Monomer, polymerizable composition containing said monomer, and polymer having repeating unit derived from said monomer

Abstract

Provided are a tetrafluorosulfanyl group-containing monomer which has excellent radical polymerization reactivity, a polymer which has a repeating unit derived from the monomer; and a method for producing the polymer.　This monomer is represented by formula (1). In the formula, R1, R2, and R3 are the same or different and each represent a fluorine atom, a chlorine atom, or a hydrogen atom. At least one moiety selected from R1, R2, and R3 represents a fluorine atom. Ar represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, which may comprises a substituent.

Description

Monomer, polymerizable composition containing the monomer, and polymer having repeating units derived from the monomer

[0001] The present invention relates to novel monomers, polymerizable compositions containing said monomers, polymers having repeating units derived from said monomers, and methods for producing said polymers.

[0002] Vinyl fluoride compounds such as hexafluoropropylene, which are one type of organic fluorine compound, are essential monomers for the synthesis of fluororesins, which have excellent properties such as heat resistance, chemical resistance, weather resistance, and electrical insulation. Furthermore, due to their high reactivity, vinyl fluoride compounds are also used as excellent building blocks in fields such as functional materials, pesticides, and pharmaceuticals. However, due to their persistence and tendency to accumulate, their use has been restricted in recent years by PFAS (perfluoroalkyl and polyfluoroalkyl compounds) regulations. Therefore, there is an urgent need to develop environmentally friendly alternative products.

[0003] Organofluorine compounds containing tetrafluorosulfanyl groups are expected to be environmentally friendly alternatives. ２ Motoi and CF ３ While possessing high lipophilicity and electron-withdrawing properties exceeding those of the CF group, ２ Motoi and CF ３ This is because it is easier to decompose than the aryl group.

[0004] Patent Document 1 describes a vinyl fluoride compound having a tetrafluorosulfanyl group as shown below.

[0005] International Publication No. 2014 / 062221

[0006] However, the vinyl fluoride compound described in Patent Document 1 has low radical polymerizability, and it has been difficult to produce a polymer containing repeating units derived from the vinyl fluoride compound as a monomer. Furthermore, at present, no tetrafluorosulfanyl group-containing monomer with excellent radical polymerization reactivity is known.

[0007] Therefore, an object of the present invention is to provide a tetrafluorosulfanyl group-containing monomer having excellent radical polymerization reactivity. Another object of the present invention is to provide a polymerizable composition containing a tetrafluorosulfanyl group-containing monomer having excellent radical polymerization reactivity. Another object of the present invention is to provide a polymer having repeating units derived from the monomer. Another object of the present invention is to provide a method for producing the polymer.

[0008] As a result of intensive research by the present inventors to solve the above-mentioned problems, it has been found that a tetrafluorosulfanyl group-containing monomer represented by the following formula (1) has excellent radical polymerization reactivity, and a polymer having a repeating unit derived from the monomer obtained by polymerizing the monomer has excellent heat resistance, chemical resistance, weather resistance, and electrical insulation. ２ Motoi and CF ３ The present invention was completed based on these findings.

[0009] That is, the present invention provides a monomer represented by the following formula (1): (In the formula, R １ , R ２ , R ３ are the same or different and represent a fluorine atom, a chlorine atom, or a hydrogen atom. １ , R ２ , and R ３ At least one selected from the group consisting of: represents a fluorine atom; and Ar represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, which may have a substituent.

[0010] The present invention also provides a polymerizable composition comprising the monomer.

[0011] The present invention also provides a polymer having repeating units derived from the above monomer.

[0012] The present invention also provides a method for producing a polymer, comprising reacting a monomer represented by the following formula (1) with a monomer represented by the following formula (2) in a molar ratio of the former / latter of 5 / 95 to 95 / 5 to obtain a polymer having a repeating unit [1] derived from the monomer represented by formula (1) and a repeating unit [2] derived from the monomer represented by formula (2), wherein the proportion of the repeating unit [1] in the total of the repeating units [1] and [2] is 5 mol % or more. (In formula (1), R １ , R ２ , R ３ are the same or different and represent a fluorine atom, a chlorine atom, or a hydrogen atom. １ , R ２ , and R ３ At least one selected from the group consisting of: represents a fluorine atom; Ar represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, which may have a substituent; (In formula (2), R １１ ~R １４ are the same or different and represent a fluorine atom, a fluoroalkyl group, a chlorine atom, or a hydrogen atom.

