Fluorine-containing polymer

Abstract

This fluorine-containing polymer is represented by formula (1). (1): Rf-Y-R1-Y-Rf. In formula (1), Rfs are each independently a C1-C10 fluorine-containing alkyl group, the carbon atom positioned at the Y-side terminal has a fluorine atom, Ys are each independently a single bond or a divalent linking group, R1 is an optionally substituted polymethylene chain, and a -C=C-group may be contained in the polymethylene chain.

Description

Fluorine-containing polymer

[0001] The present disclosure relates to fluorine-containing polymers.

[0002] Fluorine-containing polymers are used in a variety of fields because of their excellent heat resistance, chemical resistance, oil resistance, weather resistance, electrical insulation properties, and the like.

[0003] For example, Non-Patent Document 1 describes poly(fluoroalkyl acrylate).

[0004] Takahara, Macromolecules, 2005, 38, 5699-5705

[0005] There is a demand for the development of novel fluorine-containing polymers.

[0006] An object of one embodiment of the present disclosure is to provide a novel fluorine-containing polymer.

[0007] Means for solving the above problems include the following aspects: <1> A fluorine-containing polymer represented by the following formula (1): Rf-Y-R １ -Y-Rf (1) In formula (1), each Rf is independently a fluorine-containing alkyl group having 1 to 10 carbon atoms, and the carbon atom located at the terminal on the Y side has a fluorine atom; each Y is independently a single bond or a divalent linking group; R １ is a polymethylene chain which may have a substituent, and the polymethylene chain may contain a -C=C- group. <2> The fluorine-containing polymer according to <1>, wherein Rf's each independently represent a perfluoroalkyl group having 1 to 10 carbon atoms. <3> Each Y independently represents an alkylene group, -O-, -C(=O)-, or a combination thereof (with the proviso that R １ <4> The fluorine-containing polymer according to <1> or <2>, wherein each Y independently represents *, and the terminal on the Y side is not an alkylene group. １ -R ２ O-* ２ and R ２ is an alkylene group having 1 to 3 carbon atoms, and * １ means the bonding position to Rf, and * ２ is R １<5> The fluorine-containing polymer according to any one of <1> to <3>, wherein R １ is -CH ２ -(CH=CH-(CH ２ ) ｍ１ ) ｎ１ -CH=CH-CH ２ <6> The fluorine-containing polymer according to any one of <1> to <4>, wherein R １ is -(CH ２ ) ｍ２ - and m2 is 150 to 6000. <7> An article having, on a surface thereof, a film containing the fluoropolymer according to any one of <1> to <6>.

[0008] According to one embodiment of the present disclosure, a novel fluorine-containing polymer is provided.

[0009] Hereinafter, embodiments of the present disclosure will be described in detail. However, the embodiments of the present disclosure are not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the embodiments of the present disclosure.

[0010] In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in the present disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another staged numerical range. In the present disclosure, each component may contain multiple corresponding substances. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified.

[0011] The fluoropolymer of the present disclosure is represented by the following formula (1): Rf-Y-R １-Y-Rf (1) In formula (1), each Rf is independently a fluorine-containing alkyl group having 1 to 10 carbon atoms, and the carbon atom located at the terminal on the Y side has a fluorine atom; each Y is independently a single bond or a divalent linking group; R １ is a polymethylene chain which may have a substituent, and the polymethylene chain may contain a -C=C- group.

[0012] The fluoropolymer of the present disclosure has a structure in which the central portion is a polymethylene chain and both ends have fluorine-containing alkyl groups. This unconventional molecular design is expected to result in unconventional performance.

[0013] [Rf] The two Rfs may be the same or different. From the viewpoint of enhancing the intramolecular interaction, it is preferable that the two Rfs are the same.

[0014] The fluorine-containing alkyl group represented by Rf may be a partial fluoroalkyl group or a perfluoroalkyl group.

[0015] The term "partially fluoroalkyl group" refers to a group in which some of the hydrogen atoms of an alkyl group have been substituted with fluorine atoms, and the term "perfluoroalkyl group" refers to a group in which all of the hydrogen atoms of an alkyl group have been substituted with fluorine atoms.

