Fluorine-containing polymer and method for producing the same

Abstract

To provide a fluorine-containing polymer having excellent curability and low dielectric properties after being cured, and a method of producing the fluorine-containing polymer.SOLUTION: A fluorine-containing polymer has a fluorine content of 50 mass% or more, a degree of unsaturation of 0.1 mEq / g or more, and a glass transition temperature of -20°C or higher, and the relationship between the maximum value E*1 of the complex elastic modulus in the range of from -50°C to (glass transition temperature-10°C) and the minimum value E*2 of the complex elastic modulus in the range of from (glass transition temperature+10°C) to 250°C satisfies the following inequality: E*2 / E*1≤0.01.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to fluorine-containing polymers and methods for producing the same. [Background technology]

[0002] Radical polymerization reactions are widely used industrially because they are versatile in terms of monomers and can be easily carried out in polar media such as water.

[0003] When haloolefin, particularly fluoroolefin, is used as a monomer, a haloolefin polymer can be synthesized. The haloolefin polymer is useful as a raw material for low-reactivity carbon-carbon double bond solvent, low-reactivity solvent, heat transfer medium, pharmaceutical and agrochemical intermediate, fire extinguishing agent, surfactant, surface treatment agent, low-friction sliding material, mold release material, resin molding additive, chemical-resistant grease, low refractive index material, low dielectric constant material, heat-resistant elastomer, thermoplastic elastomer, flame retardant material, chemical-resistant ionomer, photoresist material, etc.

[0004] One known method for polymerizing haloolefins is the method described in Patent Document 1. Patent Document 1 describes a radical polymerization method in which a specific haloolefin is radically polymerized in the presence of a specific organotellurium compound to produce a haloolefin polymer or copolymer. This method is called the TERP (organotellurium-mediated living radical polymerization) method. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2018 / 164147 Summary of the Invention [Problem to be solved by the invention]

[0006] Since the cured product of the fluorine-containing polymer has excellent dielectric properties, it is used as a low dielectric material in various electronic components. In particular, with the recent development of high-speed communication technology, the demand for low dielectric materials capable of reducing the loss of high-frequency signals is increasing. The inventors have considered developing a fluorine-containing polymer as a lamination material for the interlayer insulating film of a multilayer wiring board. Since a multilayer wiring board is formed by repeatedly arranging metal wiring and laminating interlayer insulating films, the material of the interlayer insulating film is required to be laminationable by heat curing. In addition, in order to ensure insulation between wiring, the interlayer insulating film is required to have high dimensional accuracy. In order to achieve such lamination and dimensional accuracy, it is desirable that the material of the interlayer insulating film has high curability. However, no knowledge has been obtained so far regarding a method that can achieve both excellent curability and low dielectric properties of the cured product in a fluorine-containing polymer.

[0007] For example, the fluorine-containing polymer obtained by the method described in Patent Document 1 can be used as a curable material by introducing a curable group. However, since the molecular chain of the fluorine-containing polymer is linear, the cured product has a low crosslink density and it is difficult to obtain sufficient curability.

[0008] In view of the above circumstances, an object of the present disclosure is to provide a fluorine-containing polymer having excellent curability and low dielectric properties of a cured product, and a method for producing the fluorine-containing polymer. [Means for solving the problem]

[0009] Means for solving the above problems include the following aspects. <1> The fluorine content is 50% by mass or more, the degree of unsaturation is 0.1 mEq / g or more, the glass transition temperature is -20°C or more, and the maximum complex modulus E in the range of -50°C to (glass transition temperature -10°C) * 1 and the minimum value E of the complex modulus in the range of (glass transition temperature + 10°C) to 250°C * The relationship between 2 and E * 2 / E * Fluorine-containing polymer satisfying the relationship: 1≦0.01. <2> The polydispersity is 2.0 or less. <1> The fluorine-containing polymer according to claim 1. <3> The weight average molecular weight is 1,000 to 1,000,000. <1> or <2> The fluorine-containing polymer according to claim 1. <4> A polymer of a compound represented by the following formula (1): A copolymer of a compound represented by the following formula (1) and a compound having a reactive carbon-carbon double bond and different from the compound represented by formula (1): <1> ~ <3> 13. The fluorine-containing polymer according to claim 12.

[0010] [ka]

[0011] In formula (1), Y 7 R represents a divalent organic group having at least one fluorine atom. 1 ~R 6 R 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 5 carbon atoms. 1 and R 3 , R 4 and R 5 , R 2 and Y 7 , and R 6 and Y 7 may each independently be linked to each other to form a cyclic structure. <5> The fluorine content of the compound represented by formula (1) is 20% by mass or more. <4> The fluorine-containing polymer according to claim 1. <6> Y in the formula (1) 7 is a fluoroalkylene group having 1 to 60 carbon atoms, a fluoropolyether group having 1 to 60 carbon atoms, or a fluoroarylene group having 1 to 60 carbon atoms; <4> or <5> The fluorine-containing polymer according to claim 1. <7> The compound represented by the formula (1) contains at least one selected from the group consisting of divinylfluoroalkanes having 5 to 64 carbon atoms, divinylfluoropolyethers having 5 to 64 carbon atoms, and divinylfluoroarylenes having 5 to 64 carbon atoms. <4> ~ <6> 13. The fluorine-containing polymer according to claim 12. <8> In the presence of an ionic catalyst represented by the following formula (2) consisting of an anion and a counter cation, and a compound having a partial structure represented by the following formula (3), or In the presence of at least one compound selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the following formula (5), comprising polymerizing a compound having at least two reactive carbon-carbon double bonds, <1> ~ <7> 13. The method for producing the fluorine-containing polymer according to claim 12.

[0012] [ka]

[0013] In formula (2), A + represents a cation containing at least one element selected from the group consisting of nitrogen and phosphorus, an alkali metal ion, or a proton; B - represents a monovalent anion containing at least one element selected from the group consisting of iodine, nitrogen, and sulfur.

[0014] [ka]

[0015] In formula (3), * represents a bond bonded to an organic group. X 1 and X 2 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, or -CX 3 X 4 X 5 Represents X. 3 ~X 5 each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

[0016] [ka]

[0017] In formula (4), Y 1 represents an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, or a substituted aryl group having 3 to 16 carbon atoms. Y 2 and Y 3 Each of Y independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 4 represents a hydrogen atom, an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, a substituted 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 group, or a cyano group.

[0018] [ka]

[0019] In formula (5), Y 5 and Y 6 each independently represents an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, or a substituted aryl group having 3 to 16 carbon atoms. <9> The compound having at least two reactive carbon-carbon double bonds includes a compound represented by the following formula (1): <8> A method for producing the fluorine-containing polymer described in

[0020] [ka]

[0021] In formula (1), Y 7 R represents a divalent organic group having at least one fluorine atom. 1 ~R 6 R 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 5 carbon atoms. 1and R 3 , R 4 and R 5 , R 2 and Y 7 , and R 6 and Y 7 may each independently be linked to each other to form a cyclic structure. <10> The method includes copolymerizing the compound represented by formula (1) with a compound having a reactive carbon-carbon double bond and different from the compound represented by formula (1), <9> A method for producing the fluorine-containing polymer described in Effect of the Invention

[0022] According to the present disclosure, there are provided a fluorine-containing polymer having excellent curability and low dielectric properties of the cured product, and a method for producing the fluorine-containing polymer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] Hereinafter, the embodiment for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiment. In the following embodiment, the components (including element steps, etc.) are not essential unless specifically stated. The same applies to the numerical values ​​and their ranges, and they do not limit the present invention.

[0024] In the present disclosure, the term "step" includes not only a step that is independent of other steps, but also a step that cannot be clearly distinguished from other steps as long as the purpose of the step is achieved. In the present disclosure, a numerical range indicated using "~" includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the present disclosure, each component may contain multiple types of the corresponding substance. 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. The term "aryl group" refers to a monovalent group equivalent to the residue obtained by removing one hydrogen atom bonded to any one of the carbon atoms constituting an aromatic ring in an aromatic compound, and is used as a general term that includes both a homoaryl group derived from a carbocyclic compound and a heteroaryl group derived from a heterocyclic compound. The term "arylene group" refers to a divalent group corresponding to a residue obtained by removing one hydrogen atom bonded to any one of the carbon atoms of an aryl group. In this 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, the number of carbon atoms in a compound or a component thereof means the number including the number of carbon atoms in the substituent when the compound or component 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. A "polymer" and an "oligomer" are compounds formed by polymerization of monomers. That is, a "polymer" and an "oligomer" have a plurality of structural units. In this disclosure, unless otherwise specified, the description "polymerizing compound A" includes both the case where only compound A is polymerized and the case where compound A is polymerized with another compound. In addition, the description "polymerizing compound A and compound B" includes both the case where only compound A and compound B are polymerized, and the case where compound A, compound B and another compound are polymerized. Here, compound A and compound B represent any compound described in this disclosure having a reactive carbon-carbon double bond in the molecule. In addition, 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.

[0025] <Fluorine-containing polymer> The fluorine-containing polymer of the present disclosure (hereinafter also simply referred to as a fluorine-containing polymer) has a fluorine content of 50 mass% or more, a degree of unsaturation of 0.1 mEq / g or more, a glass transition temperature (Tg) of -20°C or more, and a maximum complex modulus E in the range of -50°C to (glass transition temperature -10°C). * 1 and the minimum value E of the complex modulus in the range of (glass transition temperature + 10°C) to 250°C * The relationship between 2 and E * 2 / E * The relationship satisfies 1≦0.01.

