Aromatic polyether, resin composition, composite material, and molded body

Abstract

Provided is an aromatic polyether that, in differential scanning calorimetry (DSC), does not crystallize in a first cooling process in which the molten aromatic polyether is cooled, but does crystallize in an isothermal holding process in which the molten aromatic polyether is held at 210°C for 5-120 min.

Description

Aromatic polyether, resin composition, composite material, and molded article

[0001] The present invention relates to an aromatic polyether, a resin composition, a composite material, and a molded article. Specifically, the present invention relates to an aromatic polyether, a resin composition, a composite material, and a molded article having excellent heat resistance and moldability.

[0002] Aromatic polyethers typified by polyether ether ketone (PEEK) are classified as semi-crystalline resins and are known to exhibit high heat resistance due to crystallization. Patent Document 1 discloses that a specific polyether-based block copolymer has crystallinity and high heat resistance.

[0003] Japanese Patent Application Laid-Open No. 3-181519

[0004] However, conventional aromatic polyethers including Patent Document 1 are liable to crystallize, and room for improvement has been found from the viewpoint of moldability.

[0005] One object of the present invention is to provide an aromatic polyether, a resin composition, a composite material, and a molded article having excellent heat resistance and moldability.

[0006] As a result of diligent research, the inventors have found that aromatic polyethers that exhibit specific crystallization behavior or are random copolymers containing specific structures exhibit excellent heat resistance and moldability, thus completing the present invention. According to the present invention, the following aromatic polyethers can be provided: 1. An aromatic polyether that, in differential scanning calorimetry (DSC), does not crystallize in a first cooling process in which the molten aromatic polyether is cooled, but crystallizes in an isothermal holding process in which the molten aromatic polyether is held at 210°C for 5 minutes or more and 120 minutes or less. 2. The aromatic polyether according to 1, wherein the differential scanning calorimetry (DSC) comprises, in this order, a first heating process in which the aromatic polyether is heated to 360°C to melt it, and the first cooling process. 3. The aromatic polyether according to 2, wherein in the first heating process, the aromatic polyether is heated from 50°C at a rate of 20°C / min. 4. 1. An aromatic polyether according to any one of 1 to 3, wherein in the first cooling process, the molten aromatic polyether is cooled to the glass transition temperature (Tg) of the aromatic polyether. 5. An aromatic polyether according to any one of 1 to 4, wherein in the first cooling process, the aromatic polyether is cooled at a rate of 20°C / min. 6. An aromatic polyether according to any one of 1 to 5, wherein the melting is by heating. 7. An aromatic polyether according to any one of 1 to 6, wherein the enthalpy change ΔH in the first cooling process is 13 J / g or less. 8. An aromatic polyether according to any one of 1 to 7, wherein the enthalpy change ΔH in the first cooling process is 0 J / g. 9. An aromatic polyether according to any one of 1 to 8, wherein the enthalpy change ΔH in the isothermal holding process is greater than 13 J / g. 10. An aromatic polyether according to any one of 1 to 9, comprising a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). [In formula (1), A includes one or more selected from the group consisting of structural units represented by the following formulas (A1) and (A2). (In formula (A1), X Ａ１ is -C (=O)- or -S (=O) ２ This indicates that X Ａ２ and XＡ３ These are, independently, -C (=O)- or -S (=O) ２ - indicates.) B includes one or more selected from the group consisting of structural units represented by the following formulas (B1) to (B3). (In formula (B1), R Ｂ (where * represents a hydrogen atom or a phenyl group.) n is an integer from 0 to 2. When n is 0, the oxygen atom in formula (1) is directly bonded to an adjacent structural unit. When n is 1, *1 of B represents a bond with the oxygen atom in formula (1), and *2 of B represents a bond with an adjacent structural unit. When n is 2, of the two Bs, *1 of B adjacent to the oxygen atom in formula (1) represents a bond with the oxygen atom in formula (1), and *2 of B furthest from the oxygen atom in formula (1) represents a bond with an adjacent structural unit. [In formula (2), B is as defined in formula (1). B in formula (1) and B in formula (2) may be the same or different. m is an integer from 0 to 2. When m is 0, the oxygen atom in formula (1) is directly bonded to an adjacent structural unit. When m is 1, *1 of B represents a bond with the oxygen atom in formula (2), and *2 of B represents a bond with an adjacent structural unit. When m is 2, of the two Bs, *1 of B adjacent to the oxygen atom in formula (2) represents a bond with the oxygen atom in formula (2), and *2 of B furthest from the oxygen atom in formula (2) represents a bond with an adjacent structural unit.] 11. The aromatic polyether according to 10, wherein the mol ratio of the structural unit represented by formula (2) to the sum of the structural units represented by formula (1) and the structural units represented by formula (2) ((2) / ((1) + (2))) is 23 to 43%. 12. The aromatic polyether according to 10 or 11, which is a random copolymer containing the structural unit represented by formula (1) and the structural unit represented by formula (2). 13. The aromatic polyether according to any one of 10 to 12, wherein formula (1) is a structural unit represented by the following formula (a) and formula (2) is a structural unit represented by the following formula (b). 14. The aromatic polyether according to any one of 1 to 13, having a melting point of 320 ° C or lower. 15. The aromatic polyether according to any one of 1 to 14, having a molecular weight distribution (Mw / Mn) of 2.0 to 3.0. 16. The aromatic polyether according to any one of 1 to 15, containing benzophenone, benzonitrile and hydroquinone as monomer units. 17. The total number of chains BHB composed of benzophenone-hydroquinone-benzophenone, the total number of chains BHN composed of benzophenone-hydroquinone-benzonitrile, and the total number of chains NHN composed of benzonitrile-hydroquinone-benzonitrile, the fraction R of the total number of the chains BHN in the total of these ＢＨＮ The aromatic polyether according to 16, wherein the fraction R is 30 to 45%. 18. The total number of chains BHB composed of benzophenone-hydroquinone-benzophenone, the total number of chains BHN composed of benzophenone-hydroquinone-benzonitrile, and the total number of chains NHN composed of benzonitrile-hydroquinone-benzonitrile, the fraction R of the total number of the chains BHN in the total of these ＢＨＮ divided by the chain fraction R of statistically random chains BHN ｒａｎｄｏｍ gives a value (R ＢＨＮ / R ｒａｎｄｏｍ) an aromatic polyether according to 16 or 17, wherein the ratio is 0.8 or higher. 19. An aromatic polyether according to any one of 1 to 18, which is a copolymer of dihalogenobenzophenone, dihalogenobenzonitrile, and hydroquinone. 20. An aromatic polyether according to 19, wherein the dihalogenobenzonitrile is 2,6-dichlorobenzonitrile. 21. An aromatic polyether according to 19 or 20, wherein the dihalogenobenzophenone is 4,4'-difluorobenzophenone. 22. A resin composition comprising an aromatic polyether according to any one of 1 to 21 and an amorphous resin. 23. The resin composition according to 22, wherein the amorphous resin comprises one or more selected from the group consisting of polyetherimide (PEI), polyethersulfone (PES), polyphenylene ether (PPE), polysulfone (PSU), and polyimide (PI). 24. The resin composition according to 22, wherein the amorphous resin comprises polyetherimide (PEI). 25. 26. A resin composition according to any one of 22 to 24, wherein the content of the amorphous resin is 10 to 300 parts by mass per 100 parts by mass of the aromatic polyether. 27. A resin composition that, in differential scanning calorimetry (DSC), does not crystallize in a first cooling process in which the molten resin composition is cooled, but crystallizes in an isothermal holding process in which the molten resin composition is held at 210°C for 5 minutes or more and 120 minutes or less. 28. A composite material comprising an aromatic polyether according to any one of 1 to 21 or a resin composition according to any one of 22 to 26, and reinforcing fibers. 29. A composite material according to 27, wherein the content of the reinforcing fibers is 10 to 500 parts by mass per 100 parts by mass of the aromatic polyether or resin composition. 21. A molded article made of an aromatic polyether according to any one of 1 to 21 or a resin composition according to any one of 22 to 26.