[0013] The monomer represented by the formula (1) has excellent radical polymerization reactivity, and by subjecting the monomer to a radical polymerization reaction, a polymer having a repeating unit derived from the monomer can be efficiently produced. In addition, the tetrafluorosulfanyl group contained in the monomer is CF ２ Motoi and CF ３ The tetrafluorosulfanyl group in the polymer has electron-withdrawing properties exceeding those of the CF group. Therefore, the monomer has high reactivity and can be suitably used as a building block in the fields of functional materials, pesticides, pharmaceuticals, etc. The polymer obtained by radical polymerization of the monomer has repeating units derived from the monomer, and therefore has excellent properties such as heat resistance, chemical resistance, weather resistance, and electrical insulation. The tetrafluorosulfanyl group contained in the polymer is CF ２ Motoi and CF ３ The polymer is more environmentally friendly than the hydroxyl group.

[0014] [Monomer (1)] The monomer (1) of the present invention is a compound represented by the following formula (1). (In the formula, R １ , R ２ , R ３ are the same or different and represent a fluorine atom, a chlorine atom, or a hydrogen atom. １ , R ２ , and R ３ At least one selected from the group consisting of: represents a fluorine atom; and Ar represents an aromatic hydrocarbon ring which may have a substituent, or an aromatic heterocycle which may have a substituent.

[0015] Examples of the aromatic hydrocarbon ring include a benzene ring and a fused ring formed by condensing two or more benzene rings (for example, a naphthalene ring, a phenalene ring, etc.).

[0016] Examples of the aromatic heterocycle include a heteroaromatic ring (e.g., a 5- or 6-membered heteroaromatic ring) having carbon atoms and at least one heteroatom (e.g., an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, etc.) as ring-constituting atoms, and a fused ring of the heteroaromatic ring. Specific examples of the aromatic heterocycle include pyrrole, furan, thiophene, phosphole, pyrazole, imidazole, oxazole, isoxazole, thiazole, indole, benzofuran, benzothiophene, isoindole, isobenzofuran, benzophosphole, benzimidazole, benzoxazole, benzothiazole, benzisoxazole, indazole, benzisothiazole, benzotriazole, purine, pyridine, phosphinine, pyrimidine, pyrazine, pyridazine, triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, hexazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, pteridine, phthalazine, acridine, 4aH-phenoxazine, and carbazole.

[0017] Examples of the substituent that the aromatic hydrocarbon ring or aromatic heterocycle may have include a halogen atom, an oxo group, a hydroxyl group, a substituted oxy group (e.g., C １－４ Alkoxy group, C ６－１０ Aryloxy group, C ７－１６ Aralkyloxy group, C １－４acyloxy group, etc.), carboxyl group, substituted oxycarbonyl group (e.g., C １－４ Alkoxycarbonyl group, C ６－１０ Aryloxycarbonyl group, C ７－１６ aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group (e.g., carbamoyl, methylcarbamoyl, etc. １－４ C such as alkyl-substituted carbamoyl and phenylcarbamoyl groups ６－１０ aryl-substituted carbamoyl group), cyano group, nitro group, substituted or unsubstituted amino group (e.g., mono- or di-C groups such as methylamino, dimethylamino, ethylamino, and diethylamino groups) １－４ alkylamino groups; 5- to 8-membered cyclic amino groups such as 1-pyrrolidinyl, piperidino, and morpholino groups; C groups such as acetylamino, propionylamino, and benzoylamino groups; １－１０ acylamino group; sulfonylamino group such as benzenesulfonylamino, p-toluenesulfonylamino group, etc.), sulfo group, amide group (for example, acetamide group, benzamide group, etc.), heterocyclic group, alkyl group (for example, C group such as methyl group, ethyl group, etc. １－４ alkyl groups, alkenyl groups (e.g., vinyl groups, allyl groups, 1-butenyl groups, etc.) ２－４ alkenyl group), alkynyl group (e.g., ethynyl group, propynyl group, etc. ２－４ alkynyl group, etc.), C ３－８ cycloalkyl groups, aryl groups (e.g., C groups such as phenyl groups and naphthyl groups) ６－１０ aryl group), substituted sulfonyl group (for example, benzenesulfonyl group, p-toluenesulfonyl group), etc. The hydroxyl group and carboxyl group may be protected with a protecting group commonly used in the field of organic synthesis.

[0018] R １ , R ２ , R ３ are the same or different and represent a fluorine atom, a chlorine atom, or a hydrogen atom. １ , R ２ , and R ３ At least one selected from R １ , R ２ , and R ３Preferably, two or more selected from are fluorine atoms.

