Fluorine-containing polyether compound

Abstract

The present invention provides a fluorine-containing polyether compound which has a repeating unit represented by formula (1). In formula (1), n represents an integer of 1 to 8; Ph represents a phenylene group; X1 represents a heterocyclic ring or a hydrocarbon ring. One or both of two phenylene groups each represented by Ph and a heterocyclic ring or a hydrocarbon ring represented by X1 may be fused with each other. The phenylene group, the heterocyclic ring and the hydrocarbon ring may have a substituent.

Description

Technical Field

[0001] The present disclosure relates to a fluorine-containing polyether compound.

Background Art

[0002] Non-Patent Document 1 describes that a poly(perfluoroalkylene aryl ether) having a specific structure was obtained by polymerizing 1,6-bis(4-fluorophenyl)perfluorohexane with bisphenol AF, bisphenol A or resorcinol.

Prior Art Documents

Non-Patent Documents

[0003]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The glass transition temperature of the poly(perfluoroalkylene aryl ether) disclosed in Non-Patent Document 1 is only 95°C at the highest. Therefore, a fluorine-containing polyether compound with higher heat resistance is required.

[0005] An object of the present disclosure is to provide a fluorine-containing polyether compound that exhibits a sufficiently low dielectric constant and dielectric tangent, and has a very high glass transition temperature and high solubility.

Means for Solving the Problems

[0006] According to the present disclosure, a fluorine-containing polyether compound having a repeating unit represented by formula (1) is provided.

[0007] Formula (1):

Chemical formula

[0008] In formula (1), it is preferable that X 1 represents an aromatic heterocyclic ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, or an aliphatic hydrocarbon ring which may have a substituent. In formula (1), it is preferable that X 1 represents at least one selected from the group consisting of rings represented by the following formulas.

[0009]

Chemical formula

[0010] Further, according to the present disclosure, a fluorine-containing polyether compound having a repeating unit represented by formula (2) is provided.

[0011] Formula (2):

Chemical formula

[0012] In formula (2), it is preferable that the polycyclic aromatic hydrocarbon ring is at least one selected from the group consisting of a biphenyl ring, a terphenyl ring, a quaterphenyl ring, a naphthalene ring, an anthracene ring, a tetracene ring, and a pentacene ring. It is preferable that the average degree of polymerization of the repeating unit represented by formula (2) is from 2 to 300.

[0013] Further, according to the present disclosure, a low dielectric material containing the above fluorine-containing polyether compound is provided.

[0014] Further, according to the present disclosure, a semiconductor package substrate, a flexible printed circuit board, or a rigid printed circuit board containing the above fluorine-containing polyether compound is provided.

Advantages of the Invention

[0015] According to the present disclosure, it is possible to provide a fluorine-containing polyether compound that exhibits a sufficiently low dielectric constant and dielectric tangent, and has a very high glass transition temperature and high solubility.

Modes for Carrying Out the Invention

[0016] Hereinafter, specific embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

[0017] The fluorine-containing polyether compound of the present disclosure has a repeating unit represented by formula (1).

[0018] Formula (1):

Chemical Formula

[0019] n represents an integer from 1 to 8. As n, an integer from 4 to 8 is preferable, and 4, 6 or 8 is more preferable.

[0020] Ph represents a phenylene group. The phenylene group may or may not have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, an alkyl group such as a methyl group, and a halogenated alkyl group such as a trifluoromethyl group.

[0021] X 1 represents a complex ring or a hydrocarbon ring. The complex ring or hydrocarbon ring represented by X 1 may be a ring having at least two bonding portions bonded to two phenylene groups, a ring having at least one bonding portion bonded to one of two phenylene groups and at least one carbon-carbon bond shared with the other of the two phenylene groups, or a ring having at least two carbon-carbon bonds shared with two phenylene groups. 1 As the complex ring or hydrocarbon ring represented by X

[0022] When the phenylene group represented by Ph and the ring represented by X 1 share at least one carbon-carbon bond, the structure represented by -Ph-X 1 -Ph- means that at least one of the phenylene groups represented by Ph and X 1It will include a condensed ring formed by the condensation of a complex ring or a hydrocarbon ring represented by . Therefore, in the present disclosure, the phenylene group represented by Ph includes not only the residue generated by removing two hydrogen atoms from benzene, but also the residue derived from benzene that removes one hydrogen atom and condenses with another ring to form a part of a polycycle. Such a structure containing a condensed ring (-Ph-X 1 -Ph-) includes, for example, the following structures.

[0023]

Chemical formula

[0024] X 1 Among the rings represented by , as the complex ring, a ring formed by atoms other than carbon atoms and carbon atoms is preferred. As the atoms other than carbon atoms, a nitrogen atom, an oxygen atom or a sulfur atom is preferred, and a nitrogen atom is more preferred. That is, as the complex ring, a nitrogen-containing complex ring is preferred. The number of atoms other than carbon atoms in the ring is preferably 1 to 3, more preferably 3.

[0025] The complex ring may be an aliphatic complex ring or an aromatic complex ring. As the complex ring, an aromatic complex ring is preferred. Also, the complex ring may be a monocyclic or polycyclic ring. As the complex ring, a monocyclic ring is preferred, a monocyclic aromatic complex ring is more preferred, and a monocyclic nitrogen-containing aromatic complex ring is even more preferred.

[0026] The number of ring members of the complex ring is not particularly limited, preferably 3 to 12, more preferably 5 or more, more preferably 9 or less, and even more preferably 6 or less.

[0027] Examples of the heterocyclic ring include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, 1,2,3-oxadiazole ring, 1,2,4-oxadiazole ring, 1,3,4-oxadiazole ring, furazan ring, 1,2,3-thiadiazole ring, 1,2,4-thiadiazole ring, 1,3,4-thiadiazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring and the like. Among them, the 1,3,5-triazine ring is preferable as the heterocyclic ring.

[0028] The heterocyclic ring may or may not have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, alkyl groups such as methyl group, halogenated alkyl groups such as trifluoromethyl group, aryl groups such as phenyl group and the like.

[0029] X 1 Among the rings represented by, the hydrocarbon ring may be an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring. The aliphatic hydrocarbon ring may be a saturated or unsaturated hydrocarbon ring having no aromaticity. The hydrocarbon ring may be a monocyclic or polycyclic ring. The polycyclic hydrocarbon ring may be a condensed ring.

[0030] The number of carbon atoms of the hydrocarbon ring is preferably 3 to 30, more preferably 5 or more, still more preferably 6 or more, more preferably 20 or less, and still more preferably 14 or less.

[0031] Examples of the hydrocarbon ring include monocyclic saturated hydrocarbon rings such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring; monocyclic non-aromatic unsaturated hydrocarbon rings such as cyclopropene ring, cyclobutene ring, cyclopropene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring; Polycyclic non-aromatic hydrocarbon rings such as norbornene rings, norbornadiene rings, decahydronaphthalene rings, bicycloundecane rings, spirobicyclopentane rings; Aromatic hydrocarbon rings such as benzene rings, naphthalene rings, phenanthrene rings, anthracene rings, fluorene rings, tetracene rings, chrysene rings, pyrene rings, pentacene rings, benzopyrene rings, triphenylene rings, biphenyl rings, diphenylmethane rings, diphenyl ether rings, diphenyl sulfone rings, diphenyl ketone rings; etc. can be mentioned.

[0032] The hydrocarbon ring may or may not have a substituent. Examples of the substituent include halogen atoms such as fluorine atoms, alkyl groups such as methyl groups, halogenated alkyl groups such as trifluoromethyl groups, and aryl groups such as phenyl groups.

[0033] X 1 As the heterocyclic ring or hydrocarbon ring represented by, at least one selected from the group consisting of rings represented by the following formulas is preferable.

Chemical formula

[0034] The glass transition temperature of the fluorine-containing polyether compound having the repeating unit represented by formula (1) is preferably 100 to 400 °C, more preferably 110 °C or higher, still more preferably 120 °C or higher, more preferably 300 °C or lower, and still more preferably 250 °C or lower. The glass transition temperature is a value measured by thermomechanical analysis (TMA), differential scanning calorimetry (DSC), or dynamic viscoelasticity measurement (DMA).

[0035] In the fluorine-containing polyether compound having the repeating unit represented by the formula (1), the number-average degree of polymerization of the repeating unit represented by the formula (1) is preferably 500 or less, more preferably 400 or less, still more preferably 300 or less, and may be 2 or more, and may be 3 or more. The number-average degree of polymerization is determined by calculation from the number-average molecular weight of the fluorine-containing polyether compound of the present disclosure.

[0036] The number-average molecular weight (Mn) of the fluorine-containing polyether compound having the repeating unit represented by the formula (1) is preferably 2,000 or more, more preferably 10,000 or more, preferably 500,000 or less, and more preferably 300,000 or less in terms of standard polystyrene by gel permeation chromatography (GPC).

[0037] The molecular weight distribution (Mw / Mn) of the fluorine-containing polyether compound having the repeating unit represented by the formula (1) is preferably 2 or more, preferably 5 or less, and more preferably 4 or less in terms of standard polystyrene by gel permeation chromatography (GPC).

[0038] The logarithmic viscosity η of the fluorine-containing polyether compound having the repeating unit represented by the formula (1) inh is preferably 0.3 dL / g or more, more preferably 0.5 dL / g or more. The logarithmic viscosity η inh can be calculated by dissolving the fluorine-containing polyether compound in N-methyl-2-pyrrolidone (NMP) or the like as a solvent to prepare a solution with a solution concentration of 0.5 g / dL, measuring the solution viscosity of the obtained solution at 30 °C, and using the following formula. The logarithmic viscosity η inh = ln (solution viscosity / solvent viscosity) / solution concentration

[0039] The fluorine-containing polyether compound having the repeating unit represented by the formula (1) can be suitably produced by polymerizing the dihydroxy compound (11) represented by the formula (11) and the active aromatic compound (12) represented by the formula (12).

[0040] Formula (11): HO-Ph-X 1 -Ph-OH (In Formula (11), Ph and X 1 are the same as in Formula (1).)