[0007] According to the present invention, it is possible to provide aromatic polyethers, resin compositions, composite materials, and molded articles that have excellent heat resistance and moldability.

[0008] Figure 1 is a DSC chart obtained during the cooling process in the measurement of the heat of crystallization of the aromatic polyether of Example 1. Figure 2 is a DSC chart obtained during the isothermal holding process in the measurement of the heat of crystallization of the aromatic polyether of Example 1. Figure 3 is an NMR chart obtained in the analysis of the monomer composition of the aromatic polyether of Example 1. Figure 4 is an NMR chart obtained in the analysis of the monomer composition of the aromatic polyether of Example 1. １３ This is a C-NMR spectrum.

[0009] The following describes in detail the aromatic polyether, resin composition, composite material, and molded article of the present invention, which are excellent in heat resistance and moldability. In this specification, "x to y" represents a numerical range of "x or more, and y or less". The upper and lower limits described for the numerical range can be combined arbitrarily. Furthermore, it is possible to combine two or more non-conflicting embodiments of the embodiments of the present invention described below, and an embodiment that combines two or more embodiments is also an embodiment of the embodiments of the present invention.

[0010] 1. Aromatic Polyether An aromatic polyether according to one aspect of the present invention (also referred to as the "first aromatic polyether") does not crystallize in a first cooling process in which the molten aromatic polyether is cooled, as observed in differential scanning calorimetry (DSC), but crystallizes in an isothermal holding process in which the molten aromatic polyether is held at 210°C for 5 minutes or more and 120 minutes or less.

[0011] The aromatic polyether according to this embodiment provides excellent heat resistance and moldability. In particular, it is possible to obtain a molded article that is fluid during molding and has excellent moldability, and has heat resistance after molding. The reason why such effects are obtained is not entirely clear, but it is thought that the above effects are produced by restricting molecular mobility below the melting point through crystallization.

[0012] Aromatic polyethers are more easily crystallized by adopting structures that allow polymer chains to easily align in close proximity, for example, by increasing the proportion of regular structures. Conversely, aromatic polyethers become less crystallized when they are made into random copolymers, for example, because the regularity of the molecular chains decreases. By adjusting the ease of crystallization in this way, it is possible to adjust the aromatic polyether to possess the crystallization behavior of the first aromatic polyether described above.

[0013] In one embodiment, differential scanning calorimetry (DSC) includes a first heating step of heating up to 360°C to melt the aromatic polyether. In one embodiment, differential scanning calorimetry (DSC) includes a first heating step of heating up to 360°C to melt the aromatic polyether, followed by a first cooling step, in that order. In one embodiment, the aromatic polyether does not crystallize during the first heating step.

[0014] In one embodiment, during the first heating process, the aromatic polyether is heated from 50°C at a rate of 20°C / min.

[0015] In one embodiment, during the first cooling process, the molten aromatic polyether is cooled to its glass transition temperature (Tg). The glass transition temperature (Tg) of the aromatic polyether can be measured by differential scanning calorimetry (DSC).

[0016] In one embodiment, during the first cooling process, the molten aromatic polyether is cooled to 150°C, 100°C, 80°C, and 50°C.

[0017] In one embodiment, during the first cooling process, the aromatic polyether is cooled at a rate of 20°C / min.

[0018] In this specification, “melted” means that the aromatic polyether is molten and in a state in which it can flow when an external force is applied. “Melted” includes a state in which the aromatic polyether is partially molten, substantially molten, or completely molten, preferably a state in which the aromatic polyether is completely molten.

[0019] To melt an aromatic polyether, it is necessary to heat it above its melting point. Melting can be observed as an endothermic peak during the heating process in differential scanning calorimetry (DSC). Normally, in differential scanning calorimetry (DSC), a solid aromatic polyether at room temperature is heated (heating process) to bring it to a melted state, and then the heat flow is observed while it is cooled (first cooling process) or while it is held at a constant temperature (isothermal holding process). However, this does not preclude the use of aromatic polyether that has been preheated and is in a molten state for differential scanning calorimetry (DSC).

[0020] In differential scanning calorimetry (DSC), if the enthalpy change ΔH (hereinafter also simply referred to as ΔH) in the first cooling process is 13 J / g or less, it is determined that the aromatic polyether "did not crystallize in the first cooling process." In one embodiment, ΔH in the first cooling process is 0 J / g or less than the detection limit.

[0021] ΔH during the first cooling process can be measured by the method described in the examples.

[0022] In differential scanning calorimetry (DSC), if ΔH in the first heating process is 13 J / g or less, it is determined that the aromatic polyether "did not crystallize in the first heating process." In one embodiment, ΔH in the first heating process is 0 J / g or below the detection limit.

[0023] ΔH during the first heating process can be measured by the method described in the examples.

[0024] In differential scanning calorimetry (DSC), if the ΔH during the isothermal holding process is greater than 13 J / g, it is determined that the aromatic polyether "crystallizes during the isothermal holding process."

[0025] In the isothermal holding process, the aromatic polyether is held at 210°C for 5 minutes to 120 minutes. The holding time at 210°C may be the time until the crystallization of the aromatic polyether is completed, for example, 5 minutes to 60 minutes, 10 minutes to 60 minutes, 5 minutes to 50 minutes, 10 minutes to 50 minutes, 5 minutes to 40 minutes, 10 minutes to 40 minutes, 5 minutes to 30 minutes, or 10 minutes to 30 minutes.

[0026] Furthermore, it is not necessary to perform the differential scanning calorimetry (DSC) for the first cooling process after melting and the differential scanning calorimetry (DSC) for the isothermal holding process in sequence. Samples can be prepared separately from the same aromatic polyether, and the differential scanning calorimetry (DSC) for the first cooling process and the differential scanning calorimetry (DSC) for the isothermal holding process can be performed independently.

[0027] In one embodiment, the aromatic polyether comprises a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). [In formula (1), A includes one or more selected from the group consisting of structural units represented by the following formulas (A1) and (A2). (In formula (A1), X Ａ１ is -C (=O)- or -S (=O) ２ This indicates that X Ａ２ and X Ａ３ These are, independently, -C (=O)- or -S (=O) ２ - indicates.) B includes one or more selected from the group consisting of structural units represented by the following formulas (B1) to (B3). (In formula (B1), R Ｂ (where * represents a hydrogen atom or a phenyl group.) n is an integer from 0 to 2. When n is 0, the oxygen atom in formula (1) is directly bonded to an adjacent structural unit. When n is 1, *1 of B represents a bond with the oxygen atom in formula (1), and *2 of B represents a bond with an adjacent structural unit. When n is 2, of the two Bs, *1 of B adjacent to the oxygen atom in formula (1) represents a bond with the oxygen atom in formula (1), and *2 of B furthest from the oxygen atom in formula (1) represents a bond with an adjacent structural unit. [In formula (2), B is as defined in formula (1). B in formula (1) and B in formula (2) may be the same or different. m is an integer from 0 to 2. When m is 0, the oxygen atom in formula (1) is directly bonded to an adjacent structural unit. When m is 1, *1 of B represents a bond with the oxygen atom in formula (2), and *2 of B represents a bond with an adjacent structural unit. When m is 2, of the two Bs, *1 of B adjacent to the oxygen atom in formula (2) represents a bond with the oxygen atom in formula (2), and *2 of B furthest from the oxygen atom in formula (2) represents a bond with an adjacent structural unit.]

[0028] (Structural units represented by formula (1)) In a structural unit represented by formula (1), if there are two or more structural units represented by formulas (A1) to (A2), each of the two or more structural units represented by formulas (A1) to (A2) may be the same as or different from each other. If there are two or more structural units represented by formulas (B1) to (B3), each of the two or more structural units represented by formulas (B1) to (B3) may be the same as or different from each other.

[0029] In formulas (A1) to (A2) and (B1) to (B2), a bond crossing the skeleton constituting a benzene ring means a bond to a carbon atom constituting the benzene ring at a bondable position. In formula (B3), a bond crossing the skeleton constituting a naphthalene ring means a bond to a carbon atom constituting the naphthalene ring at a bondable position.