[0016] In Rf, the carbon atom located at the end on the Y side has a fluorine atom. That is, in Rf, the end on the Y side is —CHF— or —CF ２ - is preferred, and -CF ２ - is more preferable.

[0017] The fluorine-containing alkyl group represented by Rf may be any of linear, branched, and cyclic. From the viewpoint of enhancing intramolecular interaction, the fluorine-containing alkyl group is preferably linear. The number of carbon atoms in the fluorine-containing alkyl group represented by Rf is 1 to 10, preferably 3 to 9.

[0018] Among these, from the viewpoint of excellent water repellency and oil repellency, Rf is preferably a perfluoroalkyl group having 1 to 10 carbon atoms, more preferably a perfluoroalkyl group having 2 to 8 carbon atoms, and even more preferably a linear perfluoroalkyl group having 2 to 8 carbon atoms.

[0019] [Y] Two Y's may be the same or different. From the viewpoint of enhancing the intramolecular interaction, it is preferable that the two Y's are the same.

[0020] The divalent linking group represented by Y includes an alkylene group, —O—, —C(═O)—, —NR Ｔ -, or a combination thereof. １ The end of the R Ｔ represents a hydrogen atom or an alkyl group. Ｔ The alkyl group represented by the formula (I) is, for example, a methyl group.

[0021] When Y is a divalent linking group, examples of Y include: １ —O—C(═O)-(alkylene group)-C(═O)-O—* ２ * １ —O-(alkylene group)-O-* ２ * １ -(alkylene group)-O-(alkylene group)-O-* ２ * １ —C(═O)—NR Ｔ -* ２ * １ -NR Ｔ -C(=O)-* ２ * １ -NR Ｔ —C(═O)—NR Ｔ -* ２ * １ -OC(=O)-NR Ｔ -* ２ * １ -O-* ２ * １ -C(=O)-* ２ * １ -C(=O)-O-* ２ * １ -(alkylene group)-O-* ２* １ -(alkylene group)-C(=O)-* ２ * １ -(alkylene group)-C(=O)-O-* ２ * １ means the bonding position to Rf, and * ２ is R １ This means the bonding position with

[0022] Among these, Y is preferably an alkylene group, —O—, —C(═O)—, or a combination thereof, and more preferably a combination of an alkylene group and —O—.

[0023] In particular, from the viewpoint of enhancing the water repellency and oil repellency derived from Rf, Y is １ -R ２ O-* ２ and R ２ is preferably an alkylene group having 1 to 3 carbon atoms. ２ The alkylene group represented by the formula (I) is preferably a methylene group.

[0024] [R １ 〕 R １ The polymethylene chain represented by -CH ２ The polymethylene chain may have a structure having two or more methylene chains represented by -. The polymethylene chain may have a substituent, or may not have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group, a trialkylsilyl ether group, a trialkylsilyl group, an amino group, a nitro group, a cyano group, a sulfonyl group, and a trifluoromethyl group. In particular, when a surface treatment is performed using the fluorine-containing polymer of the present disclosure, a trifluoromethyl group is preferred as the substituent, since this allows many fluorine atoms to be present on the film surface.

[0025] Furthermore, the polymethylene chain may or may not contain a -C=C- group.

[0026] When a -C=C- group is contained in the polymethylene chain, R １ is -CH ２ -(CH=CH-(CH ２ ) ｍ１ ) ｎ１-CH=CH-CH ２ From the viewpoint of achieving both the function as a polymer and ease of industrial production, it is preferable that each m1 is independently 2 to 8, and n1 is 20 to 730.

[0027] Each m1 is more preferably independently 3 to 6. n1 is more preferably 50 to 630.

[0028] When a —C═C— group is contained in the polymethylene chain, examples of the fluoropolymer of the present disclosure include the following fluoropolymers.

[0029]

[0030] When the polymethylene chain does not contain a -C=C- group, R １ is -(CH ２ ) ｍ２ From the viewpoint of achieving both the function as a polymer and ease of industrial production, m2 is preferably 150 to 6,000.

[0031] m2 is more preferably 400 to 5,000.

[0032] When no —C═C— group is contained in the polymethylene chain, examples of the fluoropolymer of the present disclosure include the following fluoropolymers.