[0041] Formula (12):

Chemical formula

[0042] The polymerization of the dihydroxy compound (11) and the active aromatic compound (12) can be carried out in the presence of a base. Examples of the base include carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, cesium carbonate, cesium hydrogen carbonate, hydroxides such as sodium hydroxide, potassium hydroxide, cesium hydroxide, and fluoride compounds such as sodium fluoride, potassium fluoride, cesium fluoride.

[0043] The polymerization can be carried out in a solvent. Examples of the solvent include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone (DMI), N,N'-dimethylpropyleneurea (DMPU), dimethyl sulfoxide (DMSO), sulfolane, dimethyl sulfone, diphenyl sulfone, cyclopentanone, cyclohexanone, tetrahydrofuran (THF), 1,4-dioxane, etc.

[0044] In order to remove the water generated by the polymerization of the dihydroxy compound (11) and the active aromatic compound (12) in the presence of a base, an azeotropic solvent such as toluene, o-xylene, m-xylene, p-xylene, etc. may be used.

[0045] The polymerization temperature is preferably 50 to 250 °C, more preferably 150 to 220 °C. The polymerization time is preferably 0.1 to 50 hours, more preferably 1 to 36 hours.

[0046] The average degree of polymerization of the repeating unit represented by formula (1) can be adjusted by changing the molar ratio of the dihydroxy compound (11) to the active aromatic compound (12), the polymerization temperature, the polymerization time, the polymerization solution concentration, and the like.

[0047] In addition, the fluorine-containing polyether compound of the present disclosure has a repeating unit represented by formula (2). Formula (2):

Chemical formula

[0048] n represents an integer from 1 to 8. As n, an integer from 4 to 8 is preferable, and 4, 6, or 8 is more preferable.

[0049] X 2 represents a polycyclic aromatic hydrocarbon ring. The polycyclic aromatic hydrocarbon ring represented by X 2 is a ring formed by removing two hydrogen atoms from a polycyclic aromatic hydrocarbon in which two or more aromatic rings are condensed, or a ring formed by removing two hydrogen atoms from a polycyclic aromatic hydrocarbon in which two or more aromatic rings are connected by a single bond. In formula (2), the polycyclic aromatic hydrocarbon ring is directly bonded to two adjacent oxygen atoms.

[0050] The number of carbon atoms of the polycyclic aromatic hydrocarbon ring is preferably 8 to 30, more preferably 10 or more, more preferably 26 or less, and still more preferably 22 or less.

[0051] The number of rings of the polycyclic aromatic hydrocarbon ring is preferably 2 to 8, more preferably 6 or less, and still more preferably 5 or less.

[0052] Examples of the polycyclic aromatic hydrocarbon ring include a biphenyl ring, a terphenyl ring, a quaterphenyl ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a fluorene ring, a tetracene ring, a chrysene ring, a pyrene ring, a triphenylene ring, a pentacene ring, a benzopyrene ring, a perylene ring, and the like.

[0053] Among these, as the polycyclic aromatic hydrocarbon ring, at least one selected from the group consisting of a biphenyl ring, a terphenyl ring, a quaterphenyl ring, a naphthalene ring, an anthracene ring, a tetracene ring, and a pentacene ring is preferable.

[0054] The polycyclic aromatic hydrocarbon ring may or may not have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, an alkyl group such as a methyl group, a halogenated alkyl group such as a trifluoromethyl group, and an aryl group such as a phenyl group.

[0055] The glass transition temperature of the fluorine-containing polyether compound having the repeating unit represented by the formula (2) is preferably from 96 to 400°C, more preferably 100°C or higher, preferably 300°C or lower, and more preferably 250°C or lower. The glass transition temperature is a value measured by a thermomechanical analysis method (TMA), a differential scanning calorimetry method (DSC), or a dynamic viscoelasticity measurement method (DMA).

[0056] In the fluorine-containing polyether compound having the repeating unit represented by the formula (2), the average degree of polymerization of the repeating unit represented by the formula (2) is preferably 500 or less, more preferably 400 or less, still more preferably 300 or less, and may be 2 or more, or may be 3 or more. The average degree of polymerization is determined by calculation from the number average molecular weight of the fluorine-containing polyether compound of the present disclosure.

[0057] The number average molecular weight (Mn) of the fluorine-containing polyether compound having the repeating unit represented by the formula (2) is preferably 2,000 or more, more preferably 10,000 or more, preferably 500,000 or less, and more preferably 300,000 or less in terms of standard polystyrene by gel permeation chromatography (GPC).

[0058] The molecular weight distribution (Mw / Mn) of the fluorine-containing polyether compound having the repeating unit represented by the formula (2) is preferably 2 or more, preferably 5 or less, and more preferably 4 or less in terms of standard polystyrene by gel permeation chromatography (GPC).

[0059] The logarithmic viscosity η of the fluorine-containing polyether compound having the repeating unit represented by the formula (2) inh is preferably 0.3 dL / g or more, and more preferably 0.5 dL / g or more. The logarithmic viscosity η inh can be calculated by the following formula by dissolving the fluorine-containing polyether compound in N-methyl-2-pyrrolidone (NMP) or the like as a solvent to prepare a solution with a solution concentration of 0.5 g / dL and measuring the solution viscosity of the obtained solution at 30°C. The logarithmic viscosity η inh = ln(solution viscosity / solvent viscosity) / solution concentration

[0060] The fluorine-containing polyether compound having the repeating unit represented by the formula (2) can be preferably produced by polymerizing the dihydroxy compound (21) represented by the formula (21) and the active aromatic compound (22) represented by the formula (22).

[0061] Formula (21): HO-X 2 -OH (In the formula (21), X 2 is the same as in the formula (2).)

[0062] Formula (22):

Chemical formula

[0063] The polymerization of the dihydroxy compound (21) and the active aromatic compound (22) can be carried out in the presence of a base. Examples of the base include carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, cesium carbonate, and cesium hydrogen carbonate; hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide; and fluoride compounds such as sodium fluoride, potassium fluoride, and cesium fluoride.

[0064] The polymerization can be carried out in a solvent. Examples of the solvent include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone (DMI), N,N'-dimethylpropyleneurea (DMPU), dimethyl sulfoxide (DMSO), sulfolane, dimethyl sulfone, diphenyl sulfone, cyclopentanone, cyclohexanone, tetrahydrofuran (THF), and 1,4-dioxane.

[0065] In order to remove the water generated by the polymerization of the dihydroxy compound (21) and the active aromatic compound (22) in the presence of a base, an azeotropic solvent such as toluene, o-xylene, m-xylene, or p-xylene may be used.

[0066] The polymerization temperature is preferably 50 to 250°C, more preferably 150 to 220°C. The polymerization time is preferably 0.1 to 50 hours, more preferably 1 to 36 hours.

[0067] The average degree of polymerization of the repeating unit represented by formula (2) can be adjusted by changing the molar ratio of the dihydroxy compound (21) and the active aromatic compound (22), the polymerization temperature, the polymerization time, the polymerization solution concentration, and the like.

[0068] The fluorine-containing polyether compound of the present disclosure exhibits a sufficiently low dielectric constant and dielectric tangent, and has a very high glass transition temperature and high solubility, so it can be suitably used as a low dielectric material.

[0069] The fluorine-containing polyether compound of the present disclosure exhibits a sufficiently low dielectric constant and dielectric tangent, and has a very high glass transition temperature and high solubility, so it can be suitably used as a substrate such as a semiconductor package substrate, a flexible printed circuit board, or a rigid printed circuit board.

[0070] The fluorine-containing polyether compound of the present disclosure exhibits a sufficiently low dielectric constant and dielectric tangent, and has a very high glass transition temperature and high solubility, so it can be suitably used as a cover substrate such as a semiconductor package wiring board, a flexible printed wiring board, a rigid printed wiring board, a tape for TAB, a tape for COF, or a metal wiring, and also as a chip member such as a metal wiring or an IC chip, an interlayer insulating film, a base substrate, an adhesive sheet, a prepreg, a primer, etc. for electronic components and electronic devices such as a liquid crystal display, an organic electroluminescence display, an electronic paper, or a solar cell.

[0071] The fluorine-containing polyether compound of the present disclosure is particularly suitable as a material for electronic components and electronic devices that utilize microwaves at high frequencies, especially in the range of 3 to 30 GHz, because it has a low dielectric constant and low dielectric loss at high frequencies. For example, it can be suitably used as a material for an insulating board of a high-frequency circuit, an insulating material of a connecting component, a printed circuit board, a base or an antenna cover of a high-frequency vacuum tube, a coaxial cable, a coated wire such as a LAN cable, etc. Also, it can be suitably used as a material for devices such as satellite communication devices and mobile phone base stations that utilize microwaves in the range of 3 to 30 GHz.

[0072] The printed circuit board is not particularly limited, and examples include printed wiring boards for electronic circuits such as mobile phones, various computers, and communication devices.

[0073] The coaxial cable is not particularly limited, and examples thereof include those having a structure in which an inner conductor, an insulating coating layer, an outer conductor layer, and a protective coating layer are sequentially laminated from the core portion to the outer peripheral portion.

[0074] The fluorine-containing polyether compound of the present disclosure has a low dielectric constant, a low dielectric loss, and is also excellent in heat resistance, solvent solubility, electrical insulation, colorless transparency, and flexibility, and is easy to be made into a thin film. Therefore, it can be suitably used for an interlayer insulating film, a film, an adhesive sheet, a prepreg, a primer, a resist material, and the like. Among them, it is suitable for an interlayer insulating film and a film.

[0075] The above film can be manufactured by molding the fluorine-containing polyether compound of the present disclosure by a known film molding method such as an extrusion molding method, a calender molding method, or a solution casting method. Further, the film may be subjected to sandblasting treatment, corona treatment, plasma treatment, etching treatment, or the like.

[0076] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

Examples

[0077] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to such examples.

[0078] Each numerical value in the examples was measured by the following method.

