Aromatic polyether, method for producing aromatic polyether, composition, and sheet

Abstract

This aromatic polyether contains structural units represented by formula (1), structural units represented by formula (2) and structures represented by formula (3). The peak intensity ratio of a peak having the maximum intensity among peaks derived from structures represented by formula (3), which appear within the chemical shift range of 7.55-7.65 ppm, relative to the peak intensity of a peak derived from structural units represented by formula (2), which appears at a chemical shift of approximately 7.35 ppm, is 0.20% to 2.00%, in 1H-NMR measurements.

Description

Aromatic polyether, method for producing aromatic polyether, composition and sheet

[0001] The present invention relates to an aromatic polyether, a method for producing the aromatic polyether, a composition, and a sheet. Specifically, the present invention relates to an aromatic polyether having a reduced melting point and excellent processability, a method for producing the aromatic polyether, a composition, and a sheet.

[0002] Aromatic polyethers such as polyether ether ketone (hereinafter, polyether ether ketone may be referred to as "PEEK") are known as representative resins of engineering plastics.

[0003] Regarding PEEK as a 3D printing material, Patent Document 1 discloses capping the ends of PEEK with 4-fluorodiphenyl sulfone.

[0004] Chinese Patent Application Publication No. 113736044

[0005] In general, aromatic polyethers such as PEEK have heat resistance, sliding properties, chemical resistance, and mechanical properties, and are resins that can be used in place of metals even in harsh environments due to their particularly outstanding heat resistance. However, due to the outstanding heat resistance of aromatic polyethers, a high melting temperature is required during molding, making them disadvantageous in applications that do not require outstanding heat resistance. Conventional technologies, including those described in Patent Document 1, have room for further improvement in terms of solving such problems.

[0006] An object of the present invention is to provide an aromatic polyether having a reduced melting point and excellent processability, a method for producing the aromatic polyether, a composition, and a sheet.

[0007] As a result of extensive research, the present inventors have found that aromatic polyethers having a specific structure have a lower melting point and excellent processability, and have thus completed the present invention. According to the present invention, the following aromatic polyethers and the like can be provided: 1. A polyether comprising a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structure represented by the following formula (3): １The aromatic polyether has a peak intensity ratio of 0.20 to 2.00% of the peak intensity of the peaks derived from the structure represented by formula (3) appearing in a chemical shift range of 7.55 ppm to 7.65 ppm in H-NMR measurement relative to the peak intensity of the peak derived from the structural unit represented by formula (2) appearing in a chemical shift range of around 7.35 ppm. 2. The aromatic polyether according to 1, which contains a structural unit represented by the following formula (4): 3. The aromatic polyether according to 1 or 2, wherein the ratio of the peak intensities is 0.20 to 1.80%. 4. The aromatic polyether according to any one of 1 to 3, wherein the melt flow index is 1.0 to 100 g / 10 min. 5. The aromatic polyether according to 1 or 2, wherein the melt flow index is 1.0 to 100 g / 10 min. 6. The aromatic polyether according to 1 or 2, wherein the melt flow index is 1.0 to 100 g / 10 min. 7. The aromatic polyether according to 1 or 2, wherein the melt flow index is 1.0 to 100 g / 10 min. 8. The aromatic polyether according to 1 or 2, wherein the melt flow index is 1.0 to 100 g / 10 min. １ A method for producing an aromatic polyether in which the ratio of the peak intensity of the highest peak among peaks derived from the structure represented by formula (3) appearing in a chemical shift range of 7.55 ppm to 7.65 ppm to the peak intensity of the peak derived from the structural unit represented by formula (2) appearing in a chemical shift range of around 7.35 ppm in H-NMR measurement is 0.20 to 2.00%, the method comprising reacting 4,4'-dihalogenobenzophenone, hydroquinone, and diphenyl sulfone having one reactive group. 6. The method for producing an aromatic polyether according to 5, wherein the molar ratio ([DHBP]:[HQ]) of 4,4'-dihalogenobenzophenone (DHBP) to hydroquinone (HQ) to be reacted is 0.97 to 1.06:1. 7. The method for producing an aromatic polyether according to 5 or 6, wherein the molar ratio ([DHBP]:[HQ]) of 4,4'-dihalogenobenzophenone (DHBP) to hydroquinone (HQ) to be reacted is 0.97 to 1.00:1. 8. The method for producing an aromatic polyether according to any one of 5 to 7, wherein the molar ratio ([DPS]:[HQ]) of the diphenyl sulfone (DPS) having one reactive group to be reacted to hydroquinone (HQ) to be reacted is 0.002 to 0.080:1. 9. The method for producing an aromatic polyether according to any one of 5 to 8, wherein the 4,4'-dihalogenobenzophenone comprises 4,4'-dichlorobenzophenone. 10. The method for producing an aromatic polyether according to any one of 5 to 9, wherein the 4,4'-dihalogenobenzophenone comprises 4,4'-difluorobenzophenone. 11. The method for producing an aromatic polyether according to any one of 5 to 10, wherein the diphenyl sulfone having one reactive group comprises 4-chlorodiphenyl sulfone. 12. The method for producing an aromatic polyether according to any one of 5 to 11, wherein the diphenyl sulfone having one reactive group comprises 4-fluorodiphenyl sulfone. 13. The method for producing an aromatic polyether according to any one of 5 to 12, wherein the aromatic polyether has a melt flow index of 1.0 to 100 g / 10 min. 14. A composition comprising the aromatic polyether according to any one of 1 to 4, and an inorganic compound. 15. A composition comprising an aromatic polyether containing a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structure represented by the following formula (3), wherein the composition １ The composition has a peak intensity ratio of 0.20 to 2.00% of the peak intensity of the peaks derived from the structure represented by formula (3) appearing in a chemical shift range of 7.55 ppm to 7.65 ppm in H-NMR measurement to the peak intensity of the peak derived from the structural unit represented by formula (2) appearing in a chemical shift range of around 7.35 ppm. 16. The composition according to 15, wherein the aromatic polyether contains a structural unit represented by the following formula (4): 17. The composition according to 15 or 16, wherein the peak intensity ratio is 0.20 to 1.80%. 18. The composition according to any one of 15 to 17, wherein the melt flow index of the aromatic polyether is 1.0 to 100 g / 10 min. 19. The composition according to any one of 15 to 18, comprising an inorganic compound. 20. The composition according to 14 or 19, wherein the inorganic compound is one or more selected from the group consisting of glass fiber, carbon fiber, and boron nitride. 21. The composition according to 14, 19, or 20, wherein the inorganic compound is one or more selected from the group consisting of glass fiber and carbon fiber, and in the form of one or more selected from the group consisting of chopped strands, roving, woven fabric, nonwoven fabric, and unidirectional material. 22. The composition according to 14, 19, 20, or 21, wherein the inorganic compound is glass fiber. 23. A sheet comprising a cloth containing an inorganic compound and the aromatic polyether according to any one of 1 to 4 impregnated into the cloth. 24. A sheet comprising a cloth containing an inorganic compound and a composition impregnated into the cloth, wherein the composition contains an aromatic polyether containing a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structure represented by the following formula (3), １ The ratio of the peak intensity of the peak derived from the structural unit represented by formula (2) appearing at a chemical shift of around 7.35 ppm in H-NMR measurement to the peak intensity of the peak with the greatest peak intensity among peaks derived from the structure represented by formula (3) appearing in a chemical shift range of 7.55 ppm to 7.65 ppm is 0.20 to 2.00%. 25. The sheet according to 24, wherein the aromatic polyether contains a structural unit represented by the following formula (4): 26. The sheet according to 24 or 25, wherein the peak intensity ratio is 0.20 to 1.80%. 27. The sheet according to any one of 24 to 26, wherein the aromatic polyether has a melt flow index of 1.0 to 100 g / 10 min. 28. The sheet according to any one of 23 to 27, wherein the cloth is a unidirectional material. 29. The sheet according to any one of 23 to 28, wherein the cloth contains one or more fibers selected from the group consisting of glass fiber and carbon fiber.