[0030] For example, formula (A1) encompasses all of the following structures:

[0031] In one embodiment, A in formula (1) is the structure represented by formula (A1). In one embodiment, X in formula (A1) Ａ１ This is -C (=O)-.

[0032] In one embodiment, A in formula (1) is a structure represented by the following formula (A1-1).

[0033] In one embodiment, B in formula (1) is a structure represented by formula (B1) or formula (B2). In one embodiment, R in formula (B1) Ｂ This is a hydrogen atom.

[0034] (Structural units represented by formula (2)) In a structural unit represented by formula (2), if there are two or more structural units represented by formulas (B1) to (B3), each of the two or more structural units represented by formulas (B1) to (B3) may be the same as or different from one another.

[0035] In formulas (2) and (B1) to (B2), a bond crossing the skeleton constituting the benzene ring means a bond to a carbon atom constituting the benzene ring at a bondable position. In formula (B3), a bond crossing the skeleton constituting the naphthalene ring means a bond to a carbon atom constituting the naphthalene ring at a bondable position.

[0036] In one embodiment, B in formula (2) is a structure represented by formula (B1) or formula (B2). In one embodiment, R in formula (B1) Ｂ This is a hydrogen atom.

[0037] In one embodiment, the structural unit represented by formula (2) is represented by the following formula (2-1).

[0038] In one embodiment, formula (1) is a structural unit represented by the following formula (a), and formula (2) is a structural unit represented by the following formula (b).

[0039] In one embodiment, the structural unit represented by formula (b) is the structural unit represented by the following formula (b').

[0040] In one embodiment, the molar ratio of the structural unit represented by formula (2) to the sum of the structural units represented by formula (1) and the structural units represented by formula (2) ((2) / (1)+(2)) is 23 to 43%. The molar ratio ((2) / (1)+(2)) is preferably 23 to 43%, more preferably 25 to 40%, more preferably 27 to 37%, and more preferably 30 to 35%. This molar ratio can of course also be applied as the molar ratio of the structural unit represented by formula (b) to the sum of the structural units represented by formula (a) and the structural units represented by formula (b) ((b) / (a)+(b)). If this molar ratio is within the above range, it is easy to obtain specific crystallization characteristics in which crystallization does not occur during the first cooling process in which the molten aromatic polyether is cooled, but crystallizes during the isothermal holding process in which the molten aromatic polyether is held at 210°C for 5 minutes or more and 120 minutes or less.

[0041] These mol ratios ((2) / (1)+(2)) and mol ratios ((b) / ((a)+(b))) can correspond to the mol ratios of each monomer component in the aromatic polyether. Furthermore, these mol ratios ((2) / (1)+(2)) and mol ratios ((b) / ((a)+(b))) can correspond to the mol ratios of the amounts of each monomer charged in the copolymerization reaction to produce the aromatic polyether.

[0042] In one embodiment, 50% or more by mass of the aromatic polyether is 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass, of the structural units represented by formula (1) and formula (2), or of the structural units represented by formula (a) and formula (b), or of the structural units represented by formula (a) and formula (b'). In the case of "substantially 100% by mass", unavoidable impurities may be included.

[0043] In one embodiment, the aromatic polyether is a random copolymer containing structural units represented by formula (1) and structural units represented by formula (2). In one embodiment, the aromatic polyether is a random copolymer containing structural units represented by formula (a) and structural units represented by formula (b). In one embodiment, the aromatic polyether is a random copolymer containing structural units represented by formula (a) and structural units represented by formula (b'). The random copolymer nature of the aromatic polyether reduces the regularity of the molecular chains, making it difficult to crystallize.

[0044] In one embodiment, the aromatic polyether contains benzophenone, benzonitrile, and hydroquinone as monomer units. In this embodiment, the fraction R of the total number of chained BHNs is the sum of the total number of chained BHBs consisting of benzophenone-hydroquinone-benzophenone, the total number of chained BHNs consisting of benzophenone-hydroquinone-benzonitrile, and the total number of chained NHNs consisting of benzonitrile-hydroquinone-benzonitrile. ＢＨＮ It is preferable that the ratio is 30-45%. In this embodiment, the fraction R of the total number of chained BHNs in the sum of the total number of chained BHBs consisting of benzophenone-hydroquinone-benzophenone, the total number of chained BHNs consisting of benzophenone-hydroquinone-benzonitrile, and the total number of chained NHNs consisting of benzonitrile-hydroquinone-benzonitrile ＢＨＮ R is the fraction of the total number of statistically randomly linked BHNs. ｒａｎｄｏｍ The value obtained by dividing by (R ＢＨＮ / R ｒａｎｄｏｍ ) is preferably 0.8 or higher. ＢＨＮ and R ＢＨＮ / R ｒａｎｄｏｍ This is a value measured based on the method described in the examples.

[0045] The above chain fractions (also called "chain fractions") will be explained in more detail. When an aromatic polyether contains benzophenone, benzonitrile, and hydroquinone as monomer units, these monomer units are polymerized by polycondensation reactions, and hydroquinone forms an ether bond with either benzophenone or benzonitrile. The bonding patterns (chains) consist of benzophenone-hydroquinone-benzophenone (hereinafter also called "BHB"), benzophenone-hydroquinone-benzonitrile (hereinafter also called "BHN"), and benzonitrile-hydroquinone-benzonitrile (hereinafter also called "NHN"). In general, the chain fraction is used as an indicator of randomness (Riichiro Nakajo, NMR of Polymers and Biomolecules, Tokyo Kagaku Dojin, 1992, pp. 66-67). The chain fraction is a structural factor related to crystallization behavior. A larger BHB chain fraction indicates higher blocking properties and thus easier crystallization, while a larger BHN chain fraction indicates higher randomness and thus inhibits crystallization. If the NHN chain fraction is excessively large, crystallization is inhibited and amorphous material is formed. This chain fraction is related to the quaternary carbon of hydroquinone. １３ By utilizing the fact that the C-NMR peaks are different for BHB, BHN, and NHN, an inverse gate is used. １３ It can be evaluated by the peak area of ​​C-NMR. Furthermore, the peak areas originating from BHB, BHN, and NHN correspond to the total number of chains for each. After diligent study, the chain fraction of BHN in the total of BHB, BHN, and NHN (hereafter, R) ＢＨＮ It was found that when the concentration is 30-45%, crystallization does not occur at a cooling rate of 20°C / min, but sufficient crystallinity is achieved by annealing at 210°C. From this discovery, R ＢＨＮ If the concentration is 30-45%, it is thought that the rigidification of molecules caused by chain BHB is suppressed, and as a result, crystallization does not occur at a cooling rate of 20°C / min. ＢＨＮ R is the chain fraction of BHNs that is statistically random. ｒａｎｄｏｍ The result of dividing by (R ＢＨＮ / R ｒａｎｄｏｍ If the value is 0.8 or higher, it is considered to have a moderate degree of randomness.

[0046] In one embodiment, the aromatic polyether is a copolymer of dihalogenobenzophenone, dihalogenobenzonitrile, and hydroquinone. In this embodiment, it is preferable that the dihalogenobenzonitrile is 2,6-dichlorobenzonitrile. In this embodiment, it is preferable that the dihalogenobenzophenone is 4,4'-difluorobenzophenone. This results in a molded article using the aromatic polyether having excellent mechanical strength. This effect is even more pronounced when, for example, 4,4'-dichlorobenzophenone is used instead of 4,4'-difluorobenzophenone.

[0047] The explanation given for the second aromatic polyether below can be appropriately applied to the first aromatic polyether.

