazolium chloride may also be used.

[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 aspect, a method for producing a polymer according to the fourth embodiment includes polymerizing the tellurium-containing compound according to the first embodiment (i.e., the tellurium-containing compound represented by formula (M1)) with a polymerizable compound (i.e., the first copolymerizable monomer according to the first embodiment) that has a carbon-carbon double bond in the molecule, different from the tellurium-containing compound according to the first embodiment (i.e., the tellurium-containing compound represented by formula (M1)). Details of the first copolymerizable monomer are as described above.

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

[0161] The amount of the compound represented by formula (T1) or the compound represented by formula (T2) (when the compound represented by formula (T1) and the compound represented by formula (T2) are used in combination, the total amount of these) used relative to 1 mol of the compound having a reactive carbon-carbon double bond (i.e., the total amount of the tellurium-containing compound represented by formula (M1) and the first copolymerizable 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. Moreover, 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 the azo polymerization initiator used per mole of the compound represented by formula (T1) or the compound represented by formula (T2) (when the compound represented by formula (T1) and the compound represented by formula (T2) are used in combination, the total of these) is preferably 0.01 mol or more, more preferably 0.05 mol or more, and even more preferably 0.1 mol or more. 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 the compound represented by formula (T1) and the compound represented by formula (T2) are used in combination, the amount of the compound represented by formula (T2) used per 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, and is preferably 100 mol or less, more preferably 10 mol or less, and even more preferably 5 mol or less.

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

[0165] The amount of solvent used can be adjusted appropriately. For example, the amount of solvent per 1000 g of the obtained polymer is preferably 0.01 L or more, more preferably 0.05 L or more, and even more preferably 0.1 L or more. Furthermore, the amount of solvent per 1000 g of the obtained 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 adjusted appropriately depending on the molecular weight or molecular weight distribution of the resulting polymer, and the mixture may be stirred at 60°C to 150°C for 5 to 100 hours, or at 80°C to 120°C for 10 to 30 hours. The reaction may be carried out at normal pressure, or under increased or reduced pressure.

[0167] After the reaction is completed, the target polymer is isolated by removing the solvent used, residual monomers, etc. under reduced pressure in a conventional manner, or by reprecipitation using a solvent in which the target polymer is insoluble. Any treatment method can be used for the reaction treatment as long as it does not affect the target product.

[0168] Such a polymerization method allows excellent control of molecular weight and molecular weight distribution under very mild conditions.

[0169] The tellurium-containing compound represented by formula (M1) and the first copolymerizable monomer may be used to prepare a block copolymer, an alternating copolymer, or a random copolymer.

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

[0171] [ka]

[0172] [ka]

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

[0174] Fifth Embodiment <Method of producing polymer> A method for producing a polymer according to a fifth embodiment includes polymerizing at least a tellurium-containing compound represented by 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 6represents 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 R each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 9 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, an amido group having 2 to 8 carbon atoms, an oxycarbonyl-containing group, or a cyano group.

[0177] [ka]

[0178] In formula (T2), R 10 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.

[0179] [ka]

[0180] In formula (M2), X 2 , Y 2 , and Z 2 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; X 2 , Y 2 , and Z 2 at least one of represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group; R 2 represents an organic group having 1 to 20 carbon atoms.

[0181] The polymer production method according to the fifth embodiment is a method for producing a polymer 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 polymerize at least a compound represented by formula (M2). This production method produces a polymer having a controlled molecular structure and a branched structure. The polymer obtained may be the polymer according to the second embodiment.

[0182] The 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 method for producing a polymer according to the fifth embodiment, other components such as a radical initiator, a solvent, an emulsifier, a suspending aid, an acid or an alkali may be further used. Details of the optional components are as described above.

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

[0185] [Polymerization method] The same polymerization methods as those described in the fourth embodiment can be applied to specific examples of the polymerization method in the polymer production method according to the fifth embodiment, except that "the tellurium-containing compound represented by formula (M1)" is read as "the tellurium-containing compound represented by formula (M2)", and "the first copolymerizable monomer" is read as "the second copolymerizable monomer".

[0186] Sixth Embodiment <Method of producing polymer> A 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 compounds represented by the following formula (T1) and compounds represented by the following formula (T2).

[0187] [ka]

[0188] In formula (T1), R 6 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 R each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 9 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, an amido group having 2 to 8 carbon atoms, an oxycarbonyl-containing group, or a cyano group.