[0019] R １ , R ２ , R ３ are the same or different and represent a fluorine atom or a hydrogen atom, and R １ , R ２ , and R ３ At least one selected from R １ , R ２ , and R ３ Preferably, two or more selected from the are fluorine atoms.

[0020] As the monomer (1), from the viewpoint of excellent radical polymerization reactivity, monomers represented by the following formulas (1-1), (1-2), and (1-3) are preferred, and monomers represented by the following formulas (1-1-1), (1-2-1), (1-2-2), and (1-3-1) are particularly preferred.

[0021]

[0022] In the above formula, R １ ~R ３ is the same as above. ４ represents a substituent, and s represents 0 or 1. In the above formula (1-1), n ​​represents an integer of 0 to 5. In the above formula (1-2), n represents an integer of 0 to 4. In the above formula (1-3), n represents an integer of 0 to 3.

[0023] R ４ Examples of the substituent in the above include the same examples as those of the substituent that the aromatic hydrocarbon ring and aromatic heterocycle may have. Among them, electron-withdrawing groups are preferred in terms of excellent radical polymerization reactivity, and halogen atoms, cyano groups, nitro groups, sulfo groups, and substituted oxy groups (particularly, C １－４ an alkoxy group, or C １－４ A halogen atom, a cyano group, and a substituted oxy group (particularly, C １－４ an alkoxy group, or C １－４A group selected from the group consisting of aryl, aryloxy, aryloxy groups, etc. is most preferred.

[0024] Monomer (1) is CF ２ Motoi and CF ３ The monomer (1) has a tetrafluorosulfanyl group with electron-withdrawing properties exceeding those of the tetrafluorosulfanyl group, resulting in high reactivity. Furthermore, the polymer obtained by polymerizing monomer (1) (which is a polymer having repeating units derived from monomer (1)) contains a large number of tetrafluorosulfanyl groups, and therefore has heat resistance, chemical resistance, weather resistance, and electrical insulation properties derived from fluorine atoms. Furthermore, an aromatic hydrocarbon ring or an aromatic heterocycle is bonded to the tetrafluorosulfanyl group contained in the polymer. Therefore, the polymer has superior scratch resistance compared to polymers without an aromatic hydrocarbon ring or an aromatic heterocycle. Furthermore, the polymer has a high Tg and even better heat resistance. Because monomer (1) combines the above properties, it can be suitably used as a raw material for polymers. Furthermore, monomer (1) can also be suitably used as a building block in fields such as functional materials, pesticides, and pharmaceuticals.

[0025] [Polymerizable Composition] The polymerizable composition of the present invention is a composition containing the monomer (1) as a polymerizable compound, and in particular is a radically polymerizable composition containing the monomer (1).

[0026] The polymerizable composition contains at least the monomer (1), and the content of the monomer (1) can be appropriately adjusted depending on the intended use of the polymer. For example, when a polymer having excellent properties derived from fluorine atoms, such as heat resistance, chemical resistance, weather resistance, and electrical insulation, is desired, the content of the monomer (1) is, for example, 10% by weight or more, preferably 20% by weight or more, more preferably 25% by weight or more, particularly preferably 40% by weight or more, and most preferably 45% by weight or more of the total amount of monomers (particularly radically polymerizable monomers) contained in the polymerizable composition. The upper limit of the content of the monomer (1) is, for example, 100% by weight. In particular, from the viewpoint of efficiently promoting the progress of the radical polymerization reaction and synthesizing a polymer having repeating units derived from the monomer (1), it is preferably 90% by weight, particularly preferably 80% by weight, most preferably 70% by weight, and particularly preferably 65% ​​by weight.

[0027] The polymerizable composition may contain, as a polymerizable compound, one or more other monomers (particularly, radically polymerizable monomers) in addition to the monomer (1).

[0028] Examples of the other monomer include a monomer represented by the following formula (2) (hereinafter, sometimes referred to as "monomer (2)").

[0029] The R １１ ~R １４ are the same or different and represent a fluorine atom, a fluoroalkyl group, a chlorine atom, or a hydrogen atom, and are particularly preferred in that they provide a polymer that is excellent in heat resistance, chemical resistance, weather resistance, and electrical insulation. １１ ~R １４ Preferably, at least one selected from R represents a fluorine atom or a fluoroalkyl group; １１ ~R １４ It is particularly preferred that two or more selected from R １１ ~R １４ It is most preferable that three or more selected from the above represent a fluorine atom or a fluoroalkyl group.