[0048] An aromatic polyether according to another aspect of the present invention (also referred to as the "second aromatic polyether") contains two or more structural units represented by the following formula (1). [In formula (1), A includes one or more selected from the group consisting of structural units represented by the following formulas (A1) to (A3). (In formula (A1), X Ａ１ is -C (=O)- or -S (=O) ２ This indicates that X Ａ２ and X Ａ３ These are, independently, -C (=O)- or -S (=O) ２ - indicates. In formula (A3), R Ａ (This indicates a cyano group.) B includes one or more selected from the group consisting of structural units represented by the following formulas (B1) to (B3). (In formula (B1), R Ｂ(where * represents a hydrogen atom or a phenyl group.) n is an integer from 0 to 2. When n is 0, the oxygen atom in formula (1) is directly bonded to an adjacent structural unit. When n is 1, *1 of B represents a bond with the oxygen atom in formula (1), and *2 of B represents a bond with an adjacent structural unit. When n is 2, of the two Bs, *1 of B adjacent to the oxygen atom in formula (1) represents a bond with the oxygen atom in formula (1), and *2 of B furthest from the oxygen atom in formula (1) represents a bond with an adjacent structural unit.

[0049] If there are two or more structural units represented by formulas (A1) to (A3), each of the two or more structural units represented by formulas (A1) to (A3) may be identical or different from one another. If there are two or more structural units represented by formulas (B1) to (B3), each of the two or more structural units represented by formulas (B1) to (B3) may be identical or different from one another.

[0050] In formulas (A1) to (A3) and (B1) to (B2), a bond crossing the skeleton constituting a benzene ring means a bond to a carbon atom constituting the benzene ring at a bondable position. In formula (B3), a bond crossing the skeleton constituting a naphthalene ring means a bond to a carbon atom constituting the naphthalene ring at a bondable position.

[0051] For example, formula (A1) encompasses all of the following structures:

[0052] In one embodiment, A in formula (1) is a structure represented by formula (A1) or formula (A3). In one embodiment, X in formula (A1) Ａ１ This is -C (=O)-.

[0053] In one embodiment, A in formula (1) is a structure represented by the following formula (A1-1).

[0054] In one embodiment, B in formula (1) is a structure represented by formula (B1) or formula (B2). In one embodiment, R in formula (B1) Ｂ This is a hydrogen atom.

[0055] In one embodiment, the aromatic polyether contained in the mixture includes a structural unit represented by the following formula (1-1).

[0056] In one embodiment, the second aromatic polyether is a random copolymer comprising structural units represented by the following formula (a) and structural units represented by the following formula (b), wherein the mol ratio of the structural units represented by formula (b) to the sum of the structural units represented by formula (a) and the structural units represented by formula (b) ((b) / ((a)+(b))) is 23-43%.

[0057] The aromatic polyether according to this embodiment provides excellent heat resistance and moldability. The reason for obtaining such effects is not entirely clear, but it is thought that when (b) / ((a)+(b)) is within the above range, the aromatic polyether is more likely to exhibit a predetermined crystallization behavior, and this is how the above effects are manifested.

[0058] In one embodiment, the structural unit represented by formula (b) is the structural unit represented by the following formula (b').

[0059] In one embodiment, 50% or more by mass of the second aromatic polyether is 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass is the structural unit represented by formula (a) and the structural unit represented by formula (b). In the case of "substantially 100% by mass", unavoidable impurities may be included.

[0060] In one embodiment, the second aromatic polyether is a random copolymer of 4,4'-dihalogenobenzophenone (DXBP), dihalogenobenzonitrile (DXBN), and hydroquinone (HQ). In one embodiment, the second aromatic polyether is a random copolymer containing 4,4'-dihalogenobenzophenone (DXBP), dihalogenobenzonitrile (DXBN), and hydroquinone (HQ) as monomer components. The structural unit represented by formula (a) may be a linkage of 4,4'-dihalogenobenzophenone (DXBP) and hydroquinone (HQ). The structural unit represented by formula (b) may be a linkage of dihalogenobenzonitrile (DXBN) and hydroquinone (HQ).

[0061] Examples of 4,4'-dihalogenobenzophenones (DXBP) include 4,4'-difluorobenzophenone (DFBP) and 4,4'-dichlorobenzophenone (DCBP).

[0062] Examples of dihalogenobenzonitriles (DXBNs) include difluorobenzonitrile (DFBN) and dichlorobenzonitrile (DCBN).

[0063] In one embodiment, the second aromatic polyether is a random copolymer of 4,4'-difluorobenzophenone (DFBP), dichlorobenzonitrile (DCBN), and hydroquinone (HQ).

[0064] In one embodiment, the second aromatic polyether is a random copolymer of 4,4'-dichlorobenzophenone (DCBP), dichlorobenzonitrile (DCBN), and hydroquinone (HQ).

[0065] In one embodiment, the molar ratio of the structural unit represented by formula (b) to the sum of the structural units represented by formula (a) and the structural unit represented by formula (b) ((b) / ((a) + (b))) is preferably 23 to 43%, more preferably 25 to 40%, more preferably 27 to 37%, and more preferably 30 to 35%. This makes it easier to obtain specific crystallization characteristics, such as not crystallizing in the first cooling process in which the molten aromatic polyether is cooled, but crystallizing in the isothermal holding process in which the molten aromatic polyether is held at 210°C for 5 minutes or more and 120 minutes or less.

[0066] This mol ratio ((b) / ((a)+(b))) can correspond to the mol ratio of each monomer component in the aromatic polyether. Furthermore, this mol ratio ((b) / ((a)+(b))) can correspond to the mol ratio of the amount of each monomer charged in the copolymerization reaction to produce the aromatic polyether.

[0067] The second aromatic polyether can be produced, for example, by reacting the raw materials corresponding to each monomer unit in the same reaction system. For example, 4,4'-dihalogenobenzophenone (DXBP), dihalogenobenzonitrile (DXBN), and hydroquinone (HQ) can be charged together in a reaction vessel and reacted.

[0068] In one embodiment, the second aromatic polyether does not crystallize during the first cooling process in differential scanning calorimetry (DSC), in which the molten aromatic polyether is cooled, but crystallizes during the isothermal holding process in which the molten aromatic polyether is held at 210°C for 5 minutes or more and 120 minutes or less. The matters described for the first aromatic polyether can be applied to differential scanning calorimetry (DSC), the first cooling process, the isothermal holding process, and crystallization.

[0069] An aromatic polyether according to yet another aspect of the present invention (also known as the "third aromatic polyether") is a random copolymer comprising a structural unit represented by the following formula (a) and a structural unit represented by the following formula (c), wherein the mol ratio of the structural unit represented by formula (c) to the sum of the structural units represented by formula (a) and the structural unit represented by formula (c) ((c) / ((a)+(c))) is 20-50%.

[0070] The aromatic polyether according to this embodiment provides excellent heat resistance and moldability. The reason for obtaining such effects is not entirely clear, but it is thought that when (c) / ((a)+(c)) is within the above range, the aromatic polyether is more likely to exhibit a predetermined crystallization behavior, and this is how the above effects are manifested.

[0071] In the third aromatic polyether, the substitution position (bonding position) of the phenyl group in the structural unit represented by formula (c) can be any position on the benzene ring constituting the main chain, as shown on the far right in formula (c) (the phenyl group is introduced so as to substitute for any of the four hydrogen atoms on the benzene ring). If two or more structural units represented by formula (c) are adjacent in the third aromatic polyether, the third aromatic polyether may include one or more structures selected from the group consisting of the structure represented by (c1), the structure represented by (c2), and the structure represented by (c3) below.

[0072] In each of the structures represented by formulas (c1) to (c3) above, the substitution positions of the phenyl groups in the two structural units represented by formula (c) that form the structure are different from each other. The effects of the present invention are well exhibited in any of these structures. Here, the case in which two or more structural units represented by formula (c) are adjacent to each other has been described, but even when two or more structural units represented by formula (c) are arranged via other structural units (for example, structural units represented by formula (a)), the substitution positions of the phenyl groups in these structural units represented by formula (c) may be the same or different from each other. In either case, the effects of the present invention are well exhibited.

[0073] In one embodiment, 50% or more by mass of the third aromatic polyether is 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass is the structural unit represented by formula (a) and the structural unit represented by formula (c).

[0074] In one embodiment, the third aromatic polyether is a random copolymer of 4,4'-difluorobenzophenone (DFBP), 2-phenylhydroquinone (Ph-HQ), and hydroquinone (HQ). In one embodiment, the third aromatic polyether is a random copolymer containing 4,4'-difluorobenzophenone (DFBP), 2-phenylhydroquinone (Ph-HQ), and hydroquinone (HQ) as monomer components. The structural unit represented by formula (a) may be a conjugation of 4,4'-difluorobenzophenone (DFBP) and hydroquinone (HQ). The structural unit represented by formula (c) may be 2-phenylhydroquinone (Ph-HQ).

