Fluorine-containing polymer and method for producing the same

Abstract

The fluorine-containing polymer has a fluorine content of 50 mass% or higher, a degree of unsaturation of 0.1 mEq / g or higher, 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 from -50°C to (glass transition temperature -10°C) and the minimum value E*2 of the complex elastic modulus in the range from (glass transition temperature +10°C) to 250°C satisfies E*2 / E*1 ≦ 0.01.

Description

[Technical Field]

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

[0002] Radical polymerization reactions are widely used industrially because they offer excellent monomer versatility and can be easily carried out even in polar media such as water.

[0003] When haloolefins, particularly fluoroolefins, are used as monomers, haloolefin polymers can be synthesized. Haloolefin polymers are useful as raw materials for low-reactivity carbon-carbon double bond solvents, low-reactivity solvents, heat transfer fluids, pharmaceutical and agricultural chemical intermediates, fire extinguishing agents, surfactants, surface treatment agents, low-friction sliding materials, mold release materials, resin molding additives, chemical-resistant greases, low refractive index materials, low dielectric constant materials, heat-resistant elastomers, thermoplastic elastomers, flame-retardant materials, chemical-resistant ionomers, and photoresist materials.

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

[0005] [Patent Document 1] International Publication No. 2018 / 164147 [Overview of the project] [Problems that the invention aims to solve]

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

[0007] For example, a fluorine-containing polymer obtained by the method described in Patent Document 1 can be used as a curable material by introducing curable groups. However, because the molecular chains of this fluorine-containing polymer are linear, the cured product has a low crosslinking density, making it difficult to obtain sufficient curability.

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

[0009] The means for solving the above problems include the following embodiments. <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 higher, and the maximum value of the complex modulus E in the range of -50°C to (glass transition temperature -10°C) is * 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 is E * 2 / E * A fluorine-containing polymer that satisfies the condition 1 ≤ 0.01. <2> The fluorine-containing polymer according to <1>, having a polydispersity of 2.0 or less. <3> The fluorine-containing polymer according to <1> or <2>, having a weight average molecular weight of 1,000 to 1,000,000. <4> A polymer of the compound represented by the following formula (1), or A copolymer of the 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). <1> to <3> The fluorine-containing polymer according to any one of <1> to <3>.

[0010]

Chemical formula

[0011] In formula (1), Y 7 represents a divalent organic group having at least one fluorine atom. R 1 to R 6 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. 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. <5> The fluorine-containing polymer according to <4>, wherein the fluorine content of the compound represented by the formula (1) is 20% by mass or more. <6> The fluorine-containing polymer according to <4> or <5>, wherein Y 7 in the formula (1) 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 formula (1) comprises 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> A fluorine-containing polymer as described in any one of the items. <8> In the presence of an ionic catalyst represented by the following formula (2), which consists of an anion and a countercation, and a compound having a substructure represented by the following formula (3), or, In the presence of at least one compound selected from the group consisting of the compound represented by the following formula (4) and the compound represented by the following formula (5), This involves polymerizing a compound having at least two reactive carbon-carbon double bonds. <1> ~ <7> A method for producing a fluorine-containing polymer as described in any one of the items.

[0012] [ka]

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

[0014] [ka]

[0015] In equation (3), * represents a bond attached to an organic group. 1 and X 2 Each of these independently consists of a hydrogen atom, a fluorine atom, a chlorine atom, or -CX. 3 X 4 X 5 It represents X. 3 ~X 5 Each of these independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

[0016] [ka]

[0017] In formula (4), Y 1 This 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 these 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 amide 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 of these 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 the compound represented by the following formula (1): <8> A method for producing a fluorine-containing polymer as described above.

[0020] [ka]

[0021] In formula (1), Y 7 R represents a divalent organic group having at least one fluorine atom. 1 ~R 6 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 5 carbon atoms. 1and R 3 , R 4 and R 5 , R 2 and Y 7 , and R 6 and Y 7 These elements may be independent of each other, or they may be connected to each other to form a ring structure. <10> This involves copolymerizing a compound represented by formula (1) with a compound having a reactive carbon-carbon double bond and being different from the compound represented by formula (1). <9> A method for producing a fluorine-containing polymer as described above. [Effects of the Invention]

[0022] This disclosure provides a fluorine-containing polymer having excellent curability and low dielectric properties of the cured product, as well as a method for producing the fluorine-containing polymer. [Modes for carrying out the invention]

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

[0024] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, provided that the purpose of such process is achieved. In this disclosure, the numerical range indicated using "~" includes the numbers before and after "~" as the minimum and maximum values, respectively. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. An aryl group refers to a monovalent group in aromatic compounds that corresponds to a residue obtained by removing one hydrogen atom bonded to any one of the carbon atoms forming the aromatic ring. The term is used as a general term encompassing both homoaryl groups derived from carbocyclic compounds and heteroaryl groups derived from heterocyclic compounds. An arylene group is a divalent group that corresponds to a residue obtained by removing one hydrogen atom bonded to any one of the carbon atoms in an aryl group. In this disclosure, the term "reactive carbon-carbon double bond" refers to a carbon-carbon double bond that can react in various ways as an olefin, and does not include aromatic double bonds. In this disclosure, the number of carbon atoms in a compound or its component means the number of carbon atoms in the substituent if the compound or component has substituents. In this disclosure, (meth)acrylic acid is a general term for acrylic acid and methacrylic acid. (Meth)acrylate is a general term for acrylate and methacrylate. (Meth)acrylamide is a general term for acrylamide and methacrylamide. "Polymers" and "oligomers" are compounds formed by the polymerization of monomers. In other words, "polymers" and "oligomers" have multiple structural units. In this disclosure, unless otherwise specified, the phrase "polymerizing compound A" includes both cases of polymerizing compound A alone and cases of polymerizing compound A with other compounds. Similarly, the phrase "polymerizing compound A and compound B" includes both cases of polymerizing compound A and compound B alone, and cases of polymerizing compound A, compound B, and other compounds. Here, compound A and compound B represent any compound described in this disclosure that has a reactive carbon-carbon double bond in its molecule. Furthermore, unless otherwise specified, the polymer described in this disclosure may be a homopolymer of one compound or a copolymer of two or more compounds.

[0025] Fluorine-containing polymers The fluorine-containing polymer of this disclosure (hereinafter also simply referred to as the fluorine-containing polymer) has a fluorine content of 50% by mass or more, a degree of unsaturation of 0.1 mEq / g or more, a glass transition temperature (Tg) of -20°C or higher, and a maximum value E of the complex modulus 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 is E * 2 / E * The condition satisfies 1 ≤ 0.01.

[0026] The fluorine-containing polymers of this disclosure can be used as curable materials. The fluorine-containing polymers of this disclosure are polymers obtained by polymerizing monomers having reactive carbon-carbon double bonds, for example, oligomers and compounds having unsaturated bonds. Since the degree of unsaturation of the fluorine-containing polymers of this disclosure is 0.1 mEq / g or higher, when a cured product is made using the fluorine-containing polymer, a cured product with a high crosslink density is obtained. Furthermore, since the glass transition temperature of the fluorine-containing polymers of this disclosure is -20°C or higher, good hardness is obtained when the cured product is made, and combined with the high crosslink density mentioned above, a cured product with excellent mechanical strength is obtained. In addition, since the fluorine content of the fluorine-containing polymers of this disclosure is 50% by mass or higher, a cured product with a high fluorine content and excellent low dielectric properties can be obtained. Furthermore, the fluorine-containing polymers of this disclosure are as described above. * 2 / E * The relationship 1 ≤ 0.01 is satisfied. Polymers that do not melt in the range up to 250°C are typically E * 2 / E * The relationship 1 ≤ 0.01 is not satisfied. Fluorine-containing polymers are E * 2 / E * The relationship 1 ≤ 0.01 is considered an indicator that the fluorine-containing polymer will melt. When the fluorine-containing polymer satisfies this relationship, suitable melt molding becomes possible, and it can be preferably used as a curable material. Due to these properties, the fluorine-containing polymer of this disclosure is particularly useful as a curable material for 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 a high fluorine content is preferable from the viewpoint of low dielectric properties of the cured product. 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 also 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 the compound shall be determined by combustion ion chromatography. Furthermore, the fluorine content of a compound can also be confirmed by nuclear magnetic resonance (NMR) with an error range of approximately ±10%.