[0030] The fluoroalkyl group is a group in which at least one hydrogen atom of an alkyl group is substituted with a fluorine atom. The alkyl group is, for example, an alkyl group having 1 to 5 carbon atoms, and examples thereof include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, and pentyl. Of these, the alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an alkyl group having 1 or 2 carbon atoms.

[0031] The fluoroalkyl group may be a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms, that is, a perfluoroalkyl group (for example, perfluoro C １－５ alkyl group) is preferred.

[0032] When the polymerizable composition contains both monomer (1) and monomer (2), the content ratio of monomer (1) to monomer (2) (monomer (1) / monomer (2): molar ratio) can be appropriately adjusted depending on the desired application of the polymer. For example, when a polymer with excellent fluorine-atom-derived properties such as heat resistance, chemical resistance, weather resistance, and electrical insulation is desired, it is preferable to increase the content of monomer (1), for example, preferably adjusting the content ratio to within a range of 5 / 95 to 95 / 5. The lower limit of the content ratio is preferably 10 / 90, more preferably 15 / 85, more preferably 20 / 80, even more preferably 30 / 70, particularly preferably 35 / 65, and most preferably 40 / 60. The upper limit of the content ratio is preferably 90 / 10, more preferably 80 / 20, particularly preferably 75 / 25, most preferably 60 / 40, and particularly preferably 55 / 45.

[0033] When the polymerizable composition contains monomer (1) and monomer (2), the total content of monomer (1) and monomer (2) is, for example, 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, particularly preferably 80 mol% or more, most preferably 90 mol% or more, and particularly preferably 95 mol% or more of the total amount of monomers (particularly radically polymerizable monomers) contained in the polymerizable composition. The upper limit of the total content of monomer (1) and monomer (2) is 100 mol%.

[0034] The polymerizable composition may contain, as the polymerizable compound, in addition to the monomer (1) and the monomer (2), a monomer copolymerizable with the monomer (1) (for example, a styrene derivative, a (meth)acrylic acid derivative, an olefin derivative, a vinyl ester derivative, a vinyl ether derivative, a vinyl ketone derivative, etc.) without any particular limitation.

[0035] The polymerizable composition may contain one or more other components in addition to the polymerizable compound, as needed, such as a photo- or thermal-radical polymerization initiator, a solvent, a chain transfer agent, a pigment, a dye, a photosensitizer, a dispersant, a surfactant, a filler, a leveling agent, an antifoaming agent, an antistatic agent, an ultraviolet absorber, a pH adjuster, a surface modifier, a plasticizer, and a drying accelerator.

[0036] (Photoradical polymerization initiator) Examples of the photoradical polymerization initiator include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfite, methyl orthobenzoylbenzoate, ethyl 4-dimethylaminobenzoate (manufactured by Nippon Kayaku Co., Ltd., trade name "Kayacure EPA", etc.), 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name "Kayacure DETX", etc.), 2-methyl-1-[4-(methyl)phenyl]-2-morpholinopropanone-1 (manufactured by Ciba-Geigy Co., Ltd., trade name "Irgacure 907", etc.), 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba-Geigy Co., Ltd., trade name "Irgacure 184", etc.), 2-dimethylamino-2- Examples of the compound include 2-amino-2-benzoyl-1-phenylalkane compounds such as (4-morpholino)benzoyl-1-phenylpropane; aminobenzene derivatives such as tetra(t-butylperoxycarbonyl)benzophenone, benzil, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 4,4'-bis(diethylamino)benzophenone; imidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole (manufactured by Hodogaya Chemical Co., Ltd., trade name "B-CIM", etc.); halomethylated triazine compounds such as 2,6-bis(trichloromethyl)-4-(4-methoxynaphthalen-1-yl)-1,3,5-triazine; and halomethyloxadiazole compounds such as 2-trichloromethyl-5-(2-benzofuran-2-yl-ethenyl)-1,3,4-oxadiazole. These may be used alone or in combination of two or more.

[0037] (Thermal Radical Polymerization Initiator) Examples of the thermal radical polymerization initiator include azo compounds such as azobisisobutyronitrile, and organic peroxides. Examples of the organic peroxides include hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates, peroxyketals, and ketone peroxides (specifically, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoyl)peroxyhexane, t-butylperoxybenzoate, t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-dibutylperoxyhexane, 2,4-dichlorobenzoyl peroxide, 1,4-di(2-t-butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate). These may be used alone or in combination of two or more.

[0038] The amount of the photo- or thermal radical polymerization initiator used (blended amount) is preferably 0.01 to 5% by weight, more preferably 0.1 to 3% by weight, based on the polymerizable composition (100% by weight).