[0075] In one embodiment, the third aromatic polyether is a random copolymer of 4,4'-difluorobenzophenone (DFBP), 2-phenylhydroquinone (Ph-HQ), and hydroquinone (HQ).

[0076] In one embodiment, the molar ratio of the structural unit represented by formula (c) to the sum of the structural units represented by formula (a) and the structural units represented by formula (c) ((c) / ((a)+(c))) is 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, and also 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, or 25% or less.

[0077] This mol ratio ((c) / ((a)+(c))) can correspond to the mol ratio of each monomer component in the aromatic polyether. Furthermore, this mol ratio ((c) / ((a)+(c))) can correspond to the mol ratio of the amount of each monomer charged in the copolymerization reaction to produce the aromatic polyether.

[0078] A third aromatic polyether can be produced, for example, by reacting the raw materials corresponding to each monomer unit in the same reaction system. For example, 4,4'-difluorobenzophenone (DFBP), 2-phenylhydroquinone (Ph-HQ), and hydroquinone (HQ) can be charged together in a reaction vessel and reacted.

[0079] In one embodiment, the third aromatic polyether does not crystallize in a first cooling process in differential scanning calorimetry (DSC) where the molten aromatic polyether is cooled, but crystallizes in an isothermal holding process where the molten aromatic polyether is held at 210°C for 5 minutes or more and 120 minutes or less. The matters described for the first aromatic polyether can be applied to differential scanning calorimetry (DSC), the first cooling process, the isothermal holding process, and crystallization.

[0080] In one embodiment, the reaction system for producing an aromatic polyether (also called the "reaction mixture") includes a solvent in addition to the monomers described above. The solvent is not particularly limited, and for example, a neutral polar solvent can be used. Examples of neutral 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. Examples include 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, and diphenyl sulfone. Among these, diphenyl sulfone is particularly preferred. By using diphenyl sulfone, it is easy to obtain an aromatic polyether (an aromatic polyether exhibiting specific crystallization behavior) according to one aspect of the present invention.

[0081] The reaction mixture may contain one or more solvents. It is particularly preferable that the reaction mixture contains only one solvent (single solvent), which simplifies the process.

[0082] In one embodiment, the reaction mixture contains a base. The reaction is accelerated by the presence of a base in the reaction mixture. The base is not particularly limited and examples include alkali metal salts. Examples of alkali metal salts include alkali metal carbonates and alkali metal bicarbonates. Examples of alkali metal carbonates include potassium carbonate, lithium carbonate, rubidium carbonate, and cesium carbonate. Examples of alkali metal bicarbonates include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, and cesium bicarbonate. Among these, potassium carbonate is particularly preferred. These bases may be used individually or in combination of two or more.

[0083] In one embodiment, the reaction mixture is heated. The maximum temperature of the reaction mixture during the reaction (maximum temperature reached) is not particularly limited as long as it is the temperature at which the aromatic polyether is formed, and may be, for example, 250 to 350°C. A maximum temperature of 250°C or higher makes it easier to obtain an aromatic polyether according to one aspect of the present invention (an aromatic polyether exhibiting specific crystallization behavior).

[0084] The following description of the physical properties, characteristics, and functional groups of aromatic polyethers is applicable in common to the aromatic polyethers (first aromatic polyether, second aromatic polyether, and third aromatic polyether) according to one aspect of the present invention.

[0085] The melting point (Tm) of the aromatic polyether is preferably 320°C or lower, preferably 250 to 320°C, more preferably 255 to 310°C, more preferably 260 to 300°C, and more preferably 265 to 290°C. When the melting point (Tm) of the aromatic polyether satisfies the above conditions, it is easy to obtain the effect of reducing the processing temperature during molding compared to conventional aromatic polyethers while maintaining sufficient heat resistance. The melting point (Tm) of the aromatic polyether is the value measured by the method described in the examples.

[0086] The glass transition temperature (Tg) of aromatic polyethers is preferably 140 to 200°C, more preferably 144 to 190°C, more preferably 146 to 180°C, more preferably 148 to 170°C, and more preferably 150 to 170°C. When the glass transition temperature (Tg) satisfies the above conditions (especially if it is 146°C or higher), it is easy to obtain the effect of excellent heat resistance. The glass transition temperature (Tg) of aromatic polyethers is the value measured by the method described in the examples.

[0087] The aromatic polyether preferably has a complex viscosity of 100 to 10,000 Pa.s after 1 minute, as measured using a viscoelasticity measuring device, more preferably 200 to 5,000 Pa.s, more preferably 250 to 2,000 Pa.s, and more preferably 300 to 1,500 Pa.s. The complex viscosity of the aromatic polyether after 1 minute, as measured using a viscoelasticity measuring device, is the value measured by the method described in the examples.

[0088] The molecular weight distribution (Mw / Mn) of the aromatic polyether is preferably 2.0 to 3.0, more preferably 2.1 to 2.8, or more preferably 2.2 to 2.6. When the molecular weight distribution is within the above range, it is easier to obtain a molded article using the aromatic polyether that exhibits excellent mechanical strength.

[0089] The molecular weight distribution (Mw / Mn) of the aromatic polyether is the value measured by the method described in the examples. Specifically, in the gel permeation chromatography (GPC) distribution of the aromatic polyether, the range to be analyzed is defined as LogM on the horizontal axis = 10. ６ Focusing on the main peaks shown below, the number-average molecular weight (Mn [g]) and weight-average molecular weight (Mw [g]) can be calculated from a calibration curve using a polystyrene (PS) standard, and then determined as the ratio of the number-average molecular weight (Mn) to the weight-average molecular weight (Mw) (Mw / Mn [-]).

[0090] In the aromatic polyethers shown herein (aromatic polyethers shown as structural formulas or aromatic polyethers described in text), the proton group bonded to the aromatic ring may be substituted with any functional group (substituent) as long as it does not impair the effects of the present invention, or it may not be substituted. Examples of functional groups include C1-C6 alkyl groups, alkyl ether groups, acyl groups, phenyl groups, phenyl ether groups, and benzyl groups.

[0091] The form of the aromatic polyether according to one aspect of the present invention is not particularly limited. For example, it may be in the form of a powder or pellets.

[0092] 2. Resin Composition A resin composition according to one aspect of the present invention (also referred to as the "first resin composition") comprises an aromatic polyether according to one aspect of the present invention (one or more selected from the group consisting of a first aromatic polyether, a second aromatic polyether, and a third aromatic polyether) and an amorphous resin.

[0093] The resin composition according to this embodiment provides excellent heat resistance and moldability. Although the reason for such effects is not entirely clear, it is thought that including an amorphous resin makes the resin composition more likely to exhibit a predetermined crystallization behavior, thereby resulting in the above-mentioned effects.

[0094] Examples of amorphous resins include those that do not show a clear endothermic peak in differential scanning calorimetry (DSC) but instead exhibit a stepwise endothermic change.

[0095] In one embodiment, the amorphous resin comprises one or more selected from the group consisting of polyetherimide (PEI), polyethersulfone (PES), polyphenylene ether (PPE), polysulfone (PSU), and polyimide (PI).

[0096] In one embodiment, the amorphous resin includes polyetherimide (PEI).

[0097] In one embodiment, the content of amorphous resin in the resin composition is 5 to 300 parts by mass per 100 parts by mass of aromatic polyether, and may be 10 to 300 parts by mass, 20 to 250 parts by mass, 30 to 200 parts by mass, 40 to 150 parts by mass, or 50 to 100 parts by mass.

[0098] The content of amorphous resin in the resin composition may be 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 100 parts by mass or more, or 200 parts by mass or more, per 100 parts by mass of aromatic polyether. Alternatively, the content of amorphous resin in the resin composition may be 300 parts by mass or less, 250 parts by mass or less, 200 parts by mass or less, 150 parts by mass or less, 100 parts by mass or less, or 50 parts by mass or less, per 100 parts by mass of aromatic polyether.