[0028] The degree of unsaturation of the fluorine-containing polymer is 0.1 mEq / g or higher. From the viewpoint of increasing the number of crosslinking points and further improving curability, the degree of unsaturation of the fluorine-containing polymer is preferably 0.3 mEq / g or higher, more preferably 0.4 mEq / g or higher, even more preferably 0.5 mEq / g, and may be 1.0 mEq / g or higher, or 1.5 mEq / g or higher. There is no particular upper limit to the degree of unsaturation of the fluorine-containing polymer, and it is preferable to adjust it 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 lower. The degree of unsaturation of fluorine-containing polymers can be adjusted by the type of monomer used as a raw material, the polymerization method, and other factors.

[0029] In this disclosure, the degree of unsaturation of fluorine-containing polymers shall be measured by a method conforming to the microtitration method specified in JIS K 1557-3:2007 (corresponding international standard: ISO 17710:2002). Specifically, it shall be 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 and stir, then let the solution 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 without adding the sample. To correct the results, prepare a sample solution in the system without mercuric acetate, and measure the acidity or basicity of the sample using potassium hydroxide solution or hydrochloric acid solution. Determine the degree of 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 the blank test (mL) c(KOH): Concentration of methanolic potassium hydroxide solution (mEq / mL) m: Sample quantity (g) A: Acidity (mEq / g) B: Basicity (mEq / g)

[0031] Furthermore, the degree of unsaturation of fluorine-containing polymers can also be confirmed by nuclear magnetic resonance (NMR) with an error range of approximately ±10%.

[0032] The number of reactive carbon-carbon double bonds in a 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 crosslinking 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 on average, more preferably 3 or more, and even more preferably 4 or more. From the viewpoint of efficiently suppressing gelation in the manufacturing 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 of the cured product, 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 value of the 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 is E * 2 / E * The condition 1 ≤ 0.01 is satisfied. As mentioned above, the complex modulus of the fluorine-containing polymer is E * 2 / E * The condition 1 ≤ 0.01 is an indicator that the fluorine-containing polymer will melt. * 2 / E * 1 may be less than or equal to 0.001, or less than or equal to 0.0001. The complex modulus of elasticity is measured according to 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 value E of the complex modulus of a fluorine-containing polymer in the range of (glass transition temperature + 10°C) to 250°C. * 2 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, from the viewpoint of ease of molding. * The lower limit of 2 is not particularly restricted and may be 1 Pa or higher.

[0036] The maximum value E of the complex modulus 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 restrictions as long as the relationship 1 ≤ 0.01 holds.

[0037] The weight-average molecular weight (Mw) of the fluorine-containing polymer is not particularly limited, but 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 fluidity 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 this 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, but 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 fluidity 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 this 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] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) in this disclosure were determined by SEC (Size Exclusion Chromatography) measurement, with polystyrene used as the 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 within this range, variations in curability are reduced, and a highly uniform cured product can be obtained. The lower limit of the polydispersity is 1.0 by definition.

[0041] Polydispersion (PD) is an indicator of molecular weight distribution and can be calculated using the following formula. {PD=Mw(weight average molecular weight) / Mn(number average molecular weight)} The degree of polydispersity can be adjusted to the above range by employing a highly controllable polymerization method. Examples of highly controllable polymerization methods include manufacturing methods A and B, which will be described later.

[0042] The fluorine-containing polymer is preferably soluble in a solvent in which the monomer raw material is soluble. Solubility in such a solvent is an indicator that the fluorine-containing polymer is not gelled, and the absence of gelling makes it suitable for use as a molding material. Gelation refers to a state in which the weight-average molecular weight (Mw) of a compound diverges infinitely. 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 dissolves in 100 mL of the solvent.

[0043] Fluorine-containing polymers are polymers of compounds having a reactive carbon-carbon double bond. Here, "compound having a reactive carbon-carbon double bond" refers to the constituent components of the resulting fluorine-containing polymer, which are typically monomers. The fluorine-containing polymer may be a polymer of one monomer or a copolymer of multiple 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, 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 resulting cured product. Furthermore, 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 viewpoint, the fluorine content of the compound having a reactive carbon-carbon double bond is preferably 20% to 76% by mass, more preferably 30% to 76% by mass, and even more preferably 40% 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. Polymerizing a compound having at least two reactive carbon-carbon double bonds allows for the introduction of numerous branching and crosslinking points, so that when the resulting fluorine-containing polymer is further cured, a denser crosslinked 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 the compound represented by the following formula (1), or The compound may be a copolymer of a compound represented by the following formula (1) and a compound having a reactive carbon-carbon double bond that is different from the compound represented by 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 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 5 carbon atoms. 1 and R 3 , R 4 and R 5 , R 2 and Y 7 , and R 6 and Y 7 These elements may be independent of each other, or they may be connected to each other to form a ring structure.

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

[0050] Y in equation (1) 7Examples thereof include 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. Among them, a perfluoroalkylene group having 1 to 60 carbon atoms, a perfluoropolyether group having 1 to 60 carbon atoms, or a perfluoroarylene group having 1 to 60 carbon atoms is preferable.

[0051] R 1 ~R 6 Examples of the organic group having 1 to 5 carbon atoms represented by R

[0052] ~R 1 ~R 6 include a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms and the like. Examples of the substituent include a carbonyl group and the like.

[0053] From the viewpoint of low dielectric loss, R 7 ~R 1 ~R 6 are each independently preferably a hydrogen atom, a fluorine atom, or a methyl group. 7 7 1 Here, the atoms bonded to the atoms at both ends of Y

[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. "R 1 and R 3 are linked to each other to form a cyclic structure" means that any atom contained in R 1 is linked to any atom contained in R 3 to form a cyclic structure. R 4 and R 5 R 2 and Y 7 or R6 and Y 7 The same applies when they are connected to each other to form a ring structure. The compound represented by formula (1) may also 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 resulting cured product. The fluorine content of the compound represented by formula (1) may also be 76% by mass or less. From the above viewpoint, the fluorine content of the compound represented by formula (1) is preferably 20% to 76% by mass, more preferably 30% to 76% by mass, and even more preferably 40% to 76% by mass.

[0056] The compound represented by formula (1) is 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. Among these, at least one selected from the group consisting of divinylperfluoroalkanes having 5 to 64 carbon atoms, divinylperfluoropolyethers having 5 to 64 carbon atoms, and divinylperfluoroarylenes 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] Examples of compounds represented by formula (1) include the following exemplary compounds. Among these, 1,6-divinyldodecafluorohexane and 1,4-divinyloctafluorobutane are preferred compounds. In the exemplary compounds listed below, * indicates that the substitution position of the substituent in the aromatic ring is not limited.