[0033]

[0034] The number average molecular weight (Mn) of the fluoropolymer of the present disclosure is preferably from 3,000 to 80,000, more preferably from 6,000 to 70,000, from the viewpoint of both exhibiting the functions as a polymer and being easy to produce industrially.

[0035] The dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the fluoropolymer of the present disclosure is preferably 1 to 3, and more preferably 1 to 2.

[0036] In the present disclosure, the number average molecular weight and weight average molecular weight are measured using gel permeation chromatography (GPC, JASCO Corporation's high performance liquid chromatograph EXTREMA HPLC system) using tetrahydrofuran as a solvent and calculated in terms of polystyrene.

[0037] The fluoropolymer of the present disclosure is preferably produced by the following method.

[0038] First, in the presence of a base, cis-1,4-dichloro-2-butene is reacted with a compound represented by the following formula (2) in a solvent: Rf-Y-H (2) Rf and Y in formula (2) are the same as Rf and Y in formula (1). That is, in formula (2), Rf is a fluorine-containing alkyl group having 1 to 10 carbon atoms, the carbon atom located at the terminal on the Y side has a fluorine atom, and Y is a single bond or a divalent linking group.

[0039] Preferred embodiments of Rf and Y are as described above.

[0040] Examples of the compound represented by formula (2) include 1H,1H-pentafluoro-1-propanol, 1H,1H-tridecafluoro-1-heptanol, 1H,1H-heptadecafluoro-1-octanol, 1H,1H-trifluoro-1-ethanol, and 1H,1H,3H-tetrafluoro-1-propanol.

[0041] The type of base is not particularly limited, but examples include sodium hydroxide, potassium hydroxide, and calcium hydroxide.

[0042] The solvent may be appropriately selected from those capable of dissolving the components used in the reaction.

[0043] The reaction of cis-1,4-dichloro-2-butene with the compound of formula (2) gives the compound of formula (3): Rf-Y-CH ２ -CH=CH-CH ２-Y-Rf (3) Rf and Y in formula (3) are the same as Rf and Y in formula (1). That is, in formula (3), Rf is a fluorine-containing alkyl group having 1 to 10 carbon atoms, the carbon atom located at the terminal on the Y side has a fluorine atom, and each Y is independently a single bond or a divalent linking group.

[0044] Preferred embodiments of Rf and Y are as described above.

[0045] The compound represented by formula (3) has a —CH═CH— group and is useful as a chain transfer agent in ring-opening metathesis polymerization reactions.

[0046] Examples of the compound represented by formula (3) include the following compounds:

[0047]

[0048] Next, a ring-opening metathesis polymerization reaction is carried out using a cyclic olefin having one -CH=CH- in the ring and the compound represented by the formula (3). A commonly known method can be used for the ring-opening metathesis polymerization reaction. For example, a Grubbs catalyst is used as the catalyst.

[0049] The cyclic olefin may or may not have a substituent. In the cyclic olefin, the number of carbon atoms constituting the ring is preferably 3 to 10, more preferably 6 to 8, from the viewpoint of ease of industrial synthesis. Examples of cyclic olefins include cis-cyclooctene, cis-cyclononene, cis-cyclodecene, cis-cycloheptene, cis-cyclohexene, cis-cyclopentene, and cis-cyclobutene.

[0050] In the ring-opening metathesis polymerization reaction, the molar ratio of the cyclic olefin to the compound represented by formula (3) is not particularly limited. From the viewpoint of appropriately controlling the molecular weight, the molar ratio of the content of the cyclic olefin to the content of the compound represented by formula (3) before the reaction is preferably 5 to 200.

[0051] In the ring-opening metathesis polymerization reaction, the molar ratio of the catalyst to the compound represented by formula (3) is not particularly limited. The molecular weight of the resulting fluoropolymer can be controlled by the molar ratio of the catalyst to the compound represented by formula (3). From the viewpoint of controlling the polymerization reaction at an appropriate rate, the molar ratio of the content of the catalyst to the content of the compound represented by formula (3) before the reaction is preferably 0.0005 to 0.01.

[0052] The reaction temperature of the ring-opening metathesis polymerization reaction can be set appropriately. From the viewpoint of the reaction rate, the reaction temperature is preferably 20 to 80°C, more preferably 40 to 60°C. The reaction time of the ring-opening metathesis polymerization reaction can be set appropriately. From the viewpoint of improving the yield and productivity, the reaction time is preferably 1 to 50 hours.

