Fluorine-containing polymer and method for producing the same

Abstract

To provide a novel fluorine-containing polymer with high heat resistance, and a production method thereof.SOLUTION: The invention provides a fluorine-containing polymer comprising a structural unit represented by the general formula (1) in the figure, and a production method thereof. (In the formula (1), n is an integer from 2 to 10, and Ar is a divalent aromatic group.)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a fluorine-containing polymer and a method for producing the same.

Background Art

[0002] Due to the properties of carbon-fluorine bonds, fluorine-containing polymers have excellent properties such as chemical resistance, water and oil repellency, visible light transmittance, low refractive index, and low dielectric constant, and are industrially used. Among them, fluorine-containing polymers having a perfluoroalkylene group in the main chain are known to exhibit high chemical stability and low dielectric constant.

[0003] Non-Patent Document 1 discloses a polyaryl ether having a perfluoroalkylene chain. Patent Documents 1 and 2 disclose a polyaryl thioether and a polyurethane having a perfluoroalkylene group in the main chain. However, these fluorine-containing polymers have problems such as complicated synthesis of raw material monomers and the need for high-temperature conditions of 150°C or higher during the production of the polymer.

[0004] Patent Document 3 discloses a method for producing a fluorine-containing polymer by metathesis polymerization of a diene having a perfluoroalkylene group. However, there are problems such as the need for a special catalyst for the polymerization, and there has been a demand for a fluorine-containing polymer that can be easily produced from readily available raw materials having a perfluoroalkylene group.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Non-Patent Documents

[0006] [Non-Patent Document 1] Macromolecules, 1990, Vol. 23, pp. 5371 - 5373 [Summary of the Invention] [Problems to be Solved by the Invention]

[0007] In view of the above background art, an object of the present invention is to provide a novel fluorine-containing polymer having high heat resistance and capable of being easily produced, and a method for producing the same. [Means for Solving the Problems]

[0008] As a result of intensive studies on methods for solving the above problems, the present inventors have found that the fluorine-containing polymer shown below solves the above problems, and have completed the present invention.

[0009] That is, the present invention relates to the following. [1] A fluorine-containing polymer containing a structural unit represented by the following general formula (1). [Chemical Formula] (In formula (1), n is an integer of 2 to 10, and Ar is a divalent aromatic group) [2] The fluorine-containing polymer according to [1], wherein n in general formula (1) is 4, 6 or 8. [3] The fluorine-containing polymer according to [1] or [2], wherein Ar in general formula (1) is at least one selected from the group consisting of a phenylene group which may have a substituent, a biphenylene group which may have a substituent, a terphenylene group which may have a substituent, a fluorenylene group which may have a substituent, a naphthylene group which may have a substituent, an anthracenylene group which may have a substituent, a phenanthrenylene group which may have a substituent, and a methylenediphenylene group which may have a substituent. [4] A method for producing a fluorine-containing polymer containing a structural unit represented by the following general formula (4), characterized by polymerizing a compound represented by the following general formula (2) and a compound represented by the following general formula (3) in the presence of a transition metal catalyst and a base. [Chemical formula] (In formula (2), n is an integer from 2 to 10) X-Ar-X (3) (In formula (3), Ar is a divalent aromatic group, and X is a chlorine atom, a bromine atom, an iodine atom or a trifluoromethanesulfonyl group) [Chemical formula] (In formula (4), n and Ar are the same as those in the above formula (1)) [5] The method for producing a fluorine-containing polymer according to [4], wherein n in the general formula (2) is 4 or 6. [6] The method for producing a fluorine-containing polymer according to [4] or [5], wherein Ar in the general formula (3) is at least one selected from the group consisting of a phenylene group which may have a substituent, a biphenylene group which may have a substituent, a terphenylene group which may have a substituent, a fluorenylene group which may have a substituent, a naphthylene group which may have a substituent, an anthracenylene group which may have a substituent, a phenanthrenylene group which may have a substituent, and a methylenediphenylene group which may have a substituent. [7] The method for producing a fluorine-containing polymer according to any one of [4] to [6], wherein the transition metal catalyst is a palladium catalyst or a nickel catalyst. [8] The method for producing a fluorine-containing polymer according to any one of [4] to [7], wherein the base is at least one selected from the group consisting of sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and an organic base.

[0010] Hereinafter, the present invention will be described in detail. In the fluorine-containing polymer containing the structural unit represented by the general formula (1) of the present invention, n is an integer of 2 to 10, and Ar is a divalent aromatic group. Among them, n is preferably 4 to 8, and more preferably 4, 6 or 8 because the production is easy.