[0058] [ka]

[0059] [ka]

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

[0061] [ka]

[0062] [ka]

[0063] The compound used in copolymerization, which has a reactive carbon-carbon double bond and is different from the compound represented by formula (1), is not particularly limited as long as it is a compound that can copolymerize 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; and N-2-hydroxy-3-acryloyloxypropyl Unsaturated monomers containing quaternary ammonium bases such as 2-N,N,N-trimethylammonium chloride and N-methacryloylaminoethyl-N,N,N-dimethylbenzylammonium chloride; unsaturated monomers containing epoxy groups such as glycidyl (meth)acrylate; styrene monomers such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 2-chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 1-vinylnaphthalene, divinylbenzene, 4-(chloromethyl)styrene, 2-(chloromethyl)styrene, 3-(chloromethyl)styrene, 4-styrenesulfonic acid or its alkali metal salts (sodium salt, potassium salt, etc.); unsaturated monomers containing heterocyclic compounds such as 2-vinylthiophene and N-methyl-2-vinylpyrrole; vinylamides such as N-vinylformamide and N-vinylacetamide;Diallylamine, triallyl isocyanurate, tri(2-methyl-allyl) isocyanurate, ethylene, propylene, 1-butene, 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 include α-olefins such as (Tene); alkyl vinyl ethers such as isobutene, 1, vinyl acetate, hydroxyethyl methacrylate, acrylonitrile, acrylamide, N,N-dimethylacrylamide, 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). Compounds having a reactive carbon-carbon double bond and different from the compound represented by formula (1) may be used individually or in combination of two or more.

[0064] ≪Method for producing fluorine-containing polymers≫ The method for producing the fluorine-containing polymer described herein is not particularly limited. In one embodiment, the method for producing the fluorine-containing polymer is: In the presence of an ionic catalyst represented by the following formula (2), which consists of an anion and a countercation, and a compound having a substructure represented by the following formula (3), or, In the presence of at least one compound selected from the group consisting of the compound represented by the following formula (4) and the compound represented by the following formula (5), This involves polymerizing a compound having at least two reactive carbon-carbon double bonds.

[0065] [ka]

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

[0067] [ka]

[0068] In equation (3), * represents a bond attached to an organic group. 1 and X 2 Each of these independently consists of a hydrogen atom, a fluorine atom, a chlorine atom, or -CX. 3 X 4 X 5 It represents X. 3 ~X 5 Each of these independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

[0069] [ka]

[0070] In formula (4), Y 1 This 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 these 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 amide 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, which includes 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, which includes 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 of the scheme for manufacturing method A is shown in the figure below. The ionic catalyst represented by formula (2) breaks the CI bond in the compound having the substructure represented by formula (3), generating a carbon radical. The generated carbon radical reacts with the compound having a reactive carbon-carbon double bond. On the other hand, the bonding of I from the compound having the substructure represented by formula (3) to the ionic catalyst is a reversible reaction, and I recombines with the carbon radical after the reaction with the compound having a reactive carbon-carbon double bond, so the reaction product becomes the compound having the substructure represented by formula (3) again. In other words, an insertion reaction of the compound having a reactive carbon-carbon double bond into the compound having the substructure represented by formula (3) occurs.

[0076] [ka]

[0077] In the above scheme diagram, in compounds 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 the ionic catalyst represented by formula (2) again, in which the I bonded to the compound produced by the above reaction is abstracted, thereby obtaining a polymer.

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

[0080] [Ionic catalyst] The following details the ionic catalyst represented by the following formula (2), which consists of an anion and a countercation.

[0081] [ka]

[0082] In formula (2), A + This represents a cation, alkali metal ion, or proton containing at least one element selected from the group consisting of nitrogen and phosphorus. - This 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 iodine anion is the iodide ion (I - ), triiodide ion (I3 - Other examples include azide ions (N3). - ), cyanide ion (CN - ), cyanate anion (OCN - ), thiocyanate ion (SCN - Examples include: In particular, iodine anions are preferred, and iodide ions are more preferred, from the viewpoint of interaction with the iodine atom of compounds having a substructure represented by formula (3).

[0084] A + Among the countercations represented by (C4H9)4N, a nitrogen-containing cation is, for example, tetrabutylammonium ((C4H9)4N + Examples of quaternary ammonium cations include (C6H5)4P. + Examples include quaternary phosphonium cations such as ). Examples of alkali metal ions include lithium ions, sodium ions, potassium ions, rubidium ions, and cesium ions. In particular, 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, and tetraphenylphosphonium is even more preferred.

[0085] Preferred ionic catalysts represented by formula (2) include tetraphenylphosphonium iodide, tetrabutylammonium iodide, cesium iodide, and lithium iodide. The ionic catalysts represented by formula (2) may be used individually or in combination of two or more.

[0086] [Compounds having a substructure represented by formula (3)] Compounds having the substructure represented by formula (3) will be described in detail below.

[0087] [ka]

[0088] In equation (3), * represents a bond attached to an organic group. 1 and X 2 Each of these independently consists of a hydrogen atom, a fluorine atom, a chlorine atom, or -CX. 3 X 4 X 5 It represents X. 3 ~X 5 Each of these independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

[0089] Compounds having a substructure represented by formula (3) are not limited in any way in terms of the overall structure of the compound, as long as they have the substructure represented by formula (3). The organic group to which * is attached is not limited to hydrocarbon groups, but may be various functional groups such as hydroxyl groups and amino groups, halogen groups (halogen atoms), hydrogen atoms, etc. Furthermore, the organic group may contain heteroatoms, and its valency and molecular weight are not particularly limited.

[0090] In equation (3), X 1 and X 2Preferably, at least one of them is a fluorine atom. The substructure of formula (3) is -CFX 1 I, or CFX 2 As shown in I, when a fluorine atom is directly bonded to a carbon atom, the iodine atom is easily removed, and compounds having the substructure represented by formula (3) tend to function suitably as radical initiators.

[0091] The number of substructures represented by formula (3) in a compound having a substructure represented by formula (3) is not particularly limited. For example, a compound having a substructure represented by formula (3) may be a monoiodine organic compound having one substructure represented by formula (3), a diiodine organic compound having two substructures represented by formula (3), or a polyiodine organic compound having three or more substructures represented by formula (3). Preferably, the compound having a substructure represented by formula (3) is at least one selected from the group consisting of monoiodine organic compounds and diiodine organic compounds. A compound having a substructure represented by formula (3) may be used alone or in combination of two or more.

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

[0093] Specifically, monoiodine 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-butyldifluoromethylene iodide, tert-butyl Examples include difluoromethylene iodide, 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, CF3(CF2)5I, etc.

[0094] Monoiodine organic compounds can be produced by conventionally known methods, for example, (R 10 It can also be produced by the reaction of a radical initiator such as CF2C(=O)O)2 with I2.

[0095] -Diiodo organic compound- Examples of diiodine organic compounds include diiodine-containing organic compounds having a substructure represented by formula (3) in which * is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted arylenealkylene group, a substituted or unsubstituted alkylenearylenealkylene group, a divalent organic group such as an ether bond, or a single bond.

[0096] Examples of substituted or unsubstituted alkylene groups include substituted or unsubstituted alkylene groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of unsubstituted alkylene groups include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, n-hexylene, and 1,4-cyclohexylene. Examples of substituted alkylene groups include alkylene groups having substituents such as fluorine atoms, chlorine atoms, alkoxy groups, and fluoroalkoxy groups at arbitrary positions. Among these, alkylene groups having 2 to 12 fluorine atoms are preferred, perfluoroalkylene groups are more preferred from the viewpoint of suppressing hydrogen atom abstraction reactions by radicals, perfluoroalkylene groups having 1 to 4 carbon atoms are even more preferred, and perfluoroalkylene groups having 2 to 4 carbon atoms are particularly preferred.

[0097] Examples of substituted or unsubstituted arylene groups include arylene groups having 6 to 12 carbon atoms and heteroarylene groups having 3 to 12 carbon atoms. Specifically, examples include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 4,4'-biphenylene group, 2,2'-biphenylene group, 2,6-naphthylene group, 2,7-naphthylene group, 2,4-pyridylene group, 2,5-pyridylene group, 2,6-pyridylene group, pyrlauene group, flirene group, thienylene group, and 1,5-franzyl group.