[0008] According to the present invention, it is possible to provide an aromatic polyether having a reduced melting point and excellent processability, a method for producing the aromatic polyether, a composition, and a sheet.

[0009] The aromatic polyether, method for producing the aromatic polyether, composition, and sheet of the present invention are described in detail below. In this specification, "x to y" represents a numerical range of "x or more and y or less." The upper and lower limits of the numerical ranges can be combined arbitrarily. Furthermore, among the individual embodiments of the aspects of the present invention described below, two or more embodiments that are not mutually exclusive can be combined, and an embodiment combining two or more embodiments is also an embodiment of the aspects of the present invention.

[0010] 1. Aromatic Polyether An aromatic polyether according to one embodiment of the present invention includes a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structure represented by the following formula (3): １ The ratio of the peak intensity of the peak derived from the structural unit represented by formula (2) appearing at a chemical shift of around 7.35 ppm in H-NMR measurement to the peak intensity of the peak with the greatest peak intensity among the peaks derived from the structure represented by formula (3) appearing in a chemical shift range of 7.55 ppm to 7.65 ppm (hereinafter, sometimes simply referred to as "intensity ratio X") is 0.20 to 2.00%.

[0011] The aromatic polyether according to this embodiment has a lowered melting point and excellent processability. In other words, aromatic polyethers such as PEEK generally have heat resistance, sliding properties, chemical resistance, and mechanical properties, and due to their particularly outstanding heat resistance, they are resins that can be used in place of metals even in harsh environments. However, due to the outstanding heat resistance of aromatic polyethers, the melting temperature must be high during molding, which makes them disadvantageous in applications that do not require outstanding heat resistance. In contrast, the aromatic polyether according to this embodiment has a lowered melting point, so the melting temperature during molding can be set low, resulting in excellent processability.

[0012] Furthermore, the aromatic polyether according to this embodiment can exhibit excellent mechanical strength by blending an inorganic compound. Although the reason for this effect is not entirely clear, it is presumed that the structure represented by formula (3) possessed by the aromatic polyether makes the interface between the aromatic polyether and the inorganic compound in a state suitable for exhibiting excellent mechanical strength. The mechanical strength referred to here may be, for example, tensile strength.

[0013] As described above, the aromatic polyether according to this embodiment has an intensity ratio X of 0.20 to 2.00%. １ This value was determined by H-NMR measurement.

[0014] In one embodiment, the aromatic polyether according to this aspect consists of one kind of aromatic polyether having the same intensity ratio X.

[0015] In one embodiment, the aromatic polyether according to this aspect is a mixture of two or more aromatic polyethers having different intensity ratios X. In this case, １ In H-NMR measurement, the intensity ratio X is 0.20 to 2.00%. Here, the two or more aromatic polyethers may or may not include an aromatic polyether having an intensity ratio X of 0%.

[0016] In one embodiment, the intensity ratio X is 0.20% or more, 0.30% or more, 0.50% or more, or 0.70% or more, and 2.00% or less, 1.80% or less, 1.60% or less, or 1.00% or less. The intensity ratio X may be, for example, 0.20 to 1.80%, 0.30 to 1.60%, 0.50 to 1.00%, or 0.70 to 1.00%. This allows the effects of the present invention to be exhibited favorably. In particular, when the intensity ratio X is 0.20% or more, the melting point of the aromatic polyether can be further lowered. Furthermore, when the intensity ratio X is 2.00% or less, the melt flow index of the aromatic polyether can be set within an appropriate range for exhibiting better processability.

[0017] In an aromatic polyether according to one embodiment, a structural unit represented by formula (1) is disposed at one or more ends of the main chain. In this case, the terminal structure bonded to the structural unit may be a halogen atom. The halogen atom may be, for example, a chlorine atom (Cl) or a fluorine atom (F). In an aromatic polyether according to one embodiment, a structure represented by formula (3) is bonded to a structural unit represented by formula (2) and disposed at one or more ends of the main chain. In addition, when a structure represented by formula (3) is not bonded to the structural unit represented by formula (2) disposed at the end of the main chain, the terminal structure bonded to the structural unit represented by formula (2) may be, for example, a hydrogen atom (H) or the like (when the terminal structure is a hydrogen atom (H), a hydroxyl group is formed together with the oxygen atom (O) in the structural unit). The terminal structure of the aromatic polyether may be, for example, a structure in which the above-mentioned chlorine atom (Cl) or hydroxyl group is replaced with a hydrogen atom (H). In addition, the terminal structure may have a structure other than those exemplified above.

[0018] In one embodiment, the aromatic polyether comprises a structural unit represented by the following formula (4):

[0019] The structural unit represented by formula (4) is a bond between the structural unit represented by formula (1) and the structural unit represented by formula (2).

[0020] In one embodiment, the aromatic polyether does not contain any other structure other than the structural units represented by formula (1) and formula (2) and the structure represented by formula (3).

[0021] In one embodiment, the aromatic polyether contains a structure other than the structural units represented by formula (1) and formula (2) and the structure represented by formula (3), within a range that does not impair the effects of the present invention.

[0022] In one embodiment, based on all the monomers supplied to the reaction, the total proportion (mass%) of the structural unit represented by formula (1), the structural unit represented by formula (2), and the structural unit represented by formula (3) contained in all the monomers is 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, 99 mass% or more, 99.5 mass% or more, or 100 mass%.

[0023] In one embodiment, in the aromatic polyether, the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) (structural unit represented by formula (1) : structural unit represented by formula (2)) is 47.5:52.5 to 52.5:47.5, 48.0:52.0 to 52.0:48.0, 48.5:51.5 to 51.5:48.5, 49.0:51.0 to 51.0:49.0, or 49.5:50.5 to 50.5:49.5. The number of moles of the structural unit represented by formula (1) may be greater than, smaller than, or the same as the number of moles of the structural unit represented by formula (2).

[0024] In one embodiment, the melting point T ｍ The upper limit of the melting point T of the aromatic polyether is, for example, 341° C. or less, 340° C. or less, 339° C. or less, 338° C. or less, or 335° C. or less, and the lower limit of the melting point T of the aromatic polyether is, for example, 320° C. or more, 325° C. or more, or 330° C. or more. ｍ is 320 to 341°C, 325 to 340°C, 330 to 338°C, or 330 to 335°C. ｍ is measured by the method described in the Examples.

