Aromatic polyether, composition, film, powder, pellets, composite material production method, and composite material

Abstract

An aromatic polyether containing a structural unit expressed by formula (1) and a structural unit expressed by formula (2), wherein the MFR4 [g / 10 min.] measured after preheating the aromatic polyether for 4 minutes at 380°C and the MFR30 [g / 10 min.] measured after preheating the aromatic polyether for 30 minutes at 380°C satisfy the condition that MFR4 / MFR30 ≥ 1.1.

Description

Aromatic polyether, composition, film, powder, pellet, method for producing composite material, and composite material

[0001] The present invention relates to an aromatic polyether, a composition, a film, a powder, a pellet, a method for producing a composite material, and the composite material. Specifically, the present invention relates to an aromatic polyether, a composition, a film, a powder, a pellet, a method for producing a composite material, and the composite material, which have excellent mechanical strength.

[0002] Composite materials made by reinforcing resins with continuous fibers such as carbon fiber and glass fiber are known. In recent years, such composite materials have been used as a substitute for metals, including in the exterior of aircraft. Thermosetting resins, such as epoxy resins and phenolic resins, are generally used as the resins in such composite materials. However, composite materials using thermosetting resins are difficult to bond together, and the entire part shape must be formed at once. Furthermore, thermosetting resins require a long curing time, which limits the improvement of productivity. Therefore, attempts have been made to use thermoplastic resins instead of thermosetting resins. Patent documents 1 to 3 are examples of composite materials using aromatic polyether thermoplastic resins.

[0003] Japanese Patent Application Laid-Open No. 2-247229 Japanese Patent Application Laid-Open No. 2015-17343 International Publication No. 2020 / 040121

[0004] However, it has been found that there is room for further improvement in the aromatic polyethers of conventional technologies such as Patent Document 1 in terms of improving mechanical strength, particularly the mechanical strength of composite materials containing continuous fibers and aromatic polyethers.

[0005] An object of the present invention is to provide a method for producing an aromatic polyether, a film, a powder, a pellet, or a composite material having excellent mechanical strength, and to provide the composite material.

[0006] As a result of extensive research, the present inventors have found that aromatic polyethers having specific melting properties have excellent mechanical strength, and can particularly improve the mechanical strength of composite materials containing continuous fibers and aromatic polyethers, and have thus completed the present invention. The present invention provides the following aromatic polyethers, etc.: 1. An aromatic polyether containing a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), wherein the MFR measured after preheating the aromatic polyether at 380°C for 4 minutes is: ４ [g / 10 min] and the MFR measured after preheating the aromatic polyether at 380°C for 30 minutes ３０ [g / 10 min] is MFR ４ / MFR ３０ ≧1.1. 2. The aromatic polyether according to 1, which contains a structural unit represented by the following formula (3): 3. An aromatic polyether according to 1 or 2, which satisfies one or both of the following conditions (A) and (B): (A) the fluorine atom content a is less than 2 mg / kg; (B) the chlorine atom content b is 2 mg / kg or more; 4. A composition comprising the aromatic polyether according to any one of 1 to 3. 5. A composition comprising an aromatic polyether, wherein the aromatic polyether comprises a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and the MFR measured after preheating the composition at 380°C for 4 minutes is: ４ [g / 10 min] and the MFR measured after preheating the composition at 380°C for 30 minutes ３０ [g / 10 min] is MFR ４ / MFR ３０ ≧1.1. 6. The composition according to 5, wherein the aromatic polyether contains a structural unit represented by the following formula (3): 7. The composition according to 5 or 6, which satisfies one or both of the following conditions (A) and (B): (A) the fluorine atom content a is less than 2 mg / kg; (B) the chlorine atom content b is 2 mg / kg or more. 8. A film comprising the aromatic polyether according to any one of 1 to 3 or the composition according to any one of 4 to 7. 9. A powder comprising the aromatic polyether according to any one of 1 to 3 or the composition according to any one of 4 to 7. 10. A pellet comprising the aromatic polyether according to any one of 1 to 3 or the composition according to any one of 4 to 7. 11. The aromatic polyether according to any one of 1 to 3, the composition according to any one of 4 to 7, the film according to 8, the powder according to 9, or the pellet according to 10, for use in producing a composite material comprising an aromatic polyether and continuous fibers. 12. Use of the aromatic polyether according to any one of 1 to 3, the composition according to any one of 4 to 7, the film according to 8, the powder according to 9, or the pellet according to 10, for producing a composite material comprising an aromatic polyether and continuous fibers. 13. A method for producing a composite material, comprising producing a composite material using the aromatic polyether according to any one of 1 to 3, the composition according to any one of 4 to 7, the film according to 8, the powder according to 9, or the pellet according to 10, and continuous fiber. 14. A method for producing a composite material according to 13, comprising a step of combining the aromatic polyether, the composition, the film, the powder, or the pellet, with the continuous fiber. 15. A method for producing a composite material according to 13, comprising pressing the aromatic polyether, the composition, the film, the powder, or the pellet, with the continuous fiber under heating. 16. A composite material produced using the aromatic polyether according to any one of 1 to 3, the composition according to any one of 4 to 7, the film according to 8, the powder according to 9, or the pellet according to 10, and continuous fiber. 17. A composite material comprising the aromatic polyether according to any one of 1 to 3 or the composition according to any one of 4 to 7, and continuous fiber.

[0007] According to the present invention, it is possible to provide an aromatic polyether, a composition, a film, a powder, a pellet, a method for producing a composite material, and a composite material, all of which have excellent mechanical strength.

[0008] The aromatic polyether, composition, film, powder, pellet, and method for producing a composite material, as well as the composite material, of the present invention will be 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 in any combination.

[0009] 1. Aromatic Polyether The aromatic polyether according to one embodiment of the present invention is an aromatic polyether containing a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), wherein the aromatic polyether has an MFR measured after preheating at 380°C for 4 minutes: ４ [g / 10 min] and the MFR measured after preheating the PEEK at 380°C for 30 minutes ３０ [g / 10 min] is MFR ４ / MFR ３０ ≧1.1.

[0010]

[0011] The aromatic polyether according to this embodiment has excellent mechanical strength, and in particular can impart excellent mechanical strength to a composite material containing the aromatic polyether and continuous fibers (hereinafter also referred to as an "aromatic polyether / continuous fiber composite material"). The reason why such an effect is exhibited is not entirely clear, but the following is presumed. That is, ordinary aromatic polyethers have an MFR ４ / MFR ３０ = 1.0. This means that the melt flowability of the aromatic polyether does not change substantially after preheating at 380°C. In contrast, the aromatic polyether of this embodiment has an MFR ４ / MFR ３０ ≧1.1 is satisfied. This means that the melt fluidity of the aromatic polyether decreases after preheating at 380°C. Aromatic polyethers exhibiting such a decrease in melt fluidity exhibit excellent mechanical strength due to thickening caused by heating. The cause of such a decrease in melt fluidity may be, for example, the formation of a crosslinked structure.