[0098] Examples of substituted or unsubstituted arylenealkylene groups include arylenealkylene groups having 7 to 15 carbon atoms and heteroarylenealkylene groups having 4 to 15 carbon atoms. Specifically, examples include bendiylene groups, 2-pyridylenemethylene groups, 3-pyridylenemethylene groups, and 4-pyridylenemethylene groups.

[0099] Examples of substituted or unsubstituted alkylene arylene alkylene groups include alkylene arylene alkylene groups having 8 to 18 carbon atoms and alkylene heteroarylene alkylene groups having 5 to 18 carbon atoms. Specifically, examples include 1,2-dimethylene phenylene group, 1,3-dimethylene phenylene group, 1,4-dimethylene phenylene group, 2,2'-dimethylene biphenylene group, 2,4-dimethylene pyridylene group, 2,5-dimethylene pyridylene group, 2,6-dimethylene pyridylene group, and 1,5-dimethylfranzyl group.

[0100] Examples of diiodo organic compounds include 1,2-diiodotetrafluoroethane, 1,4-diiodo-octafluorobutane, and 1,6-diiodo-dodecafluorohexane. Among these, 1,4-diiodo-octafluorobutane is preferred because it is a low-volatility liquid that is easy to handle.

[0101] The method for producing diiodine-containing fluorine organic compounds is not particularly limited, and conventionally known methods can be used.

[0102] -Polyiodide organic compounds- Examples of polyiodide organic compounds include polyiodide organic compounds having multiple substructures represented by formula (3), in which the asterisk (*) in formula (3) is bonded to a polymer substructure such as an unvulcanized fluoroelastomer; a polysiloxane bonded via a substituted or unsubstituted alkylene group, a divalent bonding group such as an ether bond; etc. Here, examples of polysiloxanes include silicones; products produced by the condensation reaction of silane coupling agents; etc.

[0103] Polyiodide organic compounds can be produced by conventionally known methods.

[0104] [Compounds having at least two reactive carbon-carbon double bonds] By polymerizing a compound having at least two reactive carbon-carbon double bonds using manufacturing method A, numerous branching and crosslinking points can be introduced, allowing the resulting fluorine-containing polymer to form a dense crosslinked structure when cured.

[0105] In a preferred embodiment, the compounds having at least two reactive carbon-carbon double bonds include the 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 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 5 carbon atoms. 1 and R 3 , R 4 and R 5 , R 2 and Y 7 , and R 6 and Y 7 These elements may be independent of each other, or they may be connected to each other to form a ring 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 manufacturing 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 be used individually or in combination of two or more.

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

[0110] [Other optional ingredients] In manufacturing method A, other components such as radical initiators, solvents, emulsifiers, suspension aids, acids, or alkalis, other than the compound having the substructure represented by formula (3), may be used.

[0111] (Radical initiator) In manufacturing method A, radical initiators other than compounds having the substructure represented by formula (3) may be used in combination. Examples of radical initiators include azo radical initiators and peroxide radical initiators. One radical initiator may be used alone, or two or more may be used in combination.

[0112] Examples of azo radical initiators include 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (AMBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1'-azobis(1-cyclohexanecarbonitride) (ACHN), dimethyl-2,2'-azobisisobutyrate (MAIB), 4,4'-azobis(4-cyanovaleric acid) (ACVA), 1,1'-azobis(1-acetoxy-1-phenylethane), 2,2'-azobis(2-methylbutylamide), and 2,2' Examples include -azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylamidinopropane) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2,4,4-trimethylpentane), 2-cyano-2-propylazoformamide, 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide).

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

[0114] (solvent) In manufacturing method A, an organic solvent or an aqueous solvent may be used. The solvent may be used alone or in combination of two or more types.

[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] An example of a specific polymerization method related to manufacturing method A is described below. In a container purged with an inert gas or under vacuum, an ionic catalyst, a compound having a substructure 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. Of these, nitrogen or argon is preferred, and nitrogen is more preferred. A radical initiator such as an azo polymerization initiator may be used in combination to accelerate the polymerization rate.

[0118] The amount of compound having the substructure represented by formula (3) used per 1 mole of a compound having a reactive carbon-carbon double bond (the total of a compound having at least two reactive carbon-carbon double bonds and any other reactive carbon-carbon double bond compounds used as needed) is preferably 0.001 mole or more, more preferably 0.005 mole or more. Furthermore, the amount used is preferably 1 mole or less, more preferably 0.5 mole or less, and even more preferably 0.1 mole or less.

[0119] The amount of ionic catalyst used per 1 mole of a compound having a reactive carbon-carbon double bond (the total of a compound having at least two reactive carbon-carbon double bonds and other reactive carbon-carbon double bond compounds used as needed) is preferably 0.001 mole or more, more preferably 0.005 mole or more, and even more preferably 0.01 mole or more. Furthermore, the amount used is preferably 1 mole or less, more preferably 0.5 mole or less, and even more preferably 0.1 mole or less.

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

[0121] When a monoiodine organic compound and a diiodine organic compound are used in combination as a compound having a substructure represented by formula (3), the amount of diiodine organic compound used per 1 mol of monoiodine 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. Furthermore, the amount of diiodine organic compound used per 1 mol of monoiodine 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 it can also be carried out using organic solvents or aqueous solvents commonly used in radical polymerization.

[0123] The amount of solvent used can be adjusted as appropriate. For example, the amount of solvent per 1000g of the resulting fluorine-containing polymer is preferably 0.01L or more, more preferably 0.05L or more, and even more preferably 0.1L or more. Also, the amount of solvent per 1000g of the resulting 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 can be appropriately adjusted depending on the molecular weight or molecular weight distribution of the fluorine-containing polymer obtained, and may be stirred at 60°C to 250°C for 5 to 100 hours. Preferably, it is stirred at 100°C to 200°C for 10 to 30 hours. The reaction may be carried out at atmospheric pressure, or under pressurized or reduced pressure.

[0125] After the reaction is complete, the target polymer is isolated by removing the solvent, residual monomers, etc., under reduced pressure using conventional methods, or by reprecipitation using a solvent in which the target polymer is insoluble. Any reaction method can be used as long as it does not impair the target product.

[0126] By such a polymerization method, excellent molecular weight control and molecular weight distribution control can be achieved 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 represent 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 amide group having 2 to 8 carbon atoms, an oxycarbonyl group, or a cyano group.

[0132] Y 1 The bases indicated by are specifically as follows: Examples of unsubstituted alkyl groups having 1 to 8 carbon atoms include linear, branched, or cyclic alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Among these, linear or branched alkyl groups having 1 to 4 carbon atoms are preferred, with methyl, ethyl, or n-butyl groups being more preferred.

[0133] Examples of substituted alkyl groups having 1 to 8 carbon atoms include alkyl groups having substituents such as fluorine atoms, chlorine atoms, alkoxy groups, and fluoroalkoxy groups at arbitrary positions. Among these, alkyl groups having 2 to 13 fluorine atoms are preferred, and (perfluoroalkyl)ethyl groups having 3 to 8 carbon atoms are more preferred from the viewpoint of suppressing hydrogen atom abstraction reactions by radicals.

[0134] Examples of unsubstituted aryl groups having 3 to 12 carbon atoms include homoaryl groups such as phenyl and naphthyl groups; and heteroaryl groups such as pyridyl, pyrrole, furyl, and thienyl groups. Among these, homoaryl groups are preferred, and phenyl groups are more preferred.

[0135] Substitutive aryl groups with 3 to 16 carbon atoms can include halogen atoms, hydroxyl groups, alkoxy groups, amino groups, nitro groups, cyano groups, and -COR groups at any position. a Examples include aryl groups having 1 to 4 substituents, preferably 1 to 3, more preferably 1, preferably at the para or ortho position, such as a carbonyl-containing group, a sulfonyl group, or a trifluoromethyl group. aThis represents an alkyl group having 1 to 8 carbon atoms, preferably a linear or branched alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 8 carbon atoms, preferably a linear or branched alkoxy group having 1 to 4 carbon atoms; an aryl group; or an aryloxy group.