[0039] The content of the photo- or thermal-radical polymerization initiator in the polymerizable composition is, for example, 0.1 to 3.0 parts by weight, preferably 0.3 to 1.0 parts by weight, relative to 100 parts by weight of the polymerizable compound contained in the polymerizable composition.

[0040] (Solvent) Examples of the solvent include halogenated hydrocarbon solvents, etc. The solvents may be used alone or in combination of two or more.

[0041] The halogenated hydrocarbon solvents include chlorine-based solvents such as tetrachloroethylene (perchloroethylene) and trichloroethylene; fluorine-based solvents such as 1,1,1,3,3-pentafluorobutane; and bromine-based solvents such as 1-bromopropane.

[0042] The content of the solvent is, for example, about 50 to 400% by weight based on the total amount of the polymerizable compounds contained in the polymerizable composition. If the amount of the solvent used exceeds the above range, the concentration of the reaction components tends to decrease, and the reaction rate tends to decrease.

[0043] (Chain Transfer Agent) A chain transfer agent is a compound that receives a radical from a growing polymer, stops the polymer growth, and attacks other monomers or the polymer whose growth has stopped with the received radical, thereby initiating polymerization again. By adding a chain transfer agent to the polymerizable composition, a polymer with a narrow molecular weight distribution and excellent uniformity can be obtained.

[0044] The chain transfer agent may be any agent that causes a chain transfer reaction during radical polymerization, and examples thereof include alkanes, halogenated hydrocarbons, phenols, and thiols.

[0045] Examples of the alkanes include methane, ethane, propane, and butane.

[0046] Examples of the halogenated hydrocarbon include alkyl halides such as bromotrichloroethane, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, 1,3-diiodo-n-propane, 1-iodoperfluoro-n-propane, 1,4-diiodoperfluoro-n-butane, 1-iodoperfluoro-n-butane, 1-iodoperfluoro-n-hexane, 1-iodoperfluorohexane, and 1,6-diiodoperfluorohexane; and aryl halides such as trichlorotoluene and tribromotoluene.

[0047] Examples of the thiol include methyl thiol, ethyl thiol, n-propyl thiol, iso-propyl thiol, n-octyl thiol, and phenyl thiol.

[0048] As the chain transfer agent, halogenated hydrocarbons are preferred, and alkyl halides are particularly preferred.

[0049] The content of the chain transfer agent is, for example, 0.5 to 10 mol % based on the polymerizable compound contained in the polymerizable composition.

[0050] The polymerizable composition can be produced by mixing the monomer (1) with other components as required.

[0051] The polymerizable composition has excellent radical polymerizability, and when subjected to a treatment that generates radicals, such as a heat treatment (e.g., a treatment of heating at a temperature of 70 to 150°C) or an active energy ray irradiation treatment (e.g., a treatment of irradiating with ultraviolet rays, electron beams, X-rays, or the like), a radical polymerization reaction is initiated, and radical polymerization of the polymerizable compound contained in the polymerizable composition is initiated, thereby forming a polymer having a repeating unit derived from monomer (1).

[0052] The polymer obtained in this manner contains a repeating unit [1] derived from the monomer (1) and has a large number of tetrafluorosulfanyl groups, and therefore has excellent properties such as heat resistance, chemical resistance, weather resistance, and electrical insulation. Furthermore, since the tetrafluorosulfanyl groups contained in the polymer are bonded to an aromatic hydrocarbon ring or an aromatic heterocycle, the polymer has excellent scratch resistance compared to a polymer without an aromatic hydrocarbon ring or an aromatic heterocycle. Furthermore, the polymer has a high Tg and has even better heat resistance. Furthermore, the tetrafluorosulfanyl groups contained in the polymer are CF ２ Motoi and CF ３ Furthermore, the polymer has thermoplastic properties and can be molded by injection molding or the like.

[0053] The polymerizable composition has the above-described properties, and therefore can be suitably used as a raw material for members (e.g., parts exposed to chemicals, sliding parts, seal materials, lining materials, protective coating materials, coated cables, etc.) used in the fields of semiconductors, automobiles, industrial machinery, chemical industry, civil engineering and construction, electronics and electricity, home appliances, etc.

[0054] [Polymer] The polymer of the present invention is a polymer having a repeating unit [1] derived from the monomer (1).

[0055] The repeating unit [1] derived from the monomer (1) is represented by the following formula (1′): １ , R ２ , R ３ , Ar are R in formula (1), １ , R ２ , R ３ , Ar.