[0011] Ar in the general formula (1) of the present invention is at least one selected from the group consisting of a phenylene group which may have a substituent, a biphenylene group which may have a substituent, a terphenylene group which may have a substituent, a fluorenylene group which may have a substituent, a naphthylene group which may have a substituent, an anthracenylene group which may have a substituent, a phenanthrenylene group which may have a substituent, and a methylenediphenylene group which may have a substituent. Specific examples of the substituent include an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, a perfluoroalkoxy group having 1 to 4 carbon atoms, and the like.

[0012] The fluorine-containing polymer containing the structural unit represented by the general formula (1) of the present invention is obtained by polymerizing a compound represented by the general formula (2) and a compound represented by the general formula (3) in the presence of a transition metal catalyst and a base.

[0013] In the compound represented by the general formula (2) of the present invention, n is an integer of 2 to 10, n is preferably 4 to 8, and more preferably 4, 6 or 8 because the production is easy.

[0014] In the compound represented by the general formula (3) of the present invention, X is a chlorine atom, a bromine atom, an iodine atom or a trifluoromethanesulfonyl group. From the viewpoint of reactivity, X is more preferably a bromine atom, an iodine atom or a trifluoromethanesulfonyl group. In the compound represented by the general formula (3) of the present invention, Ar is preferably at least one selected from the group consisting of a phenylene group which may have a substituent, a biphenylene group which may have a substituent, a terphenylene group which may have a substituent, a fluorenylene group which may have a substituent, a naphthylene group which may have a substituent, an anthracenylene group which may have a substituent, a phenanthrenylene group which may have a substituent, and a methylenediphenylene group which may have a substituent. Specific examples of the substituent include an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, a perfluoroalkoxy group having 1 to 4 carbon atoms, and the like.

[0015] In the production of the fluorine-containing polymer containing the structural unit represented by the general formula (1) of the present invention, the transition metal catalyst is preferably a palladium catalyst or a nickel catalyst. Specific examples of the palladium catalyst include palladium chloride, palladium bromide, palladium acetate, palladium trifluoroacetate, π-allylpalladium chloride dimer, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, bis(tri-t-butylphosphine)palladium, bis(acetylacetonato)palladium, dichlorobis(tricyclohexylphosphine)palladium, dichlorobis(triphenylphosphine)palladium, dichlorobis(tri-o-tolylphosphine)palladium, dichloro[1,1'-bis(di-tert-butylphosphino)ferrocene]palladium, tetrakis(acetonitrile)palladium tetrafluoroborate, Hermann catalyst, etc., and complexes in which a ligand is coordinated to the palladium salt or palladium complex. Specific examples of the nickel catalyst include nickel chloride, bis(1,5-cyclooctadiene)nickel, nickel acetylacetonate hydrate, dichlorobis(tricyclohexylphosphine)nickel, dichlorobis(triphenylphosphine)nickel, dichlorobis(dicyclohexylphenylphosphine)nickel, chlorobis[dicyclohexyl(phenyl)phosphino](o-tolyl)nickel, dichloro[1,1'-bis(diphenylphosphino)ferrocene]nickel, dichloro[1,2-bis(diphenylphosphino)ethane]nickel, dichloro[1,3-bis(diphenylphosphino)propane]nickel, etc., and complexes in which a ligand is coordinated to the nickel salt or nickel complex, etc. Among these, a palladium catalyst is preferable from the viewpoint of reactivity, and among them, the Hermann catalyst is more preferable.

[0016] The ligand is not particularly limited as long as it is a ligand capable of coordinating to a transition metal, but a phosphine ligand is preferable, and a tertiary phosphine ligand is more preferable. Specifically, triphenylphosphine, trimethylphosphine, tributylphosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 2-(diphenylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)biphenyl, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, tri(2-furyl)phosphine, tri(o-tolyl)phosphine, tris(2,5-xylyl)phosphine, (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, etc. are mentioned. The molar ratio of the tertiary phosphine to the palladium salt or palladium complex is preferably from 1:10 to 10:1, more preferably from 1:2 to 5:1.

[0017] In the production of the fluorine-containing polymer containing the structural unit represented by the general formula (1) of the present invention, the base is preferably at least one selected from the group consisting of sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and organic bases.