[0012] For example, when producing an aromatic polyether / continuous fiber composite material, a method is used in which the aromatic polyether is heated and melted and impregnated into the gaps between the continuous fibers in an assembly of continuous fibers. This heating thickens the aromatic polyether, thereby imparting excellent mechanical strength to the aromatic polyether / continuous fiber composite material.

[0013] MFR of aromatic polyether ４ and MFR ３０ is MFR ４ / MFR ３０ There are no particular limitations as long as the condition of MFR ≧1.1 is satisfied. ４ / MFR ３０ In one embodiment, the MFR of the aromatic polyether is 10.0 or less, 8.0 or less, 6.0 or less, 4.0 or less, or 3.0 or less. ４ is MFR ４ / MFR ３０ In one embodiment, the MFR of the aromatic polyether is in the range of 0.0001 to 1500.0 g / 10 min, 0.0005 to 500.0 g / 10 min, 0.001 to 100.0 g / 10 min, 0.01 to 100.0 g / 10 min, 3.5 to 50.0 g / 10 min, 5 to 50.0 g / 10 min, or 5.0 to 15.0 g / 10 min, provided that the MFR is in the range of 0.0001 to 1500.0 g / 10 min, 0.0005 to 500.0 g / 10 min, 0.001 to 100.0 g / 10 min, 0.01 to 100.0 g / 10 min, 3.5 to 50.0 g / 10 min, 5 to 50.0 g / 10 min, or 5.0 to 15.0 g / 10 min, and satisfies the condition of 1.1 or more. ３０ is MFR ４ / MFR ３０ In the range satisfying the condition of ≧1.1, the range is 0.0001 to 1500.0 g / 10 min, 0.0005 to 500.0 g / 10 min, 0.001 to 100.0 g / 10 min, 0.01 to 100.0 g / 10 min, or 0.1 to 12.0 g / 10 min.

[0014] MFR ４ and MFR ３０ is a value measured by the method described in the Examples.

[0015] In this specification, "aromatic polyether having an MFR ４ / MFR ３０ The expression "satisfies the condition of MFR ≧ 1.1" means that the aromatic polyether alone (completely isolated and purified) has an MFR ４ / MFR３０ ≧1.1, or when aromatic polyether and other coexisting components are ４ / MFR ３０ When other coexisting components are present, it can be said that the aromatic polyether constitutes a composition together with the other coexisting components, and the composition containing the aromatic polyether satisfies the condition of MFR ≥ 1.1. ４ / MFR ３０ It can also be said that the condition ≧1.1 is satisfied.

[0016] In one embodiment, the amount of a base coexisting in the aromatic polyether is adjusted to control the MFR of the aromatic polyether. ４ / MFR ３０ ≧1.1 can be satisfied. When a base is coexisted in the aromatic polyether, the base may be blended as an additive to the aromatic polyether, or potassium carbonate, which is the base used in the synthesis of the aromatic polyether, may be intentionally left in the aromatic polyether. In one embodiment, 0.02 to 0.18 parts by mass of potassium carbonate may be added to 100 parts by mass of the aromatic polyether (the "100 parts by mass" refers to the amount of the aromatic polyether alone and does not include the amounts of other components such as potassium carbonate). The amount of potassium carbonate added is more preferably 0.02 to 0.09 parts by mass, 0.02 to 0.06 parts by mass, or 0.02 to 0.04 parts by mass. This improves the MFR ４ / MFR ３０ In one embodiment, the pH during washing of the aromatic polyether is adjusted to more than 7.0 and not more than 10, more preferably 8.0 to 10, and even more preferably 8.0 to 9.5. Here, "during washing of the aromatic polyether" refers to, for example, washing after synthesis of the aromatic polyether, and in the case where washing of the aromatic polyether is carried out multiple times, it refers to the final washing. This allows the MFR ４ / MFR ３０ In other words, the aromatic polyether having a pH of more than 7.0 and not more than 10 when crushed and impregnated in water can satisfactorily satisfy the condition of MFR≧1.1. ４ / MFR ３０≧1.1 can be preferably satisfied.

[0017] MFR ４ / MFR ３０ The method for obtaining an aromatic polyether that satisfies the condition of MFR ≥ 1.1 is not limited to a method using a coexisting component such as a base, and for example, a method of introducing a functional group into an aromatic polyether that can crosslink the aromatic polyethers (for example, crosslinkable under heating at 380°C) can also be used. ４ / MFR ３０ The functional group to be introduced into the aromatic polyether can be selected so as to satisfy the condition of ≧1.1.

[0018] In one embodiment, the aromatic polyether satisfies one or both of the following conditions (A) and (B): (A) the fluorine atom content a is less than 2 mg / kg; (B) the chlorine atom content b is 2 mg / kg or more; "fluorine atom content a" is the ratio of the mass [mg] of fluorine atoms to the total mass [kg] of the aromatic polyether (excluding other coexisting components) and the other coexisting components; and "chlorine atom content b" is the ratio of the mass [mg] of chlorine atoms to the total mass [kg] of the aromatic polyether (excluding other coexisting components) and the other coexisting components.

[0019] In one embodiment, the fluorine atom content a in the aromatic polyether is less than 2 mg / kg. This allows the effects of the present invention to be exhibited satisfactorily. The lower limit is not particularly limited and may be, for example, 0 mg / kg. Here, the fluorine atom content a in the aromatic polyether is the sum of the fluorine atom content a1 contained in the molecular structure of the aromatic polyether and the fluorine atom content a2 contained as components (free components) not contained in the molecular structure of the aromatic polyether.

[0020] In one embodiment, the fluorine atom content a in the aromatic polyether can be made less than 2 mg / kg by not using a raw material containing a fluorine atom (for example, 4,4′-difluorobenzophenone) during the synthesis of the aromatic polyether or by reducing the amount of the raw material containing a fluorine atom used during the synthesis of the aromatic polyether.

[0021] In one embodiment, the free component in the fluorine atom content a2 is one or both of potassium fluoride and 4,4'-difluorobenzophenone.

[0022] In one embodiment, the chlorine atom content b in the aromatic polyether is 2 mg / kg or more, 10 mg / kg or more, 100 mg / kg or more, 500 mg / kg or more, 700 mg / kg or more, 1000 mg / kg or more, 2000 mg / kg or more, 33000 mg / kg or more, or 4000 mg / kg or more. This allows the effects of the present invention to be exhibited favorably. The upper limit is not particularly limited, and may be, for example, 10000 mg / kg or less, 9000 mg / kg or less, 8000 mg / kg or less, 7000 mg / kg or less, or 6000 mg / kg or less. Furthermore, the chlorine atom content b in the aromatic polyether is, for example, 2 to 10000 mg / kg, preferably 700 to 9000 mg / kg, and more preferably 1000 to 8000 mg / kg. Here, the content b of chlorine atoms is the sum of the content b1 of chlorine atoms contained in the molecular structure of the aromatic polyether and the content b2 of chlorine atoms contained as components (free components) not contained in the molecular structure of the aromatic polyether.