[0079] (1) GPC: High-speed GPC system HLC-8220GPC manufactured by Tosoh Corporation (column: Tosoh TSKgel (α-M), column temperature: 45 ° C, detector: UV-8020, wavelength 254 nm, eluent: N-methyl-2-pyrrolidone (NMP) (containing 0.01 mol / L lithium bromide), calibration curve: standard polystyrene, column flow rate: 0.2 mL / min) (2) Infrared spectrum (FT-IR): FT / IR-4200 manufactured by JASCO Corporation (3) Nuclear Magnetic Resonance Spectrum (NMR): AC400P manufactured by BRUKER (4) Thermogravimetric Analysis (TGA): TG / DTA7300 manufactured by Hitachi High-Tech Science Corporation, heating rate 10°C / min (5) Differential Scanning Calorimetry (DSC): DSC7000 manufactured by Hitachi High-Tech Science Corporation, heating rate 20°C / min (6) Thermomechanical Analysis (TMA): TMA7000 manufactured by Hitachi High-Tech Science Corporation, heating rate 10°C / min (7) Dynamic Viscoelasticity Measurement (DMA): DMA7100 manufactured by Hitachi High-Tech Science Corporation, heating rate 2°C / min (8) Tensile Test: Autograph AGS-D type manufactured by Shimadzu Corporation, tensile speed 1.0 mm / min (9) Ultraviolet-Visible Spectrophotometer: UV-1800 manufactured by Shimadzu Corporation (10) Refractive Index Measurement: Metricon Model 2010 / M PRISM COUPLER (11) Dielectric Constant Measurement: Dielectric Constant and Dielectric Loss Tangent Measuring Device (Cavity Resonator Type, 10 GHz, 20 GHz) manufactured by AET

[0080] <Synthesis Example 1> Synthesis of 1,6-bis(4-fluorophenyl)perfluorohexane (FPPFH) Into a eggplant-shaped flask (100 mL) equipped with a stir bar, Dimroth condenser, and nitrogen inlet tube, 1-fluoro-4-iodobenzene (1.25 mL, 10.8 mmol), dimethyl sulfoxide (DMSO, 15 mL), and 1,6-diiodoperfluorohexane (3.00 g, 5.42 mmol) were added and dissolved. Then, copper powder (1.56 g, 24.4 mmol) was added, and the temperature was gradually raised to 120 °C under a nitrogen gas atmosphere and stirred for 48 hours. After allowing to cool to room temperature, the copper powder was removed by suction filtration, and DMSO was distilled off under reduced pressure. The residue was dissolved in diethyl ether, suction filtered, and then the filtrate was washed with distilled water. The organic layer was taken out and dehydrated by adding anhydrous sodium sulfate. Then, diethyl ether was distilled off from the filtrate obtained by filtration to obtain a crude product. The crude yield was 1.73 g and the crude yield was 65%. Purification by vacuum distillation (100 °C / 0.17 Torr) gave a white crystalline product (yield 1.69 g, yield 64%). Melting point: 40 - 41 °C FT-IR (KBr, cm -1 ): 1515 (C=C), 1243 (C-F) 1 1H-NMR (DMSO-d6, ppm): 7.73 (4H), 7.41 (4H) 13 13C-NMR (DMSO-d6, ppm): 165.5, 163.5, 129.6, 129.5, 123.8, 116.6, 116.4 19 19F-NMR (DMSO-d6, ppm): -107.3, -109.4, -121.5, -122.0 Elemental analysis: Calculated C, 44.10%; H, 1.65% Found C, 43.98%; H, 1.72%

[0081] <Synthesis Example 2> Synthesis of 1,4-bis(4-fluorophenyl)perfluorobutane (FPPFB) Into a eggplant-shaped flask (100 mL) equipped with a stir bar, Dimroth condenser, and nitrogen inlet tube, 1-fluoro-4-iodobenzene (1.25 mL, 10.8 mmol), dimethyl sulfoxide (DMSO, 15 mL), and 1,4-diiodoperfluorobutane (2.46 g, 5.42 mmol) were added and dissolved. Then, copper powder (1.56 g, 24.4 mmol) was added, and the temperature was gradually raised to 120 °C in a nitrogen gas atmosphere and stirred for 48 hours. After allowing to cool to room temperature, the copper powder was removed by suction filtration, and DMSO was distilled off under reduced pressure. The residue was dissolved in diethyl ether, suction filtered, and then the filtrate was washed with distilled water. The organic layer was taken out, anhydrous sodium sulfate was added for dehydration. Then, diethyl ether was distilled off from the filtrate obtained by filtration to obtain a crude product. The crude yield was 0.95 g and the crude yield was 45%. Purification by vacuum distillation (100 °C / 0.17 Torr) gave a white crystalline product (yield 0.93 g, yield 44%). Melting point: 63 - 64 °C 1 1H-NMR (DMSO-d6, ppm): 7.69 (4H), 7.43 (4H) 13 13C-NMR (DMSO-d6, ppm): 165.4, 163.4, 129.5, 124.4, 116.5, 116.3 19 19F-NMR (DMSO-d6, ppm): -107.7, -109.3, -121.4 Elemental analysis: Calculated C, 49.24%; H, 2.07% Found C, 48.89%; H, 1.93%

[0082] <Synthesis Example 3> Synthesis of 1,6-bis(4-chlorophenyl)perfluorohexane (CPPFH) Into an eggplant-shaped flask (100 mL) equipped with a stir bar, a Dimroth condenser, and a nitrogen inlet tube, 1-chloro-4-iodobenzene (4.77 g, 20 mmol), dimethyl sulfoxide (DMSO, 15 mL), and 1,6-diiodoperfluorohexane (5.54 g, 10 mmol) were added and dissolved. Then, copper powder (3.18 g, 50 mmol) was added, and the temperature was gradually raised to 120 °C in a nitrogen gas atmosphere and stirred for 12 hours. After allowing to cool to room temperature, the copper powder was removed by suction filtration, and DMSO was distilled off under reduced pressure. The residue was dissolved in t-butyl methyl ether, suction filtered, and then the filtrate was washed with distilled water. The organic layer was taken out, anhydrous sodium sulfate was added for dehydration. Then, t-butyl methyl ether was distilled off from the filtrate obtained by filtration to obtain a crude product. The crude product was purified by sublimation (80 °C / 0.2 Torr) to obtain a product as white powder crystals (yield 4.55 g, yield 87%). Melting point: 87 - 88 °C 1 1H-NMR (CDCl3, ppm): 7.53 (4H), 7.47 (4H) 13 13C-NMR (CDCl3, ppm): 138.6, 129.1, 128.5, 128.4 19 19F-NMR (CDCl3, ppm): -111.8, -122.4, -123.0 FT-IR (KBr, cm -1 ): 1604 (C=C), 1216 - 1132 (C-F), 1092 (C-Cl) Elemental analysis (C 18 H8F 12 Cl2): Calculated value C, 41.32%; H, 1.54% Found value C, 41.41%; H, 1.68%

[0083] <Synthesis Example 4> Synthesis of 1,6-bis(4-nitrophenyl)perfluorohexane (NPPFH) Into a eggplant-shaped flask (100 mL) equipped with a stir bar, Dimroth condenser, and nitrogen inlet tube, 1-iodo-4-nitrobenzene (4.98 g, 20 mmol), dimethyl sulfoxide (DMSO, 15 mL), and 1,6-diiodoperfluorohexane (5.54 g, 10 mmol) were added and dissolved. Then, copper powder (3.18 g, 50 mmol) was added, and the temperature was gradually raised to 120 °C in a nitrogen gas atmosphere and stirred for 12 hours. After allowing to cool to room temperature, the copper powder was removed by suction filtration, and DMSO was distilled off under reduced pressure. The residue was dissolved in t-butyl methyl ether, suction filtered, and then the filtrate was washed with distilled water. The organic layer was taken out, anhydrous sodium sulfate was added for dehydration. Then, t-butyl methyl ether was distilled off from the filtrate obtained by filtration to obtain a crude product. The crude product was purified by sublimation (160 °C / 0.17 Torr) and then recrystallized from a mixed solvent of THF / hexane. By drying under reduced pressure at 100 °C for 12 hours, a product of pale yellow needle crystals (yield 2.78 g, yield 51%) was obtained. Melting point: 168 - 169 °C 1 1H-NMR (CDCl3, ppm): 8.39 (4H), 7.82 (4H) 13 13C-NMR (CDCl3, ppm): 150.3, 135.1, 128.6, 124.0 19 19F-NMR (CDCl3, ppm): -112.0, -122.0, -122.4 FT-IR (KBr, cm -1 ): 1550 (NO2), 1291 (NO2), 1215 - 1132 (C-F) Elemental analysis (C 18 H8N2O4F 12 ): Calculated: C, 39.72%; H, 1.48%; N, 5.15% Found: C, 39.46%; H, 1.55%; N, 5.12%

[0084] <Example 1> Synthesis of fluorine-containing polyether (FPPFH-BisZ) Into a two-necked flask (50 mL) equipped with a stir bar, a nitrogen inlet tube, a Dean-Stark trap, and a Dimroth condenser, FPPFH (0.981 g, 2.0 mmol) and 4,4'-(cyclohexylidene)bisphenol (BisZ, 0.537 g, 2.0 mmol) were added and dissolved in distilled 1,3-dimethyl-2-imidazolidinone (DMI, 5.0 mL). Then, potassium carbonate (0.332 g, 2.4 mmol) and toluene (20 mL) were added. The temperature was raised stepwise to 150 °C and stirred at 150 °C for 2 hours to remove water by azeotropy. Then, it was stirred at 170 °C for 12 hours. After cooling to room temperature, the polymer was recovered with methanol, washed by heating with methanol, and then dried under reduced pressure at room temperature. The polymer was dissolved in chloroform and poured into a large amount of methanol for reprecipitation purification. The polymer was dried under reduced pressure at room temperature for 10 hours. Yield of polymer: 1.09 g (Yield: 72%) Limiting viscosity number (η inh ): 1.26 dL / g (measured in an NMP solution with a concentration of 0.5 g / dL at 30 °C) Number average molecular weight (M n ): 200,000, Molecular weight distribution (Mw / Mn): 2.4 This polymer was dissolved in chloroform and cast on a glass plate, and dried under reduced pressure at room temperature for 6 hours, at 50 °C for 3 hours, and at 100 °C for 3 hours to prepare a colorless transparent cast film (film thickness 35 μm). FT-IR (film, cm -1 ): 2937 (C-H), 2862 (C-H), 1600 (C=C), 1504 (C=C), 1292 - 1143 (C-F) Solubility: Dissolved at room temperature in NMP, DMAc, TMU, DMI, THF, chloroform, ethyl acetate, cyclohexanone, cyclopentanone 5% weight loss temperature: 387 °C (in air), 492 °C (in nitrogen) 10% weight loss temperature: 404 °C (in air), 504 °C (in nitrogen) Char yield: 42% (in nitrogen, 800 °C) Glass transition temperature (Tg): 112 °C (DSC), 113 °C (TMA), 109 °C (DMA) Coefficient of thermal expansion (CTE): 88 ppm / °C (50 °C - 80 °C) Tensile breaking strength: 45 MPa Elongation at break: 5.2% Tensile modulus of elasticity: 1.4 GPa Cut-off wavelength: 290 nm Transmittance at 500 nm: 83%, Average refractive index (n ave ): 1.538 (d-line) Birefringence (Δn): 0.001 (d-line) Dielectric constant (ε) calculated from refractive index: 2.37 (ε = n ave 2 ) Dielectric constant (Dk): 2.44 (TE mode, 10 GHz), 2.38 (TE mode, 20 GHz) Dielectric loss tangent (Df): 0.0021 (TE mode, 10 GHz), 0.0022 (TE mode, 20 GHz)