[0018] In the production of the fluorine-containing polymer containing the structural unit represented by the general formula (1) of the present invention, a solvent may be used. The solvent to be used is not particularly limited as long as it is a solvent inert to the polymerization reaction, but hydrocarbon solvents such as pentane, hexane, cyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene, cumene, etc., (halogenated) hydrocarbon solvents such as dichloromethane, chloroform, etc., ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc., polar aprotic solvents such as acetonitrile, propionitrile, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, etc., water and the like can be mentioned. These solvents may be used alone or in combination of two or more.

[0019] In the present invention, the solvent to be used is preferably used in an amount of 2 to 100 times by weight, more preferably 5 to 50 times by weight, based on the compound represented by the general formula (2) involved in the reaction.

[0020] In the production of the fluorine-containing polymer containing the structural unit represented by the general formula (1) of the present invention, the reaction temperature is preferably in the range of 0°C to 140°C, more preferably in the range of room temperature to 125°C. The reaction time is preferably in the range of 1 hour to 96 hours, more preferably in the range of 4 hours to 48 hours. After the coincidence reaction is completed, the obtained fluorine-containing polymer is recovered by any method, and post-treatment such as washing is performed as necessary. Examples of the method for recovering the fluorine-containing polymer from the reaction solution include known methods such as reprecipitation.

[0021] The weight average molecular weight (hereinafter abbreviated as Mw) of the fluorine-containing polymer of the present invention is preferably in the range of 1,000 to 1,000,000, more preferably 3,000 to 500,000 in terms of polystyrene conversion by gel permeation chromatography (GPC).

Advantages of the Invention

[0022] According to the present invention, a novel fluorine-containing polymer having high heat resistance and the like and usable as a functional material can be provided.

Examples

[0023] Examples of the present invention are shown below, but the present invention is not limited to these examples.

[0024] In the analysis of the results, the following equipment was used. 1 H NMR, 19 F NMR, 13 C NMR: AVANCE-III NMR spectrometer manufactured by Bruker BioSpin Corporation Measurement 1 by gel permeation chromatography (GPC) (hereinafter referred to as "GPC measurement 1"): Apparatus: HLC-8320GPC manufactured by Tosoh Corporation Column: TSKgel G4000HXL, G3000HXL, G2500HXL, G2000HXL manufactured by Tosoh Corporation Column temperature: 40 ° C Solvent: Tetrahydrofuran Flow rate: 1 mL / min Detector: UV (254 nm) Measurement 2 by gel permeation chromatography (GPC) (hereinafter referred to as "GPC measurement 2"): Apparatus: LC-20AD GPC system manufactured by Shimadzu Corporation Column: Tosoh TSK-gel GMHHR-M Column temperature: 40 °C Solvent: chloroform Flow rate: 1 mL / min Detector: UV (254 nm) Thermogravimetric derivative thermal analysis (TG-DTA): Rigaku Thermo plus EVO high-resolution operating pyrolysis apparatus Differential scanning calorimetry (DSC): TA Instruments DSC Q2000

[0025] Example 1 Synthesis of polymer (a) [Chemical formula] To a solution of 0.74 g (3.1 mmol) of 1,4-dibromobenzene, 0.77 g (9.4 mmol) of sodium acetate, and 0.15 g (described as Hermann's catalyst (Hermann catalyst) in the above reaction formula, 0.16 mmol) of trans-bis(acetato)bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II) in DMF (6 mL), 0.60 mL (3.1 mmol) of 1,4-divinylperfluorobutane was added under a nitrogen atmosphere, and the mixture was stirred at 125 °C for 24 hours. 200 mL of methanol was added to the reaction mixture for reprecipitation, and then polymer (a) was obtained as a brown solid (0.80 g, 2.4 mmol) by filtration. The yield was 77%.

[0026] The analysis results of the product are shown below. 1 H NMR (400 MHz, THF-d 8 , ppm) δ = 7.52 - 7.25 (4H), 7.22 - 6.96 (2H), 6.77 - 6.50 (2H) 19 F NMR (376 MHz, THF-d 8 , ppm) δ = -111.03 - -12.02 (m, 4F), -122.92 - -123.68 (m, 4F) M n = 5,400, M w = 11,000, M w / M n = 1.9 (Molecular weight measurement by GPC measurement 1) T d5% = 297 °C T g = 133 °C

[0027] Example 2 Synthesis of Polymer (b)

Chemical formula

[0028] The analysis results of the product are shown below. 1 H NMR (400 MHz, THF-d 8 , ppm) δ = 7.52 - 7.43 (4H), 7.18 - 6.14 (2H), 6.30 - 6.24 (2H) 19 F NMR (376 MHz, THF-d 8 , ppm) δ = -111.35 - -111.37 (m, 4F), -122.83 - -122.85 (m, 4F) M n = 2,300, M w = 3,700, M w / M n = 1.6 (Molecular weight measurement by GPC measurement 2 by) T d5% = 281 °C