[0189] [ka]

[0190] In formula (T2), R 10 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.

[0191] [ka]

[0192] In formula (M3), X 3 , Y 3 , and Z 3 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, R 3 represents an organic group having 1 to 20 carbon atoms.

[0193] [ka]

[0194] In 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; X 11 ~X 14 At least one of represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.

[0195] The method for producing a polymer according to the sixth embodiment is a method for producing a polymer 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 produces a polymer having a controlled molecular structure and a branched structure, which is produced by polymerizing a fluorine-containing monomer. 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 method for producing a polymer according to the sixth embodiment, other components such as a radical initiator, a solvent, an emulsifier, a suspending aid, an acid or an alkali may be further used. Details of the optional components are as described above.

[0198] [Polymerization method] The same polymerization methods as those described in the fourth embodiment can be applied to specific examples of the polymerization method in the polymer production method according to the sixth embodiment. However, the "tellurium-containing compound represented by formula (M1)" should be read as the "tellurium-containing compound represented by formula (M3)" and the "first copolymerizable monomer" should be read as the "compound represented by formula (M11)." Furthermore, at least the tellurium-containing compound represented by formula (M3) and the compound represented by formula (M11) are copolymerized. [Example]

[0199] The following examples will be used to specifically explain the embodiments of the present disclosure, but the embodiments of the present disclosure are not limited to these examples.

[0200] In the following examples, nuclear magnetic resonance spectra (NMR) were measured by Fourier transform NMR. 1 H-NMR was measured at 300 MHz using tetramethylsilane as the reference for the chemical shift value of 0 ppm. 19 F-NMR was measured at 282 MHz using 1,4-bis(trifluoromethyl)benzene as the reference with a chemical shift value of −63.9 ppm. The abbreviations used in the 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, MS (mass spectrum) was measured by GC / MS (gas chromatograph mass spectrometer). EI (electron ionization) was used as the ionization method. Positive ionization mode (EI+) was used. Data shown are actual measurements (found).

[0202] (Example 1) Synthesis of phenyl(trifluorovinyl) telluride (CF2=CFTePh) A magnetic rotor was added to a 300 mL glass flask, and the inside air was replaced 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 (1.6 mol / L, 0.16 mol) of n-butyllithium / hexane solution was added, and the internal temperature was maintained at -78°C while stirring for 30 minutes. This solution is designated as A. A magnetic rotor and 15 g (36 mmol) of diphenyl ditelluride were placed in a 100 mL glass flask, and the inside was replaced with nitrogen. Under a nitrogen atmosphere, 45 g of frozen and degassed tetrahydrofuran was added, and the internal temperature was cooled to 0°C with 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 B. A magnetic rotor was added to a 500 mL glass flask, and the inside atmosphere was replaced 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 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. While continuing to stir, the internal temperature was raised to room temperature over 30 minutes. The mixture was stirred for 1 hour while maintaining the internal temperature at room temperature. The reaction vessel was opened in a nitrogen-substituted glove box, and the reaction mixture was suction filtered to remove solids. The filtrate was washed three times with ion-exchanged water, and the organic phase was recovered. The solvent in the organic phase was distilled off under reduced pressure, and the residue was purified by vacuum distillation to obtain 5.7 g of the title compound as an oil. 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 telluride (CF2=CHTePh) A magnetic rotor was added to a 100 mL glass flask, and the inside air was replaced with nitrogen. Under a nitrogen atmosphere, 6.7 g of frozen, degassed tetrahydrofuran was added, and the internal temperature was cooled to -78°C with stirring. Under a nitrogen atmosphere, 25 mL (1.3 mol / L, 33 mmol) of s-butyllithium / hexane / cyclohexane solution was added, and the internal temperature was maintained at -78°C while stirring for 30 minutes. This solution is designated as A. A magnetic rotor and 5.5 g (14 mmol) of diphenyl ditelluride were placed in a 100 mL glass flask, and the inside was replaced with nitrogen. Under a nitrogen atmosphere, 45 g of frozen and degassed tetrahydrofuran was added, and the internal temperature was cooled to 0°C with 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 B. 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 with 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 the internal temperature was maintained 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 the internal temperature was maintained 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 the internal temperature was maintained at -108°C. While continuing to stir, the internal temperature was raised to -78°C. While continuing to stir, the internal temperature was raised to room temperature over 30 minutes. While continuing to stir, the mixture was stirred for 1 hour while the internal temperature was maintained at room temperature. The reaction vessel was opened in a nitrogen-substituted glove box, and the reaction mixture was suction filtered to remove solids. The filtrate was washed three times with ion-exchanged water, and the organic phase was recovered. The solvent in the organic phase was distilled off under reduced pressure, and the residue was purified by vacuum distillation to obtain 1.1 g of the title compound as an oil. 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 inside atmosphere was replaced with nitrogen. Under a nitrogen atmosphere, 10 g (15 wt%, 39 mmol) of a vacuum-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 collected, washed three times with ion-exchanged water, and dried over anhydrous sodium sulfate to obtain 2.1 g of the title compound as a liquid. This compound was used in the next step without further purification. MS(EI+):[M+]176.0