[0026] The fluorine-containing polymer of the present disclosure can be used as a curable material. The fluorine-containing polymer of the present disclosure is a polymer, for example, an oligomer, formed by polymerizing a monomer having a reactive carbon-carbon double bond, and is a compound having an unsaturated bond. The fluorine-containing polymer of the present disclosure has a degree of unsaturation of 0.1 mEq / g or more, and therefore, when a cured product is produced using the fluorine-containing polymer, a cured product with high crosslink density can be obtained. Furthermore, the glass transition temperature of the fluorine-containing polymer of the present disclosure is -20°C or more, and therefore, when the cured product is cured, good hardness can be obtained, and in combination with the above-mentioned high crosslink density, a cured product with excellent mechanical strength can be obtained. In addition, the fluorine-containing polymer of the present disclosure has a fluorine content of 50% by mass or more, and therefore, a cured product with high fluorine content and excellent low dielectric properties can be obtained. In addition, the fluorine-containing polymer of the present disclosure has the above-mentioned E * 2 / E * 1≦0.01. Usually, polymers that do not melt at temperatures up to 250°C have an E * 2 / E * The relationship of 1≦0.01 is not satisfied. Fluorine-containing polymer is E * 2 / E * Satisfying the relationship of 1≦0.01 is considered to be an index of the melting of the fluorine-containing polymer. When the fluorine-containing polymer satisfies the above relationship, it becomes possible to perform suitable melt molding, and it can be preferably used as a curable material. Due to the above characteristics, the fluorine-containing polymer of the present disclosure is particularly useful as a curable material used in applications where excellent curability and low dielectric properties are desired.

[0027] The fluorine content of the fluorine-containing polymer is 50% by mass or more, and from the viewpoint of low dielectric properties of the cured product, a high fluorine content is preferable. For example, the fluorine content of the fluorine-containing polymer is preferably 55% by mass or more, and more preferably 60% by mass or more. The fluorine content of the fluorine-containing polymer may be 76% by mass or less. From this viewpoint, the fluorine content of the fluorine-containing polymer is preferably 50% by mass to 76% by mass, more preferably 55% by mass to 76% by mass, and even more preferably 60% by mass to 76% by mass. The fluorine content of a compound is a value determined by combustion ion chromatography. The fluorine content of a compound can also be confirmed by nuclear magnetic resonance (NMR) within an error range of, for example, about ±10%.

[0028] The degree of unsaturation of the fluorine-containing polymer is 0.1 mEq / g or more. From the viewpoint of increasing the number of crosslinking points and further improving the curability, the degree of unsaturation of the fluorine-containing polymer is preferably 0.3 mEq / g or more, more preferably 0.4 mEq / g or more, even more preferably 0.5 mEq / g or more, and may be 1.0 mEq / g or more, or may be 1.5 mEq / g or more. The upper limit of the degree of unsaturation of the fluorine-containing polymer is not particularly limited, and is preferably adjusted according to the desired physical properties of the cured product. For example, the degree of unsaturation of the fluorine-containing polymer may be 10 mEq / g or less. The degree of unsaturation of the fluorine-containing polymer can be adjusted by the type of the raw material monomer, the polymerization method, and the like.

[0029] In the present disclosure, the degree of unsaturation of a fluorine-containing polymer is measured by a method based on the microtitration method specified in JIS K 1557-3:2007 (corresponding international standard: ISO 17710:2002). Specifically, it is measured by the following method. Prepare the following reagents: 0.05 mol / L methanolic mercuric acetate solution (Hg(C2H3O2)2), 0.05 mol / L methanolic potassium hydroxide solution, 0.05 mol / L methanolic hydrochloric acid solution, sodium bromide, and methanol. Add 2 mL of mercuric acetate solution to the tetrahydrofuran solution of the sample, stir, and allow the solution to stand for 30 minutes. Add 50 mL of methanol, then add 0.25 g of sodium bromide. Titrate with potassium hydroxide solution using an automatic titrator. Perform a blank test in the same manner, but without adding the sample. To correct the results, prepare a sample solution in a system excluding mercuric acetate, and measure the acidity or basicity of the sample using potassium hydroxide solution or hydrochloric acid solution. Calculate the unsaturation of the sample using the following formula.

[0030] U=[(V S -V B )×c(KOH) / m]-A+B U: Unsaturation degree (mEq / g) V S : Amount of 0.05 mol / L potassium hydroxide solution required for the sample solution (mL) V B : Amount of 0.05 mol / L potassium hydroxide solution required for blank test (mL) c(KOH): Concentration of methanolic potassium hydroxide solution (mEq / mL) m: sample size (g) A: Acidity (mEq / g) B: Basicity (mEq / g)

[0031] The degree of unsaturation of the fluorine-containing polymer can also be confirmed by nuclear magnetic resonance (NMR) within an error range of, for example, about ±10%.

[0032] The number of reactive carbon-carbon double bonds in the fluorine-containing polymer is not particularly limited as long as the fluorine-containing polymer satisfies the above-mentioned degree of unsaturation. From the viewpoint of increasing the crosslink density to obtain good mechanical strength and dielectric properties, the number of reactive carbon-carbon double bonds contained in one molecule of the fluorine-containing polymer is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more on average. From the viewpoint of efficiently suppressing gelation in the production process of the fluorine-containing polymer, the number of reactive carbon-carbon double bonds contained in one molecule of the fluorine-containing polymer may be 10 or less on average. From this viewpoint, the number of reactive carbon-carbon double bonds contained in one molecule of the fluorine-containing polymer is preferably 2 to 10 on average, more preferably 3 to 10, and even more preferably 4 to 10.

[0033] The glass transition temperature of the fluorine-containing polymer is -20°C or higher. From the viewpoint of mechanical strength when cured, the glass transition temperature of the fluorine-containing polymer is preferably -10°C or higher, more preferably -5°C or higher, and even more preferably 0°C or higher. There is no particular upper limit to the glass transition temperature, and from the viewpoint of melt moldability, it may be, for example, 150°C or lower. The glass transition temperature is measured by differential scanning calorimetry (DSC).

[0034] In fluorine-containing polymers, the maximum complex modulus E in the range of -50°C to (glass transition temperature -10°C) * 1 and the minimum value E of the complex modulus in the range of (glass transition temperature + 10°C) to 250°C * The relationship between 2 and E * 2 / E * As described above, the complex modulus of the fluorine-containing polymer satisfies E * 2 / E * Satisfying the relationship of 1≦0.01 is an indicator that the fluorine-containing polymer melts. * 2 / E * 1 may be 0.001 or less, or may be 0.0001 or less. The complex elastic modulus is measured based on JIS K 7244-1:1998 (corresponding to ISO 6721-1:1994), JIS K 7244-4:1999 (corresponding to ISO 6721-4:1994), and JIS K 7244-6:1999 (corresponding to ISO 6721-6:1996).

[0035] The minimum complex modulus E of a fluorine-containing polymer in the range of (glass transition temperature + 10°C) to 250°C * From the viewpoint of ease of molding, E2 is preferably 10,000,000 Pa or less, more preferably 1,000,000 Pa or less, even more preferably 100,000 Pa or less, and particularly preferably 10,000 Pa or less. * The lower limit of 2 is not particularly limited, and may be 1 Pa or more.

[0036] The maximum complex modulus E of a fluorine-containing polymer in the range of -50°C to (glass transition temperature -10°C) * The range of 1 is E * 2 / E * There are no particular limitations as long as the relationship 1≦0.01 is satisfied.

[0037] The weight average molecular weight (Mw) of the fluorine-containing polymer is not particularly limited, and from the viewpoint of mechanical strength and low dielectric loss characteristics, it is preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 5,000 or more. From the viewpoint of flowability during melt molding, the weight average molecular weight of the fluorine-containing polymer is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less. From such a viewpoint, the weight average molecular weight of the fluorine-containing polymer is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000, and even more preferably 5,000 to 200,000.

[0038] The number average molecular weight (Mn) of the fluorine-containing polymer is not particularly limited, and from the viewpoint of mechanical strength and low dielectric loss characteristics, it is preferably 500 or more, more preferably 1,000 or more, and even more preferably 2,500 or more. From the viewpoint of flowability during melt molding, it is preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From such a viewpoint, the weight average molecular weight of the fluorine-containing polymer is preferably 500 to 500,000, more preferably 1,000 to 250,000, and even more preferably 2,500 to 100,000.

[0039] In the present disclosure, the number average molecular weight (Mn) and weight average molecular weight (Mw) are determined by SEC (Size Exclusion Chromatography) measurement, and polystyrene is used as a standard substance for molecular weight conversion.

[0040] The polydispersity of the fluorine-containing polymer is preferably 2.0 or less, more preferably 1.8 or less, even more preferably 1.6 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less. By having the polydispersity in this range, the variation in curability is reduced, and a highly uniform cured product is obtained. The lower limit of the polydispersity is 1.0 by definition.

[0041] Polydispersity (PD) is an index of molecular weight distribution and is calculated by the following formula: {PD=Mw(weight average molecular weight) / Mn(number average molecular weight)} The polydispersity can be adjusted to the above range by employing a polymerization method with high controllability, such as Production Method A and Production Method B described below.

[0042] The fluorine-containing polymer is preferably soluble in a solvent in which the raw material monomer can be dissolved. The fact that it is soluble in such a solvent is an indicator that the fluorine-containing polymer is not gelled, and since the fluorine-containing polymer is not gelled, it can be suitably used as a molding material. Gelled means a state in which the weight-average molecular weight (Mw) of the compound is infinitely dispersed. A gelled compound has an insoluble and infusible three-dimensional network structure. The fluorine-containing polymer is preferably soluble in, for example, 1H-perfluorohexane, benzotrifluoride, or tetrahydrofuran. Soluble means that 1 g or more of the fluorine-containing polymer is dissolved in 100 mL of the solvent.

[0043] The fluorine-containing polymer is a polymer of a compound having a reactive carbon-carbon double bond. Here, the "compound having a reactive carbon-carbon double bond" is a constituent of the obtained fluorine-containing polymer, typically a monomer. The fluorine-containing polymer may be a polymer of one type of monomer, or a copolymer of multiple types of monomers. The copolymer may be a block copolymer, a random copolymer, or an alternating copolymer.

[0044] The fluorine content of the compound having a reactive carbon-carbon double bond is preferably 20% by mass or more, and from the viewpoint of low dielectric properties of the obtained cured product, it is more preferably 30% by mass or more, and even more preferably 40% by mass or more. From the viewpoint of moldability such as solvent solubility, the fluorine content of the compound having a reactive carbon-carbon double bond may be 76% by mass or less. From the above viewpoints, the fluorine content of the compound having a reactive carbon-carbon double bond is preferably 20% by mass to 76% by mass, more preferably 30% by mass to 76% by mass, and even more preferably 40% by mass to 76% by mass.