[0136] Y 2 and Y 3 Each of the groups indicated by the symbol is specifically as follows: As a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, the above Y 1 Examples include substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, as shown above. 2 and Y 3 Preferably, the element is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0137] Y 4 Each of the groups indicated by the symbol is specifically as follows: As for unsubstituted alkyl groups having 1 to 8 carbon atoms, substituted alkyl groups having 1 to 8 carbon atoms, unsubstituted aryl groups having 3 to 12 carbon atoms, and substituted aryl groups having 3 to 16 carbon atoms, the above Y 1 Examples of the same groups as those shown are listed below.

[0138] Examples of acyl groups having 2 to 8 carbon atoms include acetyl groups and benzoyl groups.

[0139] Examples of amide groups having 2 to 8 carbon atoms include carbamoyl group-containing groups such as carbamoylmethyl group, dicarbamoylmethyl group, and 4-carbamoylphenyl group; thiocarbamoyl group-containing groups such as thiocarbamoylmethyl group and 4-thiocarbamoylphenyl group; and N-substituted carbamoyl group-containing groups such as dimethylcarbamoylmethyl group.

[0140] As for the oxycarbonyl group, -COOR b The group shown is the group represented by . Here, R bThis represents a hydrogen atom; an alkyl group having 1 to 8 carbon atoms, preferably a linear or branched alkyl group having 1 to 4 carbon atoms; an alkenyl group having 2 to 8 carbon atoms, preferably a linear or branched alkenyl group having 2 to 4 carbon atoms; an alkynyl group having 2 to 8 carbon atoms, preferably a linear or branched alkynyl group having 2 to 4 carbon atoms; or an aryl group having 3 to 12 carbon atoms.

[0141] R b The C1-C8 alkyl group, C2-C8 alkenyl group, C2-C8 alkynyl group, and C3-C12 aryl group represented by may have 1 to 4 substituents, preferably 1 to 3, and more preferably 1, such as halogen atoms, hydroxyl groups, alkoxy groups, trialkylsilyl ether groups, trialkylsilyl groups, amino groups, nitro groups, cyano groups, sulfonyl groups, and trifluoromethyl groups, at any position.

[0142] Examples of oxycarbonyl groups include carboxyl groups, methoxycarbonyl groups, ethoxycarbonyl groups, propoxycarbonyl groups, n-butoxycarbonyl groups, sec-butoxycarbonyl groups, tert-butoxycarbonyl groups, n-pentoxycarbonyl groups, and phenoxycarbonyl groups. Among these, methoxycarbonyl groups or ethoxycarbonyl groups are preferred.

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

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

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

[0146] Examples of compounds represented by formula (4) include (methylteranylmethyl)benzene, (methylteranylmethyl)naphthalene, ethyl-2-methyl-2-methylteranyl-propionate, ethyl-2-methyl-2-n-butylteranyl-propionate, (2-trimethylsiloxyethyl)-2-methyl-2-methylteranyl-propinate, (2-hydroxyethyl)-2-methyl-2-methylteranyl-propinate, (3-trimethylsilylpropargyl)-2-methyl-2-methylteranyl-propinate, and other compounds described in International Publication Nos. 2004 / 014848 and 2004 / 014962. Furthermore, examples include compounds such as ethyl-2-methyl-2-1H,1H,2H,2H-heptadecafluorodecylteranyl-propionate, methyl-2-methyl-2-1H,1H,2H,2H-heptadecafluorodecylteranyl-propionate, and N,N-diethyl-2-methyl-2-1H,1H,2H,2H-heptadecafluorodecylteranyl-propionamide, as described in publication number 2D03 of Polymer Preprints, Japan Vol.65, No.1 (2016). The compounds represented by formula (4) may be used individually or in combination of two or more.

[0147] The method for producing the compound represented by formula (4) is not particularly limited and can be produced by known methods described in International Publication No. 2004 / 014848, International Publication No. 2004 / 014962, and International Publication No. 2018 / 164147.

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

[0149] [Chemical formula]

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

[0152] Specific examples of the compound represented by formula (5) include dimethylditelluride, diethylditelluride, di-n-propylditelluride, diisopropylditelluride, dicyclopropylditelluride, di-n-butylditelluride, di-sec-butylditelluride, di-tert-butylditelluride, dicyclobutylditelluride, diphenylditelluride, bis-(p-methoxyphenyl)ditelluride, bis-(p-aminophenyl)ditelluride, bis-(p-nitrophenyl)ditelluride, bis-(p-cyanophenyl)ditelluride, bis-(p-sulfonylphenyl)ditelluride, dinaphthylditelluride, dipyridilditelluride, and the like. The compound represented by formula (5) may be used alone or in combination of two or more.

[0153] Among them, dimethylditelluride, diethylditelluride, di-n-propylditelluride, di-n-butylditelluride, or diphenylditelluride is preferred.

[0154] [Compound having at least two reactive carbon-carbon double bonds] Details of the compound having at least two reactive carbon-carbon double bonds used in manufacturing method B, and the compound represented by formula (1) in a preferred embodiment thereof, are the same as those described for manufacturing method A.

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

[0156] [Other optional ingredients] In manufacturing method B, other components such as radical initiators, solvents, emulsifiers, suspension aids, acids, or alkalis, other than the compound having the substructure represented by formula (3), may be used. Details of the other optional components are the same as those described in the explanation for manufacturing method A.

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

[0158] The amount of compound represented by formula (4) or formula (5) (the total amount when both compounds are used in combination) used per 1 mole of a compound having a reactive carbon-carbon double bond (the total amount of a compound having at least two reactive carbon-carbon double bonds and any other reactive carbon-carbon double bond compounds used as needed) is preferably 0.001 mole or more, more preferably 0.005 mole or more, and even more preferably 0.01 mole or more. Furthermore, the amount used is preferably 1 mole or less, more preferably 0.5 mole or less, and even more preferably 0.1 mole or less.

[0159] When an azo polymerization initiator is used in combination, the amount of azo polymerization initiator used per 1 mol of the compound represented by formula (4) or formula (5) (the total amount when both formulas are used in combination) is preferably 0.01 mol or more, more preferably 0.05 mol or more, and even more preferably 0.1 mol or more. Furthermore, the amount used is preferably 50 mol or less, more preferably 10 mol or less, and even more preferably 5 mol or less.

[0160] When using a compound represented by formula (4) and a compound represented by formula (5) in combination, the amount of compound represented by formula (5) used per 1 mole of 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. Furthermore, 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 it can also be carried out using organic solvents or aqueous solvents commonly used in radical polymerization.

[0162] The amount of solvent used can be adjusted as appropriate. For example, the amount of solvent per 1000g of the resulting fluorine-containing polymer is preferably 0.01L or more, more preferably 0.05L or more, and even more preferably 0.1L or more. Also, the amount of solvent per 1000g of the resulting 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 can be appropriately adjusted depending on the molecular weight or molecular weight distribution of the fluorine-containing polymer obtained, and may be stirred at 60°C to 150°C for 5 to 100 hours. Preferably, it is stirred at 80°C to 120°C for 10 to 30 hours. The reaction may be carried out at atmospheric pressure, or under pressurized or reduced pressure.

[0164] After the reaction is complete, the target polymer is isolated by removing the solvent, residual monomers, etc., under reduced pressure using conventional methods, or by reprecipitation using a solvent in which the target polymer is insoluble. Any reaction method can be used as long as it does not impair the target product.

[0165] This polymerization method allows for excellent molecular weight control and molecular weight distribution control under very mild conditions.

[0166] Block copolymers, alternating copolymers, or random copolymers may be produced by using two or more compounds having reactive carbon-carbon double bonds and depending on the polymerization method. [Examples]

[0167] The embodiments of this disclosure will be specifically described below with reference to examples, but the embodiments of this disclosure are not limited to the examples described below. Examples 1 to 12 below are examples, and Examples 13 and 14 are reference examples.