[0085] <Example 2> Synthesis of fluorine-containing polyether (FPPFH-BisP3MZ) To a two-necked flask (50 mL) equipped with a stirrer, a nitrogen inlet tube, a Dean-Stark trap, and a Dimroth condenser, FPPFH (0.981 g, 2.0 mmol) and 4,4'-(3-methylcyclohexylidene) bisphenol (BisP3MZ, 0.565 g, 2.0 mmol) were added and dissolved in distilled 1,3-dimethyl-2-imidazolidinone (DMI, 5.0 mL). Then, potassium carbonate (0.332 g, 2.4 mmol) and toluene (20 mL) were added. The temperature was gradually raised to 150 °C and stirred at 150 °C for 2 hours to remove water by azeotropy. Then, it was stirred at 170 °C for 24 hours. After cooling to room temperature, the polymer was recovered with methanol, washed by heating with methanol, and then dried under reduced pressure at room temperature. The polymer was dissolved in chloroform and poured into a large amount of methanol for reprecipitation purification. The polymer was dried under reduced pressure at room temperature for 10 hours. Polymer yield: 1.19 g (yield: 77%) Logarithmic viscosity (η inh ): 0.76 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30 °C) Number-average molecular weight (M n): 98,000, Molecular weight distribution (Mw / Mn): 2.7 This polymer was dissolved in chloroform, cast on a glass plate, and dried under reduced pressure at room temperature for 6 hours, at 50 °C for 3 hours, and at 120 °C for 3 hours to prepare a colorless and transparent cast film (film thickness: 50 μm). FT-IR (film, cm -1 ): 2937 (C-H), 2862 (C-H), 1600 (C=C), 1504 (C=C), 1292 - 1143 (C-F) 1 1H-NMR (CDCl3, ppm): 7.51 (d, 4H), 7.37 (d, 2H), 7.18 (d, 2H), 7.02 (q, 6H), 6.91 (d, 2H), 2.62 (q, 2H), 1.82 (t, 1H), 1.71 (d, 2H), 1.52 (q, 3H), 0.96 (d, 4H) 13 13C-NMR (CDCl3, ppm): 160.9, 153.4, 148.0, 141.9, 129.7, 128.8, 127.9, 123.1, 119.9, 117.8, 46.3, 37.0, 35.2, 28.8, 23.1 19 19F-NMR (CDCl3, ppm): -111.1, -122.6, -123.2 Solubility: Soluble in NMP, DMAc, TMU, DMI, THF, chloroform, ethyl acetate, cyclohexanone, and cyclopentanone at room temperature 5% weight loss temperature: 379 °C (in air), 479 °C (in nitrogen) 10% weight loss temperature: 393 °C (in air), 490 °C (in nitrogen) Carbonization yield: 46% (in nitrogen, 800 °C) Glass transition temperature (Tg): 132 °C (DSC), 132 °C (TMA), 128 °C (DMA) Coefficient of thermal expansion (CTE): 88 ppm / °C (50 °C - 80 °C) Tensile breaking strength: 53 MPa Elongation at break: 4.3% Tensile modulus: 1.4 GPa Cut-off wavelength: 292 nm Transmittance at 500 nm: 80%, Average refractive index (n ave): 1.531 (d-line) Birefringence (Δn): 0.004 (d-line) Dielectric constant (ε) calculated from refractive index: 2.34 (ε = n ave 2 ) Dielectric constant (Dk): 2.43 (TE mode, 10 GHz), 2.37 (TE mode, 20 GHz) Dielectric loss tangent (Df): 0.0015 (TE mode, 10 GHz), 0.0016 (TE mode, 20 GHz)

[0086] <Example 3> Synthesis of fluorine-containing polyether (FPPFH-BisPHTG) Into a two-necked flask (50 mL) equipped with a stirrer, a nitrogen inlet tube, a Dean-Stark trap, and a Dimroth condenser, FPPFH (0.981 g, 2.0 mmol) and 4,4'-(3,3,5-trimethylcyclohexylidene) bisphenol (BisPHTG, 0.621 g, 2.0 mmol) were added and dissolved in distilled 1,3-dimethyl-2-imidazolidinone (DMI, 5.0 mL). Then, potassium carbonate (0.332 g, 2.4 mmol) and toluene (20 mL) were added. The temperature was gradually raised to 150 °C and stirred at 150 °C for 2 hours to remove water by azeotropy. Then, it was stirred at 170 °C for 24 hours. After cooling to room temperature, the polymer was recovered with methanol, washed by heating with methanol, and then dried under reduced pressure at room temperature. The polymer was dissolved in chloroform and poured into a large amount of methanol for reprecipitation purification. The polymer was dried under reduced pressure at room temperature for 10 hours. Polymer yield: 1.33 g (Yield: 83%) Logarithmic viscosity (η inh ): 0.45 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30 °C) Number average molecular weight (M n ): 43,000, Molecular weight distribution (Mw / Mn): 2.2 This polymer was dissolved in chloroform and cast on a glass plate, and dried under reduced pressure at room temperature for 6 hours, at 50 °C for 3 hours, and at 120 °C for 3 hours to prepare a colorless transparent cast film (film thickness 51 μm). FT-IR (film, cm -1): 2937 (C-H), 2862 (C-H), 1600 (C=C), 1504 (C=C), 1292 - 1143 (C-F) 1 1H-NMR (CDCl3, ppm): 7.49 (t, 4H), 7.38 (d, 2H), 7.25 (t, 2H), 6.99 (q, 6H), 6.92 (d, 2H), 2.72 (d, 1H), 2.49 (d, 1H), 2.04 (s, 1H), 1.96 (d, 1H), 1.44 (d, 1H), 1.21 (t, 1H), 1.01 (d, 6H), 0.90 (t, 1H), 0.41 (s, 3H) 13 13C-NMR (CDCl3, ppm): 160.9, 153.1, 148.8, 143.3, 129.3, 128.8, 127.6, 123.1, 119.8, 117.6, 48.8, 48.4, 46.3, 45.4, 35.0, 32.4, 26.9, 25.7, 22.8 19 19F-NMR (CDCl3, ppm): -111.1, -122.6, -123.2 Solubility: Soluble in NMP, DMAc, TMU, DMI, THF, chloroform, ethyl acetate, cyclohexanone, cyclopentanone, acetone at room temperature 5% Weight loss temperature: 458 °C (in air), 493 °C (in nitrogen) 10% Weight loss temperature: 482 °C (in air), 503 °C (in nitrogen) Char yield: 38% (in nitrogen, 800 °C) Glass transition temperature (Tg): 140 °C (DSC), 136 °C (TMA), 130 °C (DMA) Coefficient of thermal expansion (CTE): 96 ppm / °C (50 °C - 80 °C) Tensile breaking strength: 53 MPa Elongation at break: 4.8% Tensile modulus: 1.5 GPa Cut-off wavelength: 293 nm Transmittance at 500 nm: 85%, Average refractive index (n ave ): 1.523 (d line) Birefringence (Δn): 0.002 (d line) Dielectric constant (ε) calculated from refractive index: 2.32 (ε = n ave2 ) Dielectric constant (Dk): 2.42 (TE mode, 10 GHz), 2.36 (TE mode, 20 GHz) Dielectric tangent (Df): 0.0033 (TE mode, 10 GHz), 0.0036 (TE mode, 20 GHz)

[0087] <Example 4> Synthesis of fluorine-containing polyether (FPPFH-BisPCDE) To a two-necked flask (50 mL) equipped with a stir bar, a nitrogen inlet tube, a Dean-Stark trap, and a Dimroth condenser, FPPFH (0.981 g, 2.0 mmol) and 4,4'-cyclododecylidene bisphenol (BisPCDE, 0.705 g, 2.0 mmol) were added and dissolved in distilled 1,3-dimethyl-2-imidazolidinone (DMI, 5.0 mL). Then, potassium carbonate (0.332 g, 2.4 mmol) and toluene (20 mL) were added. The temperature was raised stepwise to 150 °C and stirred at 150 °C for 2 hours to remove water by azeotropy. Then, it was stirred at 170 °C for 24 hours. After cooling to room temperature, the polymer was recovered with methanol, washed by heating with methanol, and then dried under reduced pressure at room temperature. The polymer was dissolved in chloroform and poured into a large amount of methanol for reprecipitation purification. The polymer was dried under reduced pressure at room temperature for 10 hours. Polymer yield: 1.28 g (yield: 76%) Logarithmic viscosity (η inh ): 0.64 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30 °C) Number-average molecular weight (M n ): 68,000, molecular weight distribution (Mw / Mn): 2.3 This polymer was dissolved in chloroform and cast on a glass plate, and dried under reduced pressure at room temperature for 6 hours, at 50 °C for 3 hours, and at 140 °C for 5 hours to prepare a colorless transparent cast film (film thickness 56 μm). FT-IR (film, cm -1 ): 2937 (C-H), 2862 (C-H), 1600 (C=C), 1504 (C=C), 1292 - 1143 (C-F) Solubility: Soluble in NMP, DMAc, TMU, DMI, THF, chloroform, ethyl acetate, cyclohexanone, and cyclopentanone at room temperature 5% weight loss temperature: 343 °C (in air), 423 °C (in nitrogen) 10% weight loss temperature: 364 °C (in air), 441 °C (in nitrogen) Carbonization yield: 36% (in nitrogen, 800 °C) Glass transition temperature (Tg): 155 °C (DSC), 156 °C (TMA), 151 °C (DMA) Coefficient of thermal expansion (CTE): 85 ppm / °C (50 °C to 80 °C) Tensile breaking strength: 64 MPa Elongation at break: 6.1% Tensile modulus: 1.7 GPa Cut-off wavelength: 292 nm Transmittance at 500 nm: 78%, Average refractive index (n ave ): 1.527 (d line) Birefringence (Δn): 0.002 (d line) Dielectric constant (ε) calculated from refractive index: 2.33 (ε = n ave 2 ) Dielectric constant (Dk): 2.42 (TE mode, 10 GHz), 2.37 (TE mode, 20 GHz) Dissipation factor (Df): 0.0011 (TE mode, 10 GHz), 0.0012 (TE mode, 20 GHz)