[0045] The fluorine-containing polymer is preferably a polymer of a compound having at least two reactive carbon-carbon double bonds. When a compound having at least two reactive carbon-carbon double bonds is polymerized, a large number of branches and crosslinking points can be introduced, and therefore, when the obtained fluorine-containing polymer is further cured, a denser crosslinking structure can be formed. The number of reactive carbon-carbon double bonds in the compound having reactive carbon-carbon double bonds may be, for example, 2 to 6, 2 to 4, or 2 or 3.

[0046] In one embodiment, the fluorine-containing polymer is A polymer of a compound represented by the following formula (1): It may be a copolymer of a compound represented by the following formula (1) and a compound having a reactive carbon-carbon double bond and different from the compound represented by the formula (1).

[0047] [ka]

[0048] In formula (1), Y 7 R represents a divalent organic group having at least one fluorine atom. 1 ~R 6 R 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 5 carbon atoms. 1 and R 3 , R 4 and R 5 , R 2 and Y 7 , and R 6 and Y 7 may each independently be linked to each other to form a cyclic structure.

[0049] In formula (1), Y 7 The number of carbon atoms is not particularly limited, and is preferably 1 to 60, more preferably 1 to 40, and may be 2 to 30, or may be 3 to 20.

[0050] Y in formula (1) 7Examples of the alkyl group include a fluoroalkylene group having 1 to 60 carbon atoms, a fluoropolyether group having 1 to 60 carbon atoms, and a fluoroarylene group having 1 to 60 carbon atoms. Among these, a perfluoroalkylene group having 1 to 60 carbon atoms, a perfluoropolyether group having 1 to 60 carbon atoms, and a perfluoroarylene group having 1 to 60 carbon atoms are preferred.

[0051] R 1 ~R 6 Examples of the organic group having 1 to 5 carbon atoms and represented by the formula (I) include a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms. Examples of the substituent include a carbonyl group.

[0052] From the viewpoint of low dielectric loss, R 1 ~R 6 are preferably each independently a hydrogen atom, a fluorine atom, or a methyl group.

[0053] From the viewpoint of polymerization, Y 7 Atoms bonded to the atoms on both ends of and R 1 ~R 6 In this case, it is preferable that at least one selected from the group consisting of is a fluorine atom. 7 The atoms on both ends of 7 It refers to the atoms bonded to the two double bonds in formula (1).

[0054] In formula (1), R 1 and R 3 , R 4 and R 5 , R 2 and Y 7 , and R 6 and Y 7 may each independently be linked to each other to form a cyclic structure. 1 and R 3 are linked together to form a ring structure" means that R 1 Any atom in and R 3 It means that any atom included in R is bonded to form a ring structure. 4 and R 5 , R 2 and Y 7 , or R6 and Y 7 The same applies to the case where they are linked to each other to form a cyclic structure. The compound represented by formula (1) may be a compound having a cyclic structure, such as maleic anhydride or itaconic anhydride.

[0055] The fluorine content of the compound represented by formula (1) is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more from the viewpoint of low dielectric properties of the obtained cured product. The fluorine content of the compound represented by formula (1) may be 76% by mass or less. From the above viewpoints, the fluorine content of the compound represented by formula (1) is preferably 20% by mass to 76% by mass, more preferably 30% by mass to 76% by mass, and further preferably 40% by mass to 76% by mass.

[0056] The compound represented by formula (1) may be at least one selected from the group consisting of divinyl fluoroalkanes having 5 to 64 carbon atoms, divinyl fluoropolyethers having 5 to 64 carbon atoms, and divinyl fluoroarylenes having 5 to 64 carbon atoms. Among them, at least one selected from the group consisting of divinyl perfluoroalkanes having 5 to 64 carbon atoms, divinyl perfluoropolyethers having 5 to 64 carbon atoms, and divinyl perfluoroarylenes having 5 to 64 carbon atoms is preferred. The compound represented by formula (1) may be used alone or in combination of two or more.

[0057] Specific examples of the compound represented by formula (1) include the following exemplary compounds. Among them, 1,6-divinyldodecafluorohexane and 1,4-divinyloctafluorobutane are preferred. In the following exemplary compounds, * indicates that the substitution position of the substituent on the aromatic ring is not limited.

[0058] [ka]

[0059] [ka]

[0060] Further, the maleimide compounds exemplified below are also preferred examples of the compound represented by formula (1).

[0061] [ka]

[0062] [ka]

[0063] The compound having a reactive carbon-carbon double bond and different from the compound represented by formula (1) to be used in the copolymerization is not particularly limited as long as it is a compound copolymerizable with the compound represented by formula (1). For example, (meth)acrylic acid ester monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, and lauryl (meth)acrylate; 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-3-acryloyloxypropyl unsaturated monomers containing a quaternary ammonium base, such as N-methyl-N,N,N-trimethylammonium chloride and N-methacryloylaminoethyl-N,N,N-dimethylbenzylammonium chloride; unsaturated monomers containing an epoxy group, such as glycidyl (meth)acrylate; styrene monomers, such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 2-chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 1-vinylnaphthalene, divinylbenzene, 4-(chloromethyl)styrene, 2-(chloromethyl)styrene, 3-(chloromethyl)styrene, 4-styrenesulfonic acid or its alkali metal salts (sodium salt, potassium salt, etc.); unsaturated monomers containing a heterocycle, such as 2-vinylthiophene and N-methyl-2-vinylpyrrole; vinyl amides, such as N-vinylformamide and N-vinylacetamide;Diallylamine, triallyl isocyanurate, tri(2-methylallyl) isocyanurate, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 2,3,3,3-tetrafluoropropylene, vinylidene chloride, vinyl chloride, 1-chloro-1-fluoroethylene, or 1,2-dichloro-1,2-difluoroethylene, 1H,1H,2H-perfluoro(n-1-hexene), 1H,1H,2H-perfluoro(n-1-octene), Examples of the compound include α-olefins such as isobutene, 1, vinyl acetate, hydroxyethyl methacrylate, acrylonitrile, acrylamide, N,N-dimethylacrylamide, alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether; and perfluoro(alkyl vinyl ethers) such as hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), and perfluoro(n-propyl vinyl ether). The compound having a reactive carbon-carbon double bond and different from the compound represented by the formula (1) may be used alone or in combination of two or more.

[0064] <Method for producing fluorine-containing polymer> The method for producing the fluorine-containing polymer of the present disclosure is not particularly limited. In one embodiment, the method for producing the fluorine-containing polymer includes the following steps: In the presence of an ionic catalyst represented by the following formula (2) consisting of an anion and a counter cation, and a compound having a partial structure represented by the following formula (3), or In the presence of at least one compound selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the following formula (5), It involves polymerizing a compound having at least two reactive carbon-carbon double bonds.

[0065] [ka]

[0066] In formula (2), A + represents a cation containing at least one element selected from the group consisting of nitrogen and phosphorus, an alkali metal ion, or a proton; B - represents a monovalent anion containing at least one element selected from the group consisting of iodine, nitrogen, and sulfur.

[0067] [ka]

[0068] In formula (3), * represents a bond bonded to an organic group. X 1 and X 2 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, or -CX 3 X 4 X 5 Represents X. 3 ~X 5 each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

[0069] [ka]

[0070] In formula (4), Y 1 represents an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, or a substituted aryl group having 3 to 16 carbon atoms. Y 2 and Y 3 Each of Y independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 4 represents a hydrogen atom, an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, a substituted 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 group, or a cyano group.

[0071] [ka]

[0072] In formula (5), Y 5 and Y 6 each independently represents an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, or a substituted aryl group having 3 to 16 carbon atoms.

[0073] The method for producing the above fluorine-containing polymer uses a polymerization method with high controllability. Although the fluorine-containing polymer of the present disclosure can also be produced by free radical polymerization, when the above polymerization method with high controllability is adopted, gelation due to the rapid progress of crosslinking is suppressed, and a fluorine-containing polymer with a high degree of unsaturation and moldability can be preferably obtained. Further, by using such a fluorine-containing polymer, a cured product with a high crosslink density can be preferably obtained.

[0074] <A method for producing a fluorine-containing polymer, comprising polymerizing a compound having at least two reactive carbon-carbon double bonds in the presence of an ionic catalyst represented by formula (2) composed of an anion and a counter cation and a compound having a partial structure represented by formula (3)> A method for producing a fluorine-containing polymer, comprising polymerizing a compound having at least two reactive carbon-carbon double bonds in the presence of an ionic catalyst represented by formula (2) composed of an anion and a counter cation and a compound having a partial structure represented by formula (3), is based on a polymerization method called the RCMP (Reversible Complexation Mediated living radical Polymerization) method. Hereinafter, this production method is also referred to as production method A.

[0075] The schematic diagram of the manufacturing method A is shown in the figure below. The CI bond in the compound having the partial structure represented by formula (3) is broken by the ionic catalyst represented by formula (2) to generate a carbon radical. The generated carbon radical reacts with the compound having a reactive carbon-carbon double bond. On the other hand, the bond between I derived from the compound having the partial structure represented by formula (3) and the ionic catalyst is a reversible reaction, and I is recombined with the carbon radical after the reaction with the compound having a reactive carbon-carbon double bond, so that the reaction product becomes the compound having the partial structure represented by formula (3) again. That is, an insertion reaction of the compound having a reactive carbon-carbon double bond into the compound having the partial structure represented by formula (3) occurs.

[0076] [ka]

[0077] In the above scheme, in the compound having a reactive carbon-carbon double bond, R represents any atom or group of atoms, and * represents a single bond or a divalent organic group.

[0078] The insertion reaction is repeated by extracting again I bound to the compound produced by the above reaction by the ionic catalyst represented by formula (2), thereby producing a polymer.

[0079] A compound having a partial structure represented by formula (3) functions as a radical initiator. Conventionally, azo compounds, peroxides, etc. have generally been used as radical initiators, but when these radical initiators are used, the reaction rate is generally very fast, making it difficult to control the reaction. In contrast, by using a compound having a partial structure represented by formula (3) as a radical initiator in the presence of an ionic catalyst represented by formula (2), the reaction proceeds very slowly, making it possible to control the reaction.