[0168] (Example 1) In a nitrogen-substituted glove box, a 100 mL light-shielded glass reactor was charged with 28 g (80 mmol) of 1,6-divinyldodecafluorhexane, 0.082 g (0.40 mmol) of diphenylditelluride, 0.10 g (0.40 mmol) of an azo radical initiator "V-40" (trade name, Fujifilm Wako Pure Chemical Corporation), 72 g of benzotrifluoride, and a magnetic stir bar. Stirring was started while raising the temperature of the oil bath to 100 °C. Stirring was carried out 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 obtained polymer solution was dried under vacuum to obtain a viscous liquid. This liquid was added to 50 mL of methanol and stirred for 10 minutes, and then the liquid and the supernatant were separated 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. When the obtained liquid was dried under vacuum, 2.1 g of a fluorine-containing polymer was obtained. The obtained fluorine-containing polymer was dissolved in tetrahydrofuran. The Mn of the obtained polymer measured by size exclusion chromatography was 2,800, and the Mw was 3,900. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.4. The fluorine content of the obtained polymer determined by the above method was 60% by mass. The fluorine content of 1,6-divinyldodecafluorhexane is 64% by mass. The unsaturation of the obtained polymer measured by the above method was 1.0 mEq / g. The Tg of the obtained polymer measured by the above method was 9 °C. The maximum value of the complex elastic modulus (E * 1) of the obtained polymer measured by the above method at -50 °C to (Tg - 10 °C), relative to the minimum value of the complex elastic modulus (E * 2) at (Tg + 10 °C) to 250 °C, the ratio (E* 2 / E * 1) is 0.01 or less. Based on the results of solubility and complex modulus measurements, the production of a non-gelling fluorine-containing polymer was confirmed.

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

[0171] The resulting polymer solution was vacuum-dried to obtain a viscous liquid. This liquid was added to 50 mL of methanol and stirred for 10 minutes, after which the liquid and supernatant were separated using a centrifuge. The resulting liquid was added again to 50 mL of methanol and stirred for 10 minutes. Then, the precipitated solid and the supernatant were separated using a centrifuge. When the obtained solid was vacuum-dried, 1.3 g of fluorine-containing polymer was obtained. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The resulting polymer had a manganese (Mn) of 3,300 and a manganese (Mw) of 5,300, as measured by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.6. The fluorine content of the polymer obtained by the method described above was 61% by mass. The degree of unsaturation of the obtained polymer, as measured by the method described above, was 0.5 mEq / g. The Tg of the obtained polymer, as measured by the method described above, was 16°C. The maximum value (E) of the complex modulus of the obtained polymer at -50°C to (Tg-10°C), measured by the method described above. * 1) The minimum value of the complex modulus (E) between (Tg+10℃) and 250℃ for 1). * 2) Ratio (E * 2 / E * 1) is 0.01 or less. Based on the results of solubility and complex modulus measurements, the production of a non-gelling fluorine-containing polymer was confirmed.

[0172] (Example 3) When the procedure was carried out in the same manner as in Example 2, except that the reaction time was changed to 18 hours, the internal pressure decreased from 0.8 MPa to 0.6 MPa. After cooling the autoclave in an ice bath, the unreacted tetrafluoroethylene was purged.

[0173] The resulting polymer solution was vacuum-dried to obtain a viscous liquid. This liquid was added to 50 mL of methanol and stirred for 10 minutes, after which the liquid and supernatant were separated using a centrifuge. The resulting liquid was added again to 50 mL of methanol and stirred for 10 minutes. Then, the precipitated solid and the supernatant were separated using a centrifuge. The obtained solid was vacuum-dried to yield 2.6 g of fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The resulting polymer had a manganese (Mn) of 6,200 and a manganese (Mw) of 9,500, as measured by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.5. The fluorine content of the obtained polymer, as determined by the method described above, was 64% by mass. The degree of unsaturation of the obtained polymer, as measured by the method described above, was 0.4 mEq / g. The Tg of the obtained polymer, as measured by the method described above, was 20°C. The maximum value (E) of the complex modulus of the obtained polymer at -50°C to (Tg-10°C), measured by the method described above. * 1) The minimum value of the complex modulus (E) between (Tg+10℃) and 250℃ for 1). * 2) Ratio (E * 2 / E * 1) is 0.01 or less. Based on the results of solubility and complex modulus measurements, the production of a non-gelling fluorine-containing polymer was confirmed.

[0174] (Example 4) The procedure was the same 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. The internal pressure decreased from 0.8 MPa to 0.6 MPa.

[0175] The resulting polymer solution was vacuum-dried to obtain a viscous liquid. This liquid was added to 50 mL of methanol and stirred for 10 minutes, after which the liquid and supernatant were separated using a centrifuge. The resulting liquid was added back into 50 mL of methanol and stirred for 10 minutes, after which the liquid and supernatant were separated using a centrifuge. The obtained liquid was vacuum-dried to yield 2.7 g of fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The resulting polymer had a manganese content of 5,000 and a manganese content of 6,600, as measured by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.3. The fluorine content of the obtained polymer, as determined by the method described above, was 65% by mass. The degree of unsaturation of the obtained polymer, as measured by the method described above, was 0.1 mEq / g. The Tg of the obtained polymer, as measured by the method described above, was 41°C. The maximum value (E) of the complex modulus of the obtained polymer at -50°C to (Tg-10°C), measured by the method described above. * 1) The minimum value of the complex modulus (E) between (Tg+10℃) and 250℃ for 1). * 2) Ratio (E * 2 / E * 1) is 0.01 or less. Based on the results of solubility and complex modulus measurements, the production of a non-gelling fluorine-containing polymer was confirmed.

[0176] (Example 5) In a nitrogen-purged glove box, a 200 mL stainless steel autoclave equipped with a stirrer was charged with 5.7 g (16 mmol) of 1,6-divindodecafluorohexane, 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. After injecting 8.1 g (81 mmol) of tetrafluoroethylene under pressure, stirring was started while raising the internal temperature to 140°C. Stirring was carried out at 200 rpm for 18 hours while maintaining the internal temperature, and the internal pressure decreased from 1.4 MPa to 1.3 MPa. After cooling the autoclave in an ice bath, the unreacted tetrafluoroethylene was purged.

[0177] The resulting polymer solution was vacuum-dried to obtain a viscous liquid. This liquid was added to 50 mL of methanol and stirred for 10 minutes, after which the liquid and supernatant were separated using a centrifuge. The resulting polymer solution was filtered through Celite to remove the solid. The filtrate was vacuum-dried to obtain a viscous liquid. The obtained liquid was added to 30 mL of methanol and stirred for 10 minutes, after which the liquid and supernatant were separated using a centrifuge. The obtained liquid was vacuum-dried to yield 0.7 g of fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The resulting polymer had a manganese content of 2,200 and a manganese content of 3,500, as measured by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.6. The fluorine content of the obtained polymer, as determined by the method described above, was 65% by mass. The degree of unsaturation of the obtained polymer, as measured by the method described above, was 0.7 mEq / g. The Tg of the obtained polymer, as measured by the method described above, was -10°C. When the obtained polymer was placed on a glass substrate and heated to 180°C under a nitrogen atmosphere, it was visually observed to melt and spread. Due to the low yield, viscoelasticity measurements could not be performed, but from the above results, the maximum value of the complex modulus (E) of the obtained polymer at -50°C to (Tg-10°C) was estimated. * 1) The minimum value of the complex modulus (E) between (Tg+10℃) and 250℃ for 1). * 2) Ratio (E * 2 / E * 1) is considered to be 0.01 or less. Based on the results of solubility and heating tests, the production of a non-gelling fluorine-containing polymer was confirmed.