[0023] In one embodiment, by including 4,4'-dichlorobenzophenone as a raw material in the synthesis of an aromatic polyether, the chlorine atom content b in the aromatic polyether can be increased to 2 mg / kg or more. Furthermore, by using 4,4'-dichlorobenzophenone and hydroquinone as raw materials in the synthesis of an aromatic polyether and increasing the ratio of the amount of 4,4'-dichlorobenzophenone used to the amount of hydroquinone used, the chlorine atom content b in the aromatic polyether can be increased in the range of 2 mg / kg or more.

[0024] In one embodiment, the chlorine atom content b1 is 0 mg / kg or more, 100 mg / kg or more, 200 mg / kg or more, or 400 mg / kg or more. The upper limit is not particularly limited and may be, for example, 10,000 mg / kg or less, 9,000 mg / kg or less, 8,000 mg / kg or less, or 7,000 mg / kg or less. In one embodiment, the chlorine atom content b2 is 0 mg / kg or more, 2 mg / kg or more, 5 mg / kg or more, or 10 mg / kg or more. The upper limit is not particularly limited and may be, for example, 500 mg / kg or less, 400 mg / kg or less, or 300 mg / kg or less.

[0025] In one embodiment, the free component in the chlorine atom content b2 is one or both of potassium chloride and 4,4'-dichlorobenzophenone.

[0026] The chlorine atoms contained in the aromatic polyether as potassium chloride, a free component, are quantified by the following method. <Method for Measuring the Chlorine Atoms Contained in the Aromatic Polyether as Potassium Chloride, a Free Component> A solid sample (aromatic polyether) is pulverized in a blender, washed with acetone and then with water, and dried in an explosion-proof dryer at 180°C. When using the reaction mixture (product) immediately after the reaction to produce the aromatic polyether as the sample, the product is cooled and solidified after the reaction is completed to obtain the solid sample. The blender used is not particularly limited; for example, a Waring 7010HS blender can be used. Approximately 1 g of the dried sample is weighed, 100 ml of ultrapure water is added, and the mixture is stirred at 50°C for 20 minutes. After cooling, the mixture is filtered to separate the solids and the aqueous solution. The aqueous solution is analyzed by ion chromatography, and the chloride ions in the aqueous solution are quantified based on a calibration curve prepared from a reference of known concentration. The ion chromatography conditions are as follows:

[0027] <Ion chromatograph> Analytical device: Metrohm 940 IC Vario Column: A guard column (Metrosep A Supp 5 Guard) and a separation column (Metrosep A Supp 4) were used in conjunction (both columns manufactured by Metrohm). Eluent: Na２ CO ３ (1.8 mmol / l) + NaHCO (1.7 mmol / l) Flow rate: 1.0 ml / min Column temperature: 30°C Measurement mode: Suppressor method Detector: Electrical conductivity detector

[0028] The chlorine atoms contained in the aromatic polyether as 4,4'-dichlorobenzophenone, a free component, are quantified by the following method. <Method for Measuring the Chlorine Atoms Found in the Aromatic Polyether as 4,4'-dichlorobenzophenone> A solid sample (aromatic polyether) is pulverized in a blender, washed with acetone and then with water, and dried in an explosion-proof dryer at 180°C. When using the reaction mixture (product) immediately after the reaction to produce the aromatic polyether as the sample, the product is cooled and solidified after the reaction is completed to obtain the solid sample. The blender used is not particularly limited; for example, a Waring 7010HS blender can be used. Approximately 1 g of the dried sample is weighed into an eggplant flask, to which 10 ml of acetone and boiling stones are added, and the mixture is heated to reflux in a water bath for 5 hours. After cooling to room temperature, the solids are removed by filtration. The resulting acetone solution is evaporated to dryness using an evaporator, and then 10 ml of acetone is added using a volumetric pipette to redissolve the sample. This is measured by gas chromatography to calculate the amount of 4,4'-dichlorobenzophenone (mg / kg) in the sample. The amount of chlorine atoms (mg / kg) contained in the aromatic polyether as 4,4'-dichlorobenzophenone, a free component, is calculated using the following formula: Amount of chlorine atoms (mg / kg) contained in the aromatic polyether as 4,4'-dichlorobenzophenone, a free component = Amount of 4,4'-dichlorobenzophenone in the sample (mg / kg) ÷ 251.11 (molecular weight of 4,4'-dichlorobenzophenone) × 35.45 (atomic weight of chlorine) × 2

[0029] The quantitative value of 4,4'-dichlorobenzophenone is determined based on a calibration curve created from a reference of known concentration. The measurement conditions are as follows: <Gas chromatograph> Analytical device: Agilent Technologies 7890B GC column: Agilent Technologies DB-5MS (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm) Injection port temperature: 250°C Oven temperature: 100°C (1 min) → 30°C / min → 250°C (10 min) Flow rate: 1 ml / min Injection volume: 1 μl Split ratio: 40:1 Detector: FID Detector temperature: 250°C

[0030] In an aromatic polyether according to one embodiment, the structural unit represented by formula (1) is bonded to a terminal structure and is arranged at one or more ends of the molecular chain. In this case, the terminal structure bonded to the structural unit may be a chlorine atom (Cl). In an aromatic polyether according to one embodiment, the structural unit represented by formula (2) is bonded to a terminal structure and is arranged at one or more ends of the molecular chain. In this case, the terminal structure bonded to the structural unit 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). The terminal structure is not limited to these examples and may be any structure.

[0031] In one embodiment, the aromatic polyether comprises a structural unit represented by the following formula (3): The aromatic polyether comprising the structural unit represented by formula (3) is also called polyether ether ketone (abbreviated as "PEEK").

[0032]

[0033] In one embodiment, the aromatic polyether does not contain any other structural units than the structural unit represented by formula (3), but may have a terminal structure at the end of the molecular chain as described above.

[0034] In one embodiment, the proportion (mass %) of the structural unit represented by formula (3) relative to (i) the portion excluding the terminal structure from the entire PEEK, or (ii) the sum of all structural units constituting the PEEK, 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 %.

[0035] In one embodiment, the molar ratio ([1A]:[2A]) of the structural unit represented by formula (1) to the structural unit represented by formula (2) in PEEK 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. In PEEK, 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). When the total proportion of the structural units represented by formula (1) and formula (2) contained in all monomers constituting PEEK is 100% by mass, the above molar ratio is usually 1:1.

[0036] A method for producing PEEK will be described in detail below. In one embodiment, PEEK can be produced, for example, by reacting 4,4'-dihalogenobenzophenone with hydroquinone.

[0037] 4,4'-Dihalogenobenzophenone and hydroquinone are monomers for polymerizing aromatic polyethers. Through a process of reacting 4,4'-dihalogenobenzophenone and hydroquinone, aromatic polyethers can be obtained as copolymers of these compounds (monomer units). 4,4'-Dihalogenobenzophenone and hydroquinone can be easily synthesized and are also commercially available.

[0038] 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, and among these, 4,4'-dichlorobenzophenone is preferred.

[0039] In the following description, the term "reaction mixture" refers to the reaction system from the start of the reaction between 4,4'-dihalogenobenzophenone and hydroquinone 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 and hydroquinone) in the reaction mixture decrease, while the concentration of the product (aromatic polyether) increases.

[0040] 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 between 4,4'-dihalogenobenzophenone and hydroquinone 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 320°C.