[0025] In one embodiment, the melt flow index (abbreviated "MI", which is synonymous with the melt flow rate (abbreviated "MFR") described in ASTM D 1238-13) of the aromatic polyether is 1500 g / 10 min or less, 1000 g / 10 min or less, 500 g / 10 min or less, 300 g / 10 min or less, 200 g / 10 min or less, 100 g / 10 min or less, 80 g / 10 min or less, 60 g / 10 min or less, or 50 g / 10 min or less, and is 0.0001 g / 10 min or more, 0.0005 g / 10 min or more, 0.001 g / 10 min or more, 0.5 g / 10 min or more, 1.0 g / 10 min or more, or 10 g / 10 min or more. The melt flow index of the aromatic polyether is, for example, 0.0001 to 1500 g / 10 min, preferably 0.0005 to 500 g / 10 min, more preferably 0.001 to 100 g / 10 min, and even more preferably 0.5 to 100 g / 10 min, 1.0 to 100 g / 10 min, 10 to 80 g / 10 min, or 10 to 50 g / 10 min.

[0026] The melt flow index of the aromatic polyether is preferably 100 g / 10 min or less. Aromatic polyethers with a melt flow index of 100 g / 10 min or less have a sufficiently high molecular weight, and can be preferably pelletized using an extruder, for example. Furthermore, even aromatic polyethers with such a high molecular weight can have a low melting point by satisfying the above-mentioned intensity ratio X, allowing them to be molded at low temperatures and exhibiting excellent processability. Furthermore, a melt flow index of 1.0 g / 10 min or more increases the fluidity of the aromatic polyether when molten, improving its suitability for injection molding. From these perspectives, the melt flow index of the aromatic polyether is particularly preferably 1.0 to 100 g / 10 min. The melt flow index of the aromatic polyether is a value measured by the method described in the Examples. The melt flow index of the aromatic polyether can be adjusted by the temperature conditions of the reaction mixture (maximum temperature, temperature retention time, heating rate, etc.) and the ratio of raw materials (monomers, etc.) in the reaction mixture.

[0027] The aromatic polyether according to this embodiment can be used to produce, for example, pellets containing the aromatic polyether. These pellets can be used as various molding materials requiring heat resistance, solvent resistance, insulation, etc. These pellets can be used to produce molded articles by molding methods such as injection molding using a mold. These pellets can also be used to produce molded articles by molding methods such as extrusion molding, press molding, sheet molding, and film molding. The uses of the aromatic polyether according to this embodiment are not particularly limited. The aromatic polyether is suitable, for example, for aerospace applications, sliding members such as gears and bearings, and various resin compositions. Molded articles containing the aromatic polyether according to this embodiment are suitable, for example, for aerospace molded articles, sliding member molded articles, and 3D printer filaments. Molded articles containing the aromatic polyether are also suitable, for example, for aerospace injection molded articles and sliding member injection molded articles.

[0028] The method for producing the aromatic polyether according to one embodiment of the present invention described above is not particularly limited, and for example, the aromatic polyether can be produced by the method for producing an aromatic polyether according to one embodiment of the present invention described below.

[0029] 2. Method for Producing Aromatic Polyether A method for producing an aromatic polyether according to one aspect of the present invention is a method for producing the aromatic polyether according to the above-described aspect of the present invention, and includes reacting 4,4′-dihalogenobenzophenone, hydroquinone, and diphenyl sulfone having one reactive group.

[0030] 4,4'-Dihalogenobenzophenone, hydroquinone, and diphenyl sulfone having one reactive group are monomers for polymerizing aromatic polyethers. In particular, diphenyl sulfone having one reactive group forms a structure represented by formula (3) at one or more ends of the main chain of the aromatic polyether. Through a process of reacting 4,4'-dihalogenobenzophenone, hydroquinone, and diphenyl sulfone having one reactive group, an aromatic polyether can be obtained as a copolymer of these compounds (monomer units). 4,4'-Dihalogenobenzophenone, hydroquinone, and diphenyl sulfone having one reactive group are commercially available.

[0031] The 4,4'-dihalogenobenzophenone is not particularly limited, and the two halogen atoms may be the same or different. The two halogen atoms may each independently be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Specific examples of 4,4'-dihalogenobenzophenone include 4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone. One type of 4,4'-dihalogenobenzophenone may be used alone, or two or more types may be used in combination.

[0032] The diphenyl sulfone having one reactive group is not particularly limited. Examples of diphenyl sulfones having one reactive group include those in which one hydrogen atom on one of the two benzene rings in diphenyl sulfone is substituted with one reactive group. The reactive group is not particularly limited, and examples include a halogen atom, a hydroxyl group, and the like. The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Specific examples of diphenyl sulfones having one reactive group include 4-halogenobenzophenones such as 4-fluorodiphenyl sulfone and 4-chlorodiphenyl sulfone; and 4-hydroxydiphenyl sulfone, with 4-chlorodiphenyl sulfone being preferred. The diphenyl sulfones having one reactive group may be used alone or in combination of two or more.

[0033] In the following description, the term "reaction mixture" refers to a reaction system from the start of the reaction of 4,4'-dihalogenobenzophenone, hydroquinone, and diphenyl sulfone having one reactive group to the completion of the reaction, and is preferably in the form of a solution containing these monomers as well as a solvent described below. The composition of the reaction mixture may change as the reaction progresses. Typically, as the reaction progresses, the concentrations of the reactants (4,4'-dihalogenobenzophenone, hydroquinone, and diphenyl sulfone having one reactive group) in the reaction mixture decrease, while the concentration of the product (aromatic polyether) increases.

[0034] The "maximum temperature" of the reaction mixture refers to the maximum temperature (maximum temperature reached) that the reaction mixture reaches during the process from the start of the reaction of 4,4'-dihalogenobenzophenone, hydroquinone, and diphenyl sulfone having one reactive group to the completion of the reaction. The maximum temperature of the reaction mixture is not particularly limited, and is, for example, 260 to 360°C, preferably higher than 290°C and not higher than 360°C, more preferably 295 to 360°C, and even more preferably 295 to 340°C.

[0035] In one embodiment, the method for producing an aromatic polyether according to this aspect includes holding the reaction mixture at 180 to 220°C for 0.5 to 2 hours, preferably 0.6 to 1.8 hours, and more preferably 0.7 to 1.5 hours (hereinafter also referred to as "temperature holding (i)"). This allows the reaction to be promoted while suppressing volatilization of the raw materials, and enables the production of an aromatic polyether with a higher molecular weight. In one embodiment, the method for producing an aromatic polyether according to this aspect includes holding the reaction mixture at 230 to 270°C for 0.5 to 2 hours, preferably 0.6 to 1.8 hours, and more preferably 0.7 to 1.5 hours (hereinafter also referred to as "temperature holding (ii)"). This allows the reaction to be promoted while suppressing volatilization of the raw materials, and enables the production of an aromatic polyether with a higher molecular weight.

[0036] In one embodiment, the method for producing an aromatic polyether according to this aspect includes holding a reaction mixture at 280 to 360°C for 0.5 to 8 hours, preferably 0.7 hours or more, 1 hour or more, 2 hours or more, 3 hours or more, 4 hours or more, 5 hours or more, 8 hours or less, or 6 hours or less, for example, 0.5 hours or more and 3 hours or less (the upper and lower limits can be arbitrarily combined) (hereinafter also referred to as "temperature holding (iii)"). This allows an aromatic polyether having a desired molecular weight to be obtained.

[0037] In one embodiment, the method for producing an aromatic polyether according to this aspect can include two or three temperature holds selected from the group consisting of the above temperature holds (i) to (iii). The two or three temperature holds are preferably performed in order from lowest to highest temperature. Between the two or three temperature holds, the reaction mixture can be heated.