[0053] The reactor is not particularly limited. A complete mixing type stirred tank reactor or a piston flow type tubular reactor can be used as the reactor. Materials for the reactor, stirring blades, piping, etc. include stainless steels such as SUS304, SUS304L, SUS316, and SUS316L; Hastelloy; and glass.

[0054] The fluoropolymer of the present disclosure, which contains a —C═C— group in the polymethylene chain, can be obtained by ring-opening metathesis polymerization reaction between a cyclic olefin and a compound represented by formula (3).

[0055] Furthermore, by subjecting a fluoropolymer containing a —C═C— group in the polymethylene chain to a hydrogenation reaction, a fluoropolymer of the present disclosure containing no —C═C— group in the polymethylene chain can be obtained.

[0056] The method of the hydrogenation reaction is not particularly limited. For example, by using para-toluenesulfonyl hydrazide, the —C═C— group contained in the polymethylene chain can be hydrogenated.

[0057] The reaction temperature of the hydrogenation reaction can be set appropriately. From the viewpoint of the reaction rate, the reaction temperature is preferably 40 to 180°C, more preferably 80 to 160°C. The reaction time of the hydrogenation reaction can be set appropriately. From the viewpoint of improving the yield and productivity, the reaction time is preferably 1 to 50 hours.

[0058] The reactor is not particularly limited. A complete mixing type stirred tank reactor or a piston flow type tubular reactor can be used as the reactor. Materials for the reactor, stirring blades, piping, etc. include stainless steels such as SUS304, SUS304L, SUS316, and SUS316L; Hastelloy; and glass.

[0059] The target fluorine-containing monomer may be isolated by a commonly known method, such as distillation, column chromatography, or recycle preparative HPLC, and these may be used alone or in combination as necessary.

[0060] The resulting fluorine-containing monomer can be identified by a commonly known method. Examples of analytical methods include: １ H-NMR (proton nuclear magnetic resonance), １９ F-NMR (fluorine-19 nuclear magnetic resonance), １３ Examples of such spectroscopy include C-NMR (carbon-13 nuclear magnetic resonance) and GC-MS (gas chromatography mass spectrometry), and these may be used alone or in combination as needed.

[0061] [Article] The article of the present disclosure preferably has a film containing the fluoropolymer of the present disclosure on its surface. By having a film containing the fluoropolymer of the present disclosure on its surface, the article of the present disclosure can obtain good water and oil repellency.

[0062] Next, embodiments of the present disclosure will be specifically described using examples, but the embodiments of the present disclosure are not limited to these examples.

[0063] [Identification of Compounds and Polymers] The synthesized and purified products were １ H-NMR, １９The structure was identified by F-NMR (JNM-ECZ400S / L1, manufactured by JEOL Corporation). The number average molecular weight (Mn) of the polymer was determined in polystyrene equivalent terms using gel permeation chromatography (GPC, JASCO Corporation's high performance liquid chromatograph EXTREMA HPLC system) with tetrahydrofuran as the solvent. Measurements were carried out at a temperature of 40°C and a flow rate of 1 mL / min. Shodex GPC KF-804 and KF-803 columns were connected in series, and a JASCO Corporation RI-4030 differential refractive index detector was used as the detector.

[0064] <Synthesis of Compound A> Under a nitrogen atmosphere, sodium hydroxide (80 mmol) was dissolved in dimethylformamide (DMF) (24 mL) in a flask, and cis-1,4-dichloro-2-butene (8.0 mmol) and 1H,1H-pentafluoro-1-propanol (80 mmol) were added, followed by stirring at 60°C for 21 hours. The reaction solution was extracted with hexane and ethyl acetate, washed with water, and then dried over magnesium sulfate. The mixture obtained after concentration under reduced pressure was purified by silica gel column chromatography (hexane:ethyl acetate = 9:1 (volume ratio)), yielding 1.2 g (3.4 mmol) of Compound A. The structure of Compound A is as follows:

[0065]

[0066] Compound A １ H-NMR and １９ The F-NMR is as follows:

[0067] １ H-NMR (400 MHz, solvent: CDCl ３ ) δ (ppm): 5.78 (t, J = 3.9Hz, 2H), 4.21 (d, J = 3.9Hz, 4H), 3.88 (t, J = 13.3Hz, 4H) １９ F-NMR (376 MHz, solvent: CDCl ３ ) δ (ppm): -83.52 (s, 6F), -123.23 (t, J=13.0Hz, 4F)

[0068] ​<Synthesis of Compound B> Under a nitrogen atmosphere, sodium hydroxide (12 mmol) was dissolved in DMF (7 mL) in a flask, and cis-1,4-dichloro-2-butene (5.5 mmol) and 1H,1H-tridecafluoro-1-heptanol (12 mmol) were added, followed by stirring at 80°C for 19 hours. The reaction solution was extracted with hexane and ethyl acetate, washed with water, and then dried over magnesium sulfate. The mixture obtained after concentration under reduced pressure was purified by silica gel column chromatography (hexane:ethyl acetate = 10:1 (volume ratio)), yielding 2.7 g (3.6 mmol) of Compound B. The structure of Compound B is as follows:

[0069]

[0070] Compound B １ H-NMR and １９ The F-NMR is as follows:

[0071] １ H-NMR (400 MHz, solvent: CDCl ３ ) δ (ppm): 5.79 (t, J = 3.9Hz, 2H), 4.23 (d, J = 3.9Hz, 4H), 3.93 (t, J = 13.9Hz, 4H) １９ F-NMR (376 MHz, solvent: CDCl ３ ) δ (ppm): -80.73 (t, J=9.4Hz, 6F), -119.43 (t, J=13.7Hz, 4F), -122.17 (m, 4F), -122.81 (m, 4F), -123.34 (m, 4F), -126.10 (m, 4F)

[0072] <Synthesis of Compound C> Under a nitrogen atmosphere, sodium hydroxide (3.5 mmol) was dissolved in DMF (4 mL) in a flask, and cis-1,4-dichloro-2-butene (1.6 mmol) and 1H,1H-heptadecafluoro-1-octanol (3.5 mmol) were added, followed by stirring at 80°C for 19 hours. The reaction solution was extracted with hexane and ethyl acetate, washed with water, and then dried over magnesium sulfate. The mixture obtained after concentration under reduced pressure was purified by silica gel column chromatography (hexane:ethyl acetate = 9:1 (volume ratio)) to obtain 670 mg (0.7 mmol) of Compound C. The structure of Compound C is as follows:​

[0073]

[0074] Compound C １ H-NMR and １９ The F-NMR is as follows:

[0075] １ H-NMR (400 MHz, solvent: CDCl ３ ) δ (ppm): 5.79 (t, J = 3.9Hz, 2H), 4.23 (d, J = 3.9Hz, 4H), 3.95 (t, J = 13.8Hz, 4H) １９ F-NMR (376 MHz, solvent: CDCl ３ ) δ (ppm): -80.73 (t, J = 10.1Hz, 6F), -119.44 (m, 4F), -121.94 (m, 12F), -122.67 (m, 4F), -123.31 (m, 4F), -126.09 (m, 4F)

[0076] [Example 1-1] Under a nitrogen atmosphere, cis-cyclooctene (4.0 g, 36 mmol) was dissolved in tetrahydrofuran (16 mL) in a flask, and compound A (0.36 mmol) and a tetrahydrofuran solution of Grubbs second-generation catalyst (1.8 μmol dissolved in 1 mL under an argon atmosphere) were added, followed by stirring for 4 hours at 40° C. Ethyl vinyl ether (0.1 mL) was added to terminate the polymerization, and the reaction solution was then added dropwise to methanol (200 mL) for reprecipitation, filtered, and dried under vacuum at 40° C. to obtain 3.5 g of a white solid of polymer D1 (Mn=36,000, Mw / Mn=1.6).

[0077] Example 1-2 Polymer D2 was obtained in the same manner as in Example 1-1, except that the amounts of compound A and Grubbs second generation catalyst were changed to those shown in Table 1.

[0078]

[0079] The structures of polymers D1 and D2 are as follows: n1 of polymer D1 is 324. n1 of polymer D2 is 87.