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

[0179] The resulting polymer solution was vacuum-dried to obtain a viscous liquid. This liquid was added to 50 mL of methanol and stirred for 10 minutes, after which the precipitated solid and supernatant were separated using a centrifuge. The obtained solid was added again to 50 mL of methanol and stirred for 10 minutes, after which the solid and supernatant were separated using a centrifuge. The obtained liquid was vacuum-dried to yield 0.5 g of fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The resulting polymer had a manganese (Mn) of 4,100 and a manganese (Mw) of 6,600, as measured by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.6. The fluorine content of the polymer obtained by the method described above was 67% by mass. The degree of unsaturation of the obtained polymer, as measured by the method described above, was 0.5 mEq / g. The Tg of the obtained polymer, as measured by the method described above, was 97°C. When the obtained polymer was placed on a glass substrate and heated to 180°C under a nitrogen atmosphere, it was visually observed to melt and spread. Due to the low yield, viscoelasticity measurements could not be performed, but from the above results, the maximum value of the complex modulus (E) of the obtained polymer at -50°C to (Tg-10°C) was estimated. * 1) The minimum value of the complex modulus (E) between (Tg+10℃) and 250℃ for 1). * 2) Ratio (E * 2 / E * 1) is considered to be 0.01 or less. Based on the results of solubility and heating tests, the production of a non-gelling fluorine-containing polymer was confirmed.

[0180] (Example 7) In a nitrogen-purged glove box, a 100 mL stainless steel autoclave with a stirrer was charged with 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 diterlide, 0.092 g (0.40 mmol) of the azo radical initiator "V-601" (trade name, Fujifilm Wako Pure Chemical Industries, Ltd.), and 100 g of 1H-perfluorohexane. After injecting 7.4 g (74 mmol) of tetrafluoroethylene under pressure, stirring was started while raising the internal temperature to 80°C. Stirring was carried out at 200 rpm (200 revolutions per minute) for 7 hours while maintaining the internal temperature, and the internal pressure decreased from 0.8 MPa (gauge pressure) to 0.6 MPa. After cooling the autoclave in an ice bath, the unreacted tetrafluoroethylene was purged.

[0181] The resulting polymer solution was vacuum-dried to obtain a viscous liquid. This liquid was added to 50 mL of methanol and stirred for 10 minutes, after which the liquid and supernatant were separated using a centrifuge. The resulting liquid was added again to 50 mL of methanol and stirred for 10 minutes. Then, the precipitated solid and the supernatant were separated using a centrifuge. The obtained solid was vacuum-dried to yield 2.8 g of fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The resulting polymer had a manganese content of 4,000 and a manganese content of 5,700, as measured by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.4. The fluorine content of the obtained polymer, as determined by the method described above, was 66% by mass. The degree of unsaturation of the obtained polymer, as measured by the method described above, was 0.3 mEq / g. The Tg of the obtained polymer, as measured by the method described above, was 92°C. The maximum value (E) of the complex modulus of the obtained polymer at -50°C to (Tg-10°C), measured by the method described above. * 1) The minimum value of the complex modulus (E) between (Tg+10℃) and 250℃ for 1). * 2) Ratio (E * 2 / E * 1) is 0.01 or less. Based on the results of solubility and complex modulus measurements, the production of a non-gelling fluorine-containing polymer was confirmed.

[0182] (Example 8) In a nitrogen-purged glove box, a 200 mL stainless steel autoclave with a stirrer was charged with 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. After injecting 8.1 g (81 mmol) of tetrafluoroethylene under pressure, stirring was started while raising the internal temperature to 140°C. Stirring was carried out at 200 rpm for 18 hours while maintaining the internal temperature, and the internal pressure decreased from 1.4 MPa to 1.3 MPa. After cooling the autoclave in an ice bath, the unreacted tetrafluoroethylene was purged.

[0183] The resulting polymer solution was vacuum-dried to obtain a viscous liquid. This liquid was added to 50 mL of methanol and stirred for 10 minutes, after which the liquid and supernatant were separated using a centrifuge. The resulting polymer solution was filtered through Celite to remove the solid. The filtrate was vacuum-dried to obtain a viscous liquid. The obtained liquid was added to 30 mL of methanol and stirred for 10 minutes, after which the liquid and supernatant were separated using a centrifuge. The obtained liquid was vacuum-dried to yield 0.9 g of fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The resulting polymer had a manganese (Mn) of 2,400 and a manganese (Mw) of 3,500, as measured by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.5. The fluorine content of the obtained polymer, as determined by the method described above, was 65% by mass. The degree of unsaturation of the obtained polymer, as measured by the method described above, was 0.4 mEq / g. The Tg of the obtained polymer, as measured by the method described above, was 77°C. When the obtained polymer was placed on a glass substrate and heated to 180°C under a nitrogen atmosphere, it was visually observed to melt and spread. Due to the low yield, viscoelasticity measurements could not be performed, but from the above results, the maximum value of the complex modulus (E) of the obtained polymer at -50°C to (Tg-10°C) was estimated. * 1) The minimum value of the complex modulus (E) between (Tg+10℃) and 250℃ for 1). * 2) Ratio (E * 2 / E * 1) is considered to be 0.01 or less. Based on the results of solubility and heating tests, the production of a non-gelling fluorine-containing polymer was confirmed.

[0184] (Example 9) In a nitrogen-purged glove box, a 100 mL stainless steel autoclave with a stirrer was charged with 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 the azo radical initiator "VAm-110" (trade name, Fujifilm Wako Pure Chemical Industries, Ltd.), and 100 g of 1H-perfluorohexane. After injecting 2.2 g (22 mmol) of tetrafluoroethylene under pressure, stirring was started while raising the internal temperature to 125°C. Stirring was carried out at 200 rpm for 20 minutes while maintaining the internal temperature, and the internal pressure decreased from 0.9 MPa to 0.7 MPa. After cooling the autoclave in an ice bath, the unreacted tetrafluoroethylene was purged.

[0185] The resulting polymer solution was vacuum-dried to obtain a viscous liquid. This liquid was added to 50 mL of methanol and stirred for 10 minutes, after which the precipitated solid and supernatant were separated using a centrifuge. The obtained solid was added again to 50 mL of methanol and stirred for 10 minutes, after which the solid and supernatant were separated using a centrifuge. The obtained solid was vacuum-dried to yield 0.9 g of fluorine-containing polymer. The resulting fluorine-containing polymer was dissolved in tetrahydrofuran. The resulting polymer had a manganese (Mn) of 7,900 and a manganese (Mw) of 12,200, as measured by size exclusion chromatography. The calculated polydispersity (Mw / Mn) of the fluorine-containing polymer was 1.5. The fluorine content of the obtained polymer, as determined by the method described above, was 68% by mass. The degree of unsaturation of the obtained polymer, as measured by the method described above, was 0.2 mEq / g. The Tg of the obtained polymer, as measured by the method described above, was 109°C. When the obtained polymer was placed on a glass substrate and heated to 180°C under a nitrogen atmosphere, it was visually observed to melt and spread. Due to the low yield, viscoelasticity measurements could not be performed, but from the above results, the maximum value of the complex modulus (E) of the obtained polymer at -50°C to (Tg-10°C) was estimated. * 1) The minimum value of the complex modulus (E) between (Tg+10℃) and 250℃ for 1). * 2) Ratio (E * 2 / E * 1) is considered to be 0.01 or less. Based on the results of solubility and heating tests, the production of a non-gelling fluorine-containing polymer was confirmed.