[0038] The temperature increase rate when increasing the temperature of the reaction mixture is not particularly limited and may be, for example, 0.1 to 15°C / min, 0.1 to 10°C / min, 0.1 to 8°C / min, or 0.1 to 5°C / min. This makes it possible to promote the reaction while suppressing volatilization of the raw materials, and to obtain an aromatic polyether with a higher molecular weight.

[0039] In one embodiment, in the method for producing an aromatic polyether according to this aspect, the time from when the temperature of the reaction mixture reaches 150° C. to when it reaches the maximum temperature is 2.0 to 10 hours.

[0040] In one embodiment, the reaction mixture includes a solvent. The reaction mixture including the solvent may be in the form of a solution. The solution may include 4,4'-dihalogenobenzophenone, hydroquinone, and a diphenyl sulfone having one reactive group dissolved in the solvent. The solvent is not particularly limited, and for example, an aprotic polar solvent may be used. Examples of aprotic polar solvents include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-n-propyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, and N-methyl-3-methyl-2-pyrrolidone. , N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5-trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, N-isopropyl-2-piperidone, N-methyl-6-methyl-2-piperidone, N-methyl-3-ethylpiperidone, dimethyl sulfoxide, diethyl sulfoxide, 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, N,N'-dimethylimidazolidinone, diphenyl sulfone, etc. Among these, diphenyl sulfone is particularly preferred.

[0041] In one embodiment, the reaction mixture contains an aromatic sulfone such as diphenyl sulfone, and the content of the solvent having a boiling point of 270 to 330° C. is 0 part by mass or more and less than 1 part by mass per 100 parts by mass of the aromatic sulfone, which makes it easier to control the reaction temperature.

[0042] The reaction mixture may contain one or more solvents, and it is particularly preferred that the reaction mixture contains only one solvent (single solvent), which simplifies the process.

[0043] In one embodiment, the reaction mixture contains a base. The reaction is promoted by including a base in the reaction mixture. The base is not particularly limited, and for example, an alkali metal salt is preferred. The alkali metal salt is not particularly limited, and for example, an alkali metal carbonate, an alkali metal bicarbonate, an alkali metal hydride salt, an alkali metal hydroxide, and the like are included. Examples of the alkali metal carbonate include potassium carbonate, sodium carbonate, lithium carbonate, rubidium carbonate, and cesium carbonate. Examples of the alkali metal bicarbonate include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, and cesium bicarbonate. Among these, potassium carbonate is particularly preferred. These bases may be used alone or in combination of two or more.

[0044] In one embodiment, the reaction mixture includes potassium carbonate. In one embodiment, the reaction mixture includes a base other than potassium carbonate. These bases may be used in combination with potassium carbonate. For example, potassium carbonate may be used in combination with sodium carbonate.

[0045] The total concentration of the base in the reaction mixture is not particularly limited. In one embodiment, the total amount of base in the reaction mixture is 100 mol parts or more, and 180 mol parts or less, 160 mol parts or less, 140 mol parts or less, or 120 mol parts or less, relative to 100 mol parts of hydroquinone in the reaction mixture. When the total amount of base in the reaction mixture is 100 mol parts or more, the reaction time can be shortened. When the total amount of base in the reaction mixture is 180 mol parts or less, the formation of a gel component can be suppressed. Furthermore, the total amount of base in the reaction mixture is, for example, 100 to 180 mol parts, preferably 100 to 140 mol parts, and more preferably 100 to 120 mol parts, relative to 100 mol parts of hydroquinone in the reaction mixture. In one embodiment, potassium carbonate is blended as the base in the above-mentioned amount.

[0046] The molar ratio ([DHBP]:[HQ]) of 4,4'-dihalogenobenzophenone (DHBP) to hydroquinone (HQ) used in the reaction is not particularly limited. The molar ratio ([DHBP]:[HQ]) can be adjusted appropriately for purposes such as controlling the molecular weight of the resulting aromatic polyether. In one embodiment, the molar ratio ([DHBP]:[HQ]) is 0.970 to 1.006:1, 0.970 to 1.00:1, 0.980 to 0.999:1, or 0.985 to 0.998:1. The number of moles of 4,4'-dihalogenobenzophenone (DHBP) is preferably the same as or smaller than the number of moles of hydroquinone (HQ). This allows the structure represented by formula (3) to be efficiently introduced into one or more ends of the main chain of the aromatic polyether, and the intensity ratio X described above can be suitably satisfied in the obtained aromatic polyether.

[0047] The molar ratio ([DPS]:[HQ]) of diphenyl sulfone (DPS) having one reactive group to be reacted and hydroquinone (HQ) to be reacted is not particularly limited and is, for example, 0.002 to 0.080:1.

[0048] In one embodiment, the total concentration (based on the amount of addition) of 4,4'-dihalogenobenzophenone, hydroquinone, and diphenyl sulfone having one reactive group in the reaction mixture is not particularly limited and is, for example, 1.0 mol / L or more, 1.2 mol / L or more, 1.3 mol / L or more, 1.4 mol / L or more, or 1.5 mol / L or more, and 6.0 mol / L or less, 5.0 mol / L or less, or 4.0 mol / L or less. The total concentration (based on the amount of addition) of 4,4'-dihalogenobenzophenone, hydroquinone, and diphenyl sulfone having one reactive group in the reaction mixture is, for example, 1.0 to 6.0 mol / L, preferably 1.3 to 5.0 mol / L, and more preferably 1.5 to 4.0 mol / L.

[0049] In one embodiment, the monomers used in the above reaction are 4,4'-dihalogenobenzophenone, hydroquinone, and diphenyl sulfone having one reactive group, and no other monomers are used.

[0050] In one embodiment, in the above reaction, a monomer other than 4,4'-dihalogenobenzophenone, hydroquinone, and diphenyl sulfone having one reactive group is used in combination within a range that does not impair the effects of the present invention.

[0051] In one embodiment, based on all monomers to be reacted, the total proportion (mass%) of 4,4'-dihalogenobenzophenone, hydroquinone, and diphenyl sulfone having one reactive group is 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, 99 mass% or more, 99.5 mass% or more, or 100 mass%.

[0052] In one embodiment, at the start of the reaction, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.9% by mass or more, or substantially 100% by mass of the reaction mixture is 4,4'-dihalogenobenzophenone, hydroquinone, diphenyl sulfone having one reactive group, alkali metal salt, and solvent, or 4,4'-dihalogenobenzophenone, hydroquinone, diphenyl sulfone having one reactive group, potassium carbonate, and sodium carbonate, and one or more alkali metal salts selected from the group consisting of potassium carbonate and sodium carbonate, and diphenyl sulfone, or 4,4'-dihalogenobenzophenone, hydroquinone, diphenyl sulfone having one reactive group, potassium carbonate, and diphenyl sulfone. Note that "substantially 100% by mass" may contain inevitable impurities.

[0053] The reaction of 4,4'-dihalogenobenzophenone, hydroquinone, and diphenyl sulfone having one reactive group can be carried out in an inert gas atmosphere, which is not particularly limited and includes, for example, nitrogen and argon gas.

[0054] 3. Composition A composition according to one aspect of the present invention (hereinafter also referred to as the "composition according to the first aspect") contains the aromatic polyether according to the first aspect of the present invention described above and an inorganic compound. The composition according to this aspect exhibits excellent mechanical strength.