[0080] [Ionic Catalyst] The ionic catalyst represented by the following formula (2) consisting of an anion and a counter cation will be described in detail below.

[0081] [ka]

[0082] In formula (2), A + represents a cation containing at least one element selected from the group consisting of nitrogen and phosphorus, an alkali metal ion, or a proton. - represents a monovalent anion containing at least one element selected from the group consisting of iodine, nitrogen, and sulfur.

[0083] B - Among the monovalent anions represented by the formula, the iodine anion is the iodide ion (I - ), triiodide ion (I3 - ) and others. Other anions include azide ion (N3 - ), cyanide ion (CN - ), cyanate anion (OCN - ), thiocyanate ion (SCN - ) etc. Among these, from the viewpoint of interaction with the iodine atom of the compound having the partial structure represented by formula (3), iodine anion is preferred, and iodide ion is more preferred.

[0084] A + Among the counter cations represented by the formula (I), examples of cations containing nitrogen include tetrabutylammonium ((C4H9)4N + Examples of quaternary ammonium cations that contain phosphorus include tetraphenylphosphonium ((C6H5)4P + ) and other quaternary phosphonium cations. Examples of the alkali metal ion include a lithium ion, a sodium ion, a potassium ion, a rubidium ion, and a cesium ion. Among these, from the viewpoint of heat resistance, phosphorus-containing cations or alkali metal ions are preferred, and from the viewpoint of reactivity, quaternary phosphonium cations are more preferred, with tetraphenylphosphonium being even more preferred.

[0085] The ionic catalyst represented by formula (2) is preferably tetraphenylphosphonium iodide, tetrabutylammonium iodide, cesium iodide, lithium iodide, etc. The ionic catalyst represented by formula (2) may be used alone or in combination of two or more.

[0086] [Compound having a partial structure represented by formula (3)] The compound having the partial structure represented by formula (3) will be described in detail below.

[0087] [ka]

[0088] In formula (3), * represents a bond bonded to an organic group. X 1 and X 2 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, or -CX 3 X 4 X 5 Represents X. 3 ~X 5 each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

[0089] The compound having a partial structure represented by formula (3) is not limited in any way to the overall structure of the compound, so long as it has the partial structure represented by formula (3). The organic group to which * is bonded is not limited to a hydrocarbon group, and may be various functional groups such as a hydroxyl group or an amino group, a halogeno group (a halogen atom), or a hydrogen atom. The organic group may contain a heteroatom, and the valence and molecular weight of the organic group are not particularly limited.

[0090] In formula (3), X 1 and X 2At least one of the partial structures of formula (3) is preferably a fluorine atom. 1 I or CFX 2 When the compound has a structure in which a fluorine atom is directly bonded to a carbon atom, as in I, the iodine atom is easily removed, and the compound having the partial structure represented by the formula (3) easily functions as a radical initiator.

[0091] In the compound having a partial structure represented by formula (3), the number of partial structures represented by formula (3) is not particularly limited. For example, the compound having a partial structure represented by formula (3) may be a monoiodo organic compound having one partial structure represented by formula (3), a diiodo organic compound having two partial structures represented by formula (3), or a polyiodide organic compound having three or more partial structures represented by formula (3). The compound having a partial structure represented by formula (3) is preferably at least one selected from the group consisting of monoiodo organic compounds and diiodo organic compounds. The compound having a partial structure represented by formula (3) may be used alone or in combination of two or more.

[0092] -Monoiodo organic compounds- The monoiodo organic compound may be a monoiodo fluorine-containing organic compound in which a substituted or unsubstituted alkyl group, a halogen atom or a hydrogen atom is bonded to * in formula (3). Examples of the substituted or unsubstituted alkyl group include substituted or unsubstituted alkyl groups having 1 to 7 carbon atoms. Examples of the substituent of the substituted alkyl group include a fluorine atom, a chlorine atom, an alkoxy group, and a fluoroalkoxy group.

[0093] Specific examples of monoiodo organic compounds include difluoroiodomethane, trifluoroiodomethane, chlorodifluoroiodomethane, 1,1-difluoroethyl iodide, 1,1-difluoro-n-propyl iodide, 1,1-difluoro-n-butyl iodide, 1,1-difluoro-isobutyl iodide, 1,1-difluoro-n-pentyl iodide, sec-butyl difluoromethylene iodide, tert-butyl Examples of such fluoromethylene iodide include 1,1-difluoro-n-hexyl iodide, 1,1-difluoro-n-heptyl iodide, 1,1-difluoro-n-octyl iodide, cyclohexyldifluoromethylene iodide, C2F5I, CHF2CF2I, CF3CF2CF2I, (CF3)2CFI, CF3(CF2)3I, (CF3)2CFCF2I, CF3(CF2)4I, and CF3(CF2)5I.

[0094] The monoiodo organic compound can be produced by a conventional method. For example, 10 It can also be prepared by reaction of a radical initiator such as CF2C(=O)O)2 with I2.

[0095] -Diiodo organic compound- Examples of the diiodo organic compound include diiodo fluorine-containing organic compounds having a partial structure represented by formula (3) in which * in formula (3) is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted arylene alkylene group, a substituted or unsubstituted alkylene arylene alkylene group, a divalent organic group such as an ether bond, or a bond via a single bond.

[0096] The substituted or unsubstituted alkylene group includes a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of unsubstituted alkylene groups include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an n-pentylene group, an n-hexylene group, and a 1,4-cyclohexylene group. The substituted alkylene group may be an alkylene group having a substituent such as a fluorine atom, a chlorine atom, an alkoxy group, or a fluoroalkoxy group at any position. Among them, an alkylene group having 2 to 12 fluorine atoms is preferred, and from the viewpoint of suppressing hydrogen atom abstraction reaction by radicals, a perfluoroalkylene group is more preferred, a perfluoroalkylene group having 1 to 4 carbon atoms is further preferred, and a perfluoroalkylene group having 2 to 4 carbon atoms is particularly preferred.

[0097] Examples of the substituted or unsubstituted arylene group include an arylene group having 6 to 12 carbon atoms and a heteroarylene group having 3 to 12 carbon atoms. Specific examples include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 4,4'-biphenylene group, a 2,2'-biphenylene group, a 2,6-naphthylene group, a 2,7-naphthylene group, a 2,4-pyridylene group, a 2,5-pyridylene group, a 2,6-pyridylene group, a pyrrolene group, a furylene group, a thienylene group, and a 1,5-furandiyl group.

[0098] Examples of the substituted or unsubstituted arylene alkylene group include an arylene alkylene group having 7 to 15 carbon atoms and a heteroarylene alkylene group having 4 to 15 carbon atoms. Specific examples include a benzylene group, a 2-pyridylene methylene group, a 3-pyridylene methylene group, and a 4-pyridylene methylene group.

[0099] Examples of the substituted or unsubstituted alkylenearylenealkylene group include an alkylenearylenealkylene group having 8 to 18 carbon atoms and an alkyleneheteroarylenealkylene group having 5 to 18 carbon atoms. Specific examples include a 1,2-dimethylenephenylene group, a 1,3-dimethylenephenylene group, a 1,4-dimethylenephenylene group, a 2,2'-dimethylenebiphenylene group, a 2,4-dimethylenepyridylene group, a 2,5-dimethylenepyridylene group, a 2,6-dimethylenepyridylene group, and a 1,5-dimethylfurandiyl group.

[0100] Specific examples of diiodo organic compounds include 1,2-diiodotetrafluoroethane, 1,4-diiodo-octafluorobutane, 1,6-diiodo-dodecafluorohexane, etc. Among them, 1,4-diiodo-octafluorobutane is preferred because it is an easy-to-handle, low-volatile liquid.

[0101] The method for producing the diiodo fluorine-containing organic compound is not particularly limited, and any method known in the art can be used.

[0102] -Polyiodide organic compounds- Examples of the polyiodide organic compound include polyiodide organic compounds having a plurality of partial structures represented by formula (3), in which the * in formula (3) is bonded with a partial structure of a polymer such as an unvulcanized fluoroelastomer, a polysiloxane bonded via a divalent bonding group such as a substituted or unsubstituted alkylene group or an ether bond, etc. Examples of the polysiloxane include silicone, a product produced by a condensation reaction of a silane coupling agent, etc.

[0103] The polyiodide organic compound can be produced by a conventionally known method.

[0104] [Compounds having at least two reactive carbon-carbon double bonds] By using Production Method A, a compound having at least two reactive carbon-carbon double bonds can be polymerized, which allows the introduction of a large number of branching and crosslinking points, and therefore allows the formation of a dense crosslinked structure when the resulting fluorine-containing polymer is cured.

[0105] In a preferred embodiment, the compound having at least two reactive carbon-carbon double bonds includes a compound represented by the following formula (1):

[0106] [ka]

[0107] In formula (1), Y 7R represents a divalent organic group having at least one fluorine atom. 1 ~R 6 R 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 5 carbon atoms. 1 and R 3 , R 4 and R 5 , R 2 and Y 7 , and R 6 and Y 7 may each independently be linked to each other to form a cyclic structure.

[0108] The details of the compound having at least two reactive carbon-carbon double bonds and the compound represented by formula (1) used in the production method A are the same as those described above in the section on «Fluorine-containing polymers». The compound having at least two reactive carbon-carbon double bonds and the compound represented by formula (1) may each be used alone or in combination of two or more.

[0109] In the production method A, the compound represented by formula (1) may be copolymerized with a compound having a reactive carbon-carbon double bond and different from the compound represented by formula (1). Details of the compound having a reactive carbon-carbon double bond and different from the compound represented by formula (1) used in the copolymerization are the same as those described above in the section on «Fluorine-containing polymer».

[0110] [Other optional components] In the production method A, other components such as a radical initiator, a solvent, an emulsifier, a suspending aid, an acid or an alkali may be further used in addition to the compound having the partial structure represented by formula (3).

[0111] (Radical initiator) In the production method A, a radical initiator other than the compound having the partial structure represented by formula (3) may be used in combination. Examples of the radical initiator include an azo radical initiator and a peroxide radical initiator. The radical initiator may be used alone or in combination of two or more.

[0112] 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.

[0113] Examples of the peroxide radical initiator include diisopropyl peroxydicarbonate, tert-butyl peroxypivalate, and benzoyl peroxide.