[0080]

[0081] Polymers D1 and D2​１ H-NMR and １９ The F-NMR is as follows:

[0082] １ H-NMR (400 MHz, solvent: CDCl ３ ) δ (ppm): 5.78-5.72 (m), 5.54-5.47 (m), 5.38-5.33 (m), 4.18 (d), 4.06 (d), 3.86 (t), 3.84 (t), 2.02-1.96 (brd), 1.34-1.27 (brd) １９ F-NMR (376 MHz, solvent: CDCl ３ ) δ (ppm): -83.5 (s), -123.2 (t)

[0083] [Example 2-1] Under a nitrogen atmosphere, cis-cyclooctene (4.0 g, 36 mmol) was dissolved in tetrahydrofuran (16 mL) in a flask, and compound B (0.36 mmol) and a tetrahydrofuran solution of Grubbs second-generation catalyst (1.8 μmol dissolved in 1 mL under an argon atmosphere) were added, followed by stirring for 4 hours at 40° C. Ethyl vinyl ether (0.1 mL) was added to terminate the polymerization, and the reaction solution was then added dropwise to methanol (200 mL) for reprecipitation, filtered, and dried under vacuum at 40° C. to obtain 3.8 g of a white solid polymer E1 (Mn=28,000, Mw / Mn=1.9).

[0084] Examples 2-2 to 2-4 Polymers E2 to E4 were obtained in the same manner as in Example 2-1, except that the amounts of compound B and Grubbs second generation catalyst were changed to those shown in Table 2.

[0085]

[0086] The structures of polymers E1 to E4 are as follows: Polymer E1 has an n1 of 248. Polymer E2 has an n1 of 193. Polymer E3 has an n1 of 102. Polymer E4 has an n1 of 58.

[0087]

[0088] Polymers E1 to E4 １ H-NMR and １９ The F-NMR is as follows: ​

[0089] １ H-NMR (400 MHz, solvent: CDCl ３ ) δ (ppm): 5.78-5.65 (m), 5.54-5.48 (m), 5.38-5.33 (m), 4.19 (d), 4.08 (d), 3.91 (t), 3.89 (t), 2.07-1.96 (brd), 1.33-1.29 (brd) １９ F-NMR (376 MHz, solvent: CDCl ３ ) δ (ppm): -80.7 (t), -119.4 (t), -122.1 (s), -122.7 (s), -123.3 (s), -126.0 (s)

[0090] [Example 3-1] Under a nitrogen atmosphere, cis-cyclooctene (2.0 g, 18 mmol) was dissolved in tetrahydrofuran (16 mL) in a flask, and compound C (0.18 mmol) and a tetrahydrofuran solution of Grubbs second generation catalyst (0.9 μmol dissolved in 1 mL under an argon atmosphere) were added, followed by stirring at 40°C for 4 hours. After terminating the polymerization by adding ethyl vinyl ether (0.1 mL), the reaction solution was added dropwise to methanol (200 mL) for reprecipitation, filtered, and dried under vacuum at 40°C to obtain 1.9 g of a white solid polymer F1 (Mn=40,000, Mw / Mn=1.5). １ H-NMR and １９ The F-NMR is as follows:

[0091] Example 3-2 Polymer F2 was obtained in the same manner as in Example 3-1, except that the amounts of compound C and Grubbs second generation catalyst were changed to those shown in Table 3.

[0092]

[0093] The structures of polymers F1 and F2 are as follows: n1 of polymer F1 is 355. n1 of polymer F2 is 128.

[0094]

[0095] Polymers F1 and F2 １ H-NMR and １９ The F-NMR is as follows:

[0096] ​​１ H-NMR (400 MHz, solvent: CDCl ３ ) δ (ppm): 5.79-5.68 (m), 5.56-5.49 (m), 5.39-5.34 (m), 4.20 (d), 4.09 (d), 3.92 (t), 3.91 (t), 2.03-1.97 (brd), 1.34-1.29 (brd) １９ F-NMR (376 MHz, solvent: CDCl ３ ) δ (ppm): -80.7 (t), -119.3 (s), -121.8 (s), -122.6 (s), -123.2 (s), -126.0 (s)

[0097] [Examples 4-1 and 4-2] Polymer D1 (2.0 g) and ortho-xylene (100 mL) were placed in a flask under a nitrogen atmosphere, and para-toluenesulfonylhydrazide (6.7 g) and propylamine (5.1 g) were added, followed by stirring at 140°C for 18 hours. The reaction solution was added to ethanol (150 mL) to reprecipitate, filtered, and dried under vacuum at 70°C, yielding 1.9 g of a white solid of polymer G1. Polymer G2 was obtained in the same manner using polymer D2. １ Analysis by H-NMR revealed that the conversion rate of the hydrogenation reaction was 99% or more.