[0055] In one embodiment, the inorganic compound is one or more selected from the group consisting of glass fiber, carbon fiber, and boron nitride. This further improves the strength of the composition. In one embodiment, the inorganic compound is one or more selected from the group consisting of glass fiber and carbon fiber, and is in the form of one or more selected from the group consisting of chopped strands, roving, woven fabric, nonwoven fabric, and unidirectional material (also referred to as "UD material"). This further improves the strength of the composition. In one embodiment, the inorganic compound is glass fiber.

[0056] In one embodiment, the composition may be a fiber composite material containing an aromatic polyether as a matrix and a fibrous inorganic compound such as glass fiber, carbon fiber, etc. The fiber composite material may be a so-called fiber reinforced thermoplastic (FRTP).

[0057] The fibrous inorganic compound may be one that has been treated with a sizing agent. The sizing agent can bind the fibrous inorganic compound into bundles. The fibrous inorganic compound that has been treated with a sizing agent has the sizing agent adhered to its surface. The sizing agent is not particularly limited, and examples thereof include epoxy-based sizing agents, urethane-based sizing agents, and polyamide-based sizing agents. Furthermore, an aromatic polyether according to one embodiment of the present invention can also be used as the sizing agent. As the sizing agent, one of these may be used alone, or two or more may be used in combination. As the sizing agent, one that has not been treated with a sizing agent may also be used.

[0058] In one embodiment, the inorganic compound is an inorganic compound that has a toughening effect on the aromatic polyether.

[0059] The content of the inorganic compound in the composition is not particularly limited. In one embodiment, the content of the inorganic compound in the composition is, for example, 5 parts by mass or more, 10 parts by mass or more, or 20 parts by mass or more, and 60 parts by mass or less, 55 parts by mass or less, or 50 parts by mass or less, relative to 100 parts by mass of the aromatic polyether. The upper and lower limits can be combined arbitrarily.

[0060] The composition may contain other components in addition to the aromatic polyether and the inorganic compound. The other components are not particularly limited, and examples thereof include other resins other than aromatic polyethers. Examples of the other resins include fluororesins such as polytetrafluoroethylene. One type of the other components may be used alone, or two or more types may be used in combination.

[0061] In one embodiment, the composition comprises at least 50 mass%, at least 60 mass%, at least 70 mass%, at least 80 mass%, at least 90 mass%, at least 95 mass%, at least 97 mass%, at least 99 mass%, at least 99.5 mass%, or substantially 100 mass% of the composition. The composition comprises: an aromatic polyether; an aromatic polyether and an inorganic compound; an aromatic polyether and the other components described above; or an aromatic polyether, an inorganic compound, and the other components described above. Note that "substantially 100 mass%" may contain inevitable impurities.

[0062] The method for preparing the composition is not particularly limited, and examples thereof include mixing using a known mixer, melt kneading using an extruder, etc. A twin-screw kneader may be used to side-feed the inorganic compound into the aromatic polyether.

[0063] Pellets of the composition may be produced. The pellets can be used as a raw material for producing a molded body. In one embodiment, the method for producing pellets includes cutting a fibrous inorganic compound into short pieces to form chopped strands, and then adding an aromatic polyether to the short fibers. The short fibers and the aromatic polyether are mixed and granulated to produce pellets (also referred to as "short fiber pellets"). In one embodiment, the method for producing pellets includes immersing a roving of the fibrous inorganic compound in molten aromatic polyether, pultrusion molding the mixture, and then cutting the roving into a desired pellet length to produce pellets (also referred to as "long fiber pellets"). When long fiber pellets are produced as described above, breakage of the fibrous inorganic compound can be suppressed.

[0064] A molded article can be produced by molding the composition (which may be in the form of pellets as described above). Known methods such as injection molding, extrusion molding, and blow molding can be used for molding. The composition can also be press-molded, and known methods such as cold pressing and hot pressing can be used. Furthermore, the composition can be used as a resin composition for 3D printers and molded using a 3D printer.

[0065] A composition according to another aspect of the present invention (hereinafter also referred to as "composition according to a second aspect") is a composition containing an aromatic polyether containing a structural unit represented by formula (1), a structural unit represented by formula (2), and a structure represented by formula (3), １ In H-NMR measurement, the ratio of the peak intensity of the peak derived from the structural unit represented by formula (2) appearing at a chemical shift of around 7.35 ppm to the peak intensity of the peak with the greatest peak intensity among the peaks derived from the structure represented by formula (3) appearing in a chemical shift range of 7.55 ppm to 7.65 ppm (hereinafter, sometimes simply referred to as the "intensity ratio Y") is 0.20 to 2.00%. The composition according to this embodiment has a lowered melting point and exhibits excellent processability. Furthermore, the composition according to this embodiment can exhibit excellent mechanical strength by incorporating an inorganic compound.

[0066] For the aromatic polyether contained in the composition, the description given for the aromatic polyether according to one embodiment of the present invention is applicable.

[0067] As described above, the composition according to this embodiment has an intensity ratio Y of 0.20 to 2.00%. The intensity ratio Y is the same as the intensity ratio X except that the composition is used as the measurement object instead of the aromatic polyether. １ In the H-NMR measurement, the intensity ratio Y can be determined by measuring the composition instead of the aromatic polyether. The explanation given for the intensity ratio X is applicable to the intensity ratio Y.

[0068] In one embodiment, the intensity ratio Y is 0.20% or more, 0.30% or more, 0.50% or more, or 0.70% or more, and 2.00% or less, 1.80% or less, 1.60% or less, or 1.00% or less. The intensity ratio Y may be, for example, 0.20 to 1.80%, 0.30 to 1.60%, 0.50 to 1.00%, or 0.70 to 1.00%. This allows the effects of the present invention to be exhibited effectively. In particular, when the intensity ratio Y is 0.20% or more, the melting point of the aromatic polyether in the composition can be further lowered. Furthermore, when the intensity ratio Y is 2.00% or less, the melt flow index of the aromatic polyether in the composition can be set within an appropriate range for exhibiting better processability.

[0069] In one embodiment, the composition includes an inorganic compound. For the inorganic compound that can be included in the composition, the description of the inorganic compound included in the composition according to the first aspect above is incorporated herein by reference.

[0070] For the composition of this embodiment, the explanation given for the composition according to the first embodiment is applicable, except that instead of the aromatic polyether satisfying the intensity ratio X, the composition satisfies the intensity ratio Y.

[0071] 4. Sheet A sheet according to one aspect of the present invention (hereinafter also referred to as the "sheet according to the first aspect") comprises a cloth containing an inorganic compound and the aromatic polyether according to one aspect of the present invention impregnated into the cloth. The sheet according to this aspect exhibits excellent mechanical strength, similar to when an aromatic polyether is impregnated with an inorganic compound.

[0072] The cloth is not particularly limited as long as it contains fibers of an inorganic compound. In one embodiment, the cloth is made of fibers arranged in a plane. The cloth may be, for example, a woven fabric, a nonwoven fabric, or a unidirectional material. The unidirectional material is made of fibers aligned in one direction.