[0205] Synthesis of (1-chlorodifluorovinyl)phenyl telluride (CF2=CClTePh) A magnetic rotor was added to a 300 mL glass flask, and the inside air was replaced with nitrogen. Under a nitrogen atmosphere, 86 g of frozen degassed diethyl ether was added, and the internal temperature was cooled to -78°C with stirring. Under a nitrogen atmosphere, 8.0 mL (1.6 mol / L, 13 mmol) of n-butyllithium / hexane solution was added, and the internal temperature was maintained at -78°C while stirring for 30 minutes. This solution is designated as A. A magnetic rotor and 2.0 g (4.8 mmol) of diphenyl ditelluride were placed in a 50 mL glass flask, and the inside was replaced with nitrogen. Under a nitrogen atmosphere, 13 g of frozen and degassed tetrahydrofuran was added, and the internal temperature was cooled to 0°C with 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 B. A magnetic rotor was added to a 300 mL glass flask, and the inside atmosphere was replaced 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 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. While continuing to stir, the internal temperature was raised to room temperature over 30 minutes. The mixture was stirred for 1 hour while maintaining the internal temperature at room temperature. The reaction vessel was opened in a nitrogen-substituted glove box, and the reaction mixture was suction filtered to remove solids. The filtrate was washed three times with ion-exchanged water, and the organic phase was recovered. The solvent in the organic phase was distilled off under reduced pressure, and the residue was purified by vacuum distillation to obtain 0.5 g of the title compound as an oil. 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 ditelluride in Example 1 was changed to dibutyl ditelluride. 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] The following Example 5 is an example that is expected to be synthesizable based on the findings of the present disclosure and known techniques.

[0208] (Example 5) Synthesis of methyl(trifluorovinyl) telluride (CF2=CFTeMe) The procedure of Example 1 is repeated except that diphenyl ditelluride is replaced with dimethyl ditelluride to give the title compound as an oil.

[0209] (Example 6) Copolymerization of phenyltrifluorovinyl telluride with chlorotrifluoroethylene. In a nitrogen-purged glove box, 0.061 g (0.27 mmol) of an azo-based radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, 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 benzotrifluoride were charged into a 30 mL stainless steel autoclave equipped with a stirrer in a nitrogen-purged glove box. After 3.3 g (28 mmol) of chlorotrifluoroethylene was injected, stirring was initiated while the internal temperature was raised to 80° C. While maintaining the internal temperature, stirring was carried out at 200 rpm (200 revolutions per minute) for 7 hours. The autoclave was cooled in an ice-water bath and then purged of unreacted chlorotrifluoroethylene.

[0210] The resulting polymer solution was dried under vacuum to obtain an oil. This oil was added to 40 mL of frozen, degassed methanol in a nitrogen-substituted glove box and stirred for 5 minutes. The oil and supernatant were then separated using a centrifuge. The resulting oil was dried under vacuum to obtain 0.2 g of oil. The obtained oil 19 F-NMR analysis revealed a peak at δ-177 ppm, which was attributed to a fluorine atom bonded to a tertiary carbon atom, indicating that the polymer had a branched main chain. Here, a tertiary carbon atom refers to a carbon atom to which three carbon atoms are directly bonded.