[0041] 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. 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 1 to 8 hours, preferably 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, 3 hours or more and 6 hours or less (the upper and lower limits can be arbitrarily combined) (hereinafter also referred to as "temperature hold (iii)"). This allows an aromatic polyether having a desired molecular weight to be obtained. 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.

[0042] 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.

[0043] 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.

[0044] 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'-dichlorobenzophenone and hydroquinone 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.

[0045] 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.

[0046] 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.

[0047] In one embodiment, the reaction mixture includes potassium carbonate, which facilitates the reaction.

[0048] In one embodiment, the reaction mixture contains an alkali metal salt other than potassium carbonate, such as an alkali metal carbonate or an alkali metal bicarbonate. These alkali metal salts may be used in combination with potassium carbonate. For example, potassium carbonate may be used in combination with sodium carbonate.

[0049] Examples of alkali metal carbonates include lithium carbonate, rubidium carbonate, cesium carbonate, etc. Examples of alkali metal hydrogen carbonates that can be used in combination with potassium carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate, etc. These alkali metal salts may be used alone or in combination of two or more.

[0050] The total concentration of alkali metal salts (including potassium carbonate and the other alkali metal salts described above) in the reaction mixture is not particularly limited. In one embodiment, the total amount of alkali metal salts 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 alkali metal salts is 100 mol parts or more, the reaction time can be shortened. When the total amount of alkali metal salts is 180 mol parts or less, the formation of a gel component can be suppressed. Furthermore, the total amount of alkali metal salts 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 used as the alkali metal salt in the amount described above.

[0051] In one embodiment, the reaction mixture does not contain any of sodium fluoride, potassium fluoride, rubidium fluoride, and cesium fluoride. In this embodiment, a high molecular weight aromatic polyether can be obtained without containing these compounds. Furthermore, by not containing these compounds, it is possible to prevent these compounds from remaining in the resulting aromatic polyether, thereby reducing purification costs. This allows for the low-cost production of aromatic polyethers that can exhibit excellent mechanical strength by incorporating inorganic compounds.

[0052] 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 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 4,4'-dihalogenobenzophenone (DHBP) may be larger than, smaller than, or the same as the number of moles of hydroquinone (HQ).

[0053] In one embodiment, the total concentration (based on the amount of addition) of 4,4'-dihalogenobenzophenone and hydroquinone 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 and hydroquinone in the reaction mixture is, for example, 1.0 to 6.0 mol / L, preferably 1.3 to 5.0 mol / L, more preferably 1.5 to 4.0 mol / L.

[0054] In one embodiment, no other monomers than 4,4'-dihalogenobenzophenone and hydroquinone are used as the monomers subjected to the above-mentioned reaction.

[0055] In one embodiment, in the above-described reaction, a monomer other than 4,4'-dihalogenobenzophenone and hydroquinone is used in combination within a range that does not impair the effects of the present invention.

[0056] In one embodiment, the total proportion (mass%) of 4,4'-dihalogenobenzophenone and hydroquinone based on all monomers subjected to the reaction 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%.

[0057] 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, an alkali metal salt, and a solvent, or 4,4'-dihalogenobenzophenone, hydroquinone, 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, potassium carbonate, and diphenyl sulfone. Note that "substantially 100% by mass" may contain inevitable impurities.

[0058] The reaction between 4,4'-dihalogenobenzophenone and hydroquinone can be carried out in an inert gas atmosphere, which is not particularly limited and includes, for example, nitrogen and argon gas.

[0059] In one embodiment, the aromatic polyether comprises a structural unit represented by the following formula (4): The aromatic polyether comprising the structural unit represented by formula (4) is also called polyether ether ketone (abbreviated as "PEEEK").

[0060] The structural unit represented by formula (3) and the structural unit represented by formula (4) are different from each other, and in an aromatic polyether, a partial structure corresponding to the structural unit represented by formula (4) is considered to be the structural unit represented by formula (4), but is not considered to be the structural unit represented by formula (3).

[0061] In one embodiment, the aromatic polyether does not contain any other structural units than the structural unit represented by formula (4), but may have a terminal structure at the end of the molecular chain as described above.

[0062] In one embodiment, a method for producing an aromatic polyether containing a structural unit represented by formula (4) is the same as a method for producing PEEK, except that 4,4'-dihydroxydiphenyl ether is used instead of hydroquinone, and the description of the method for producing PEEK is incorporated herein by reference.

[0063] In one embodiment, the aromatic polyether contains a structural unit represented by formula (3) and a structural unit represented by formula (4). An aromatic polyether containing a structural unit represented by formula (3) and a structural unit represented by formula (4) is also referred to as a polyether ether ketone / polyether ether ether ketone copolymer (abbreviated as "PEEK / PEEEK copolymer"). The ratio [mol %] of the number of moles of the structural unit represented by formula (4) to the total number of moles of the structural unit represented by formula (3) and the structural unit represented by formula (4) contained in the PEEK / PEEEK copolymer is not particularly limited, and is, for example, more than 0% and less than 100%, preferably 0.1 to 99.9 mol %, more preferably 0.1 to 50.0 mol %, more preferably 0.1 to 10.0 mol %, and more preferably 0.1 to 5.0 mol %. In one embodiment, the aromatic polyether does not contain any structural units other than the structural unit represented by formula (3) and the structural unit represented by formula (4). However, the molecular chain may have a terminal structure at its end as described above.

[0064] In one embodiment, a method for producing an aromatic polyether containing a structural unit represented by formula (3) and a structural unit represented by formula (4) is similar to a method for producing PEEK, except that part of hydroquinone is replaced with 4,4'-dihydroxydiphenyl ether (hydroquinone and 4,4'-dihydroxydiphenyl ether are used in combination), and the description of the method for producing PEEK is incorporated herein by reference.

[0065] In one embodiment, the aromatic polyether does not contain any other structural units than the structural units represented by formula (1) and formula (2), but may have a terminal structure at the end of the molecular chain as described above.

[0066] In one embodiment, the aromatic polyether contains structural units other than the structural units represented by formula (1) and formula (2) within a range that does not impair the effects of the present invention.

[0067] In one embodiment, based on all the monomers supplied to the reaction, the total proportion (mass%) of the structural units represented by formula (1) and formula (2) 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%.

[0068] 2. Composition The composition according to the first aspect of the present invention contains the aromatic polyether according to one aspect of the present invention. The composition according to the first aspect has excellent mechanical strength, and in particular, can impart excellent mechanical strength to an aromatic polyether / continuous fiber composite material.

[0069] The composition according to a second aspect of the present invention is a composition containing an aromatic polyether, wherein the aromatic polyether contains a structural unit represented by formula (1) and a structural unit represented by formula (2), and the composition has an MFR measured after preheating at 380° C. for 4 minutes. ４ [g / 10 min] and the MFR measured after preheating the composition at 380°C for 30 minutes ３０ [g / 10 min] is MFR ４ / MFR ３０The composition according to the second aspect also has excellent mechanical strength, and in particular can impart excellent mechanical strength to an aromatic polyether / continuous fiber composite material.