[0029] Example 3 Synthesis of Polymer (c)

Chemical formula

[0030] The analysis results of the product are shown below. 1 H NMR (400 MHz, THF-d 8 , ppm) δ = 7.31 - 7.30 (1H), 7.17 - 7.10 (4H), 6.27 - 6.24 (2H) 19 F NMR (376 MHz, THF-d 8 , ppm) δ = -111.47 - -111.67 (m, 5F), -122.82 (m, 4F) M n = 2,700, M w = 5,300, M w / M n = 2.0 (Molecular weight measurement was by GPC measurement 2) T d5% = 358 °C

[0031] Example 4 Synthesis of polymer (d)

Chemical formula

[0032] The analysis results of the product are shown below. 1 H NMR(400MHz,THF-d 8 ,ppm)δ=7.71(3H),7.18 - 7.12(2H), 6.40 - 6.33(2H) 19 F NMR(376MHz,THF-d 8 ,ppm)δ=-63.07--63.08(m,3F),-111.73(m,4F),-122.71 (m,4F) M n =3,800,M w =7,000,M w / M n =1.8(The molecular weight measurement was by GPC measurement 2) T d5% =291℃

[0033] Example 5 Synthesis of Polymer (e)

Chemical formula

[0034] The analysis results of the product are shown below. 1 H NMR(400MHz,Acetone-d 6 ,ppm)δ=7.87 - 7.82(2H), 7.44 - 7.40(2H),6.92 - 6.82(2H) 19 F NMR(376MHz,Acetone-d 6 ,ppm)δ= -112.19 (m,4F),-121.94--122.09(m,6F), -123.72(m,4F) M n =4,800,M w =7,500,Mw / M n = 1.6 (Molecular weight measurement by GPC measurement 1) T d5% = 325 °C

[0035] Example 6 Synthesis of Polymer (f)

Chemical formula

[0036] The analysis results of the product are shown below. T d5% = 403 °C

[0037] Example 7 Synthesis of Polymer (g)

Chemical formula

[0038] The analysis results of the product are shown below. T d5% = 415 °C

Claims

1. A fluorine-containing polymer comprising a structural unit represented by the following general formula (1). 【Chemical Formula 11】 (In formula (1), n is an integer of 2 to 10, and Ar is a divalent aromatic group)

2. The fluorine-containing polymer according to claim 1, wherein n in general formula (1) is 4, 6 or 8.

3. The fluorine-containing polymer according to claim 1 or 2, wherein Ar in general formula (1) is at least one selected from the group consisting of a phenylene group which may have a substituent, a biphenylene group which may have a substituent, a terphenylene group which may have a substituent, a fluorenylene group which may have a substituent, a naphthylene group which may have a substituent, an anthracenylene group which may have a substituent, a phenanthrenylene group which may have a substituent, and a methylenediphenylene group which may have a substituent.

4. A method for producing a fluorine-containing polymer comprising a structural unit represented by the following general formula (4), characterized in that a compound represented by the following general formula (2) and a compound represented by the following general formula (3) are polymerized in the presence of a transition metal catalyst and a base. 【Chemical Formula 12】 (In formula (2), n is an integer of 2 to 10) X-Ar-X (3) (In formula (3), Ar is a divalent aromatic group, and X is a chlorine atom, a bromine atom, an iodine atom or a trifluoromethanesulfonyl group) 【Chemical 13】 (In formula (4), n and Ar are the same as those in formula (1) above)

5. The method for producing a fluorine-containing polymer according to claim 4, wherein n in general formula (2) is 4, 6 or 8.

6. The method for producing a fluorine-containing polymer according to claim 4 or 5, wherein Ar in general formula (3) is at least one selected from the group consisting of a phenylene group which may have a substituent, a biphenylene group which may have a substituent, a terphenylene group which may have a substituent, a fluorenylene group which may have a substituent, a naphthylene group which may have a substituent, an anthracenylene group which may have a substituent, a phenanthrenylene group which may have a substituent, and a methylenediphenylene group which may have a substituent.

7. The method for producing a fluorine-containing polymer according to any one of claims 4 to 6, wherein the transition metal catalyst is a palladium catalyst or a nickel catalyst.

8. The production method of the fluorine-containing polymer according to any one of claims 4 to 7, wherein the base is at least one selected from the group consisting of sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and organic bases.

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