[0088] <Example 5> Synthesis of fluorine-containing polyether (FPPFH-BisPIND) In a two-necked flask (50 mL) equipped with a stir bar, a nitrogen inlet tube, a Dean-Stark trap, and a Dimroth condenser, FPPFH (0.981 g, 2.0 mmol) and 3-(4-hydroxyphenyl)-1,1,3-trimethyl-5-indanol (BisPIND, 0.537 g, 2.0 mmol) were added and dissolved in distilled 1,3-dimethyl-2-imidazolidinone (DMI, 5.0 mL). Then, potassium carbonate (0.332 g, 2.4 mmol) and toluene (20 mL) were added. The temperature was gradually raised to 150 °C and stirred at 150 °C for 2 hours to remove water by azeotropy. Then, it was stirred at 170 °C for 24 hours. After cooling to room temperature, the polymer was recovered with methanol, washed by heating with methanol, and then dried under reduced pressure at room temperature. The polymer was dissolved in chloroform and poured into a large amount of methanol for reprecipitation purification. The polymer was dried under reduced pressure at room temperature for 10 hours. Yield of polymer: 0.97 g (Yield: 64%) Logarithmic viscosity (η inh ): 0.91 dL / g (measured in an NMP solution with a concentration of 0.5 g / dL at 30 °C) Number-average molecular weight (M n ): 116,000, Molecular weight distribution (Mw / Mn): 2.7 This polymer was dissolved in chloroform and cast on a glass plate, and dried under reduced pressure at room temperature for 6 hours, at 50 °C for 3 hours, and at 110 °C for 3 hours to prepare a colorless transparent cast film (film thickness 58 μm). FT-IR (film, cm -1 ): 2937 (C-H), 2862 (C-H), 1600 (C=C), 1504 (C=C), 1292 - 1143 (C-F) 1 H-NMR (CDCl3, ppm): 7.49 (d, 4H), 7.19 (t, 3H), 7.04 - 6.92 (q, 7H), 6.84 (d, 1H), 2.45 (d, 1H), 2.27 (d, 1H), 1.68 (s, 3H), 1.37 (s, 3H), 1.09 (s, 3H) 1313C-NMR (CDCl3, ppm): 161.4, 161.0, 154.5, 153.4, 151.1, 148.7, 146.9, 128.8, 128.3, 124.2, 119.7, 117.6, 116.8, 59.6, 50.5, 42.7, 30.9 19 19F-NMR (CDCl3, ppm): -111.1, -122.6, -123.1 Solubility: Soluble in DMF, DMAc, NMP, TMU, DMI, THF, chloroform, ethyl acetate, cyclohexanone, cyclopentanone, and acetone at room temperature 5% weight loss temperature: 425 °C (in air), 493 °C (in nitrogen) 10% weight loss temperature: 440 °C (in air), 501 °C (in nitrogen) Carbonization yield: 51% (in nitrogen, 800 °C) Glass transition temperature (Tg): 123 °C (DSC), 125 °C (TMA), 121 °C (DMA) Coefficient of thermal expansion (CTE): 90 ppm / °C (50 °C to 80 °C) Tensile breaking strength: 43 MPa Elongation at break: 3.6% Tensile modulus: 1.1 GPa Cut-off wavelength: 293 nm Transmittance at 500 nm: 84%, Average refractive index (n ave ): 1.527 (d line) Birefringence (Δn): 0.001 (d line) Dielectric constant (ε) calculated from refractive index: 2.33 (ε = n ave 2 ) Dielectric constant (Dk): 2.43 (TE mode, 10 GHz), 2.36 (TE mode, 20 GHz) Dissipation factor (Df): 0.0031 (TE mode, 10 GHz), 0.0033 (TE mode, 20 GHz)

[0089] <Example 6> Synthesis of fluorine-containing polyether (FPPFH-BPFL) Into a two-necked flask (50 mL) equipped with a stir bar, a nitrogen inlet tube, a Dean-Stark trap, and a Dimroth condenser, FPPFH (0.981 g, 2.0 mmol) and 9,9-bis(4-hydroxyphenyl)fluorene (BPFL, 0.701 g, 2.0 mmol) were added and dissolved in distilled 1,3-dimethyl-2-imidazolidinone (DMI, 5.0 mL). Then, potassium carbonate (0.332 g, 2.4 mmol) and toluene (20 mL) were added. The temperature was gradually raised to 150 °C and stirred at 150 °C for 2 hours to remove water by azeotropy. Then, it was stirred at 170 °C for 24 hours. After cooling to room temperature, the polymer was recovered with methanol, washed by heating with methanol, and then dried under reduced pressure at room temperature. The polymer was dissolved in chloroform and poured into a large amount of methanol for reprecipitation purification. The polymer was dried under reduced pressure at room temperature for 10 hours. Yield of polymer: 1.28 g (Yield: 76%) Logarithmic viscosity (η inh ): 1.15 dL / g (measured in a 0.5 g / dL NMP solution at 30 °C) Number-average molecular weight (M n ): 144,000, Molecular weight distribution (Mw / Mn): 2.3 This polymer was dissolved in chloroform and cast on a glass plate, and dried under reduced pressure at room temperature for 6 hours, at 50 °C for 3 hours, and at 160 °C for 3 hours to prepare a colorless transparent cast film (film thickness 53 μm). FT-IR (film, cm -1 ): 2937 (C-H), 2862 (C-H), 1600 (C=C), 1504 (C=C), 1292 - 1143 (C-F) 1 1H-NMR (CDCl3, ppm): 7.78 (d, 2H), 7.49 (d, 4H), 7.41 (d, 4H), 7.32 (t, 2H), 7.23 (d, 4H), 7.02 (d, 4H), 6.90 (d, 4H) 13 13C-NMR (CDCl3, ppm): 160.6, 154.6, 151.1, 142.0, 140.2, 129.8, 128.8, 127.9, 126.2, 123.4, 120.5, 119.7, 117.9, 64.6 19F-NMR (CDCl3, ppm): -111.2, -122.7, -123.2 Elemental analysis: Calculated values: C, 64.50%; H, 3.02% Found values: C, 64.17%; H, 3.14% Solubility: Soluble in DMF, DMAc, NMP, TMU, DMI, THF, chloroform, ethyl acetate, cyclohexanone, cyclopentanone at room temperature 5% weight loss temperature: 530 °C (in air), 546 °C (in nitrogen) 10% weight loss temperature: 550 °C (in air), 562 °C (in nitrogen) Char yield: 57% (in nitrogen, 800 °C) Glass transition temperature (Tg): 172 °C (DSC), 172 °C (TMA), 171 °C (DMA) Coefficient of thermal expansion (CTE): 71 ppm / °C (50 °C - 80 °C) Tensile break strength: 54 MPa Elongation at break: 4.8% Tensile modulus: 1.6 GPa Cut-off wavelength: 316 nm Transmittance at 500 nm: 80%, Average refractive index (n ave ): 1.572 (d line) Birefringence (Δn): 0.002 (d line) Dielectric constant (ε) calculated from refractive index: 2.47 (ε = n ave 2 ) Dielectric constant (Dk): 2.46 (TE mode, 10 GHz), 2.41 (TE mode, 20 GHz) Dissipation factor (Df): 0.0019 (TE mode, 10 GHz), 0.0020 (TE mode, 20 GHz)

[0090] <Example 7> Synthesis of fluorine-containing polyether (FPPFH - BMPFL) In a two-necked flask (50 mL) equipped with a stir bar, a nitrogen inlet tube, a Dean-Stark trap, and a Dimroth condenser, FPPFH (0.981 g, 2.0 mmol) and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (BMPFL, 0.757 g, 2.0 mmol) were added and dissolved in distilled 1,3-dimethyl-2-imidazolidinone (DMI, 5.0 mL). Then, potassium carbonate (0.332 g, 2.4 mmol) and toluene (20 mL) were added. The temperature was raised stepwise to 150 °C and stirred at 150 °C for 2 hours to remove water by azeotropy. Then, it was stirred at 170 °C for 24 hours. After cooling to room temperature, the polymer was recovered with methanol, washed by heating with methanol, and then dried under reduced pressure at room temperature. The polymer was dissolved in chloroform and poured into a large amount of methanol for reprecipitation purification. The polymer was dried under reduced pressure at room temperature for 10 hours. Yield of polymer: 1.41 g (Yield: 81%) Limiting viscosity number (η inh ): 0.42 dL / g (measured at 30 °C in an NMP solution with a concentration of 0.5 g / dL) Number-average molecular weight (M n ): 45,000, Molecular weight distribution (Mw / Mn): 2.4 This polymer was dissolved in chloroform and cast onto a glass plate, and dried under reduced pressure at room temperature for 6 hours, at 50 °C for 3 hours, and at 160 °C for 3 hours to prepare a colorless and transparent cast film (film thickness 53 μm). 1 1H-NMR (CDCl3, ppm): 7.81 (d, 2H), 7.47 (m, 6H), 7.40 (t, 2H), 7.32 (t, 2H), 7.11 (d, 4H), 6.94 (d, 4H), 6.85 (d, 2H), 2.08 (s, 6H) 19 19F-NMR (CDCl3, ppm): -110.9, -122.5, -123.0 Solubility: Soluble at room temperature in DMF, DMAc, NMP, TMU, DMI, THF, chloroform, ethyl acetate, cyclohexanone, cyclopentanone 5% weight loss temperature: 426 °C (in air), 439 °C (in nitrogen) 10% weight loss temperature: 452 °C (in air), 461 °C (in nitrogen) Carbonization yield: 64% (in nitrogen, 800 °C) Glass transition temperature (Tg): 168 °C (DSC), 169 °C (TMA), 166 °C (DMA) Coefficient of thermal expansion (CTE): 81 ppm / °C (50 °C to 80 °C) Tensile breaking strength: 61 MPa Elongation at break: 5.1% Tensile modulus of elasticity: 2.1 GPa Cut-off wavelength: 316 nm Transmittance at 500 nm: 79%, Average refractive index (n ave ): 1.568 (d line) Birefringence (Δn): 0.002 (d line) Dielectric constant (ε) calculated from refractive index: 2.46 (ε = n ave 2 ) Dielectric constant (Dk): 2.45 (TE mode, 10 GHz), 2.40 (TE mode, 20 GHz) Dissipation factor (Df): 0.0020 (TE mode, 10 GHz), 0.0019 (TE mode, 20 GHz)