[0099] In one embodiment, 50% or more by mass of the resin composition is 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass is an aromatic polyether and an amorphous resin.

[0100] A resin composition according to another aspect of the present invention (also referred to as the "second resin composition") does not crystallize in a first cooling process in differential scanning calorimetry (DSC), but crystallizes in an isothermal holding process in which the molten resin composition is held at 210°C for 5 minutes or more and 120 minutes or less.

[0101] The differential scanning calorimetry (DSC), the first cooling process, the isothermal holding process, and crystallization can be addressed using the methods described in the description of the aromatic polyether resin composition according to one aspect of the present invention.

[0102] The method for producing the resin composition is not particularly limited. For example, the resin composition can be produced by the method described in the examples.

[0103] 3. Composite Material A composite material according to one aspect of the present invention comprises an aromatic polyether or a resin composition according to one aspect of the present invention and reinforcing fibers.

[0104] The resin composition according to this embodiment provides excellent heat resistance and moldability. Although the reason for such effects is not entirely clear, it is believed that these effects are achieved by including an aromatic polyether or resin composition that exhibits a predetermined crystallization behavior.

[0105] In one embodiment, the content of reinforcing fibers in the composite material is 0.01 to 500 parts by mass per 100 parts by mass of aromatic polyether or resin composition, and may be 0.05 to 400 parts by mass, 0.1 to 300 parts by mass, or 1 to 200 parts by mass. The content of reinforcing fibers in the composite material is preferably 1 to 500 parts by mass, more preferably 10 to 400 parts by mass, more preferably 15 to 300 parts by mass, and more preferably 20 to 200 parts by mass per 100 parts by mass of aromatic polyether or resin composition. If the content of reinforcing fibers is 1 part by mass or more per 100 parts by mass of aromatic polyether or resin composition, an effect of improved mechanical strength can be obtained, and if it is 500 parts by mass or less, the reinforcing fibers are dispersed in the matrix resin, and an effect of excellent mechanical strength can be easily obtained.

[0106] The reinforcing fiber content in the composite material may be 0.01 parts by mass or more, 0.05 parts by mass or more, 0.1 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, or 40 parts by mass or more, per 100 parts by mass of the aromatic polyether or resin composition. Alternatively, the reinforcing fiber content in the composite material may be 500 parts by mass or less, 400 parts by mass or less, 300 parts by mass or less, or 200 parts by mass or less, per 100 parts by mass of the aromatic polyether or resin composition.

[0107] In one embodiment, the reinforcing fibers include one or more selected from the group consisting of carbon fibers, glass fibers, and aramid fibers. In one embodiment, 50% or more by mass of the reinforcing fibers is one or more selected from the group consisting of carbon fibers, glass fibers, and aramid fibers, and this amount is 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass of the reinforcing fibers is one or more selected from the group consisting of carbon fibers, glass fibers, and aramid fibers.

[0108] In one embodiment, the carbon fiber includes one or more 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). In one embodiment, 50% or more by mass of the carbon fiber is 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass is one or more 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).

[0109] The types of glass fibers and aramid fibers are not particularly limited. As glass fibers, for example, glass fibers of various compositions such as E-glass, low-dielectric glass, and silica glass can be selected and used according to the purpose and application.

[0110] In one embodiment, from the viewpoint of mechanical properties such as strength, elastic modulus, and impact resistance of a molded article formed using a composite material, the average fiber length of the reinforcing fibers in the composite material is 5 mm or more. The average fiber length is determined by the arithmetic mean of the values ​​measured with a caliper.

[0111] In one embodiment, 50% or more by mass of the composite material is 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass is an aromatic polyether or resin composition and reinforcing fibers.

[0112] The method for manufacturing (compounding) the composite material is not particularly limited. For example, a method of melt-kneading aromatic polyether and reinforcing fibers, or a method of melting and impregnating an aggregate of reinforcing fibers with aromatic polyether in one or more forms selected from the group consisting of powder, film, and pellet forms, can be used. The composite material containing continuous fibers with an average fiber length of 5 mm or more may be, for example, one or more forms selected from the group consisting of woven fabrics, nonwoven fabrics, and unidirectional materials (also called "UD materials").

[0113] 4. Molded Articles A molded article according to one aspect of the present invention contains an aromatic polyether according to one aspect of the present invention or a resin composition according to one aspect of the present invention. Therefore, it has excellent heat resistance and moldability. A molded article according to another aspect of the present invention contains a composite material according to one aspect of the present invention. Therefore, heat resistance and moldability can be improved.

[0114] The form of the molded article according to one aspect of the present invention is not particularly limited. In one embodiment, the molded article is an injection-molded article, an extruded article, or a compression-molded article (also referred to as a "press-molded article").

[0115] The applications of the aromatic polyethers, resin compositions, composite materials, and molded articles described above are not particularly limited and can be broadly applied to various applications where dimensional stability and strength are required. Aromatic polyethers, resin compositions, composite materials, and molded articles are particularly suitable as metal substitutes for applications requiring heat resistance, solvent resistance, and durability. More specifically, they can be suitably used in aerospace components, automotive components, sliding components such as gears and bearings, 3D printer filaments, semiconductor manufacturing equipment components, and the like.

[0116] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments.

[0117] 1. Production of Aromatic Polyethers (Example 1) 176.65 g (0.810 mol) of 4,4'-difluorobenzophenone (DFBP), 127.20 g (1.155 mol) of hydroquinone (HQ), and 62.52 g (0.363 mol) of 2,6-dichlorobenzonitrile (DCBN) were added to a 2 L separable flask. Potassium carbonate (K) was added as a base. ２ CO ３ 167.60 g (1.213 mol) of ) was added, and 1000 g of diphenyl sulfone (DPS) (concentration: HQ × 2 [mol] / DPS [kg] = 2.31 mol / kg) was added as a solvent. A ribbon heater was wrapped around the top of the separable flask, and glass wool was wrapped over it to maintain the temperature. The mixture was heated and stirred using a mechanical stirrer under nitrogen (flow rate: 0.06 L / min). The ribbon heater was set to 150°C and the mantle heater to 165°C, and the stirring blades were manually rotated until the liquid temperature reached 150°C. After the liquid temperature reached 150°C, the mixture was stirred at 250 rpm with a mechanical stirrer and heated to 200°C over 30 minutes. After the heating was complete, the temperature was maintained at 200°C for 1 hour, and then heated to 250°C over 70 minutes. The temperature was maintained at 250°C for 1 hour, and then increased to 300°C over 150 minutes. After the temperature increase, the mixture was maintained at 300°C until the desired complex viscosity was reached, at which point 40.82 g (0.187 mol) of DFBP was added to stop the reaction. Since the complex viscosity of the aromatic polyether product is correlated with the viscosity of the reaction solution, the reaction can be stopped using the viscosity of the reaction solution as an indicator to produce an aromatic polyether with the desired complex viscosity. When adding the DFBP, the nitrogen flow rate was temporarily increased to prevent the introduction of oxygen and other substances into the system. After adding the DFBP, the temperature was maintained at 300°C for the specified time, and then the reaction was terminated and the mother liquor was removed. The recovered product was pulverized and washed with acetone and water to obtain the target product (aromatic polyether). NMR confirmed that the aromatic polyether was formed as a random copolymer.

[0118] (Example 2) The aromatic polyether was produced in the same manner as in Example 1, except that 168.83 g (0.774 mol) of DFBP and 68.57 g (0.399 mol) of DCBN were used. NMR confirmed that the aromatic polyether was formed as a random copolymer.