[0186] (Example 10) A glass container with an internal volume of 20 mL was filled with 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 then sealed. A homogeneous solution was obtained by mixing the tubes at room temperature for 30 minutes using a tube rotator. The glass container was opened and dried at 60°C for 12 hours under nitrogen flow to obtain a solid. The obtained solid was placed on a glass substrate and heated at 200°C for 1 hour under a nitrogen atmosphere, and then allowed to cool to room temperature under an air atmosphere to obtain a solid. The obtained solid was insoluble in 1H-perfluorohexane and tetrahydrofuran. When the obtained solid was placed on a glass substrate and heated to 250°C under a nitrogen atmosphere, no visible signs of melting were observed. The above results indicate that the fluorine-containing polymer is thermosetting.

[0187] (Example 11) A solid was obtained by following the same procedure as in Example 10, except that the fluorine-containing polymer obtained in Example 8 was used in place of the fluorine-containing polymer obtained in Example 7. The obtained solid was insoluble in tetrahydrofuran. When the obtained solid was placed on a glass substrate and heated to 250°C under a nitrogen atmosphere, no visible signs of melting were observed. The above results indicate that the fluorine-containing polymer is thermosetting.

[0188] (Example 12) A solid was obtained by following the same procedure as in Example 10, except that the fluorine-containing polymer obtained in Example 9 was used in place of the fluorine-containing polymer obtained in Example 7. The obtained solid was insoluble in 1H-perfluorohexane and tetrahydrofuran. When the obtained solid was placed on a glass substrate and heated to 250°C under a nitrogen atmosphere, no visible signs of melting were observed. The above results indicate that the fluorine-containing polymer is thermosetting.

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

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

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

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

[0193] This 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 higher, and the maximum value of the complex modulus E in the range of -50°C to the glass transition temperature is * 1 and the minimum value E of the complex modulus in the glass transition temperature range of ~250°C. * The relationship between 2 and is E * 2 / E * A fluorine-containing polymer that satisfies the condition 1 ≤ 0.01. <2> The polydispersity is 2.0 or less. <1> The fluorine-containing polymer described above. <3> The weight-average molecular weight is between 1,000 and 1,000,000. <1> or <2> The fluorine-containing polymer described above. <4> A polymer of the compound represented by the following formula (1), or The copolymer is a compound represented by the following formula (1) and a compound having a reactive carbon-carbon double bond that is different from the compound represented by formula (1). <1> ~ <3> A fluorine-containing polymer as described in any one of the items.

[0194] [ka]

[0195] In formula (1), Y 7 R represents a divalent organic group having at least one fluorine atom. 1 ~R 6 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 5 carbon atoms. 1 and R 3 , R4 and R 5 , R 2 and Y 7 , and R 6 and Y 7 These elements may be independent of each other, or they may be connected to each other to form a ring structure. <5> The compound represented by formula (1) has a fluorine content of 20% by mass or more. <4> The fluorine-containing polymer described above. <6> Y in equation (1) above 7 However, it 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 described above. <7> The compound represented by formula (1) comprises 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> A fluorine-containing polymer as described in any one of the items. <8> In the presence of an ionic catalyst represented by the following formula (2), which consists of an anion and a countercation, and a compound having a substructure represented by the following formula (3), or, In the presence of at least one compound selected from the group consisting of the compound represented by the following formula (4) and the compound represented by the following formula (5), This involves polymerizing a compound having at least two reactive carbon-carbon double bonds. <1> ~ <7> A method for producing a fluorine-containing polymer as described in any one of the items.

[0196] [ka]

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

[0198] [ka]

[0199] In equation (3), * represents a bond attached to an organic group. 1 and X 2 Each of these independently consists of a hydrogen atom, a fluorine atom, a chlorine atom, or -CX. 3 X 4 X 5 It represents X. 3 ~X 5 Each of these independently represents a hydrogen atom, a fluorine atom, or a chlorine atom.

[0200] [ka]

[0201] In formula (4), Y 1 This 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 these 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 amide 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 of these 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 the compound represented by the following formula (1): <8> A method for producing a fluorine-containing polymer as described above.

[0204] [ka]

[0205] In formula (1), Y 7 R represents a divalent organic group having at least one fluorine atom. 1 ~R 6 Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 5 carbon atoms. 1 and R 3 , R 4 and R 5 , R 2 and Y 7 , and R 6 and Y 7 These elements may be independent of each other, or they may be connected to each other to form a ring structure. <10> This involves copolymerizing a compound represented by formula (1) with a compound having a reactive carbon-carbon double bond and being different from the compound represented by formula (1). <9> A method for producing a fluorine-containing polymer as described above.

[0206] The disclosures of Japanese Patent Application No. 2020-023636 and Japanese Patent Application No. 2020-087582 are incorporated herein by reference in their entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted as being incorporated by reference.

Claims

1. In the presence of an ionic catalyst represented by the following formula (2) consisting of an anion and a countercation, and a compound having a substructure represented by the following formula (3), In the presence of at least one compound selected from the group consisting of the compound represented by the following formula (4) and the compound represented by the following formula (5), A method for producing a fluorine-containing polymer, comprising polymerizing a compound having at least two reactive carbon-carbon double bonds, The fluorine content of the compound having at least two reactive carbon-carbon double bonds is 20% by mass or more. The fluorine-containing polymer has a fluorine content of 50% by mass or more, a degree of unsaturation of 0.1 mEq / g or more, a glass transition temperature of -20°C or higher, and a maximum value E of the complex modulus in the range of -50°C to (glass transition temperature -10°C). ＊ 1. 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 ＊ A method for producing a fluorine-containing polymer that satisfies the condition 1 ≤ 0.

01. 【Chemistry 1】 In formula (2), A+ represents a cation, alkali metal ion, or proton containing at least one element selected from the group consisting of nitrogen and phosphorus, and B- represents a monovalent anion containing at least one element selected from the group consisting of iodine, nitrogen, and sulfur. 【Chemistry 2】 In formula (3), * represents a bond attached to an organic group. X1 and X2 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or -CX3X4X5. X3 to X5 each independently represent a hydrogen atom, a fluorine atom, or a chlorine atom. 【Transformation 3】 In formula (4), Y1 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. Y2 and Y3 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. Y4 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 amide group having 2 to 8 carbon atoms, an oxycarbonyl group, or a cyano group. 【Chemistry 4】 In formula (5), Y5 and Y6 each independently represent 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. The method for producing a fluorine-containing polymer according to Claim 1, wherein the polydispersity of the fluorine-containing polymer is 2.0 or less.

3. The method for producing a fluorine-containing polymer according to claim 1 or claim 2, wherein the weight-average molecular weight of the fluorine-containing polymer is 1,000 to 1,000,000.

4. The fluorine-containing polymer is A polymer of the compound represented by the following formula (1), or The copolymer is a compound represented by the following formula (1) and a compound having a reactive carbon-carbon double bond that is different from the compound represented by formula (1). A method for producing a fluorine-containing polymer according to any one of claims 1 to 3. 【Transformation 5】 In formula (1), Y ７ represents a divalent organic group having at least one fluorine atom. R １ ~R ６ 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. 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 connected to each other to form a cyclic structure.

5. Y in formula (1) above ７ The method for producing a fluorine-containing polymer according to claim 4, wherein the group 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.

6. A method for producing a fluorine-containing polymer according to claim 4 or claim 5, wherein the compound represented by formula (1) comprises 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.

7. A method for producing a fluorine-containing polymer according to any one of claims 1 to 3, wherein the compound having at least two reactive carbon-carbon double bonds includes a compound represented by the following formula (1). 【Transformation 6】 In formula (1), Y ７ R represents a divalent organic group having at least one fluorine atom. １ ~R ６ Each of these independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an organic group having 1 to 5 carbon atoms. １ and R ３ , R ４ and R ５ , R ２ and Y ７ , and R ６ and Y ７ These elements may be independent of each other, or they may be connected to each other to form a ring structure.

8. A method for producing a fluorine-containing polymer according to claim 7, comprising copolymerizing a compound represented by formula (1) with a compound having a reactive carbon-carbon double bond and being different from the compound represented by formula (1).

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