[0073] The fibers contained in the cloth are not particularly limited. The cloth preferably contains one or more fibers selected from the group consisting of glass fibers and carbon fibers. In one embodiment, the cloth contains glass fibers. In one embodiment, the sheet may be a fiber composite material containing an aromatic polyether as a matrix and a fibrous inorganic compound such as glass fibers or carbon fibers. Such a fiber composite material may be a so-called fiber-reinforced thermoplastic (FRTP). For example, a unidirectional fiber-reinforced plastic can be obtained by using a unidirectional material as the cloth.

[0074] In one embodiment of the sheet, the aromatic polyether is impregnated between the fibers contained in the cloth. The cloth may be a single sheet or a laminate of two or more sheets. When the cloth is a laminate, the aromatic polyether may also contribute to the bonding between the sheets of cloth.

[0075] The sheet may contain other components in addition to the aromatic polyether and the cloth, and as the other components, those described in the composition can be used.

[0076] In one embodiment, the sheet comprises at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 97%, at least 99%, at least 99.5%, or at least 100% by weight of the aromatic polyether and crosslinked copolymer, or at least 100% by weight of the aromatic polyether, crosslinked copolymer, and the other components described above. Note that "substantially 100% by weight" may include unavoidable impurities.

[0077] The method for manufacturing the above-described sheet is not particularly limited. In one embodiment, the method for manufacturing the sheet includes immersing a cloth in an aromatic polyether. In this case, for example, a solution obtained by dissolving an aromatic polyether in a suitable solvent, a mixture obtained by mixing an aromatic polyether in a suitable vehicle, or a melt of an aromatic polyether can be applied to carbon fibers and then the fibers are immersed. In one embodiment, the method for manufacturing the sheet includes preparing a cloth from fibers bound with a sizing agent containing an aromatic polyether. In one embodiment, the method for manufacturing the sheet includes laminating a film containing an aromatic polyether onto the cloth and melt-pressing the resulting film. In one embodiment, the method for manufacturing the sheet includes adding an aromatic polyether powder directly to the cloth and then melting the powder.

[0078] In the above description of the sheet manufacturing method, the cloth impregnated with the aromatic polyether may be the above-mentioned laminate.

[0079] In one embodiment, the sheet is planar over its entire surface. In one embodiment, the sheet is given a three-dimensional shape. The "three-dimensional" shape of the sheet means that the sheet includes curved portions (including bent portions). The method for producing a three-dimensionally shaped sheet is not particularly limited. In one embodiment, the method for producing a three-dimensionally shaped sheet includes impregnating a cloth having a three-dimensional shape with an aromatic polyether. In one embodiment, the method for producing a three-dimensionally shaped sheet includes impregnating a cloth with an aromatic polyether to obtain a sheet (e.g., a flat sheet), and then molding the sheet to give it a three-dimensional shape. The molding can be performed, for example, by applying pressure to the sheet under heating.

[0080] In the above description of the sheet, the aromatic polyether may be impregnated into the cloth as the composition according to one aspect of the present invention. In this case, the composition may or may not contain an inorganic compound.

[0081] A sheet according to another embodiment of the present invention (hereinafter also referred to as a "sheet according to a second embodiment") is a sheet comprising a cloth containing an inorganic compound and a composition impregnated into the cloth, wherein the composition comprises an aromatic polyether comprising a structural unit represented by formula (1), a structural unit represented by formula (2), and a structure represented by formula (3), and the composition １ In H-NMR measurement, the ratio of the peak intensity of the peak derived from the structural unit represented by formula (2) appearing at a chemical shift of around 7.35 ppm to the peak intensity of the peak with the highest intensity among the peaks derived from the structure represented by formula (3) appearing in a chemical shift range of 7.55 ppm to 7.65 ppm is 0.20 to 2.00%. The sheet according to this embodiment exhibits excellent mechanical strength, similar to when an inorganic compound is contained in an aromatic polyether.

[0082] The composition contained in the sheet is described in the description of the composition according to the second aspect of the present invention, and the cloth contained in the sheet is described in the description of the sheet according to the first aspect of the present invention.

[0083] For the sheet of this embodiment, the explanation given for the sheet according to the first embodiment is applicable, except that instead of the aromatic polyether satisfying the intensity ratio X, the composition satisfies the intensity ratio Y.

[0084] Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0085] Example 1 34.9333 g (0.160 mol) of 4,4′-difluorobenzophenone, 17.6938 g (0.161 mol) of hydroquinone, 0.8112 g (0.00321 mol) of 4-chlorodiphenyl sulfone, 25.4395 g (0.184 mol) of potassium carbonate, and 139.04 g of diphenyl sulfone were placed in a 300 ml four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a water collection container connected to a condenser, and nitrogen gas was passed through the flask.

[0086] The reaction mixture was reacted under the following temperature control: <Temperature control> (1) The temperature was raised to 150°C, and then raised to 200°C over 30 minutes. (2) The temperature was maintained at 200°C for 1 hour. (3) The temperature was raised from 200°C to 250°C (heating rate: 1.7°C / min). (4) The temperature was maintained at 250°C for 1 hour. (5) The temperature was raised from 250°C to 340°C (maximum temperature of the reaction mixture) (heating rate: 3.0°C / min). (6) The temperature was maintained at 340°C (maximum temperature of the reaction mixture) for 1 hour.

[0087] After the reaction was completed, the product was pulverized in a blender (7010HS manufactured by Waring), washed with acetone and then with water, and then dried in a dryer at 180°C to obtain a powdery aromatic polyether (PEEK).

[0088] The obtained aromatic polyether was subjected to the following measurements (1) to (5).

[0089] (1) Melt Flow Index (MI) The melt flow index of the aromatic polyether was measured using a melt indexer (L-220) manufactured by Tateyama Kagaku High-Technologies Co., Ltd. in accordance with JIS K 7210-1:2014 (ISO 1133-1:2011) under the following measurement conditions. [Measurement Conditions] Measurement temperature (resin temperature): 380°C Measurement load: 2.16 kg Cylinder inner diameter: 9.550 mm Die inner diameter: 2.095 mm Die length: 8.000 mm Piston head length: 6.35 mm Piston head diameter: 9.474 mm Piston weight: 110.0 g (the above measurement load includes the piston weight) Procedure: The sample is dried in advance at 150°C for at least 2 hours. The sample is placed in the cylinder, the piston is inserted, and the mixture is preheated for 6 minutes. A load is applied, the piston guide is removed, and the molten sample is extruded from the die. A sample is cut out at a predetermined range of piston movement and a predetermined time (t [s]) and its weight is measured (m [g]). MI is calculated using the following formula: MI [g / 10 min] = 600 / t × m

[0090] (2) １ H-NMR measurement (intensity ratio X) Aromatic polyether １ H-NMR measurement was performed, and the peak intensity (I２ ) with respect to the peak intensity (I ３ The ratio (intensity ratio X) of the intensity ratios was calculated using the following formula: Intensity ratio X [%] = (I ３ / I ２ ) × 100 Note that the "peak originating from the structure represented by formula (2) appearing at a chemical shift of around 7.35 ppm" specifically originates from the four hydrogen atoms on the benzene ring in the structure represented by formula (2). This peak may appear at a chemical shift of around 7.35 ppm, for example, in the chemical shift range of 7.32 to 7.40 ppm. Furthermore, the "peak with the highest peak intensity among the peaks originating from the structure represented by formula (3) appearing at a chemical shift range of 7.55 ppm to 7.65 ppm" specifically originates from the two hydrogen atoms bonded to the carbon atoms marked with dots in formula (3') below.