[0119] (Example 3) 100 parts by mass of aromatic polyether obtained in Example 1 was mixed with 100 parts by mass of water. Then, a metal salt (Na, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added. ２ HPO ４ " and Fujifilm Wako Pure Chemical Industries Ltd.'s "NaH ２ PO ４ The mass ratio of (Na ２ HPO ４ : Na H ２ PO ４ 0.10 parts by mass of (2:3) was added and mixed at 25°C for 30 minutes. After mixing, the mixture was dried at 140°C for 24 hours. Then, 21 parts by mass of an amorphous resin, polyetherimide (SABIC, Ultem 1000, glass transition temperature 217°C:337°C, MFR = 9 g / 10 min at 6.6 kg) was dry-blended to obtain the dry-blended raw material, which was then melt-kneaded using a twin-screw extruder with an 11 mm cylinder diameter (Thermo Fisher Scientific "Process-11", cylinder volume 20 cc) at a screw rotation speed of 200 rpm and a set temperature of 350°C. Here, the dry-blended raw material was supplied at a rate of 7 g / min from the base of the twin-screw extruder (upstream side of the screw). The residence time in the twin-screw extruder was 3 minutes. After cooling the strands extruded from the twin-screw extruder in water, they were pelletized using a pelletizer to obtain a resin composition.

[0120] (Examples 4-6) The production of aromatic polyethers was carried out in the same manner as in Example 2, except that the complex viscosity setting was changed. NMR confirmed that the aromatic polyethers were formed as random copolymers.

[0121] (Example 7) The production of an aromatic polyether was carried out in the same manner as in Example 1, except that 191.85 g (0.879 mol) of DFBP and 50.41 g (0.293 mol) of DCBN were used for the reaction, and 15.12 g (0.069 mol) of DFBP was used to stop the reaction. NMR confirmed that the aromatic polyether was formed as a random copolymer.

[0122] (Example 8) The production of an aromatic polyether was carried out in the same manner as in Example 1, except that 157.82 g (0.723 mol) of DFBP and 76.25 g (0.443 mol) of DCBN were used for the reaction, and 30.24 g (0.139 mol) of DFBP was used to stop the reaction. NMR confirmed that the aromatic polyether was formed as a random copolymer.

[0123] (Comparative Example 1) The production of an aromatic polyether was carried out in the same manner as in Example 1, except that 204.64 g (0.938 mol) of DFBP and 40.33 g (0.234 mol) of DCBN were used for the reaction, and 15.12 g (0.069 mol) of DFBP was used to stop the reaction. NMR confirmed that the aromatic polyether was formed as a random copolymer.

[0124] (Comparative Example 2) The aromatic polyether was produced in the same manner as in Example 1, except that 127.90 g (0.586 mol) of DFBP and 100.83 g (0.586 mol) of DCBN were used for the reaction, and 30.24 g (0.139 mol) of DFBP was used to stop the reaction. NMR confirmed that the aromatic polyether was formed as a random copolymer.

[0125] (Comparative Example 3) (1) Synthesis of DFBP oligomers 38.811 g (0.178 mol) of 4,4'-difluorobenzophenone (DFBP) and 17.805 g (0.162 mol) of hydroquinone (HQ) were added to a 300 mL separable flask. Potassium carbonate (K) was added as a base. ２ CO ３23.464 g (0.170 mol) of ) was added, and 140 g of diphenyl sulfone (DPS) (concentration: HQ × 2 [mol] / DPS [kg] = 2.31 mol / kg) was added as the solvent. A ribbon heater was wrapped around the top of the separable flask, and glass wool was wrapped over it to maintain the temperature. The mixture was heated and stirred using a mechanical stirrer under nitrogen (flow rate: 0.01 L / min). The ribbon heater was set to 150°C and the mantle heater to 180°C, and the stirring blades were manually rotated until the liquid temperature reached 150°C. After the liquid temperature reached 150°C, the mixture was stirred at 210 rpm with a mechanical stirrer and heated to 200°C over 30 minutes. After the heating was complete, the temperature was maintained at 200°C for 1 hour, and then heated to 250°C over 30 minutes. The temperature was maintained at 250°C for 3 hours. After that, the reaction mixture was removed into a stainless steel tray to obtain the solid. Next, the solid material was pulverized using a lab mixer, and the reaction mixture was recovered as a powder.

[0126] (2) Synthesis of DCBN oligomers 30.595 g (0.178 mol) of 2,6-dichlorobenzonitrile (DCBN) and 17.805 g (0.162 mol) of hydroquinone (HQ) were added to a 300 mL separable flask. 23.464 g (0.170 mol) of potassium carbonate (K2CO3) was added as the base, and 140 g of diphenyl sulfone (DPS) was added as the solvent (concentration: HQ × 2 [mol] / DPS [kg] = 2.31 mol / kg). A ribbon heater was wrapped around the top of the separable flask, and glass wool was wrapped over it to maintain the temperature. The mixture was heated and stirred using a mechanical stirrer under nitrogen (flow rate: 0.01 L / min). The ribbon heater was set to 150°C and the mantle heater to 180°C, and the stirring blades were manually rotated until the liquid temperature reached 150°C. After the liquid temperature reached 150°C, it was stirred at 210 rpm using a mechanical stirrer and heated to 200°C over 30 minutes. After the heating was complete, the temperature was maintained at 200°C for 1 hour. Subsequently, the reaction mixture was transferred to a stainless steel tray to obtain a solid. Next, the solid was pulverized using a lab mixer, and the reaction mixture was recovered as a powder.

[0127] (3) Synthesis of block copolymers 133.7 g of the reaction mixture from (1) above (DFBP oligomer) and 55.0 g of the reaction mixture from (2) above (DCBN oligomer) were placed in a 300 mL separable flask. 1.619 g of hydroquinone (HQ) and potassium carbonate (K) as a base were added to the flask. ２ CO ３ 2.235 g of ) was added. A ribbon heater was wrapped around the top of the separable flask, and glass wool was wrapped over it to maintain the temperature. The mixture was heated and stirred using a mechanical stirrer under nitrogen (flow rate: 0.01 L / min). The ribbon heater was set to 150°C and the mantle heater to 180°C, and the stirring blades were manually rotated until the liquid temperature reached 150°C. After the liquid temperature reached 150°C, the mixture was stirred at 210 rpm with a mechanical stirrer and heated to 260°C over 110 minutes. After the heating was completed, the temperature was maintained at 260°C for 3 hours. The reaction mixture was then removed into a stainless steel tray to obtain a solid. Subsequently, the solid was pulverized using a lab mixer, and the reaction mixture was recovered as a powder. The mixture was repeatedly washed with acetone and water to obtain the target aromatic polyether polymer. NMR confirmed that the aromatic polyether was formed as a block copolymer.

[0128] (Comparative Example 4) The aromatic polyether was produced in the same manner as in Comparative Example 3, except that the amount of DFBP oligomer used was 114.5 g, the amount of DCBN oligomer used was 73.39 g, and the holding time at 260°C was changed to 4 hours. NMR confirmed that the aromatic polyether was formed as a block copolymer.

[0129] (Comparative Example 5) 285.63 g (1.140 mol) of 4,4'-dichlorobenzophenone (DCBP) and 123.40 g (1.121 mol) of hydroquinone (HQ) were added to a 2 L separable flask. Potassium carbonate (K) was added as the base. ２ CO ３162.62 g (1.177 mol) of ) was added, and 970 g of diphenyl sulfone (DPS) (concentration: HQ × 2 [mol] / DPS [kg] = 2.31 mol / kg) was added as a solvent. A ribbon heater was wrapped around the top of the separable flask, and glass wool was wrapped over it to maintain the temperature. The mixture was heated and stirred using a mechanical stirrer under nitrogen (flow rate: 0.06 L / min). The ribbon heater was set to 150°C and the mantle heater to 165°C, and the stirring blades were manually rotated until the liquid temperature reached 150°C. After the liquid temperature reached 150°C, the mixture was stirred at 250 rpm with a mechanical stirrer and heated to 200°C over 30 minutes. After the heating was complete, the temperature was maintained at 200°C for 1 hour, and then heated to 250°C over 70 minutes. The temperature was maintained at 250°C for 1 hour, and then heated to 300°C over 150 minutes. After raising the temperature, the mixture was maintained at 300°C until the desired viscosity was reached, and 45.03 g (0.179 mol) of DCBP was added to stop the reaction. During the addition, the nitrogen flow rate was temporarily increased to prevent the introduction of oxygen or other contaminants into the system. After the addition, the temperature was maintained at 300°C for the specified time, after which the reaction was terminated and the mother liquor was collected. The recovered product was pulverized and washed with acetone and water to obtain the target product (aromatic polyether). The formation of aromatic polyether was confirmed by NMR.