[0114] (solvent) An organic solvent or an aqueous solvent may be used in the production method A. The solvent may be used alone or in combination of two or more kinds.

[0115] Examples of organic solvents include benzene, toluene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, hexafluoroisopropanol, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, 1H-perfluorohexane, 1H,1H,1H,2H,2H-perfluorooctane, trifluoromethylbenzene, 1,3-bis(trifluoromethyl)benzene, 1,4-bis(trifluoromethyl)benzene, benzotrifluoride, and chlorobenzene. In addition, ionic liquids such as N-methyl-N-methoxymethylpyrrolidium tetrafluoroborate, N-methyl-N-ethoxymethyl tetrafluoroborate, 1-methyl-3-methylimidazolium tetrafluoroborate, 1-methyl-3-methylimidazolium hexafluorophosphate, and 1-methyl-3-methylimidazolium chloride may be used.

[0116] Examples of aqueous solvents include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol.

[0117] [Polymerization method] A specific example of the polymerization method according to Production Method A will be described below. In a container purged with an inert gas or evacuated, an ionic catalyst, a compound having a partial structure represented by formula (3), and a compound having at least two reactive carbon-carbon double bonds are mixed. Examples of inert gases include nitrogen, argon, and helium. Among these, nitrogen or argon is preferred, and nitrogen is more preferred. A radical initiator such as an azo-based polymerization initiator may be used in combination to accelerate the polymerization rate.

[0118] The amount of the compound having the partial structure represented by formula (3) used relative to 1 mol of the compound having a reactive carbon-carbon double bond (the total of the compound having at least two reactive carbon-carbon double bonds and other compounds having reactive carbon-carbon double bonds used as necessary) is preferably 0.001 mol or more, more preferably 0.005 mol or more. 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.

[0119] The amount of the ionic catalyst used per mol of the compound having a reactive carbon-carbon double bond (the total of the compound having at least two reactive carbon-carbon double bonds and other compounds having reactive carbon-carbon double bonds used as necessary) is preferably 0.001 mol or more, more preferably 0.005 mol or more, and even more preferably 0.01 mol or more. 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.

[0120] When a compound having a partial structure represented by formula (3) is used in combination with another radical initiator, the amount of the other radical initiator used per 1 mol of the compound having a partial structure represented by formula (3) may be 0.01 mol or more, or may be 0.1 mol or more, and the amount used may be 100 mol or less, 10 mol or less, or 1 mol or less.

[0121] When a monoiodo organic compound and a diiodo organic compound are used in combination as a compound having a partial structure represented by formula (3), the amount of the diiodo organic compound used relative to 1 mol of the monoiodo organic compound 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 of the diiodo organic compound used relative to 1 mol of the monoiodo organic compound is preferably 100 mol or less, more preferably 10 mol or less, and even more preferably 5 mol or less.

[0122] The above 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.

[0123] The amount of the solvent used can be appropriately adjusted. For example, the amount of the solvent per 1000g of the obtained fluorine-containing polymer is preferably 0.01L or more, more preferably 0.05L or more, and even more preferably 0.1L or more. In addition, the amount of the solvent per 1000g of the obtained fluorine-containing polymer is preferably 50L or less, more preferably 10L or less, and even more preferably 5L or less.

[0124] Next, the mixture obtained above is stirred. The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the obtained fluorine-containing polymer, and may be stirred at 60°C to 250°C for 5 hours to 100 hours. Preferably, the mixture is stirred at 100°C to 200°C for 10 hours to 30 hours. The reaction may be carried out at normal pressure, or under increased or reduced pressure.

[0125] 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 adversely affect the target product.

[0126] By such a polymerization method, excellent molecular weight control and molecular weight distribution control can be carried out under very mild conditions.

[0127] By using two or more compounds having reactive carbon-carbon double bonds, a block copolymer, an alternating copolymer, or a random copolymer may be produced by the polymerization method.

[0128] <B. A method for producing a fluorine-containing polymer, comprising polymerizing a compound having at least two reactive carbon-carbon double bonds in the presence of at least one compound selected from the group consisting of the compound represented by formula (4) and the compound represented by formula (5)> A method for producing a fluorine-containing polymer, which comprises polymerizing a compound having at least two reactive carbon-carbon double bonds in the presence of at least one compound selected from the group consisting of the compound represented by formula (4) and the compound represented by formula (5), is based on a polymerization method called the TERP method. Hereinafter, this production method is also referred to as production method B. For the principle and specific examples of the TERP method, reference can be made to, for example, International Publication No. 2018 / 164147.

[0129] 〔Compound represented by formula (4)〕 The compound represented by formula (4) is the following organic monotellurium compound.

[0130]

Chemical formula

[0131] In formula (4), Y 1 represents an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, or a substituted aryl group having 3 to 16 carbon atoms. Y 2 and Y 3 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. Y 4represents a hydrogen atom, an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, a substituted 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 group, or a cyano group.

[0132] Y 1 The group represented by the formula (I) is specifically as follows. Examples of the unsubstituted alkyl group having 1 to 8 carbon atoms include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, n-hexyl, n-heptyl and n-octyl groups. Of these, linear or branched alkyl groups having 1 to 4 carbon atoms are preferred, and methyl, ethyl or n-butyl groups are more preferred.

[0133] 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, a fluoroalkoxy group, etc. at any position. Among them, an alkyl group having 2 to 13 fluorine atoms is preferred, and from the viewpoint of suppressing hydrogen atom abstraction reaction by radicals, a (perfluoroalkyl)ethyl group having 3 to 8 carbon atoms is more preferred.

[0134] Examples of the unsubstituted aryl group having 3 to 12 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. Among these, a homoaryl group is preferable, and a phenyl group is more preferable.

[0135] The substituted aryl group having 3 to 16 carbon atoms includes a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, -COR a Examples of the substituents include an aryl group having 1 to 4, preferably 1 to 3, and more preferably 1, substituent such as a carbonyl-containing group, a sulfonyl group, or a trifluoromethyl group, represented by the formula (I), preferably at the para or ortho position. arepresents 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.

[0136] Y 2 and Y 3 The specific groups represented by the formula are as follows. As the substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, the above Y 1 The substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms are the same as those shown in Y 2 and Y 3 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0137] Y 4 The specific groups represented by the formula are as follows. Examples of the unsubstituted alkyl group having 1 to 8 carbon atoms, the substituted alkyl group having 1 to 8 carbon atoms, the unsubstituted aryl group having 3 to 12 carbon atoms, and the substituted aryl group having 3 to 16 carbon atoms include those listed above for Y 1 The groups are the same as those shown in the above.

[0138] Examples of the acyl group having 2 to 8 carbon atoms include an acetyl group and a benzoyl group.

[0139] 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.

[0140] The oxycarbonyl group is -COOR b In this case, R brepresents 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.

[0141] 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 following 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, a trifluoromethyl group, etc. at any position.

[0142] Examples of the oxycarbonyl 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 preferable.

[0143] Among these, Y 4 is preferably an aryl group having 5 to 12 carbon atoms, an oxycarbonyl group, or a cyano group.

[0144] In a preferred embodiment, the compound represented by formula (4) is Y 1 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, Y 2 and Y 3 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; Y 4 may be a compound represented by an aryl group or an oxycarbonyl group having 5 to 12 carbon atoms.

[0145] In a particularly preferred embodiment, the compound represented by formula (4) is Y 1is an alkyl group having 1 to 4 carbon atoms or a phenyl group, Y 2 and Y 3 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; Y 4 may be a compound represented by a phenyl group, a methoxycarbonyl group or an ethoxycarbonyl group.

[0146] Specific examples of the compound represented by formula (4) include (methyltellanylmethyl)benzene, (methyltellanylmethyl)naphthalene, ethyl-2-methyl-2-methyltellanyl propionate, ethyl-2-methyl-2-n-butyltellanyl propionate, (2-trimethylsiloxyethyl)-2-methyl-2-methyltellanyl propionate, (2-hydroxyethyl)-2-methyl-2-methyltellanyl propionate, and (3-trimethylsilylpropargyl)-2-methyl-2-methyltellanyl propionate, as well as the compounds described in WO 2004 / 014848 and WO 2004 / 014962. Further, 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, can be mentioned. Compounds represented by formula (4) may be used alone or in combination of two or more.

[0147] The method for producing the compound represented by formula (4) 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.

[0148] [Compound represented by formula (5)] The compound represented by formula (5) is the following organoditellurium compound.

[0149] [ka]

[0150] In formula (5), Y 5 and Y 6 each independently represents an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, or a substituted aryl group having 3 to 16 carbon atoms.

[0151] In formula (5), Y 5 and Y 6 The details of each independently are as follows: 1 The details are the same as in In a preferred embodiment, the compound represented by formula (5) is Y 5 and Y 6 may be a compound in which each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.

[0152] Specific examples of the compound represented by formula (5) 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 (5) may be used alone or in combination of two or more.

[0153] Among these, dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, di-n-butyl ditelluride, or diphenyl ditelluride is preferred.

[0154] [Compounds having at least two reactive carbon-carbon double bonds] The details of the compound having at least two reactive carbon-carbon double bonds used in Production Method B and the compound represented by Formula (1), which is a preferred embodiment of the compound, are the same as those described for Production Method A.

[0155] In the production method B, the compound represented by the above formula (1) may be copolymerized with a compound having a reactive carbon-carbon double bond and different from the compound represented by formula (1). Details of the compound having a reactive carbon-carbon double bond and different from the compound represented by formula (1) used in the copolymerization are the same as those described for the production method A.

[0156] [Other optional components] In the production method B, other components such as a radical initiator, a solvent, an emulsifier, a suspending aid, an acid or an alkali, other than the compound having the partial structure represented by formula (3), may be further used. Details of the other optional components are the same as those described in the explanation of the production method A.

[0157] [Polymerization method] A specific example of the polymerization method according to Production Method B will be described below. In a container purged with an inert gas or evacuated, at least one compound selected from the group consisting of the compound represented by formula (4) and the compound represented by the following formula (5) is mixed with a compound having at least two reactive carbon-carbon double bonds. Examples of the inert gas include nitrogen, argon, and helium. Among these, nitrogen or argon is preferred, and nitrogen is more preferred. A radical initiator such as an azo-based polymerization initiator may be used in combination to accelerate the polymerization rate.