[0056] The proportion of the repeating unit [1] in the total amount of the polymer is, for example, 5 mol % or more. As the proportion of the repeating unit [1] increases, the properties derived from fluorine atoms (for example, heat resistance, chemical resistance, weather resistance, electrical insulation, etc.) tend to improve.

[0057] When a polymer having excellent heat resistance, chemical resistance, weather resistance, and electrical insulation properties is desired, the proportion of the repeating unit [1] in the total amount of the polymer is preferably 10% by weight or more, more preferably 20% by weight or more, even more preferably 25% by weight or more, particularly preferably 40% by weight or more, and most preferably 45% by weight or more. The upper limit of the proportion of the repeating unit [1] is, for example, 100% by weight, preferably 90% by weight, particularly preferably 80% by weight, most preferably 70% by weight, and particularly preferably 65% ​​by weight.

[0058] The polymer may have repeating units derived from the monomer (2) in addition to repeating units derived from the monomer (1).

[0059] The repeating unit [2] derived from the monomer (2) is represented by the following formula (2'): １１ , R １２ , R １３ , R １４ are R in formula (2), respectively. １１ , R １２ , R １３ , R １４ Corresponds to.

[0060] That is, the polymer may be a copolymer having the following repeating unit [1] and the following repeating unit [2]:

[0061] When the polymer is a copolymer, it may be a block copolymer, a graft copolymer, or a random copolymer.

[0062] When the polymer is a copolymer having the repeating unit [1] and the repeating unit [2], the molar ratio of the repeating unit [1] / the repeating unit [2] is preferably adjusted to, for example, a range of 5 / 95 to 95 / 5. The lower limit of the content ratio is preferably 10 / 90, more preferably 15 / 85, more preferably 20 / 80, even more preferably 30 / 70, particularly preferably 35 / 65, and most preferably 40 / 60. The upper limit of the content ratio is preferably 90 / 10, more preferably 80 / 20, particularly preferably 75 / 25, most preferably 60 / 40, and particularly preferably 55 / 45.

[0063] When the polymer is a copolymer having the repeating unit [1] and the repeating unit [2], the total content of the repeating unit [1] and the repeating unit [2] is, for example, 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, particularly preferably 80 mol% or more, most preferably 90 mol% or more, and particularly preferably 95 mol% or more of the total amount of the polymer. The upper limit of the total content of the repeating unit [1] and the repeating unit [2] is 100 mol%.

[0064] The number average molecular weight (Mn) of the polymer is, for example, 1000 or more, and preferably 2000 or more. The upper limit of the number average molecular weight (Mn) is, for example, 100,000, 50,000, or 30,000.

[0065] The molecular weight distribution (Mw / Mn) of the polymer is, for example, 1 to 2.5, preferably 1 to 2.3, and particularly preferably 1 to 2.2.

[0066] In the present invention, Mw and Mn are values ​​calculated as polystyrene equivalents determined by gel permeation chromatography (hereinafter referred to as GPC) analysis.

[0067] The polymer can be produced by polymerizing the monomer (1). For example, the polymer can be produced by subjecting a polymerizable composition containing the monomer (1) to a treatment for generating radicals (heat treatment or active energy ray irradiation treatment).

[0068] When the polymer is a copolymer having the repeating unit [1] and the repeating unit [2], it can be produced by reacting monomer (1) with monomer (2) in a molar ratio of the former / the latter in the range of 5 / 95 to 95 / 5. The copolymer can be produced, for example, by subjecting a polymerizable composition containing monomer (1) and monomer (2) in a molar ratio of the former / the latter in the range of 5 / 95 to 95 / 5 to a treatment that generates radicals, such as a heat treatment or an active energy ray irradiation treatment.

[0069] The polymer contains the repeating unit [1] and has a large number of tetrafluorosulfanyl groups, and therefore has excellent properties such as heat resistance, chemical resistance, weather resistance, and electrical insulation. Furthermore, since the tetrafluorosulfanyl groups contained in the polymer are bonded to aromatic hydrocarbon rings or aromatic heterocycles, the polymer has excellent scratch resistance compared to polymers without aromatic hydrocarbon rings or aromatic heterocycles. Furthermore, the polymer has a high Tg and has even better heat resistance. Furthermore, the tetrafluorosulfanyl groups contained in the polymer are CF ２ Motoi and CF ３ Furthermore, the polymer has thermoplastic properties and can be molded by injection molding or the like.