[0091] <Example 8> Synthesis of fluorine-containing polyether (FPPFH-BP) To a two-necked flask (50 mL) equipped with a stir bar, a nitrogen inlet tube, a Dean-Stark trap, and a Dimroth condenser, FPPFH (0.981 g, 2.0 mmol) and 4,4-dihydroxybiphenyl (BP, 0.372 g, 2.0 mmol) were added and dissolved in distilled 1,3-dimethyl-2-imidazolidinone (DMI, 5.0 mL). Then, potassium carbonate (0.332 g, 2.4 mmol) and toluene (20 mL) were added. The temperature was gradually raised to 150 °C and stirred at 150 °C for 2 hours to remove water by azeotropy. Then, it was stirred at 170 °C for 12 hours. After cooling to room temperature, the polymer was recovered with methanol, washed by heating with methanol, and then dried under reduced pressure at room temperature. The polymer was dissolved in tetrahydrofuran (THF) and poured into a large amount of methanol for reprecipitation purification. The polymer was dried under reduced pressure at room temperature for 10 hours. Polymer yield: 0.93 g (yield: 69%) Logarithmic viscosity (η inh ): 0.85 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30 °C) This polymer was dissolved in THF, cast onto a glass plate, and dried under reduced pressure at room temperature for 6 hours, at 50 °C for 3 hours, and at 90 °C for 3 hours to produce a colorless and transparent cast film (film thickness: 42 μm). FT-IR (film, cm -1 ): 1600 (C=C), 1504 (C=C), 1292 - 1143 (C-F) Solubility: Dissolved in DMAc, NMP, TMU, DMI, THF, and cyclopentanone at room temperature 5% weight loss temperature: 507 °C (in air), 542 °C (in nitrogen) 10% weight loss temperature: 531 °C (in air), 555 °C (in nitrogen) Char yield: 44% (in nitrogen, 800 °C) Glass transition temperature (Tg): 103 °C (DSC), 105 °C (TMA), 114 °C (DMA) Coefficient of thermal expansion (CTE): 94 ppm / °C (50 °C - 80 °C) Tensile breaking strength: 27 MPa Elongation at break: 16.7% Tensile modulus: 1.1 GPa Cut-off wavelength: 308 nm Transmittance at 500 nm: 86%, Average refractive index (n ave ): 1.551 (d line) Birefringence (Δn): 0.011 (d line) Dielectric constant (ε) calculated from the refractive index: 2.41 (ε = n ave 2 ) Dielectric constant (Dk): 2.44 (TE mode, 10 GHz), 2.40 (TE mode, 20 GHz) Dissipation factor (Df): 0.0021 (TE mode, 10 GHz), 0.0023 (TE mode, 20 GHz)

[0092] <Example 9> Synthesis of fluorine-containing polyether (FPPFH-NDO) In a two-necked flask (50 mL) equipped with a stir bar, a nitrogen inlet tube, a Dean-Stark trap, and a Dimroth condenser, FPPFH (0.981 g, 2.0 mmol) and 2,6-dihydroxynaphthalene (NDO, 0.320 g, 2.0 mmol) were added and dissolved in distilled 1,3-dimethyl-2-imidazolidinone (DMI, 5.0 mL). Then, potassium carbonate (0.332 g, 2.4 mmol) and toluene (20 mL) were added. The temperature was gradually raised to 150 °C and stirred at 150 °C for 2 hours to remove water by azeotropy. Then, it was stirred at 170 °C for 24 hours. After cooling to room temperature, the polymer was recovered with methanol, washed by heating with methanol, and then dried under reduced pressure at room temperature. The polymer was dissolved in tetrahydrofuran (THF) and poured into a large amount of methanol for reprecipitation purification. The polymer was dried under reduced pressure at room temperature for 10 hours. Logarithmic viscosity (η inh ): 0.41 dL / g (measured in a 0.5 g / dL concentration NMP solution at 30 °C) This polymer was dissolved in THF and cast on a glass plate, and dried under reduced pressure at room temperature for 6 hours, at 50 °C for 3 hours, and at 90 °C for 3 hours to prepare a pale yellow transparent cast film. Solubility: Soluble at room temperature in DMF, DMAc, NMP, TMU, DMI, THF, and cyclopentanone 5% weight loss temperature: 438 °C (in air), 535 °C (in nitrogen) 10% weight loss temperature: 484 °C (in air), 556 °C (in nitrogen) Char yield: 49% (in nitrogen, 800 °C) Glass transition temperature (Tg): 97 °C (DSC), 98 °C (TMA), 98 °C (DMA) Coefficient of thermal expansion (CTE): 99 ppm / °C (50 °C - 80 °C) Tensile breaking strength: 28 MPa Elongation at break: 3.9% Tensile modulus: 1.3 GPa Cut-off wavelength: 348 nm Transmittance at 500 nm: 55%, Average refractive index (n ave ): 1.554 (d line) Birefringence (Δn): 0.002 (d line) Dielectric constant (ε) calculated from refractive index: 2.41 (ε = n ave 2 ) Dielectric constant (Dk): 2.45 (TE mode, 10 GHz), 2.42 (TE mode, 20 GHz) Dissipation factor (Df): 0.0032 (TE mode, 10 GHz), 0.0032 (TE mode, 20 GHz)

[0093] <Example 10> Synthesis of fluorine-containing polyether (FPPFH-TMPBP) Instead of 4,4-dihydroxybiphenyl (BP) in Example 8, 4,4'-dihydroxy-2,2',3,3',5,5'-hexamethylbiphenyl (TMPBP) was used to synthesize a polyether by polymerization at 190 °C for 24 hours. Polymer yield: 76% Logarithmic viscosity (η inh ): 0.47 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30 °C) Number average molecular weight (M n ): 50,000, molecular weight distribution (Mw / Mn): 2.4 This polymer was dissolved in THF to prepare a transparent cast film (film thickness 60 μm). FT-IR (film, cm -1 ): 1600 (C=C), 1504 (C=C), 1292 - 1143 (C-F) Elemental analysis (C 36 H 28 O2F 12 ): Calculated value C, 60.00%; H, 3.92% Measured value C, 60.22%; H, 3.98% Solubility: Soluble in NMP, TMU, DMI, DMAc, THF, chloroform, ethyl acetate, cyclohexanone, cyclopentanone 5% weight loss temperature: 415 °C (in air), 432 °C (in nitrogen) 10% weight loss temperature: 439 °C (in air), 446 °C (in nitrogen) Char yield: 52% (in nitrogen, 800 °C) Glass transition temperature (Tg): 167 °C (DSC), 169 °C (TMA), 166 °C (DMA) Coefficient of thermal expansion (CTE): 82 ppm / °C (50 °C to 80 °C) Tensile breaking strength: 48 MPa Elongation at break: 4.3% Tensile modulus: 1.3 GPa Cut-off wavelength: 308 nm Transmittance at 500 nm: 57%, Average refractive index (n ave ): 1.522 (d line) Birefringence (Δn): 0.006 (d line) Dielectric constant (ε) calculated from refractive index: 2.32 (ε = n ave 2 ) Dielectric constant (Dk): 2.39 (TE mode, 10 GHz), 2.33 (TE mode, 20 GHz) Dissipation factor (Df): 0.0015 (TE mode, 10 GHz), 0.0016 (TE mode, 20 GHz)

[0094] <Example 11> Synthesis of fluorine-containing polyether (FPPFH-BisTPM) Instead of 4,4-dihydroxybiphenyl (BP) in Example 8, 4,4-dihydroxytetraphenylmethane (BisTPM) was used to synthesize a polyether by polymerization at 170 °C for 12 hours. Polymer yield: 80% Logarithmic viscosity (η inh ): 0.65 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30 °C) Number average molecular weight (M n ): 61,000, molecular weight distribution (Mw / Mn): 2.8 This polymer was dissolved in THF to prepare a colorless and transparent cast film (film thickness 46 μm). FT-IR (film, cm -1 ): 1600 (C=C), 1504 (C=C), 1292 - 1143 (C-F) Elemental analysis: Calculated value C, 64.34%; H, 3.27% Measured value C, 64.15%; H, 3.35% Solubility: Soluble in NMP, TMU, DMI, DMAc, THF 5% Weight loss temperature: 498 °C (in air), 508 °C (in nitrogen) 10% Weight loss temperature: 514 °C (in air), 520 °C (in nitrogen) Carbonization yield: 57% (in nitrogen, 800 °C) Glass transition temperature (Tg): 133 °C (DSC), 143 °C (TMA), 135 °C (DMA) Coefficient of thermal expansion (CTE): 70 ppm / °C (50 °C - 80 °C) Tensile breaking strength: 46 MPa Elongation at break: 3.2% Tensile modulus: 1.5 GPa Cut-off wavelength: 292 nm Transmittance at 500 nm: 79%, Average refractive index (n ave ): 1.566 (d line) Birefringence (Δn): 0.008 (d line) Dielectric constant (ε) calculated from refractive index: 2.45 (ε = n ave 2 ) Dielectric constant (Dk): 2.45 (TE mode, 10 GHz), 2.44 (TE mode, 20 GHz) Dissipation factor (Df): 0.0036 (TE mode, 10 GHz), 0.0038 (TE mode, 20 GHz)