[0158] The amount of the compound represented by formula (4) or the compound represented by formula (5) (when the compound represented by formula (4) and the compound represented by formula (5) are used in combination, the total of these) used relative to 1 mol of the compound having a reactive carbon-carbon double bond (the total of the compound having at least two reactive carbon-carbon double bonds and the other compounds having a reactive carbon-carbon double bond used as necessary) 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.

[0159] When an azo-based polymerization initiator is used in combination, the amount of the azo-based polymerization initiator used per mol of the compound represented by formula (4) or the compound represented by formula (5) (when the compound represented by formula (4) and the compound represented by formula (5) 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.

[0160] When the compound represented by formula (4) and the compound represented by formula (5) are used in combination, the amount of the compound represented by formula (5) used per 1 mol of the compound represented by formula (4) 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 100 mol or less, more preferably 10 mol or less, and even more preferably 5 mol or less.

[0161] The above 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.

[0162] The amount of the solvent used can be appropriately adjusted. For example, the amount of the solvent per 1000g of the obtained fluorine-containing polymer is preferably 0.01L or more, more preferably 0.05L or more, and even more preferably 0.1L or more. In addition, the amount of the solvent per 1000g of the obtained fluorine-containing polymer is preferably 50L or less, more preferably 10L or less, and even more preferably 5L or less.

[0163] Next, the mixture obtained above is stirred. The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the obtained fluorine-containing polymer, and the mixture may be stirred at 60°C to 150°C for 5 hours to 100 hours. Preferably, the mixture is stirred at 80°C to 120°C for 10 hours to 30 hours. The reaction may be carried out at normal pressure, or under increased or reduced pressure.

[0164] 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 adversely affect the target product.

[0165] Such a polymerization method allows excellent control of molecular weight and molecular weight distribution to be achieved under very mild conditions.

[0166] Two or more types of compounds having reactive carbon-carbon double bonds may be used to prepare block copolymers, alternating copolymers, or random copolymers by the polymerization method. EXAMPLES

[0167] The following examples are provided to specifically explain the embodiments of the present disclosure, but the embodiments of the present disclosure are not limited to the following examples. Note that the following Examples 1 to 12 are Examples, and Examples 13 and 14 are Reference Examples.

[0168] (Example 1) In a nitrogen-purged glove box, 28 g (80 mmol) of 1,6-divinyldodecafluorohexane, 0.082 g (0.40 mmol) of diphenyl ditelluride, 0.10 g (0.40 mmol) of an azo radical initiator "V-40" (product name, Fujifilm Wako Pure Chemical Industries, Ltd.), 72 g of benzotrifluoride, and a magnetic stirrer were placed in a light-shielded glass reactor having an internal volume of 100 mL. Stirring was started while increasing the temperature of the oil bath to 100° C. Stirring was continued at 200 rpm (200 revolutions per minute) for 16 hours while maintaining the temperature. The reactor was allowed to cool to room temperature.

[0169] The resulting polymer solution was dried under vacuum to obtain a viscous liquid, which was then added to 50 mL of methanol and stirred for 10 minutes, after which the liquid was separated from the supernatant using a centrifuge. The obtained liquid was added again to 50 mL of methanol and stirred for 10 minutes, and then the liquid and the supernatant were separated using a centrifuge. The resulting liquid was dried in a vacuum to obtain 2.1 g of a fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The Mn and Mw of the resulting polymer were 2,800 and 3,900, respectively, as determined by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.4. The fluorine content of the obtained polymer, determined by the above-mentioned method, was 60% by mass. The fluorine content of 1,6-divinyldodecafluorohexane is 64% by mass. The degree of unsaturation of the resulting polymer, as measured by the method described above, was 1.0 mEq / g. The Tg of the resulting polymer was 9° C., as measured by the method described above. The maximum complex modulus (E * 1) The minimum value of the complex modulus of elasticity (E * 2) ratio (E* 2 / E * 1) is less than 0.01. The results of solubility and complex modulus measurements confirmed the production of a non-gelled fluorine-containing polymer.

[0170] (Example 2) In a nitrogen-purged glove box, 5.7 g (16 mmol) of 1,6-divinyldodecafluorohexane, 0.082 g (0.20 mmol) of diphenyl ditelluride, 0.092 g (0.40 mmol) of an azo radical initiator "V-601" (trade name, Fujifilm Wako Pure Chemical Industries, Ltd.), and 100 g of 1H-perfluorohexane were charged into a 100 mL stainless steel autoclave equipped with a stirrer. After 7.4 g (74 mmol) of tetrafluoroethylene was injected, stirring was started while raising the internal temperature to 80° C. After stirring at 200 rpm (200 revolutions per minute) for 7 hours while maintaining the internal temperature, the internal pressure decreased from 0.8 MPa (gauge pressure) to 0.7 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted tetrafluoroethylene.

[0171] The resulting polymer solution was dried under vacuum to obtain a viscous liquid, which was then added to 50 mL of methanol and stirred for 10 minutes, after which the liquid was separated from the supernatant using a centrifuge. The obtained liquid was added again to 50 mL of methanol and stirred for 10 minutes, and then the precipitated solid was separated from the supernatant using a centrifuge. The resulting solid was dried in a vacuum to obtain 1.3 g of a fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The Mn and Mw of the resulting polymer were 3,300 and 5,300, respectively, as measured by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.6. The fluorine content of the resulting polymer, determined by the above-mentioned method, was 61% by mass. The degree of unsaturation of the resulting polymer, measured by the method described above, was 0.5 mEq / g. The Tg of the resulting polymer was 16° C., as measured by the method described above. The maximum complex modulus (E * 1) The minimum value of the complex modulus of elasticity (E * 2) ratio (E * 2 / E * 1) is less than 0.01. The results of solubility and complex modulus measurements confirmed the production of a non-gelled fluorine-containing polymer.

[0172] (Example 3) The same procedure was followed as in Example 2 except that the reaction time was changed to 18 hours, and the internal pressure decreased from 0.8 MPa to 0.6 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted tetrafluoroethylene.

[0173] The resulting polymer solution was dried under vacuum to obtain a viscous liquid, which was then added to 50 mL of methanol and stirred for 10 minutes, after which the liquid was separated from the supernatant using a centrifuge. The obtained liquid was added again to 50 mL of methanol and stirred for 10 minutes, and then the precipitated solid was separated from the supernatant using a centrifuge. The resulting solid was dried in a vacuum to obtain 2.6 g of a fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The Mn and Mw of the resulting polymer were 6,200 and 9,500, respectively, as determined by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.5. The fluorine content of the resulting polymer, determined by the above-mentioned method, was 64% by mass. The degree of unsaturation of the resulting polymer, measured by the method described above, was 0.4 mEq / g. The Tg of the resulting polymer was 20° C., as measured by the above-mentioned method. The maximum complex modulus (E * 1) The minimum value of the complex modulus of elasticity (E * 2) ratio (E * 2 / E * 1) is less than 0.01. The results of solubility and complex modulus measurements confirmed the production of a non-gelled fluorine-containing polymer.

[0174] (Example 4) The same procedure was followed as in Example 2 except that 4.1 g (16 mmol) of 1,4-divinyloctafluorobutane was used instead of 5.7 g (16 mmol) of 1,6-divinyldodecafluorohexane, and the internal pressure decreased from 0.8 MPa to 0.6 MPa.

[0175] The resulting polymer solution was dried under vacuum to obtain a viscous liquid, which was then added to 50 mL of methanol and stirred for 10 minutes, after which the liquid was separated from the supernatant using a centrifuge. The obtained liquid was added again to 50 mL of methanol and stirred for 10 minutes, and then the liquid and the supernatant were separated using a centrifuge. The resulting liquid was dried in a vacuum to obtain 2.7 g of a fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The Mn and Mw of the resulting polymer were 5,000 and 6,600, respectively, as determined by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.3. The fluorine content of the resulting polymer, determined by the above-mentioned method, was 65% by mass. The degree of unsaturation of the resulting polymer, measured by the method described above, was 0.1 mEq / g. The Tg of the resulting polymer was 41° C., as measured by the method described above. The maximum complex modulus (E * 1) The minimum value of the complex modulus of elasticity (E * 2) ratio (E * 2 / E * 1) is less than 0.01. The results of solubility and complex modulus measurements confirmed the production of a non-gelled fluorine-containing polymer.

[0176] (Example 5) In a nitrogen-purged glove box, 5.7 g (16 mmol) of 1,6-divinyldodecafluorohexane, 0.75 g (1.6 mmol) of tetraphenylphosphonium iodide, 0.14 g (0.40 mmol) of n-nonafluorobutyl iodide, and 200 g of 1H-perfluorohexane were charged into a 200 mL stainless steel autoclave equipped with a stirrer. After 8.1 g (81 mmol) of tetrafluoroethylene was injected, stirring was started while raising the internal temperature to 140° C. After stirring at 200 rpm for 18 hours while maintaining the internal temperature, the internal pressure decreased from 1.4 MPa to 1.3 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted tetrafluoroethylene.

[0177] The resulting polymer solution was dried under vacuum to obtain a viscous liquid, which was then added to 50 mL of methanol and stirred for 10 minutes, after which the liquid was separated from the supernatant using a centrifuge. The resulting polymer solution was filtered through Celite to remove solids, and the filtrate was dried in vacuum to obtain a viscous liquid. The obtained liquid was added to 30 mL of methanol and stirred for 10 minutes, and then the liquid and the supernatant were separated using a centrifuge. The resulting liquid was dried in a vacuum to obtain 0.7 g of a fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The Mn and Mw of the resulting polymer were 2,200 and 3,500, respectively, as determined by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.6. The fluorine content of the resulting polymer, determined by the above-mentioned method, was 65% by mass. The degree of unsaturation of the resulting polymer, measured by the method described above, was 0.7 mEq / g. The Tg of the resulting polymer was -10°C, as measured by the above-mentioned method. The obtained polymer was placed on a glass substrate and heated to 180°C under a nitrogen atmosphere, and it was visually observed that it melted and spread out. Although viscoelasticity measurements could not be performed due to the small yield, the above results indicate that the maximum complex modulus (E * 1) The minimum value of the complex modulus of elasticity (E * 2) ratio (E * 2 / E * 1) is considered to be less than 0.01. The results of solubility and heat tests confirmed the production of a non-gelled fluorine-containing polymer.