[0070] The aromatic polyether contained in the composition according to the second aspect of the present invention is the same as that described for the aromatic polyether according to the first aspect of the present invention, except that the aromatic polyether contained in the composition according to the second aspect of the present invention has an MFR measured after preheating the aromatic polyether at 380°C for 4 minutes. ４ [g / 10 min] and the MFR measured after preheating the aromatic polyether at 380°C for 30 minutes ３０ [g / 10 min] is MFR ４ / MFR ３０ That is, the composition according to the second aspect may have an MFR of 1.1 or more, as measured after preheating the composition at 380° C. for 4 minutes. ４ [g / 10 min] and the MFR measured after preheating the composition at 380°C for 30 minutes ３０ [g / 10 min] is MFR ４ / MFR ３０ The melt viscosity of the composition may be any of those satisfying the condition of MFR≧1.1. ４ and MFR ３０ Regarding the MFR of the aromatic polyether, the preferred ranges thereof are also described. ４ and MFR ３０ The explanation given above regarding the MFR of the composition is incorporated herein by reference. ４ and MFR ３０ The measurement method is the same as that of the MFR of the aromatic polyether except that a composition is used instead of the aromatic polyether as a sample. ４ and MFR ３０ The measurement method is the same as that of

[0071] In one embodiment of the second aspect, the composition satisfies one or both of the following conditions (A) and (B): (A) the fluorine atom content a is less than 2 mg / kg; (B) the chlorine atom content b is 2 mg / kg or more; "fluorine atom content a" is the ratio of the mass [mg] of fluorine atoms to the total mass [kg] of the aromatic polyether (excluding other coexisting components) and the other coexisting components. Here, the total mass [kg] of the aromatic polyether (excluding other coexisting components) and the other coexisting components corresponds to the mass [kg] of the entire composition. "chlorine atom content b" is the ratio of the mass [mg] of chlorine atoms to the total mass [kg] of the aromatic polyether (excluding other coexisting components) and the other coexisting components. Here again, the total mass [kg] of the aromatic polyether (excluding other coexisting components) and the other coexisting components corresponds to the mass [kg] of the entire composition. The method for measuring the fluorine atom content a and the chlorine atom content b in the composition is the same as the method for measuring the fluorine atom content a and the chlorine atom content b in the aromatic polyether, except that a composition is used as the sample instead of the aromatic polyether.

[0072] In the following description, the composition according to the first aspect of the present invention and the composition according to the second aspect of the present invention may be collectively referred to as the "composition according to one aspect of the present invention." Components other than the aromatic polyether contained in the composition according to one aspect of the present invention are not particularly limited. The composition according to one aspect of the present invention is suitably used, for example, in the production of a composite material containing an aromatic polyether and continuous fibers.

[0073] 3. Film A film according to an embodiment of the present invention comprises the aromatic polyether according to an embodiment of the present invention or the composition according to an embodiment of the present invention. The film according to an embodiment of the present invention is suitable for use in producing a composite material containing, for example, an aromatic polyether and continuous fibers.

[0074] 4. Powder A powder according to an embodiment of the present invention includes the aromatic polyether according to an embodiment of the present invention or the composition according to an embodiment of the present invention. The powder according to an embodiment of the present invention is suitable for use in producing a composite material including, for example, the aromatic polyether and continuous fibers.

[0075] 5. Pellets The pellets according to one aspect of the present invention contain the aromatic polyether according to one aspect of the present invention or the composition according to one aspect of the present invention. The pellets according to one aspect of the present invention are suitable for use in, for example, producing a composite material containing the aromatic polyether and continuous fibers.

[0076] In one embodiment, the composition, film, powder, or pellet according to one aspect of the present invention contains an aromatic polyether and another component. The other component is not particularly limited, and examples thereof include potassium carbonate and other resins that are not aromatic polyethers. Examples of the other resin include fluororesins such as polytetrafluoroethylene. One type of the other component may be used alone, or two or more types may be used in combination.

[0077] In one embodiment, the composition, film, powder, or pellet according to one aspect of the present invention 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 an aromatic polyether, or at least one selected from an aromatic polyether and the other components described above. Note that "substantially 100 mass%" may contain inevitable impurities.

[0078] The film, powder, and pellets according to the above-described embodiment of the present invention can be formed from the respective constituent components using methods known in the art.

[0079] 6. Composite Material The composite material according to the first aspect of the present invention is produced using the aromatic polyether according to one aspect of the present invention, the composition according to one aspect of the present invention, the film according to one aspect of the present invention, the powder according to one aspect of the present invention, or the pellet according to one aspect of the present invention, and continuous fibers. The composite material according to the first aspect exhibits excellent mechanical strength. The aromatic polyether contained in the composite material according to the first aspect may be the aromatic polyether according to one aspect of the present invention, or may not be the aromatic polyether according to one aspect of the present invention. That is, the aromatic polyether contained in the composite material according to the first aspect has an MFR of 1000 kJ / 2 ... ４ [g / 10 min] and the MFR measured after preheating the aromatic polyether at 380°C for 30 minutes ３０ [g / 10 min] is MFR ４ / MFR ３０ The condition of MFR ≧1.1 may or may not be satisfied. ４ / MFR ３０ ≧1.1.

[0080] The composite material according to the second aspect of the present invention comprises the aromatic polyether according to one aspect of the present invention or the composition according to one aspect of the present invention and continuous fibers. The composite material according to the second aspect also exhibits excellent mechanical strength.

[0081] In the following description, the composite material according to the first aspect of the present invention and the composite material according to the second aspect of the present invention may be collectively referred to as a “composite material according to one aspect of the present invention.” The composite material according to one aspect of the present invention will be described in more detail below.

[0082] In this specification, the term "continuous fiber" refers to a fiber that constitutes a woven fabric or a fiber that constitutes a unidirectional fiber that is aligned in one direction.

[0083] In one embodiment, the continuous fibers are included in the composite material in the form of a woven fabric or unidirectional fibers. The woven fabric and unidirectional fibers are not particularly limited as long as they contain continuous fibers. In one embodiment, the woven fabric and unidirectional fibers are composed of continuous fibers arranged in a plane.

[0084] The continuous fibers contained in the composite material are preferably one or more fibers selected from the group consisting of glass fibers and carbon fibers.

[0085] The shape of the continuous fiber is not particularly limited and can be one or more shapes selected from the group consisting of roving and woven fabrics made of roving. Furthermore, when the component containing continuous fibers is in the form of a woven fabric or a unidirectional material, a unidirectional bundle of continuous fibers (fiber bundle) can be used. The component containing continuous fibers may be a bundle of 3,000 (3K), 6,000 (6K), 12,000 (12K), 24,000 (24K), or 60,000 (60K) monofilaments supplied by a fiber manufacturer, or a product obtained by further bundling these monofilaments. The fiber bundle may be any of untwisted yarn, twisted yarn, and untwisted yarn. The fiber bundle may be contained in a molded product in an opened state or may be contained as a fiber bundle without being opened. When the component containing continuous fibers is a woven fabric or a unidirectional material, a molded product can be obtained by immersing the component in a resin.