[0095] <Example 12> Synthesis of fluorine-containing polyether (FPPFH-TBISRX) Instead of 9,9-bis(4-hydroxyphenyl)fluorene (BPFL) in Example 6, spiro[fluorene-9,9'-xanthene]-3',6'-diol (TBISRX) was used to synthesize a polyether by polymerization at 190 °C for 4 hours. Polymer yield: 81% Logarithmic viscosity (η inh ): 0.81 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30 °C) Number average molecular weight (M n ): 94,000, Molecular weight distribution (Mw / Mn): 2.9 This polymer was dissolved in chloroform to prepare a colorless and transparent cast film (film thickness: 50 μm). FT-IR (film, cm -1 ): 1600 (C=C), 1504 (C=C), 1292 - 1143 (C-F) Elemental analysis: Calculated value for C, 63.40%; for H, 2.72% Measured value for C, 63.69%; for H, 2.89% Solubility: Soluble in NMP, TMU, DMI, DMAc, DMF, THF, chloroform, ethyl acetate, cyclohexanone, cyclopentanone 5% weight loss temperature: 507 °C (in air), 545 °C (in nitrogen) 10% weight loss temperature: 525 °C (in air), 561 °C (in nitrogen) Char yield: 60% (in nitrogen, 800 °C) Glass transition temperature (Tg): 190 °C (DSC), 205 °C (TMA), 189 °C (DMA) Coefficient of thermal expansion (CTE): 65 ppm / °C (50 °C - 80 °C) Tensile breaking strength: 58 MPa Elongation at break: 5.8% Tensile modulus: 1.2 GPa Cut-off wavelength: 315 nm Transmittance at 500 nm: 86%, Average refractive index (n ave ): 1.579 (d line) Birefringence (Δn): 0.003 (d line) Dielectric constant (ε) calculated from refractive index: 2.49 (ε = n ave 2 ) Dielectric constant (Dk): 2.46 (TE mode, 10 GHz), 2.44 (TE mode, 20 GHz) Dissipation factor (Df): 0.0014 (TE mode, 10 GHz), 0.0015 (TE mode, 20 GHz)

[0096] <Example 13> Synthesis of fluorine-containing polyether (FPPFB-BisA) Instead of FPPFH in Comparative Example 1, 1,4-bis(4-fluorophenyl)perfluorobutane (FPPFB) was used to synthesize a polyether by polymerization at 190 °C for 3 hours. Polymer yield: 80% Logarithmic viscosity (η inh ): 1.06 dL / g (NMP solution at a concentration of 0.5 g / dL, measured at 30 °C) Number-average molecular weight (M n ): 119,000, molecular weight distribution (Mw / Mn): 2.5 This polymer was dissolved in chloroform to prepare a colorless and transparent cast film (film thickness 48 μm). FT-IR (film, cm -1 ): 1600 (C=C), 1502 (C=C), 1287 - 1139 (C-F) Elemental analysis (C 31 H 22 O2F8): Calculated value C, 64.36%; H, 3.83% Measured value C, 64.72%; H, 3.87% Solubility: Soluble in NMP, TMU, DMI, DMAc, THF, chloroform, cyclohexanone, cyclopentanone 5% weight loss temperature: 445 °C (in air), 495 °C (in nitrogen) 10% weight loss temperature: 458 °C (in air), 503 °C (in nitrogen) Carbonization yield: 60% (in nitrogen, 800 °C) Glass transition temperature (Tg): 113 °C (DSC), 112 °C (TMA), 111 °C (DMA) Coefficient of thermal expansion (CTE): 105 ppm / °C (50 °C - 80 °C) Tensile breaking strength: 35 MPa Elongation at break: 3.7% Tensile modulus of elasticity: 1.3 GPa Cut-off wavelength: 289 nm Transmittance at 500 nm: 87%, Average refractive index (n ave ): 1.556 (d line) Birefringence (Δn): 0.004 (d line) Dielectric constant (ε) calculated from the refractive index: 2.42 (ε = n ave2 ) Dielectric constant (Dk): 2.44 (TE mode, 10 GHz), 2.40 (TE mode, 20 GHz) Dielectric loss tangent (Df): 0.0016 (TE mode, 10 GHz), 0.0017 (TE mode, 20 GHz)

[0097] <Example 14> Synthesis of fluorine-containing polyether (FPPFB-BisAF) Instead of FPPFH in Comparative Example 2, 1,4-bis(4-fluorophenyl)perfluorobutane (FPPFB) was used to polymerize at 190 °C for 3 hours to synthesize a polyether. Polymer yield: 76% Logarithmic viscosity (η inh ): 0.80 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30 °C) Number average molecular weight (M n ): 86,000, molecular weight distribution (Mw / Mn): 2.6 This polymer was dissolved in chloroform to prepare a colorless and transparent cast film (film thickness: 40 μm). FT-IR (film, cm -1 ): 1603 (C=C), 1507 (C=C), 1251 - 1138 (C-F), 1103 (C-O) Elemental analysis (C 31 H 16 O2F 14 ): Calculated value C, 54.24%; H, 2.35% Measured value C, 54.30%; H, 2.41% Solubility: Soluble in NMP, TMU, DMI, DMF, THF, chloroform, acetone, ethyl acetate 5% weight loss temperature: 483 °C (in air), 507 °C (in nitrogen) 10% weight loss temperature: 500 °C (in air), 518 °C (in nitrogen) Carbonization yield: 50% (in nitrogen, 800 °C) Glass transition temperature (Tg): 122 °C (DSC), 122 °C (TMA), 119 °C (DMA) Coefficient of thermal expansion (CTE): 84 ppm / °C (50 °C - 80 °C) Tensile breaking strength: 36 MPa Elongation at break: 3.0% Tensile modulus of elasticity: 2.3 GPa Cut-off wavelength: 281 nm Transmittance at 500 nm: 85%, Average refractive index (n ave ): 1.518 (d line) Birefringence (Δn): 0.003 (d line) Dielectric constant (ε) calculated from refractive index: 2.30 (ε = n ave 2 ) Dielectric constant (Dk): 2.21 (TE mode, 10 GHz), 2.18 (TE mode, 20 GHz) Dielectric loss tangent (Df): 0.0017 (TE mode, 10 GHz), 0.0019 (TE mode, 20 GHz)

[0098] <Example 15> Synthesis of fluorine-containing polyether (FPPFB-BPFL) Instead of FPPFH in Example 6, 1,4-bis(4-fluorophenyl)perfluorobutane (FPPFB) was used to synthesize a polyether by polymerization at 190 °C for 6 hours. Polymer yield: 74% Logarithmic viscosity (η inh ): 1.11 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30 °C) Number average molecular weight (M n ): 130,000, molecular weight distribution (Mw / Mn): 2.5 This polymer was dissolved in chloroform to prepare a colorless and transparent cast film (film thickness 46 μm). FT-IR (film, cm -1 ): 1599 (C=C), 1500 (C=C), 1286 - 1139 (C-F), 1104 (C-O) Elemental analysis (C 41 H 24 O2F8): Calculated value C, 70.28%; H, 3.45% Measured value C, 70.47%; H, 3.46% Solubility: Soluble in NMP, TMU, DMI, DMAc, DMF, THF, chloroform, ethyl acetate, cyclohexanone, cyclopentanone 5% Weight loss temperature: 507 °C (in air), 533 °C (in nitrogen) 10% Weight loss temperature: 518 °C (in air), 547 °C (in nitrogen) Carbonization yield: 69% (in nitrogen, 800 °C) Glass transition temperature (Tg): 196 °C (DSC), 194 °C (TMA), 193 °C (DMA) Coefficient of thermal expansion (CTE): 72 ppm / °C (50 °C - 80 °C) Tensile break strength: 60 MPa Elongation at break: 4.7% Tensile modulus: 1.6 GPa Cut-off wavelength: 319 nm Transmittance at 500 nm: 82%, Average refractive index (n ave ): 1.596 (d line) Birefringence (Δn): 0.003 (d line) Dielectric constant (ε) calculated from refractive index: 2.55 (ε = n ave 2 ) Dielectric constant (Dk): 2.53 (TE mode, 10 GHz), 2.49 (TE mode, 20 GHz) Dissipation factor (Df): 0.0011 (TE mode, 10 GHz), 0.0013 (TE mode, 20 GHz)

[0099] <Example 16> Synthesis of fluorine-containing polyether (FPPFB-TBISRX) Instead of FPPFH in Example 12, 1,4-bis(4-fluorophenyl) perfluorobutane (FPPFB) was used to polymerize at 190 °C for 4 hours to synthesize a polyether. Polymer yield: 79% Logarithmic viscosity (η inh ): 0.92 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30 °C) Number average molecular weight (M n ): 89,000, molecular weight distribution (Mw / Mn): 2.4 This polymer was dissolved in chloroform to prepare a colorless and transparent cast film (film thickness: 42 μm). FT-IR (film, cm -1 ): 1602 (C=C), 1510 (C=C), 1284 - 1154 (C-F), 1104 (C-O) Elemental analysis (C 41 H 22 O3F8): Calculated value: C, 68.91%; H, 3.10% Measured value: C, 68.90%; H, 3.15% Solubility: Soluble in NMP, TMU, DMI, DMAc, DMF, THF, chloroform, cyclohexanone, cyclopentanone 5% weight loss temperature: 501 °C (in air), 546 °C (in nitrogen) 10% weight loss temperature: 522 °C (in air), 563 °C (in nitrogen) Char yield: 64% (in nitrogen, 800 °C) Glass transition temperature (Tg): 211 °C (DSC), 211 °C (TMA), 210 °C (DMA) Coefficient of thermal expansion (CTE): 74 ppm / °C (50 °C - 80 °C) Tensile breaking strength: 59 MPa Elongation at break: 4.5% Tensile modulus: 2.4 GPa Cut-off wavelength: 312 nm Transmittance at 500 nm: 83%, Average refractive index (n ave ): 1.601 (d line) Birefringence (Δn): 0.004 (d line) Dielectric constant (ε) calculated from refractive index: 2.56 (ε = n ave 2 ) Dielectric constant (Dk): 2.54 (TE mode, 10 GHz), 2.51 (TE mode, 20 GHz) Dissipation factor (Df): 0.0010 (TE mode, 10 GHz), 0.0012 (TE mode, 20 GHz)