[0070] Because the polymer has the above-mentioned properties, it can be suitably used as a constituent material for parts (e.g., parts exposed to chemicals, sliding parts, seal materials, lining materials, protective coating materials, coated cables, etc.) used in fields such as semiconductors, automobiles, industrial machinery, chemical industry, civil engineering and construction, electronics and electricity, and home appliances.

[0071] The above-described configurations and combinations of the present invention are merely examples, and the configurations may be added, omitted, substituted, or modified as appropriate without departing from the spirit of the present invention. Furthermore, the present invention is not limited to the embodiments, but is limited only by the claims.

[0072] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0073] Example 1 (Synthesis of Monomer (1-1)) 5-bromopyridin-2-yltetrafluoro-λ ６ 1.5 g of α-sulfanyl chloride and 20 mL of ethyl acetate were added. 2.4 g of trifluoroethylene was introduced thereto, and the mixture was allowed to react at 50°C for 70 hours while irradiating light using a 365 nm LED irradiation device. The mixture was returned to room temperature, and 30 mL of saturated aqueous sodium bicarbonate solution was added little by little to the reaction vessel. Then, organic layer (1) and aqueous layer (1) were separated by a separation operation. The aqueous layer (1) was extracted three times with 20 mL of diethyl ether, and the resulting organic layer (2) was combined with the organic layer (1) and washed three times with 20 mL of water. Then, organic layer (3) was obtained by a separation operation. The solvent was distilled off from the resulting organic layer (3) under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 1.6 g of a yellow liquid (yield 42%). １ H-NMR and １９ It was confirmed by F-NMR that the obtained yellow liquid was a compound represented by the following formula (F-1) (=compound (F-1)).

[0074]

[0075] 0.38 g of compound (F-1) and 10 mL of toluene were added to a reaction vessel, and 0.28 g of potassium hydroxide was added thereto and stirred at room temperature for 24 hours. The reaction solution was filtered, and the filtrate was concentrated to obtain a light brown solid. The obtained light brown solid was purified by silica gel column chromatography to obtain 0.21 g of a white solid (yield 60%). １ H-NMR and １９From F-NMR, it was found that the obtained white solid was 1-(5-bromopyridin-2-yltetrafluoro-λ) represented by the following formula (1-1): ６ The compound was confirmed to be (-sulfanyl)-1,2,2-trifluoroethylene.

[0076] Example 2 (Synthesis of Monomer (1-2)) The same procedure as in Example 1 was carried out except that 2.4 g of trifluoroethylene was changed to 1.8 g of 1,1-difluoroethylene, and 0.18 g of a white solid was obtained (yield 55%). １ H-NMR and １９ F-NMR revealed that the obtained white solid was 1-(5-bromopyridin-2-yltetrafluoro-λ) represented by the following formula (1-2): ６ The compound was confirmed to be (-sulfanyl)-2,2-difluoroethylene.

[0077] Example 3 (Synthesis of Monomer (1-3)) The same procedure as in Example 1 was carried out except that 2.4 g of trifluoroethylene was changed to 1.8 g of 1,2-difluoroethylene, and 0.20 g of a white solid was obtained (yield 61%). １ H-NMR and １９ F-NMR revealed that the obtained white solid was 1-(5-bromopyridin-2-yltetrafluoro-λ) represented by the following formula (1-3): ６ The compound was confirmed to be (-sulfanyl)-1,2-difluoroethylene.

[0078] Example 4 (Synthesis of Monomer (1-4)) The same procedure as in Example 1 was carried out except that 2.4 g of trifluoroethylene was changed to 1.5 g of monofluoroethylene, and 0.16 g of a pale yellow liquid was obtained (yield 52%). １ H-NMR and １９ F-NMR showed that the obtained pale yellow liquid was 1-(5-bromopyridin-2-yltetrafluoro-λ) represented by the following formula (1-4): ６ The compound was confirmed to be (-sulfanyl)-2-fluoroethylene.

[0079] Examples 5 to 20 (Synthesis of Monomers (1-5) to (1-20)) Monomers (1-5) to (1-20) represented by the following formulas were obtained in the same manner as in Example 1.

[0080]

[0081]

[0082] Example 21 (Polymer Synthesis) 3.5 g of monomer (1-1), 0.03 g of di-tert-butyl peroxide, and 20 g of 1,1,1,3,3-pentafluorobutane were added to an autoclave. 1.5 g of monomer (2-1) was added thereto, and the mixture was gradually heated from room temperature to 140°C while stirring. After stirring at 140°C for 5 hours, the mixture was cooled to room temperature. Unreacted monomer (2-1) was removed from the reaction solution. The reaction solution from which the unreacted monomer had been removed was poured into methanol, and the resulting solid was filtered off and dried under vacuum. １９ F-NMR analysis of the obtained solid showed that the polymer had a molar ratio of repeating units derived from monomer (1-1) to repeating units derived from monomer (2-1) [(1-1) / (2-1)] of 20 / 80. GPC analysis of the polymer showed that it had a number average molecular weight (Mn) of about 2,800 and a molecular weight distribution (Mn / Mw) of 2.2.