[0098] The structures of polymers G1 and G2 are as follows: m2 of polymer G1 is 2597. m2 of polymer G2 is 698.

[0099]

[0100] Polymers G1 and G2 １ H-NMR and １９ The F-NMR is as follows:

[0101] １ H-NMR (400MHz, solvent: toluene-d8, 100°C) δ (ppm): 3.47 (t), 3.22 (t), 1.31 (brd) １９ F-NMR (376MHz, solvent: toluene-d8, 100°C) δ (ppm): -83.3 (s), -122.5 (t)

[0102] ​[Examples 5-1 to 5-4] Polymer E1 (2.0 g) and ortho-xylene (100 mL) were placed in a flask under a nitrogen atmosphere, and para-toluenesulfonyl hydrazide (6.5 g) and propylamine (5.0 g) were added, followed by stirring at 140°C for 18 hours. The reaction solution was added to ethanol (150 mL) and reprecipitated, filtered, and vacuum dried at 70°C, yielding 2.0 g of a white solid polymer H1. Polymers H2 to H4 were obtained in a similar manner using polymers E2 to E4. １ Analysis by H-NMR revealed that the conversion rate of the hydrogenation reaction was 99% or more.

[0103] The structures of polymers H1 to H4 are as follows: Polymer H1 has an m2 of 1986. Polymer H2 has an m2 of 1549. Polymer H3 has an m2 of 822. Polymer H4 has an m2 of 466.

[0104]

[0105] Polymers H1 to H4 １ H-NMR and １９ The F-NMR is as follows:

[0106] １ H-NMR (400MHz, solvent: toluene-d8, 100°C) δ (ppm): 3.58 (t), 3.26 (t), 1.33 (brd) １９ F-NMR (376MHz, solvent: toluene-d8, 100°C) δ (ppm): -80.9 (t), -118.7 (t), -121.4 (s), -122.1 (s), -122.7 (s), -125.5 (s)

[0107] [Examples 6-1 to 6-2] Polymer F1 (1.3 g) and ortho-xylene (65 mL) were placed in a flask under a nitrogen atmosphere, and para-toluenesulfonylhydrazide (4.2 g) and propylamine (3.2 g) were added, followed by stirring at 140°C for 18 hours. The reaction solution was added to ethanol (150 mL) to cause reprecipitation, followed by filtration and vacuum drying at 70°C, yielding 1.3 g of a white solid of polymer K1. Polymer K2 was obtained in the same manner using polymer F2. １ ​Analysis by H-NMR revealed that the conversion rate of the hydrogenation reaction was 99% or more.

[0108] The structures of polymers K1 and K2 are as follows: m2 of polymer K1 is 2844. m2 of polymer K2 is 1026.

[0109]

[0110] Polymers K1 and K2 １ H-NMR and １９ The F-NMR is as follows:

[0111] １ H-NMR (400MHz, solvent: toluene-d8, 100°C) δ (ppm): 3.57 (t), 3.25 (t), 1.31 (brd) １９ F-NMR (376MHz, solvent: toluene-d8, 100°C) δ (ppm): -80.9 (t), -118.7 (s), -121.1 (s), -121.2 (s), -122.0 (s), -122.7 (s), -125.5 (s)

[0112] [Evaluation] Each of the obtained polymers was evaluated as follows.

[0113] <Melting Point> The melting point was measured using a differential scanning calorimeter DSC-2500 (manufactured by TA Instruments) by raising the temperature at a rate of 10° C. per minute.

[0114] <Crystallization degree> The polymer was dissolved in para-xylene at 130°C to prepare a 10% by mass solution. This was dropped into a Teflon (registered trademark) container and dried at room temperature. The solution was then heated at 150°C for 2 hours under vacuum and slowly cooled at a rate of approximately 0.3°C per minute to prepare a free-standing film. The crystallinity of the obtained free-standing film was measured using a fully automatic multipurpose X-ray diffractometer (Rigaku).