[0178] (Example 6) In a nitrogen-purged glove box, 1.4 g (4.0 mmol) of 1,6-divinyldodecafluorohexane, 0.13 g (0.40 mmol) of an azo radical initiator "VAm-110" (product name, Fujifilm Wako Pure Chemical Industries, Ltd.), and 100 g of 1H-perfluorohexane were charged into a 100 mL stainless steel autoclave equipped with a stirrer. After 2.2 g (22 mmol) of tetrafluoroethylene was injected, stirring was started while raising the internal temperature to 125° C. Stirring was continued at 200 rpm for 20 minutes while maintaining the internal temperature, and the internal pressure decreased from 0.9 MPa to 0.8 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted tetrafluoroethylene.

[0179] The resulting polymer solution was dried under vacuum to obtain a viscous liquid, which was then added to 50 mL of methanol and stirred for 10 minutes, after which the precipitated solid was separated from the supernatant using a centrifuge. The obtained solid was added again to 50 mL of methanol and stirred for 10 minutes, and then the solid was separated from the supernatant using a centrifuge. The resulting liquid was dried in a vacuum to obtain 0.5 g of a fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The Mn and Mw of the resulting polymer were 4,100 and 6,600, respectively, as determined by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.6. The fluorine content of the resulting polymer, determined by the above-mentioned method, was 67% by mass. The degree of unsaturation of the resulting polymer, measured by the method described above, was 0.5 mEq / g. The Tg of the resulting polymer was 97° C., as measured by the method described above. The obtained polymer was placed on a glass substrate and heated to 180°C under a nitrogen atmosphere, and it was visually observed that it melted and spread out. Although viscoelasticity measurements could not be performed due to the small yield, the above results indicate that the maximum complex modulus (E * 1) The minimum value of the complex modulus of elasticity (E * 2) ratio (E * 2 / E * 1) is considered to be less than 0.01. The results of solubility and heat tests confirmed the production of a non-gelled fluorine-containing polymer.

[0180] (Example 7) In a nitrogen-purged glove box, 2.0 g (8.0 mmol) of 1,4-divinyloctafluorobutane, 2.8 g (8.0 mmol) of 1,6-divinyldodecafluorohexane, 0.082 g (0.20 mmol) of diphenyl ditelluride, 0.092 g (0.40 mmol) of an azo radical initiator "V-601" (trade name, Fujifilm Wako Pure Chemical Industries, Ltd.), and 100 g of 1H-perfluorohexane were charged into a stainless steel autoclave with an internal volume of 100 mL and equipped with a stirrer. After 7.4 g (74 mmol) of tetrafluoroethylene was injected, stirring was started while raising the internal temperature to 80° C. After stirring at 200 rpm (200 revolutions per minute) for 7 hours while maintaining the internal temperature, the internal pressure decreased from 0.8 MPa (gauge pressure) to 0.6 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted tetrafluoroethylene.

[0181] The resulting polymer solution was dried under vacuum to obtain a viscous liquid, which was then added to 50 mL of methanol and stirred for 10 minutes, after which the liquid was separated from the supernatant using a centrifuge. The obtained liquid was added again to 50 mL of methanol and stirred for 10 minutes, and then the precipitated solid was separated from the supernatant using a centrifuge. The resulting solid was dried in a vacuum to obtain 2.8 g of a fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The Mn and Mw of the resulting polymer were 4,000 and 5,700, respectively, as determined by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.4. The fluorine content of the resulting polymer, determined by the above-mentioned method, was 66% by mass. The degree of unsaturation of the resulting polymer, as measured by the method described above, was 0.3 mEq / g. The Tg of the resulting polymer was 92° C., as measured by the method described above. The maximum complex modulus (E * 1) The minimum value of the complex modulus of elasticity (E * 2) ratio (E * 2 / E * 1) is less than 0.01. The results of solubility and complex modulus measurements confirmed the production of a non-gelled fluorine-containing polymer.

[0182] (Example 8) In a nitrogen-purged glove box, 2.0 g (8.0 mmol) of 1,4-divinyloctafluorobutane, 2.8 g (8.0 mmol) of 1,6-divinyldodecafluorohexane, 0.75 g (1.6 mmol) of tetraphenylphosphonium iodide, 0.14 g (0.40 mmol) of n-nonafluorobutyl iodide, and 200 g of 1H-perfluorohexane were charged into a 200 mL stainless steel autoclave equipped with a stirrer. After 8.1 g (81 mmol) of tetrafluoroethylene was injected, stirring was started while raising the internal temperature to 140° C. After stirring at 200 rpm for 18 hours while maintaining the internal temperature, the internal pressure decreased from 1.4 MPa to 1.3 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted tetrafluoroethylene.

[0183] The resulting polymer solution was dried under vacuum to obtain a viscous liquid, which was then added to 50 mL of methanol and stirred for 10 minutes, after which the liquid was separated from the supernatant using a centrifuge. The resulting polymer solution was filtered through Celite to remove solids, and the filtrate was dried in vacuum to obtain a viscous liquid. The obtained liquid was added to 30 mL of methanol and stirred for 10 minutes, and then the liquid and the supernatant were separated using a centrifuge. The resulting liquid was dried in a vacuum to obtain 0.9 g of a fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The Mn and Mw of the resulting polymer were 2,400 and 3,500, respectively, as determined by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.5. The fluorine content of the resulting polymer, determined by the above-mentioned method, was 65% by mass. The degree of unsaturation of the resulting polymer, measured by the method described above, was 0.4 mEq / g. The Tg of the resulting polymer was 77° C., as measured by the method described above. The obtained polymer was placed on a glass substrate and heated to 180°C under a nitrogen atmosphere, and it was visually observed that it melted and spread out. Although viscoelasticity measurements could not be performed due to the small yield, the above results indicate that the maximum complex modulus (E * 1) The minimum value of the complex modulus of elasticity (E * 2) ratio (E * 2 / E * 1) is considered to be less than 0.01. The results of solubility and heat tests confirmed the production of a non-gelled fluorine-containing polymer.

[0184] (Example 9) In a nitrogen-purged glove box, 0.51 g (2.0 mmol) of 1,4-divinyloctafluorobutane, 0.82 g (2.0 mmol) of 1,6-divinyldodecafluorohexane, 0.13 g (0.40 mmol) of an azo radical initiator "VAm-110" (product name, Fujifilm Wako Pure Chemical Industries, Ltd.), and 100 g of 1H-perfluorohexane were charged into a 100 mL stainless steel autoclave equipped with a stirrer. After 2.2 g (22 mmol) of tetrafluoroethylene was injected, stirring was started while raising the internal temperature to 125° C. Stirring was continued at 200 rpm for 20 minutes while maintaining the internal temperature, and the internal pressure decreased from 0.9 MPa to 0.7 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted tetrafluoroethylene.

[0185] The resulting polymer solution was dried under vacuum to obtain a viscous liquid, which was then added to 50 mL of methanol and stirred for 10 minutes, after which the precipitated solid was separated from the supernatant using a centrifuge. The obtained solid was added again to 50 mL of methanol and stirred for 10 minutes, and then the solid was separated from the supernatant using a centrifuge. The resulting solid was dried in a vacuum to obtain 0.9 g of a fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The Mn and Mw of the resulting polymer were 7,900 and 12,200, respectively, as determined by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.5. The fluorine content of the resulting polymer, determined by the above-mentioned method, was 68% by mass. The degree of unsaturation of the resulting polymer, measured by the method described above, was 0.2 mEq / g. The Tg of the resulting polymer was 109° C., as measured by the method described above. The obtained polymer was placed on a glass substrate and heated to 180°C under a nitrogen atmosphere, and it was visually observed that it melted and spread out. Although viscoelasticity measurements could not be performed due to the small yield, the above results indicate that the maximum complex modulus (E * 1) The minimum value of the complex modulus of elasticity (E * 2) ratio (E * 2 / E * 1) is considered to be less than 0.01. The results of solubility and heat tests confirmed the production of a non-gelled fluorine-containing polymer.

[0186] (Example 10) Into a glass container having an internal volume of 20 mL were placed 0.1 g of the fluorine-containing polymer obtained in Example 7, 0.001 g (0.004 mmol) of dicumyl peroxide, and 20 g of 1H-perfluorohexane, and the container was sealed. After mixing for 30 minutes at room temperature using a tube rotator, a homogenous solution was obtained. The glass container was opened and dried at 60° C. for 12 hours under a nitrogen stream to obtain a solid. The obtained solid was placed on a glass substrate and heated at 200° C. for 1 hour in a nitrogen atmosphere, and then allowed to cool to room temperature in an air atmosphere to obtain a solid. The resulting solid was insoluble in 1H-perfluorohexane and tetrahydrofuran. The obtained solid was placed on a glass substrate and heated to 250°C in a nitrogen atmosphere, but no visible melting was observed. The above results show that the fluorine-containing polymer has thermosetting properties.

[0187] (Example 11) The same procedure as in Example 10 was conducted except that the fluorine-containing polymer obtained in Example 8 was used instead of the fluorine-containing polymer obtained in Example 7, and a solid was obtained. The resulting solid was insoluble in tetrahydrofuran. The obtained solid was placed on a glass substrate and heated to 250°C in a nitrogen atmosphere, but no visible melting was observed. The above results show that the fluorine-containing polymer has thermosetting properties.

[0188] (Example 12) The same procedure as in Example 10 was conducted except that the fluorine-containing polymer obtained in Example 9 was used instead of the fluorine-containing polymer obtained in Example 7, and a solid was obtained. The resulting solid was insoluble in 1H-perfluorohexane and tetrahydrofuran. The obtained solid was placed on a glass substrate and heated to 250°C in a nitrogen atmosphere, but no visible melting was observed. The above results show that the fluorine-containing polymer has thermosetting properties.