[0086] The type of carbon fiber is not particularly limited, and various types of carbon fibers can be used, such as PAN-based carbon fibers made from polyacrylonitrile, pitch-based carbon fibers made from coal tar pitch in petroleum or coal, and phenol-based carbon fibers made from thermosetting resins, such as phenolic resins. The carbon fiber may be obtained by a vapor growth method or may be recycled carbon fiber (RCF). While the carbon fiber is not particularly limited, it is preferable to use at least one type of carbon fiber selected from the group consisting of PAN-based carbon fiber, pitch-based carbon fiber, thermosetting carbon fiber, phenol-based carbon fiber, vapor-grown carbon fiber, and recycled carbon fiber (RCF). The average fiber diameter of the carbon fiber is preferably 3 to 15 μm, more preferably 5 to 7 μm, of single fibers. The average fiber diameter of the carbon fiber is determined by the arithmetic mean of values ​​measured in accordance with JIS R 7607:2000.

[0087] The carbon fiber may have a sizing agent attached to its surface. When using carbon fiber with a sizing agent attached, the type of sizing agent can be appropriately selected depending on the type of carbon fiber and is not particularly limited. Various carbon fibers are commercially available, such as those treated with epoxy-based sizing agents, urethane-based sizing agents, and polyamide-based sizing agents, or those containing no sizing agent. However, in the present invention, carbon fibers can be used regardless of the type or presence or absence of a sizing agent. In addition, the sizing agent can be used in combination with a silane coupling agent such as aminosilane, isocyanate silane, or acrylic silane.

[0088] The type of glass fiber is not particularly limited, and glass fibers of various compositions, such as E-glass, low dielectric glass, and silica glass, can be selected and used depending on the purpose and application. The average fiber diameter of the glass fiber is preferably 5 to 20 μm, more preferably 7 to 17 μm, and single fibers can be used. The average fiber diameter of the glass fiber is determined as the arithmetic mean of values ​​measured in accordance with JIS R 7607:2000.

[0089] The glass fiber may have a sizing agent attached to its surface. When using glass fiber with a sizing agent attached, the type of sizing agent can be appropriately selected depending on the type of glass fiber and is not particularly limited. Various glass fibers are available, such as those treated with epoxy-based sizing agents, urethane-based sizing agents, and vinyl acetate-based sizing agents, or those containing no sizing agent. However, in the present invention, glass fibers can be used regardless of the type or presence of a sizing agent. In addition, the sizing agent can be used in combination with a silane coupling agent such as aminosilane, isocyanate silane, or acrylic silane.

[0090] In one embodiment, the average fiber length of the continuous fibers (e.g., carbon fibers or glass fibers) is 25 mm or more, 50 mm or more, or 100 mm or more, and 100 km or less, 10 km or less, 1 km or less, or 100 m or less. The average fiber length of the continuous fibers is determined by arithmetic mean.

[0091] In one embodiment, the composite material comprises continuous fibers and an aromatic polyether impregnated in the interstices between the continuous fibers. Such a composite material may, for example, comprise a woven fabric or unidirectional fabric comprising the continuous fibers and an aromatic polyether impregnated in the interstices between the continuous fibers.

[0092] In one embodiment, the composite material comprises continuous fibers and an aromatic polyether as a matrix. Such a composite material may be a so-called fiber-reinforced thermoplastic (FRTP). For example, by using unidirectional fibers as the continuous fibers, a unidirectional fiber-reinforced plastic is obtained.

[0093] The composite material may be a single sheet or a laminate of two or more sheets. When the composite material is a laminate, the aromatic polyether can also contribute to bonding the composite materials together.

[0094] In addition to the aromatic polyether and continuous fibers, the composite material may contain other components, including those described for the films, powders, and pellets according to one aspect of the present invention.

[0095] In one embodiment, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, 99.5% by mass or more, or substantially 100% by mass of the composite material is an aromatic polyether and continuous fiber, or is one or more selected from an aromatic polyether, a continuous fiber, and the other components described above. Note that "substantially 100% by mass" may contain inevitable impurities.

[0096] The method for producing the composite material described above is not particularly limited. In one embodiment, the method for producing a composite material includes contacting and integrating continuous fibers with an aromatic polyether according to one aspect of the present invention. In one embodiment, the continuous fibers can be contacted and integrated with a solution obtained by dissolving the aromatic polyether according to one aspect of the present invention in a suitable solvent, a mixture obtained by mixing the aromatic polyether according to one aspect of the present invention in a suitable vehicle, or a melt of the aromatic polyether according to one aspect of the present invention. In one embodiment, the method for producing a composite material includes producing a composite material from continuous fibers bound with a sizing agent containing the aromatic polyether.

[0097] In one embodiment, a method for producing a composite material includes a step of compounding the aromatic polyether according to one aspect of the present invention, the composition according to one aspect of the present invention, the film according to one aspect of the present invention, the powder according to one aspect of the present invention, or the pellet according to one aspect of the present invention with continuous fibers. In one embodiment, a method for producing a composite material includes pressing the aromatic polyether according to one aspect of the present invention, the composition according to one aspect of the present invention, the film according to one aspect of the present invention, the powder according to one aspect of the present invention, or the pellet according to one aspect of the present invention with continuous fibers under heated conditions. Here, "pressing under heated conditions" refers to pressing the aromatic polyether, composition, film, powder, or pellet under heated conditions so as to melt the aromatic polyether, composition, film, powder, or pellet, and is hereinafter also referred to as "melt pressing." In one embodiment, a method for producing a composite material includes a step of contacting the film according to one aspect of the present invention with a woven fabric or unidirectional fibers composed of continuous fibers, followed by melt pressing. In one embodiment, a method for producing a composite material includes a step of contacting the powder according to one aspect of the present invention with a woven fabric or unidirectional fibers composed of continuous fibers, followed by melt pressing. In one embodiment, a method for producing a composite material includes melting pellets according to one aspect of the present invention, contacting them with a woven fabric or unidirectional fibers composed of continuous fibers, and then melt pressing them.

[0098] In the above description of the method for producing a composite material, a composite material in the form of a laminate may be produced by alternately arranging two or more layers of the aromatic polyether according to one embodiment of the present invention and a woven fabric or unidirectional fiber.

[0099] In one embodiment, the composite material is flat (sheet) over its entire surface. In one embodiment, the composite material is given a three-dimensional shape. When the shape of the composite material is "three-dimensional," for example, the composite material may be a sheet including curved portions (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 three-dimensionally shaped woven fabric or unidirectional fibers 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 heat.

[0100] The applications of the aromatic polyether, film, powder, pellets, and composite material according to one embodiment of the present invention are not particularly limited and can be widely used in a variety of applications. The aromatic polyether, film, powder, pellets, and composite material according to one embodiment of the present invention are suitable as, for example, aerospace components, sliding components such as gears and bearings, filaments for 3D printers, and the like.