[0091] As mentioned above １ The measurement conditions for H-NMR measurement are as follows. <Measurement conditions for 1H-NMR measurement> NMR apparatus: "Ascend 500" manufactured by Bruker Japan Co., Ltd. Probe: 5 mm diameter TCI cryoprobe NMR sample tube diameter: 5 mm diameter Sample solution preparation: 0.6 ml of methanesulfonic acid was added to approximately 20 mg of sample and stirred at room temperature for 1 hour, after which 0.4 ml of deuterated dichloromethane was added and stirred at room temperature for an additional 30 minutes to dissolve the sample, thereby obtaining a sample solution. Observation range: 20 ppm Observation center: 6.175 ppm Number of data points: 64 kB Pulse repetition time: 10 seconds Number of accumulations: 256 times Flip angle: 30° Measurement temperature: 25°C Chemical shift reference: The central peak of the three peaks of deuterated dichloromethane was set to 5.32 ppm.

[0092] The aromatic polyether contains the structure represented by formula (3) １ This can be confirmed by a combination of H-NMR measurement, two-dimensional NMR measurement, mass spectrometry, and the like.

[0093] (3) Melting point T ｍ5 mg of aromatic polyether (sample) was weighed into an aluminum pan and subjected to temperature scanning measurement using a differential scanning calorimeter (PerkinElmer "DSC8500"). The temperature scanning was performed in the following order: with nitrogen flowing at 20 ml / min, the sample temperature was raised from 50°C to 420°C at 20°C / min (first temperature rise), held at 420°C for 1 minute, lowered from 420°C to 50°C at 20°C / min (first temperature drop), held at 50°C for 1 minute, and raised from 50°C to 420°C at 20°C / min (second temperature rise). Melting point T ｍ The endothermic peak due to melting observed during the second temperature rise was read and calculated as the peak top temperature.

[0094] The results are shown in Table 1.

[0095] Example 2 An aromatic polyether (PEEK) was obtained in the same manner as in Example 1, except that the composition of the reaction mixture in Example 1 was changed to 34.9359 g (0.160 mol) of 4,4'-difluorobenzophenone, 17.8118 g (0.162 mol) of hydroquinone, 0.8128 g (0.00322 mol) of 4-chlorodiphenyl sulfone, 25.7026 g (0.186 mol) of potassium carbonate, and 140.00 g of diphenyl sulfone. The obtained aromatic polyether was subjected to the same measurements as in Example 1. The results are shown in Table 1.

[0096] Example 3 An aromatic polyether (PEEK) was obtained in the same manner as in Example 1, except that the composition of the reaction mixture in Example 1 was changed to 35.6442 g (0.163 mol) of 4,4'-difluorobenzophenone, 17.8042 g (0.162 mol) of hydroquinone, 0.2877 g (0.001 mol) of 4-chlorodiphenyl sulfone, 25.6959 g (0.186 mol) of potassium carbonate, and 139.98 g of diphenyl sulfone. The obtained aromatic polyether was subjected to the same measurements as in Example 1. The results are shown in Table 1.

[0097] (Comparative Example 1) A commercially available PEEK ("90G" manufactured by Victrex) was used as the aromatic polyether in Comparative Example 1. This aromatic polyether was subjected to the same measurements as in Example 1. The results are shown in Table 1.

[0098] (Comparative Example 2) A commercially available PEEK ("151G" manufactured by Victrex) was used as the aromatic polyether in Comparative Example 2. This aromatic polyether was subjected to the same measurements as in Example 1. The results are shown in Table 1.

[0099] Comparative Example 3 35.6129 g (0.163 mol) of 4,4′-difluorobenzophenone, 17.6167 g (0.160 mol) of hydroquinone, 26.7477 g (0.194 mol) of potassium carbonate, and 160.00 g of diphenyl sulfone were placed in a 300 ml four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet pipe, and a water collection container connected to a cooling pipe, and nitrogen gas was passed through the flask.

[0100] The reaction mixture was reacted under the following temperature control: <Temperature Control> (1) After heating to 170°C, the mixture was maintained for 2 hours. (2) The mixture was heated from 170°C to 210°C (heating rate: 1.3°C / min). (3) The mixture was maintained at 210°C for 1 hour. (4) The mixture was heated from 210°C to 250°C (heating rate: 1.3°C / min). (5) The mixture was maintained at 250°C for 2 hours. (6) The mixture was heated from 250°C to 310°C (maximum temperature of the reaction mixture) (heating rate: 2.0°C / min). (7) The mixture was maintained at 310°C (maximum temperature of the reaction mixture) for 1 hour. (8) 0.3597 g (0.0015 mol) of 4-fluorodiphenyl sulfone was added to the reaction mixture. (9) The mixture was maintained at 310°C (maximum temperature of the reaction mixture) for 1 hour.

[0101] After the reaction was completed, the product was pulverized in a blender (7010HS manufactured by Waring Co.), washed with acetone and then with water, and then dried in a dryer at 180°C to obtain a powdery aromatic polyether (PEEK). This aromatic polyether was subjected to the same measurements as in Example 1. The results are shown in Table 1.

[0102]

[0103] From Table 1, it can be seen that the aromatic polyethers of Examples 1 and 2 have a lower melting point T ｍ It can be seen that

[0104] Example 4 243.32 g (1.12 mol) of 4,4′-difluorobenzophenone, 5.66 g (0.02 mol) of 4-chlorophenyl phenyl sulfone, 123.40 g (1.12 mol) of hydroquinone, 178.11 g (1.29 mol) of potassium carbonate, and 970.3 g of diphenyl sulfone were placed in a 2 L four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a water collection container connected to a condenser, and nitrogen gas was passed through the flask.

[0105] The reaction mixture was reacted under the following temperature control: <Temperature Control> (1) The temperature was raised to 150°C, and then raised to 200°C over 30 minutes. (2) The temperature was maintained at 200°C for 1 hour. (3) The temperature was raised from 200°C to 250°C (heating rate: 1.7°C / min). (4) The temperature was maintained at 250°C for 1 hour. (5) The temperature was raised from 250°C to 300°C (maximum temperature of the reaction mixture) (heating rate: 3.0°C / min). (6) The temperature was maintained at 300°C (maximum temperature of the reaction mixture) for 5 hours.

[0106] After the reaction was completed, the product was pulverized in a blender (7010HS manufactured by Waring Co.), washed with acetone and then with water, and then dried in a dryer at 180°C to obtain a powdery aromatic polyether (PEEK). The MI and intensity ratio X of this aromatic polyether were measured in the same manner as in Example 1. The results were as follows: MI: 47.6 g / 10 cm; Intensity ratio X: 0.70%

[0107] Example 5 The aromatic polyether (PEEK) obtained in Example 4 and an inorganic compound (glass fiber, chopped strand ECS03 T-786H, average fiber diameter 10 μm, average fiber length 3 mm, manufactured by Nippon Electric Glass Co., Ltd.) were kneaded at a mass ratio (aromatic polyether:inorganic compound) of 70:30 at 400°C using a twin-screw kneader (Process 11, manufactured by Termo Fisher) to obtain a composition.