[0189] (Example 13) In a nitrogen-purged glove box, 5.7 g (16 mmol) of 1,6-divinyldodecafluorohexane, 0.092 g (0.40 mmol) of an azo radical initiator "V-601" (product name, Fujifilm Wako Pure Chemical Industries, Ltd.), and 100 g of 1H-perfluorohexane were charged into a 100 mL stainless steel autoclave equipped with a stirrer. After 7.4 g (74 mmol) of tetrafluoroethylene was injected, stirring was started while raising the internal temperature to 80° C. After stirring at 200 rpm for 5 hours while maintaining the internal temperature, the internal pressure decreased from 0.8 MPa (gauge pressure) to 0.5 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted tetrafluoroethylene.

[0190] The resulting polymer solution was dried under vacuum to obtain a solid, which was then added to 50 mL of methanol and stirred for 10 minutes, after which the solid was separated from the supernatant using a centrifuge. The resulting solid was dried in a vacuum to obtain 3.9 g of a fluorine-containing polymer. The fluorine-containing polymer was insoluble and infusible.

[0191] (Example 14) In a nitrogen-purged glove box, 5.7 g (16 mmol) of 1,6-divinyldodecafluorohexane, 0.55 g (1.6 mmol) of n-nonafluorobutyl iodide, 0.092 g (0.40 mmol) of an azo radical initiator "V-601" (trade name, Fujifilm Wako Pure Chemical Industries, Ltd.), and 100 g of 1H-perfluorohexane were charged into a 100 mL stainless steel autoclave equipped with a stirrer. After 7.4 g (74 mmol) of tetrafluoroethylene was injected, stirring was started while raising the internal temperature to 80° C. After stirring at 200 rpm for 7 hours while maintaining the internal temperature, the internal pressure decreased from 0.8 MPa (gauge pressure) to 0.5 MPa. The autoclave was cooled in an ice-water bath and then purged of unreacted tetrafluoroethylene.

[0192] The resulting polymer solution was dried under vacuum to obtain a solid, which was then added to 50 mL of methanol and stirred for 10 minutes, after which the solid was separated from the supernatant using a centrifuge. The resulting solid was dried in a vacuum to obtain 4.1 g of a fluorine-containing polymer. The fluorine-containing polymer was insoluble and infusible.

[0193] The present disclosure also includes the following aspects. <1> The fluorine content is 50% by mass or more, the degree of unsaturation is 0.4 mEq / g or more, the glass transition temperature is -20°C or more, and the maximum complex elastic modulus E in the range of -50°C to the glass transition temperature * 1 and the minimum value E of the complex modulus in the range from the glass transition temperature to 250°C * The relationship between 2 and E * 2 / E * Fluorine-containing polymer satisfying the relationship: 1≦0.01. <2> The polydispersity is 2.0 or less. <1> The fluorine-containing polymer according to claim 1. <3> The weight average molecular weight is 1,000 to 1,000,000. <1> or <2> The fluorine-containing polymer according to claim 1. <4> A polymer of a compound represented by the following formula (1): A copolymer of a compound represented by the following formula (1) and a compound having a reactive carbon-carbon double bond and different from the compound represented by formula (1): <1> ~ <3> 13. The fluorine-containing polymer according to claim 12.

[0194] [ka]

[0195] In formula (1), Y 7 R represents a divalent organic group having at least one fluorine atom. 1 ~R 6 R 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 5 carbon atoms. 1 and R 3 , R4 and R 5 , R 2 and Y 7 , and R 6 and Y 7 may each independently be linked to each other to form a cyclic structure. <5> The fluorine content of the compound represented by formula (1) is 20% by mass or more. <4> The fluorine-containing polymer according to claim 1. <6> Y in the formula (1) 7 is a fluoroalkylene group having 1 to 60 carbon atoms, a fluoropolyether group having 1 to 60 carbon atoms, or a fluoroarylene group having 1 to 60 carbon atoms; <4> or <5> The fluorine-containing polymer according to claim 1. <7> The compound represented by the formula (1) contains at least one selected from the group consisting of divinylfluoroalkanes having 5 to 64 carbon atoms, divinylfluoropolyethers having 5 to 64 carbon atoms, and divinylfluoroarylenes having 5 to 64 carbon atoms. <4> ~ <6> 13. The fluorine-containing polymer according to claim 12. <8> In the presence of an ionic catalyst represented by the following formula (2) consisting of an anion and a counter cation, and a compound having a partial structure represented by the following formula (3), or In the presence of at least one compound selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the following formula (5), comprising polymerizing a compound having at least two reactive carbon-carbon double bonds, <1> ~ <7> 13. The method for producing the fluorine-containing polymer according to claim 12.

[0196] [ka]

[0197] In formula (2), A + represents a cation containing at least one element selected from the group consisting of nitrogen and phosphorus, an alkali metal ion, or a proton; B - represents a monovalent anion containing at least one element selected from the group consisting of iodine, nitrogen, and sulfur.

[0198] [ka]

[0199] In formula (3), * represents a bond bonded to an organic group. X 1 and X 2 each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, or -CX 3 X 4 X 5 Represents X. 3 ~X 5 each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

[0200] [ka]

[0201] In formula (4), Y 1 represents an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, or a substituted aryl group having 3 to 16 carbon atoms. Y 2 and Y 3 Each of Y independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. 4 represents a hydrogen atom, an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, a substituted 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 group, or a cyano group.

[0202] [ka]

[0203] In formula (5), Y 5 and Y 6 each independently represents an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, or a substituted aryl group having 3 to 16 carbon atoms. <9> The compound having at least two reactive carbon-carbon double bonds includes a compound represented by the following formula (1): <8> A method for producing the fluorine-containing polymer described in

[0204] [ka]

[0205] In formula (1), Y 7 R represents a divalent organic group having at least one fluorine atom. 1 ~R 6 R 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 5 carbon atoms. 1 and R 3 , R 4 and R 5 , R 2 and Y 7 , and R 6 and Y 7 may each independently be linked to each other to form a cyclic structure. <10> The method includes copolymerizing the compound represented by formula (1) with a compound having a reactive carbon-carbon double bond and different from the compound represented by formula (1), <9> A method for producing the fluorine-containing polymer described in

[0206] The disclosures of Japanese Patent Application No. 2020-023636 and Japanese Patent Application No. 2020-087582 are incorporated by reference in their entirety into this specification. 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, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. The fluorine content is 50% by mass or more, the degree of unsaturation is 0.1 mEq / g or more, the glass transition temperature is -20°C or more, and the maximum complex elastic modulus E in the range of -50°C to (glass transition temperature -10°C) ＊ 1 and the minimum value E of the complex elastic modulus in the range of (glass transition temperature + 10 ° C) to 250 ° C. ＊ The relationship between 2 and E ＊ 2 / E ＊ A fluorine-containing polymer satisfying the relationship: 1≦0.

01.

2. The fluorine-containing polymer according to claim 1, having a polydispersity of 2.0 or less.

3. 3. The fluorine-containing polymer according to claim 1, having a weight average molecular weight of 1,000 to 1,000,000.

4. A polymer of a compound represented by the following formula (1): A copolymer of a compound represented by the following formula (1) and a compound having a reactive carbon-carbon double bond and different from the compound represented by the formula (1): The fluorine-containing polymer according to any one of claims 1 to 3. 【Chemistry 1】 In formula (1), Y ７ R represents a divalent organic group having at least one fluorine atom. １ ~R ６ R 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 5 carbon atoms. １ and R ３ , R ４ and R ５ , R ２ and Y ７ , and R ６ and Y ７ may each independently be linked to each other to form a cyclic structure.

5. The fluorine-containing polymer according to claim 4, wherein the compound represented by formula (1) has a fluorine content of 20 mass% or more.

6. Y in the formula (1) ７ The fluorine-containing polymer according to claim 4 or claim 5, wherein is a fluoroalkylene group having 1 to 60 carbon atoms, a fluoropolyether group having 1 to 60 carbon atoms, or a fluoroarylene group having 1 to 60 carbon atoms.

7. The compound represented by the formula (1) comprises at least one selected from the group consisting of divinyl fluoroalkanes having 5 to 64 carbon atoms, divinyl fluoropolyethers having 5 to 64 carbon atoms, and divinyl fluoroarylenes having 5 to 64 carbon atoms. The fluorine-containing polymer according to any one of claims 4 to 6.

8. In the presence of an ionic catalyst represented by the following formula (2) consisting of an anion and a counter cation, and a compound having a partial structure represented by the following formula (3), or In the presence of at least one compound selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the following formula (5), A method for producing the fluorine-containing polymer according to any one of claims 1 to 7, comprising polymerizing a compound having at least two reactive carbon-carbon double bonds. 【Chemistry 2】 In formula (2), A ＋ represents a cation containing at least one element selected from the group consisting of nitrogen and phosphorus, an alkali metal ion, or a proton; B － represents a monovalent anion containing at least one element selected from the group consisting of iodine, nitrogen, and sulfur. 【Chemistry 3】 In formula (3), * represents a bond bonded to an organic group. １ and X ２ each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, or -CX ３ X ４ X ５ Represents: X ３ ~X ５ each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom. 【Chemistry 4】 In formula (4), Y １ represents an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, or a substituted aryl group having 3 to 16 carbon atoms. ２ and Y ３ Each of Y independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. ４ represents a hydrogen atom, an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, a substituted 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 group, or a cyano group. 【Chemistry 5】 In formula (5), Y ５ and Y ６ each independently represents an unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted aryl group having 3 to 12 carbon atoms, or a substituted aryl group having 3 to 16 carbon atoms.

9. The method for producing a fluorine-containing polymer according to claim 8, wherein the compound having at least two reactive carbon-carbon double bonds includes a compound represented by the following formula (1): 【Chemistry 6】 In formula (1), Y ７ R represents a divalent organic group having at least one fluorine atom. １ ~R ６ R 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 5 carbon atoms. １ and R ３ , R ４ and R ５ , R ２ and Y ７ , and R ６ and Y ７ may each independently be linked to each other to form a cyclic structure.

10. The method for producing a fluorine-containing polymer according to claim 9, comprising copolymerizing the compound represented by formula (1) with a compound having a reactive carbon-carbon double bond and different from the compound represented by formula (1).

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