[0211] (Example 7) Copolymerization of butyltrifluorovinyl telluride with tetrafluoroethylene. In a nitrogen-purged glove box, 0.038 g (0.17 mmol) of an azo-based radical initiator "V-601" (FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.057 g (0.15 mmol) of dibutyl ditelluride, 1.3 g (4.6 mmol) of the butyl trifluorovinyl telluride synthesized in Example 4, and 13 g of 1H-perfluorohexane were placed in a 30 mL stainless steel autoclave equipped with a stirrer. After 5.0 g (50 mmol) of tetrafluoroethylene was injected, the internal temperature was raised to 72°C while stirring was started to allow the reaction to proceed. Stirring was continued at 200 rpm for 7 hours while maintaining the internal temperature. The autoclave was cooled in an ice-water bath, and then unreacted tetrafluoroethylene was purged.

[0212] The resulting polymer solution was dried under vacuum to obtain a solid. This solid was added to 40 mL of frozen and degassed methanol in a nitrogen-substituted glove box and stirred for 5 minutes. The solid was then separated from the supernatant using a centrifuge. The resulting solid was dried under vacuum to obtain 0.5 g of solid.

[0213] The following Examples 8 to 13 are examples that are expected to be synthesizable based on the findings of the present disclosure and known techniques. In all of these examples, a highly reactive fluorine-containing monomer is used as a copolymerizable monomer, and therefore it is believed that copolymers can be suitably synthesized.

[0214] (Example 8) Copolymerization of (2,2-difluorovinyl)phenyl telluride with chlorotrifluoroethylene In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with an azo-based radical initiator "V-601" (Fujifilm Wako Pure Chemical Industries, Ltd.), diphenyl ditelluride, the (2,2-difluorovinyl)phenyl telluride synthesized in Example 2, benzotrifluoride, and chlorotrifluoroethylene, and the internal temperature was raised to 80°C while stirring was initiated to allow the reaction to proceed.

[0215] (Example 9) Copolymerization of (1-chlorodifluorovinyl)phenyl telluride with chlorotrifluoroethylene In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with an azo-based radical initiator "V-601" (Fujifilm Wako Pure Chemical Industries, Ltd.), diphenyl ditelluride, the (1-chlorodifluorovinyl)phenyl telluride synthesized in Example 3, benzotrifluoride, and chlorotrifluoroethylene, and the internal temperature was raised to 80°C while stirring was initiated to allow the reaction to proceed.

[0216] (Example 10) Copolymerization of (2-nonafluorobutylvinyl)phenyl telluride with chlorotrifluoroethylene In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with an azo-based radical initiator "V-601" (Fujifilm Wako Pure Chemical Industries, Ltd.), diphenyl ditelluride, (2-nonafluorobutylvinyl)phenyl telluride synthesized according to a known literature, benzotrifluoride, and chlorotrifluoroethylene, and the internal temperature was then raised to 80°C while stirring was initiated to allow the reaction to proceed.

[0217] (Example 11) Copolymerization of (1-chlorovinyl)phenyl telluride with chlorotrifluoroethylene In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with an azo-based radical initiator "V-601" (Fujifilm Wako Pure Chemical Industries, Ltd.), diphenyl ditelluride, (1-chlorovinyl)phenyl telluride synthesized according to a known literature, benzotrifluoride, and chlorotrifluoroethylene, and the internal temperature was raised to 80°C while stirring was initiated to allow the reaction to proceed.

[0218] (Example 12) Copolymerization of (2-chlorovinyl)phenyl telluride with chlorotrifluoroethylene In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with an azo-based radical initiator "V-601" (Fujifilm Wako Pure Chemical Industries, Ltd.), diphenyl ditelluride, (2-chlorovinyl)phenyl telluride synthesized according to a known literature, benzotrifluoride, and chlorotrifluoroethylene, and the internal temperature was raised to 80°C while stirring was initiated to allow the reaction to proceed.

[0219] (Example 13) Copolymerization of (1-phenylvinyl)phenyl telluride with chlorotrifluoroethylene In a nitrogen-substituted glove box, a 30 mL stainless steel autoclave equipped with a stirrer was charged with an azo-based radical initiator "V-601" (Fujifilm Wako Pure Chemical Industries, Ltd.), diphenyl ditelluride, (1-phenylvinyl)phenyl telluride synthesized according to a known literature, benzotrifluoride, and chlorotrifluoroethylene, and the internal temperature was raised to 80°C while stirring was initiated to allow the reaction to proceed.

[0220] The disclosure of Japanese Patent Application No. 2020-207031 is incorporated herein by reference in its entirety. All publications, patent applications, and technical standards mentioned in this specification are incorporated by reference into this specification to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A tellurium-containing compound represented by the following formula (M1): 【Chemistry 1】 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; X １ , Y １ , and Z １ At least one of represents a fluorine atom, R １ represents an organic group having 1 to 20 carbon atoms.