[0101] Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0102] 1. MFR ４ / MFR ３０Tests for Conditions of ≥ 1.1 (Example 1) A reactor was assembled by attaching a stirring blade, a stirrer, a thermocouple, a nitrogen inlet tube, a condenser, and a receiver to a four-necked, 2-L separable flask. 485.14 g (2.22 mol) of diphenyl sulfone (manufactured by Sino-High Corporation) was added to the reactor, and the reactor was conditioned under a nitrogen atmosphere. The diphenyl sulfone was then heated with a mantle heater to melt. Next, 144.23 g (0.574 mol) of 4,4'-dichlorobenzophenone (manufactured by Sino-High Corporation) and 61.70 g (0.560 mol) of hydroquinone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) were added to the reactor and allowed to melt. Next, when the temperature of the molten mixture reached 150°C, 89.06 g (0.644 mol) of potassium carbonate (Junsei Chemical Co., Ltd., special grade) was added to the reactor, and the temperature was increased to 200°C at a rate of 1°C / min. The reactor was then held at 200°C for 1 hour, then heated to 250°C over 70 minutes and held there for 1 hour, and then heated to 300°C over 110 minutes and held there for 5 hours. The reactor was then opened, and the reaction mixture was removed from the vessel and allowed to cool and solidify. The solidified material was then washed to ensure that potassium carbonate remained in the PEEK. Specifically, the solidified material was first pulverized using a blender (Waring 7010HS), followed by repeated washing with acetone and filtration. The filtered solidified material was then dispersed in ion-exchanged water, washed at 80°C, and filtered. Next, the solidified product after filtration was repeatedly washed with ion-exchanged water and filtered until the pH of the filtrate reached the value shown in Table 1. Here, in the "washing with ion-exchanged water" step, 800 ml of ion-exchanged water was added to the solidified product, and the solidified product was washed with stirring at 60°C for 20 minutes. Next, the solidified product after filtration was dried in a hot air dryer at 180°C for 5 hours to obtain PEEK.

[0103] Example 2 PEEK was obtained in the same manner as in Example 1, except that the amounts of 4,4'-dichlorobenzophenone, hydroquinone, potassium carbonate, and diphenyl sulfone used were changed as follows: 4,4'-dichlorobenzophenone: 289.01 g (1.151 mol) Hydroquinone: 123.40 g (1.121 mol) Potassium carbonate: 178.12 g (1.289 mol) Diphenyl sulfone: 970.28 g (4.45 mol)

[0104] Example 3: Commercially available PEEK (450G, manufactured by Victrex) was freeze-pulverized. An aqueous solution containing 10% potassium carbonate by mass was then added to the resulting powder, with the potassium carbonate content being 0.09 parts by mass per 100 parts by mass of PEEK. The mixture was then thoroughly mixed. The mixture was then dried in a hot air dryer at 180°C for 5 hours to obtain PEEK.

[0105] Example 4 PEEK was obtained in the same manner as in Example 3, except that commercially available PEEK (Victrex, 450G) was replaced with commercially available PEEK (Victrex, 151G).

[0106] Example 5: 41.203 g (0.164 mol) of 4,4'-dichlorobenzophenone, 17.804 g (0.162 mol) of hydroquinone, 25.707 g (0.186 mol) of potassium carbonate (Fujifilm Wako Pure Chemical Industries, Ltd., fine powder), and 140.0 g of diphenyl sulfone were placed in a 300 ml four-neck flask equipped with a stirrer, thermometer, nitrogen inlet tube, and a water collection container connected to a condenser, and nitrogen gas was circulated. The mixture was heated to 150°C, then heated to 200°C over 30 minutes and held there for 60 minutes. The mixture was then heated to 250°C over 30 minutes and held there for 60 minutes, and then heated to 300°C over 30 minutes and held there for 2 hours. After the reaction was complete, the product was pulverized in a blender (Waring, 7010HS), washed with acetone and then water, and dried in a dryer at 180°C to obtain powdered PEEK. 40 g of the resulting PEEK and 400 ml of N-methyl-2-pyrrolidone (NMP) were loaded into a separable slab and stirred at 180°C for 1 hour. The resulting mixture was then cooled to below 100°C and filtered to obtain a solid. 1000 ml of a 10% by mass aqueous solution of oxalic acid was added to the resulting solid, and the mixture was stirred at 80°C for 1 hour. The solid was then separated by filtration. This solid was washed with 1000 ml of hot water at 80°C and filtered, a cycle repeated three times. The solid was then dried at 180°C for 5 hours to obtain a powder. The total potassium (K) concentration of the resulting powder was measured and found to be less than the lower limit of quantitation, 1 ppm. An aqueous solution containing 10% by mass of potassium carbonate was added to the solid with the total K (potassium) concentration reduced as described above, so that the amount of potassium carbonate was 0.09 parts by mass per 100 parts by mass of PEEK, and the mixture was thoroughly mixed. After the addition of the aqueous solution, the total K (potassium) concentration of the PEEK was 500 ppm. The mixture was then dried in a hot air dryer at 180° C. for 5 hours to obtain PEEK.

[0107] Comparative Example 1 Commercially available PEEK (450G, manufactured by Victrex) was used as the PEEK in Comparative Example 1. The total K (potassium) concentration of the PEEK in Comparative Example 1 was less than the lower limit of quantitation, 1 ppm.

[0108] Combustion ion chromatography The fluorine atom content a and chlorine atom content b of PEEK were measured by combustion ion chromatography. Specifically, the sample was introduced into a combustion furnace and burned in combustion gas containing oxygen. The generated gas was collected in an absorption liquid, and the absorption liquid was then separated and quantified using an ion chromatograph. The quantitative values ​​were determined based on a calibration curve created from references of known concentrations. The measurement conditions are shown below. <Sample combustion> Combustion apparatus: AQF-2100H combustion furnace manufactured by Mitsubishi Chemical Analytech Co., Ltd. Set temperatures: 800°C in front, 1100°C in rear Argon flow rate: 400 ml / min Oxygen flow rate: 200 ml / min Absorbent: hydrogen peroxide <Ion chromatograph> Analytical device: Integration manufactured by Thermo Fisher Scientific Co., Ltd. Column: A guard column (Dionex IonPac AG12A) and a separation column (Dionex IonPac AS12A) were used in conjunction (both columns manufactured by Dionex). Eluent: Na ２ CO ３ (2.7 mmol / l) + NaHCO (0.3 mmol / l) Flow rate: 1.5 ml / min Column temperature: 30°C Measurement mode: Suppressor method Detector: Electrical conductivity detector The measurement results are shown below. Note that the detection limit for fluorine atoms and chlorine atoms in the above measurement method is 2 mg / kg. When these atoms are below the detection limit, they are expressed as "<2 mg / kg". Example 1: a < 2 mg / kg, b = 3200 mg / kg Example 2: a < 2 mg / kg, b = 2800 mg / kg Example 3: a = 1100 mg / kg, b < 2 mg / kg Example 4: a = 1800 mg / kg, b < 2 mg / kg Example 5: a < 2 mg / kg, b = 2100 mg / kg Comparative Example 1: a = 1100 mg / kg, b < 2 mg / kg

[0109] Measurement of MFR (Melt Flow Rate) For each of the PEEK samples of Examples 1 to 5 and Comparative Example 1, the MFR was measured using a melt indexer (L-220) manufactured by Tateyama Kagaku High-Technologies Corporation 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 was dried at 150°C for at least 2 hours. The sample was placed in a cylinder, the piston was inserted, and the sample was preheated in the cylinder for the specified time. Next, a load was applied, the piston guide was removed, and the molten sample was extruded from the die. Samples were cut out at a predetermined range of piston movement and a predetermined time (t [s]), and their masses were measured (m [g]). The MFR was calculated using the following formula: MFR [g / 10 min] = 600 / t × m The MFR measured when the preheating time was 4 minutes was used as the MFR. ４ [g / 10 min], and the MFR measured when the preheating time is 30 minutes is ３０ The ratio of these values ​​(MFR [g / 10 min]) ４ / MFR ３０ ) was calculated.