[0083] Examples 22 to 34 (Synthesis of Polymers) Polymers were synthesized in the same manner as in Example 21, except that Monomer (1) and Monomer (2) were changed as shown in the table below.

[0084]

[0085] The monomers (2) used in the examples are explained below: Monomer (2-1): vinylidene fluoride Monomer (2-2): tetrafluoroethylene Monomer (2-3): hexafluoropropene Monomer (2-4): chlorotrifluoroethylene

[0086] Example 35 (Polymer Synthesis) To an autoclave were added 3.5 g of monomer (1-1), 0.3 g of di-tert-butyl peroxide, 1.4 g of 1-iodoperfluorohexane as a chain transfer agent (corresponding to 2.3 mol % relative to the total of monomer (1-1), monomer (2-1), and monomer (2-3)), and 35 g of 1,1,1,3,3-pentafluorobutane. 6.4 g of monomer (2-1) and 3.4 g of monomer (2-3) were added thereto, and the temperature was gradually increased from room temperature to 75°C with stirring. After stirring at 75°C for 6 hours, the mixture was cooled to room temperature. Unreacted monomer was removed from the reaction solution. The reaction solution from which the unreacted monomer had been removed was added to methanol, and the resulting solid was filtered off and dried under vacuum. １９ F-NMR analysis of the obtained solid revealed that the polymer had a molar ratio of repeating units derived from monomer (1-1), repeating units derived from monomer (2-1), and repeating units derived from monomer (2-3) [(1-1) / (2-1) / (2-3)] of 5 / 80 / 15. GPC analysis of the polymer revealed that the number average molecular weight (Mn) was approximately 5,200 and the molecular weight distribution (Mn / Mw) was 1.3.

[0087] The above examples demonstrate that the monomer of the present invention can be (co)polymerized to form a fluoropolymer. Furthermore, the fluoropolymer thus formed possesses various functions (e.g., water repellency, oil repellency, lubricity, transparency, heat resistance, chemical resistance, etc.) due to the inclusion of fluorine atoms. Furthermore, since the fluoropolymer contains an aromatic ring, it has a high Tg and is excellent in heat resistance and scratch resistance. Furthermore, by bonding any substituent to the aromatic ring of the monomer of the present invention, a fluoropolymer having a desired function can be easily formed. Therefore, the monomer of the present invention can be suitably used as a material for forming a functional fluoropolymer.

[0088] Comparative Example 1 An unsaturated compound represented by the following formula was obtained by the method described in International Publication No. 2014 / 062221. Polymerization was then carried out in the same manner as in Example 21, except that the obtained unsaturated compound was used instead of monomer (1). However, the obtained solid was １９F-NMR analysis revealed no peaks derived from the unsaturated compound, and the desired fluoropolymer could not be obtained.

[0089]

Claims

1. A monomer represented by the following formula (1): (In the formula, R １ , R ２ , R ３ are the same or different and represent a fluorine atom, a chlorine atom, or a hydrogen atom. １ , R ２ , and R ３ At least one selected from the group consisting of: represents a fluorine atom; and Ar represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, which may have a substituent.

2. A polymerizable composition comprising the monomer of claim 1.

3. A polymer having repeating units derived from the monomer of claim 1.

4. A method for producing a polymer, comprising reacting a monomer represented by the following formula (1) with a monomer represented by the following formula (2) in a molar ratio of the former / latter of 5 / 95 to 95 / 5 to obtain a polymer having a repeating unit [1] derived from the monomer represented by formula (1) and a repeating unit [2] derived from the monomer represented by formula (2), wherein the proportion of the repeating unit [1] in the total of the repeating units [1] and [2] is 5 mol % or more. (In formula (1), R １ , R ２ , R ３ are the same or different and represent a fluorine atom, a chlorine atom, or a hydrogen atom. １ , R ２ , and R ３ At least one selected from the group consisting of: represents a fluorine atom; Ar represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, which may have a substituent; (In formula (2), R １１ ~R １４ are the same or different and represent a fluorine atom, a fluoroalkyl group, a chlorine atom, or a hydrogen atom.

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