[0100] <Example 17> Synthesis of fluorine-containing polyether (FPPFB-BisPCDE) Instead of the FPPFH in Example 4, 1,4-bis(4-fluorophenyl) perfluorobutane (FPPFB) was used to synthesize a polyether by polymerization at 190 °C for 5 hours. Polymer yield: 80% Logarithmic viscosity (η inh ): 0.86 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30 °C) Number average molecular weight (M n ): 85,000, molecular weight distribution (Mw / Mn): 2.4 This polymer was dissolved in chloroform to prepare a colorless and transparent cast film (film thickness 44 μm). FT-IR (film, cm -1 ): 2938 (C-H), 2863 (C-H), 1600 (C=C), 1502 (C=C), 1286 - 1139 (C-F), 1103 (C-O) Elemental analysis (C 40 H 38 O2F8): Calculated value C, 68.36%; H, 5.45% Measured value C, 68.62%; H, 5.47% Solubility: Soluble in NMP, TMU, DMI, THF, chloroform, cyclohexanone, cyclopentanone 5% weight loss temperature: 323 °C (in air), 427 °C (in nitrogen) 10% weight loss temperature: 337 °C (in air), 440 °C (in nitrogen) Carbonization yield: 44% (in nitrogen, 800 °C) Glass transition temperature (Tg): 174 °C (DSC), 172 °C (TMA), 171 °C (DMA) Coefficient of thermal expansion (CTE): 84 ppm / °C (50 °C - 80 °C) Tensile breaking strength: 60 MPa Elongation at break: 5.8% Tensile modulus of elasticity: 1.4 GPa Cut-off wavelength: 292 nm Transmittance at 500 nm: 84%, Average refractive index (n ave ): 1.547 (d line) Birefringence (Δn): 0.004 (d line) Dielectric constant (ε) calculated from the refractive index: 2.39 (ε = nave 2 ) Dielectric constant (Dk): 2.44 (TE mode, 10 GHz), 2.38 (TE mode, 20 GHz) Dissipation factor (Df): 0.0008 (TE mode, 10 GHz), 0.0010 (TE mode, 20 GHz)

[0101] <Comparative Example 1> Synthesis of fluorine-containing polyether (FPPFH-BisA) To a two-necked flask (50 mL) equipped with a stir bar, a nitrogen inlet tube, a Dean-Stark trap, and a Dimroth condenser, FPPFH (0.981 g, 2.0 mmol) and 2,2-bis(4-hydroxyphenyl)propane (BisA, 0.457 g, 2.0 mmol) were added and dissolved in distilled 1,3-dimethyl-2-imidazolidinone (DMI, 5.0 mL). Then, potassium carbonate (0.332 g, 2.4 mmol) and toluene (20 mL) were added. The temperature was gradually raised to 150 °C and stirred at 150 °C for 2 hours to remove water by azeotropy. Then, it was stirred at 170 °C for 12 hours. After cooling to room temperature, the polymer was recovered with methanol, washed by heating with methanol, and then dried under reduced pressure at room temperature. The polymer was dissolved in chloroform and poured into a large amount of methanol for reprecipitation purification. The polymer was dried under reduced pressure at room temperature for 10 hours. Yield of polymer: 1.15 g (Yield: 80%) Logarithmic viscosity (η inh ): 0.71 dL / g (NMP solution with a concentration of 0.5 g / dL, measured at 30 °C) Number average molecular weight (M n ): 75,000, Molecular weight distribution (Mw / Mn): 2.5 This polymer was dissolved in chloroform and cast on a glass plate, and dried under reduced pressure at room temperature for 6 hours, at 50 °C for 3 hours, and at 85 °C for 3 hours to prepare a colorless transparent cast film (film thickness: 52 μm). FT-IR (film, cm -1 ): 2937 (C-H), 2862 (C-H), 1600 (C=C), 1504 (C=C), 1292 - 1143 (C-F) 11H-NMR (CDCl3, ppm): 7.51 (d, 4H), 7.26 (d, 4H), 7.05 (d, 4H), 6.98 (d, 4H), 1.70 (s, 6H) 13 13C-NMR (CDCl3, ppm): 161.0, 153.5, 146.9, 128.8, 128.5, 123.2, 119.7, 117.7, 42.5, 31.1 19 19F-NMR (CDCl3, ppm): -111.0, -122.6, -123.1 Elemental analysis: Calculated C, 58.41%; H, 3.27% Found C, 57.90%; H, 3.34% Solubility: Soluble in DMF, DMAc, NMP, TMU, DMI, THF, chloroform, ethyl acetate, cyclohexanone, cyclopentanone at room temperature 5% weight loss temperature: 443 °C (in air), 504 °C (in nitrogen) 10% weight loss temperature: 458 °C (in air), 511 °C (in nitrogen) Char yield: 46% (in nitrogen, 800 °C) Glass transition temperature (Tg): 93 °C (DSC), 96 °C (TMA), 93 °C (DMA) Coefficient of thermal expansion (CTE): 94 ppm / °C (50 °C - 80 °C) Tensile breaking strength: 35 MPa Elongation at break: 3.4% Tensile modulus: 1.3 GPa Cut-off wavelength: 290 nm Transmittance at 500 nm: 88%, Average refractive index (n ave ): 1.531 (d line) Birefringence (Δn): 0.001 (d line) Dielectric constant (ε) calculated from refractive index: 2.34 (ε = n ave 2 ) Dielectric constant (Dk): 2.42 (TE mode, 10 GHz), 2.35 (TE mode, 20 GHz) Dissipation factor (Df): 0.0025 (TE mode, 10 GHz), 0.0027 (TE mode, 20 GHz)

[0102] <Comparative Example 2> Synthesis of Fluorine-Containing Polyether (FPPFH-BisAF) To a two-necked flask (50 mL) equipped with a stir bar, a nitrogen inlet tube, a Dean-Stark trap, and a Dimroth condenser, FPPFH (0.981 g, 2.0 mmol) and 2,2-bis(4-hydroxyphenyl)hexafluoropropane (BisAF, 0.673 g, 2.0 mmol) were added and dissolved in distilled 1,3-dimethyl-2-imidazolidinone (DMI, 5.0 mL). Then, potassium carbonate (0.332 g, 2.4 mmol) and toluene (20 mL) were added. The temperature was gradually raised to 150 °C and stirred at 150 °C for 2 hours to remove water by azeotropy. Then, it was stirred at 170 °C for 12 hours. After allowing to cool to room temperature, the polymer was recovered with methanol, washed by heating with methanol, and then dried under reduced pressure at room temperature. The polymer was dissolved in chloroform and poured into a large amount of methanol for reprecipitation purification. The polymer was dried under reduced pressure at room temperature for 10 hours. Yield of polymer: 1.14 g (Yield: 69%) Logarithmic viscosity (η inh ): 0.73 dL / g (measured in a 0.5 g / dL NMP solution at 30 °C) Number-average molecular weight (M n ): 73,000, Molecular weight distribution (Mw / Mn): 2.6 This polymer was dissolved in chloroform and cast onto a glass plate, and dried under reduced pressure at room temperature for 6 hours, at 50 °C for 3 hours, and at 85 °C for 3 hours to prepare a colorless transparent cast film (film thickness 57 μm). FT-IR (film, cm -1 ): 1600 (C=C), 1504 (C=C), 1292 - 1143 (C-F) 1 1H-NMR (CDCl3, ppm): 7.58 (d, 4H), 7.41 (d, 4H), 7.13 (d, 4H), 7.04 (d, 4H) 13 13C-NMR (CDCl3, ppm): 159.6, 156.8, 132.1, 129.1, 129.0, 124.4, 124.3, 119.0 19F-NMR (CDCl3, ppm): -65.4, -111.2, -122.7, -123.3 Elemental analysis: Calculated values: C, 50.40%; H, 2.05% Found values: C, 50.37%; H, 2.18% Solubility: Soluble in DMF, DMAc, NMP, TMU, DMI, THF, chloroform, ethyl acetate, cyclohexanone, cyclopentanone, and acetone at room temperature 5% weight loss temperature: 505 °C (in air), 507 °C (in nitrogen) 10% weight loss temperature: 524 °C (in air), 519 °C (in nitrogen) Char yield: 42% (in nitrogen, 800 °C) Glass transition temperature (Tg): 95 °C (DSC), 105 °C (TMA), 97 °C (DMA) Coefficient of thermal expansion (CTE): 105 ppm / °C (50 °C - 80 °C) Tensile breaking strength: 34 MPa Elongation at break: 3.8% Tensile modulus: 1.2 GPa Cut-off wavelength: 282 nm Transmittance at 500 nm: 89% Average refractive index (n ave ): 1.500 (d line) Birefringence (Δn): 0.004 (d line) Dielectric constant (ε) calculated from refractive index: 2.25 (ε = n ave 2 ) Dielectric constant (Dk): 2.15 (TE mode, 10 GHz), 2.13 (TE mode, 20 GHz) Dissipation factor (Df): 0.0042 (TE mode, 10 GHz), 0.0043 (TE mode, 20 GHz)

Claims

Claim 1 A fluorine-containing polyether compound having a repeating unit represented by formula (1). Formula (1): 【Chemical Formula 10】 (In formula (1), n is an integer of 4 to 8, Ph is a phenylene group, and X1 represents an aromatic heterocyclic ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, or an aliphatic hydrocarbon ring which may have a substituent. One or both of the two phenylene groups represented by Ph and the aromatic heterocyclic ring, aromatic hydrocarbon ring, or aliphatic hydrocarbon ring represented by X １ may be condensed with each other. The phenylene group may have a substituent.) Claim 2 X １ The fluorine-containing polyether compound according to claim 1, wherein X represents at least one selected from the group consisting of rings represented by the following formulae. 【Chemical 11】 (In each formula, the wavy line represents the bonding position with the phenylene group represented by Ph, and the broken line represents the carbon-carbon bond shared with the phenylene group represented by Ph.) Claim 3 The fluorine-containing polyether compound according to claim 1 or 2, wherein the average degree of polymerization of the repeating unit represented by formula (1) is 2 to 300. Claim 4 A low dielectric material containing the fluorine-containing polyether compound according to claim 1 or 2. Claim 5 A semiconductor package substrate, a flexible printed circuit board or a rigid printed circuit board containing the fluorine-containing polyether compound according to claim 1 or 2.

Images