[0110] The results are shown in Table 1.

[0111]

[0112] Measurement of Mechanical Strength (Production of Aromatic Polyether / Continuous Fiber Composite Material) The mechanical strength of each of the PEEKs of Example 1 and Comparative Example 1 was measured by the following method. Using a flat press mold, the PEEK was first melted and retained at 400°C for 2 minutes, held under a pressure of 10 MPa for 1 minute, and cooled at 20°C for 1 minute to obtain a film with a thickness of 200 μm and a film with a thickness of 100 μm. In this case, a polyimide film or an aluminum plate was used as a spacer as appropriate to adjust the film thickness. The obtained film was cut into a size of 11 cm x 11 cm and used in the following process. A woven fabric made of carbon fiber (manufactured by Mitsubishi Chemical Corporation: Pyrofil woven fabric, TR3110M, basis weight 200 g / m) was used as the continuous fiber. ２ ) was prepared. The woven fabric was cut into an 11 cm square (11 cm long x 11 cm wide). The length of the continuous fiber (carbon fiber) contained in the woven fabric was 11 cm or more. Seven sheets of the obtained film and six sheets of woven fabric were alternately laminated so that the woven fabric was positioned between the films. In this case, a 200 μm film was placed between the woven fabrics, and a 100 μm film was placed as the outermost layer. The laminate was sandwiched between 100 μm thick polyimide films and placed in a press mold having a convex mold and a concave mold that had been preheated to 420°C. It was then pressed (melt-pressed) stepwise at 420°C under a pressure of 10 MPa for 5 minutes and then at 100 MPa for 25 minutes. The pressure was then returned to atmospheric pressure and cooled to 30°C to obtain an aromatic polyether / continuous fiber composite material. In all cases where PEEK was used in Examples 1 to 5 and Comparative Example 1, the thickness of the aromatic polyether / continuous fiber composite material was 1.7 mm, and the volume content (Vf) of the continuous fiber (carbon fiber) was 40%. Using a diamond cutter, the aromatic polyether / continuous fiber composite material was cut into 1 cm widths and dried at 150°C for 12 hours to prepare test specimens. Using these test specimens, the flexural strength [MPa] and flexural modulus [GPa] were measured in accordance with ISO 178:2010 under conditions of a temperature of 23°C, an indenter radius of 5 mm, a support distance of 6 cm, and a test speed of 3 mm / min.

[0113] The results are shown in Table 2.

[0114]

[0115] From Table 2, aromatic polyethers have an MFR ４ / MFR ３０ It can be seen that excellent mechanical strength is exhibited by satisfying the condition of ≧1.1.

[0116] 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. An aromatic polyether containing a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), the MFR measured after preheating the aromatic polyether at 380 °C for 4 minutes ４ [g / 10 min], and the MFR measured after preheating the aromatic polyether at 380 °C for 30 minutes ３０ [g / 10 min], and MFR ４ / MFR ３０ An aromatic polyether satisfying the condition of ≧ 1.1; A composition containing the aromatic polyether; A film containing the aromatic polyether or the composition; A powder containing the aromatic polyether or the composition; or A pellet containing the aromatic polyether or the composition; and Continuous fibers; A method for manufacturing a composite material, which uses these to manufacture a composite material. 【Chemical Formula 8】

2. The method for manufacturing a composite material according to Claim 1, wherein the aromatic polyether contains a structural unit represented by the following formula (3). 【Chemical Formula 9】

3. The method for manufacturing a composite material according to Claim 1 or 2, wherein the aromatic polyether satisfies one or both of the following conditions (A) and (B). (A) The content a of fluorine atoms is less than 2 mg / kg. (B) The content b of chlorine atoms is 2 mg / kg or more.

4. A composition containing an aromatic polyether, wherein the aromatic polyether contains a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and the MFR measured after preheating the composition at 380 ° C for 4 minutes ４ [g / 10 min], and the MFR ３０ [g / 10 min] measured after preheating the composition at 380 ° C for 30 minutes ４ / MFR ３０ A composition satisfying the condition of ≧ 1.1; A film containing the composition; A powder containing the composition; or A pellet containing the composition; and Continuous fibers; A method for manufacturing a composite material, which uses these to manufacture a composite material. 【Chemical Formula 10】

5. The method for manufacturing a composite material according to Claim 4, wherein the aromatic polyether contains a structural unit represented by the following formula (3). 【Chemical 11】

6. The method for manufacturing a composite material according to Claim 4 or 5, wherein the composition satisfies one or both of the following conditions (A) and (B). (A) The content a of fluorine atoms is less than 2 mg / kg. (B) The content b of chlorine atoms is 2 mg / kg or more.

7. The method for manufacturing a composite material according to Claim 1 or 4, which includes a step of composite - ing the aromatic polyether, the composition, the film, the powder or the pellet with the continuous fibers.

8. The method for manufacturing a composite material according to Claim 1 or 4, which includes pressing the aromatic polyether, the composition, the film, the powder or the pellet and the continuous fibers under heating.

9. An aromatic polyether containing a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), wherein the MFR 4 [g / 10 min] measured after pre - heating the aromatic polyether at 380°C for 4 minutes and the MFR 30 [g / 10 min] measured after pre - heating the aromatic polyether at 380°C for 30 minutes satisfy the condition of MFR 4 / MFR 30 ≧ 1.1; or A composition containing the aromatic polyether; and Continuous fibers; A composite material comprising these. 【Chemical 12】

10. The composite material according to claim 9, wherein the aromatic polyether contains a structural unit represented by the following formula (3). 【Chemical 13】

11. The composite material according to claim 9 or 10, wherein the aromatic polyether satisfies one or both of the following conditions (A) and (B). (A) The content a of fluorine atoms is less than 2 mg / kg. (B) The content b of chlorine atoms is 2 mg / kg or more.

12. A composition containing an aromatic polyether, wherein the aromatic polyether contains a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and the MFR 4 [g / 10 min] measured after preheating the composition at 380°C for 4 minutes and the MFR 30 [g / 10 min] measured after preheating the composition at 380°C for 30 minutes satisfy the condition of MFR 4 / MFR 30 ≧ 1.1, and continuous fibers, A composite material comprising 【Chemical Formula 14】

13. The composite material according to claim 12, wherein the aromatic polyether contains a structural unit represented by the following formula (3). 【Chemical Formula 15】

14. The composite material according to claim 12 or 13, wherein the composition satisfies one or both of the following conditions (A) and (B). (A) The content a of fluorine atoms is less than 2 mg / kg. (B) The content b of chlorine atoms is 2 mg / kg or more.

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