[0108] Example 6 The aromatic polyether (PEEK) obtained in Example 4 and an inorganic compound (manufactured by Mitsubishi Chemical Corporation, carbon fiber chopped fiber TR06U B4E, average fiber diameter 7 μm, average fiber length 6 mm) were kneaded at a mass ratio (aromatic polyether:inorganic compound) of 70:30 at 400°C using a twin-screw kneader (manufactured by Termo Fisher, Process 11) to obtain a composition.

[0109] <Evaluation Method> The aromatic polyether obtained in Example 4 and the compositions obtained in Examples 5 and 6 were each injection molded at 400°C using a small molding machine (MiniJet-Pro, manufactured by Haake Corporation) to prepare dumbbell-shaped 5A specimens as specified in ISO 527-2:2012, which were used as test specimens. Tensile tests were performed on the obtained test specimens at a test speed of 5 mm / min and a chuck distance of 50 mm to measure the tensile strength. The results are as follows: Example 4: 92.9 MPa Example 5: 168.0 MPa Example 6: 209.1 MPa

[0110] <Evaluation> The aromatic polyether of Example 4 exhibited superior mechanical strength (tensile strength) by blending an inorganic compound (Examples 5 and 6). In addition, in all of Examples 4 to 6, the processability (particularly moldability in a molten state) was good.

[0111] Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will readily be able to make numerous modifications to these exemplary embodiments and / or examples without substantially departing from the novel teachings and advantages of the present invention. Accordingly, these numerous modifications are within the scope of the present invention. The contents of all documents cited in this specification and of the applications from which this application claims priority under the Paris Convention are incorporated by reference in their entirety.

Claims

1. It contains a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structure represented by the following formula (3). １ An aromatic polyether, wherein the ratio of the peak intensity of the peak having the largest peak intensity among the peaks derived from the structure represented by the formula (3) appearing in the range of chemical shift 7.55 ppm to 7.65 ppm to the peak intensity of the peak derived from the structural unit represented by the formula (2) appearing near the chemical shift 7.35 ppm in the 1H-NMR measurement is 0.20 to 2.00%. 【Chemical 11】

2. The aromatic polyether according to Claim 1, which contains a structural unit represented by the following formula (4). 【Chemical 12】

3. The aromatic polyether according to Claim 1 or 2, wherein the ratio of the peak intensities is 0.20 to 1.80%.

4. The aromatic polyether according to Claim 1 or 2, having a melt flow index of 1.0 to 100 g / 10 min.

5. It includes a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structure represented by the following formula (3). １ A method for producing an aromatic polyether, which produces an aromatic polyether having a ratio of the peak intensity of the peak having the largest peak intensity among the peaks derived from the structure represented by the following formula (3) appearing in the range of chemical shift of 7.55 ppm to 7.65 ppm to the peak intensity of the peak derived from the structural unit represented by the following formula (2) appearing near the chemical shift of 7.35 ppm in 1H-NMR measurement being 0.20 to 2.00%. A method for producing an aromatic polyether, which includes reacting 4,4'-dihalogenobenzophenone, hydroquinone, and diphenyl sulfone having one reactive group. 【Chemical 13】

6. The method for producing an aromatic polyether according to Claim 5, wherein the molar ratio ([DHBP]:[HQ]) of 4,4'-dihalogenobenzophenone (DHBP) to hydroquinone (HQ) used in the reaction is 0.97 to 1.06:

1.

7. The method for producing an aromatic polyether according to Claim 5 or 6, wherein the molar ratio ([DHBP]:[HQ]) of 4,4'-dihalogenobenzophenone (DHBP) to hydroquinone (HQ) used in the reaction is 0.97 to 1.00:

1.

8. The method for producing an aromatic polyether according to Claim 5 or 6, wherein the molar ratio ([DPS]:[HQ]) of diphenyl sulfone (DPS) having one reactive group to hydroquinone (HQ) used in the reaction is 0.002 to 0.080:

1.

9. The method for producing an aromatic polyether according to Claim 5 or 6, wherein the 4,4'-dihalogenobenzophenone contains 4,4'-dichlorobenzophenone.

10. The method for producing an aromatic polyether according to Claim 5 or 6, wherein the 4,4'-dihalogenobenzophenone contains 4,4'-difluorobenzophenone.

11. The method for producing an aromatic polyether according to Claim 5 or 6, wherein the diphenyl sulfone having one reactive group contains 4-chlorodiphenyl sulfone.

12. The method for producing an aromatic polyether according to Claim 5 or 6, wherein the diphenyl sulfone having one reactive group contains 4-fluorodiphenyl sulfone.

13. The method for producing an aromatic polyether according to Claim 5 or 6, wherein the melt flow index of the aromatic polyether is 1.0 to 100 g / 10 min.

14. An aromatic polyether according to Claim 1, an inorganic compound, and a composition comprising the same.

15. A composition comprising an aromatic polyether containing a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structure represented by the following formula (3), Of the composition １ The ratio of the peak intensity of the peak with the highest peak intensity among the peaks derived from the structure represented by the formula (3) appearing in the range of chemical shift 7.55 ppm to 7.65 ppm to the peak intensity of the peak derived from the structural unit represented by the formula (2) appearing near the chemical shift 7.35 ppm in the 1H-NMR measurement is 0.20 to 2.00%, Composition. 【Chemical Formula 14】

16. The composition according to Claim 15, wherein the aromatic polyether contains a structural unit represented by the following formula (4). 【Chemical Formula 15】

17. The composition according to Claim 15 or 16, wherein the ratio of the peak intensities is 0.20 to 1.80%.

18. The composition according to Claim 15 or 16, wherein the melt flow index of the aromatic polyether is 1.0 to 100 g / 10 min.

19. The composition according to Claim 15, which contains an inorganic compound.

20. The composition according to Claim 14 or 19, wherein the inorganic compound is at least one selected from the group consisting of glass fiber, carbon fiber, and boron nitride.

21. The composition according to Claim 14 or 19, wherein the inorganic compound is at least one selected from the group consisting of glass fiber and carbon fiber, and is in at least one form selected from the group consisting of chopped strand, roving, fabric, non-woven fabric, and unidirectional material.

22. The composition according to Claim 14 or 19, wherein the inorganic compound is glass fiber.

23. A sheet comprising a cloth containing an inorganic compound and the aromatic polyether according to Claim 1 impregnated in the cloth.

24. A sheet comprising a cloth containing an inorganic compound and a composition impregnated in the cloth, wherein the composition contains an aromatic polyether containing a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structure represented by the following formula (3), Of the composition １ Sheet, wherein the ratio of the peak intensity of the peak having the largest peak intensity among the peaks derived from the structure represented by the formula (3) appearing in the range of chemical shift 7.55 ppm to 7.65 ppm to the peak intensity of the peak derived from the structural unit represented by the formula (2) appearing near the chemical shift 7.35 ppm in the 1H-NMR measurement is 0.20 to 2.00%. 【Chemical Formula 16】

25. The sheet according to Claim 24, wherein the aromatic polyether contains a structural unit represented by the following formula (4). 【Chemical 17】

26. The sheet according to Claim 24 or 25, wherein the ratio of the peak intensities is 0.20 to 1.80%.

27. The sheet according to Claim 24 or 25, wherein the melt flow index of the aromatic polyether is 1.0 to 100 g / 10 min.

28. The sheet according to Claim 23 or 24, wherein the cloth is a unidirectional material.

29. The sheet according to Claim 23 or 24, wherein the cloth contains at least one selected from the group consisting of glass fiber and carbon fiber.

Images