2. In the formula (M1), R １ 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 substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms and an 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 substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms and an oxyalkylene structure, or a substituted or unsubstituted aryl group having 3 to 20 carbon atoms.

4. A polymer obtained by polymerizing at least the tellurium-containing compound according to any one of claims 1 to 3.

5. 5. The polymer according to claim 4, obtained by polymerizing the tellurium-containing compound with a polymerizable compound that has a carbon-carbon double bond in the molecule, different from the tellurium-containing compound.

6. The polymer according to claim 5, wherein the polymerizable compound is a compound represented by the following formula (M11): 【Chemistry 2】 In 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; X １１ ~X １４ At least one of 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): 【Transformation 3】 In formula (M2), X ２ , Y ２ , and Z ２ 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; X ２ , Y ２ , and Z ２ at least one of represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group; R ２ represents an organic group having 1 to 20 carbon atoms.

8. 8. The polymer according to claim 7, obtained by polymerizing the tellurium-containing compound with a polymerizable compound that has a carbon-carbon double bond in the molecule, different from the tellurium-containing compound.

9. The polymer according to claim 8, wherein the polymerizable compound is a compound represented by the following formula (M11): 【Chemistry 4】 In 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; X １１ ~X １４ At least one of 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): 【Transformation 5】 In formula (M3), X ３ , Y ３ , and Z ３ 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, R ３ represents an organic group having 1 to 20 carbon atoms. 【Transformation 6】 In 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; X １１ ~X １４ At least one of represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.

11. A method for producing a polymer, comprising polymerizing at least the tellurium-containing compound according to any one of claims 1 to 3 in the presence of at least one compound selected from the group consisting of compounds represented by the following formula (T1) and compounds represented by the following formula (T2): 【Transformation 7】 In formula (T1), R ６ 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 R each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. ９ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, an amido group having 2 to 8 carbon atoms, an oxycarbonyl-containing group, or a cyano group. 【Transformation 8】 In formula (T2), R １０ 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.

12. 12. A method for producing the polymer according to claim 11, comprising polymerizing the tellurium-containing compound according to any one of claims 1 to 3 with a polymerizable compound that has a carbon-carbon double bond in the molecule, different from the tellurium-containing compound.

13. The method for producing a polymer according to claim 12, wherein the polymerizable compound is a compound represented by the following formula (M11): 【Chemistry 9】 In 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; X １１ ~X １４ At least one of 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 at least a tellurium-containing compound represented by 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): 【Chemistry 10】 In formula (T1), R ６ 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 R each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. ９ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, an amido group having 2 to 8 carbon atoms, an oxycarbonyl-containing group, or a cyano group. 【Chemistry 11】 In formula (T2), R １０ 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. 【Chemistry 12】 In formula (M2), X ２ , Y ２ , and Z ２ 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; X ２ , Y ２ , and Z ２ at least one of represents a chlorine atom, a perfluoroalkyl group, a monovalent hydrocarbon group having an oxyperfluoroalkylene structure, or a phenyl group; R ２ represents an organic group having 1 to 20 carbon atoms.

15. 15. A method for producing a polymer according to claim 14, comprising polymerizing the tellurium-containing compound represented by formula (M2) with a polymerizable compound that has a carbon-carbon double bond in the molecule, different from the tellurium-containing compound represented by formula (M2).

16. The method for producing a polymer according to claim 15, wherein the polymerizable compound is a compound represented by the following formula (M11): 【Chemistry 13】 In 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; X １１ ~X １４ At least one of 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): 【Chemistry 14】 In formula (T1), R ６ 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 R each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. ９ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aryl group having 3 to 16 carbon atoms, an acyl group having 2 to 8 carbon atoms, an amido group having 2 to 8 carbon atoms, an oxycarbonyl-containing group, or a cyano group. 【Chemistry 15】 In formula (T2), R １０ 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. 【Chemistry 16】 In formula (M3), X ３ , Y ３ , and Z ３ 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, R ３ represents an organic group having 1 to 20 carbon atoms. 【Chemistry 17】 In 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; X １１ ~X １４ At least one of represents a fluorine atom, a perfluoroalkyl group, or a monovalent hydrocarbon group having an oxyperfluoroalkylene structure.

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