[0115]

[0116] ​<Contact angle> A piranha-treated silicon substrate was subjected to a hydrophobic treatment using chloro(decyl)dimethylsilane under vacuum based on the gas-phase adsorption method. This was heated to 230°C on a hot plate. The polymer was dissolved in ortho-xylene at 150°C so that the polymer content was 5% by mass. The polymer solution was applied to the hydrophobic silicon substrate using a spin coater at 3000 rpm for 30 seconds.

[0117] The contact angle of the obtained thin film was measured using a contact angle meter (product name "DMo-502", manufactured by Kyowa Interface Science Co., Ltd.) when 1 μL each of distilled water and diiodomethane was dropped onto the thin film.

[0118] <Surface free energy> The surface free energy was calculated based on the Owens and Wendt equation from the contact angle results for water and diiodomethane. When polymer H4 was used, water was repelled, and the contact angle of water could not be measured. Therefore, the surface free energy could not be calculated either. In Table 5, the columns for "water contact angle" and "surface free energy" are marked with "n.d."

[0119]

[0120] <Surface Composition> Thin films were prepared using the same method as in the contact angle measurement. The elemental composition of the prepared thin film surface was evaluated using X-ray photoelectron spectroscopy (XPS). Measurements were performed using an X-ray photoelectron spectrometer JPS-9010MC (manufactured by JEOL Ltd.) with magnesium (Kα) as the X-ray source (applied voltage 10 kV, current 15 mA). The elemental composition ratio of carbon (C) to fluorine (F) on the thin film surface was calculated by taking the integral ratio of the obtained spectrum, and this was designated as F / C(XPS). Furthermore, the elemental composition ratio of carbon (C) to fluorine (F) in the bulk was calculated based on the molecular weight, and this was designated as F / C(bulk). By comparing these values, the degree of fluorine segregation on the thin film surface relative to the bulk was evaluated.

[0121]

[0122] The fluoropolymer of the present disclosure is a novel fluoropolymer. Table 5 shows that the surface-treated layer obtained by surface treatment using the fluoropolymer of the present disclosure has good water and oil repellency. Table 6 also shows that fluorine segregates on the thin film surface.

[0123] The disclosures of Japanese Patent Application No. 2024-146922 filed on August 28, 2024, and Japanese Patent Application No. 2025-021838 filed on February 13, 2025 are incorporated herein by reference in their entirety. In addition, all documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

Claims

1. A fluorine-containing polymer represented by the following formula (1): Rf-Y-R １ -Y-Rf (1) In formula (1), each Rf is independently a fluorine-containing alkyl group having 1 to 10 carbon atoms, and the carbon atom located at the terminal on the Y side has a fluorine atom; each Y is independently a single bond or a divalent linking group; R １ is a polymethylene chain which may have a substituent, and the polymethylene chain may contain a -C=C- group.

2. The fluorine-containing polymer according to claim 1, wherein each Rf is independently a perfluoroalkyl group having 1 to 10 carbon atoms.

3. Each of the Y's is independently an alkylene group, -O-, -C(=O)-, or a combination thereof (provided that R １ The fluorine-containing polymer according to claim 1 or 2, wherein the terminal of the alkylene group on the side is not an alkylene group.

4. Each Y is independently * １ -R ２ O-* ２ and R ２ is an alkylene group having 1 to 3 carbon atoms, and * １ means the bonding position to Rf, and * ２ is R １ The fluorine-containing polymer according to claim 1 or 2, wherein the bond position is a bond position between the fluorine-containing polymer and the fluorine-containing polymer.

5. The above R １ is -CH ２ -(CH=CH-(CH ２ ) ｍ１ ) ｎ１ -CH=CH-CH ２ 3. The fluorine-containing polymer according to claim 1, wherein m1 is independently 2 to 8, and n1 is 20 to 730.

6. The above R １ is -(CH ２ ) ｍ２ 3. The fluorine-containing polymer according to claim 1, wherein m2 is 150 to 6,000.

7. An article having a film containing the fluoropolymer according to claim 1 or 2 on its surface.

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