[0130] 2. Measurement and Evaluation Methods The following measurements and evaluations were performed on the aromatic polyether and resin composition of the examples.

[0131] (1) Measurement of crystallization heat: A differential scanning calorimeter (DSC) (PerkinElmar DSC 8500) was used. The instrument was calibrated using standard samples of indium and lead. 5 mg of aromatic polyether powder or resin composition pellets were placed in a PerkinElmar genuine aluminum pan and subjected to measurement. Measurement condition A was performed by heating from 50°C to 360°C at a heating rate of 20°C / min and holding for 1 minute (first heating), cooling down to 50°C at a cooling rate of 20°C / min and holding for 5 minutes (cooling), and heating up to 360°C at a heating rate of 20°C / min (second heating). The DSC chart (heat flow curve) obtained during the cooling process is shown in Figure 1. Measurement condition B was performed by raising the temperature from 50°C to 360°C at a heating rate of 20°C / min and holding for 1 minute (first heating), then lowering the temperature to 210°C at the maximum speed of the apparatus and holding for a maximum of 120 minutes (isothermal holding), then lowering the temperature to 50°C at the maximum speed of the apparatus and holding for 5 minutes, and finally raising the temperature to 360°C at a heating rate of 20°C / min (second heating). Figure 2 shows the DSC chart (heat flow curve) obtained during the isothermal holding process. When an exothermic peak due to crystallization was observed in the obtained heat flow curve, the peak top was defined as Tc (°C) and the peak area as ΔH (J / g). In addition, when an endothermic peak due to melting was observed during the second heating in measurement condition A or B, the peak top was defined as the melting point Tm (°C). Furthermore, the temperature at the point where a line equidistant in the vertical direction from the lines extending from the baselines on the low and high specific heat capacity sides of the specific heat capacity change intersects with the curve representing the stepwise transition portion of the glass transition was read as the glass transition temperature Tg (°C). The measurement results are shown in Table 1.

[0132] (2) Analysis of monomer composition NMR analysis was performed on the aromatic polyether or resin composition under the following conditions. The obtained NMR chart is shown in Figure 3. The analysis results are shown in Table 1. Table 1 shows the copolymerization amount in the "initial stage" based on the mass ratio of raw materials in the production of the aromatic polyether or resin composition, and the copolymerization amount in the "analysis" based on the monomer composition analysis by NMR.

[0133] [ １ [H-NMR Analysis Conditions] • Magnet: Ascend 500 • Spectrometer: AVANCE III HD • Probe: 5mm diameter TCI cryoprepole１ H resonance frequency: 500 MHz; Pulse program: zg30; Number of integrations: 256; Waiting time: 10 seconds; Sample preparation: Approximately 20 mg of sample was mixed with 0.6 mL of methanesulfonic acid and stirred at room temperature for 1 hour. Then 0.4 mL of deuterated dichloromethane was added to prepare the measurement sample.; Chemical shift correction: Of the three peaks of deuterated dichloromethane, the middle peak was set to 5.32 ppm.

[0134] [Procedure] The integral value A of the peak detected between chemical shifts 6.54 ppm and 6.74 ppm, and the integral value B of the peak detected between chemical shifts 8.03 ppm and 8.17 ppm were obtained, and the copolymer amount X [%] (DCBN residue / (DCBN residue + DFBP residue)) was calculated using the following formula (I). X [%] = {(A / 2) / (A / 2 + B / 4)} × 100 ... (I)

[0135] Here, the integral value A corresponds to the two hydrogen atoms at positions 3 and 5 of the benzene ring of the moiety derived from 2,6-dichlorobenzonitrile (DCBN) (H in the structure represented by formula (E1) below). Ａ ). The integral value B corresponds to the four hydrogen atoms that the benzene ring of the moiety derived from 4,4'-difluorobenzophenone (DFBP) has in the ortho position (positions 2 and 5) relative to the carbonyl group (H in the structure represented by formula (E1) below). Ｂ ).

[0136] (3) Molecular weight distribution measurement The sample (aromatic polyether) was dissolved in pentafluorophenol (PFP), and the molecular weight distribution was measured under the following measurement conditions. In the gel permeation chromatography (GPC) distribution, the range to be analyzed was set such that the horizontal axis LogM was 10 ６Focusing on the main peaks shown below, the number-average molecular weight (Mn [g]) and weight-average molecular weight (Mw [g]) were calculated from a calibration curve using a polystyrene (PS) standard, and the molecular weight distribution was determined as the ratio of the number-average molecular weight (Mn) to the weight-average molecular weight (Mw) (Mw / Mn [-]). • Test equipment: HLC-8420GPC (manufactured by Tosoh Corporation) • GPC (gel permeation chromatography) columns: TSK gel guard column H-H (4.6 mm I.D. × 35 mm) and two TSK gel Super HM-M (6 mm I.D. × 150 mm) columns were used in series in this order • Solvent: PFP / HCl ３ Mixed solvent; Temperature: 40°C; Flow rate: 0.6 ml / min; Detector: RI detector; Injection volume: 20 μl; Calibration curve: Calibration using PS standard

[0137] (4) Complex viscosity measurement The complex viscosity of the sample (aromatic polyether) was measured using a viscoelasticity measuring device under the following conditions and procedure. The complex viscosity one minute after the start of measurement is shown in the table. [Measurement conditions] ・Viscoelasticity measuring device: MCR302 (Anton Paar Co., Ltd.) ・Jig: SHAFT FOR DISPOSABLE MEASUREING SYSTEM D-CP / PP25 ・Disposable dish: Φ41 mm ・Disposable parallel plate: Φ25 mm ・Temperature: 350°C or 380°C (measured at the temperature closest to the melting point of the aromatic polyether being measured + 65°C) ・Preheating time: 3 min ・Gap: 0.8 mm ・Time: 300 min ・Shear strain: 1% ・Angular frequency: 6.28 rad / s

[0138] [Procedure] A disc-shaped aromatic polyether was placed on a disposable dish and measured under the above conditions. For measurement, the sample, sandwiched between a disposable dish and a disposable plate with a gap of 0.8 mm, was preheated and then trimmed to a diameter of Φ25 mm. The "disc" was obtained by the following method: Aromatic polyether was filled into a mold and pressed using a vacuum press (IMC-6215, manufactured by Imoto Seisakusho Co., Ltd.) at a temperature of 350°C (Examples 1, 2, 4-8, Comparative Examples 1, 2) or 380°C (Comparative Examples 3-5). After pressing, it was rapidly cooled to 25°C to form a disc with a diameter of Φ25 mm and a thickness of 1.0 mm.

[0139] (5) Chain Analysis The copolymer of difluorobenzophenone, dichlorobenzonitrile, and hydroquinone described in the example is polymerized by polycondensation reaction, so that hydroquinone forms an ether bond with benzophenone or with benzonitrile. The bonding pattern (chain) consists of benzophenone-hydroquinone-benzophenone (hereinafter also referred to as "BHB") represented by the following formula (E'1), benzophenone-hydroquinone-benzonitrile (hereinafter also referred to as "BHN") represented by the following formula (E'2), and benzonitrile-hydroquinone-benzonitrile (hereinafter also referred to as "NHN") represented by the following formula (E'3).

[0140]

[0141] R ＢＨＮ and R ｒａｎｄｏｍ of １３ The C-NMR measurement and analysis methods are as described in the measurement and analysis conditions below.

[0142] [Measurement Conditions] ・Superconducting magnet: Bruker Japan Co., Ltd. "Ascend 500" ・Spectrometer: AVANCE III HD ・Probe: 5 mm diameter TCI cryoprebe ・NMR sample tube diameter: 5 mm diameter ・Sample solution preparation 20 mg of sample was mixed with 0.6 ml of methanesulfonic acid and stirred at room temperature for 1 hour. Then, 0.4 ml of deuterated dichloromethane was added and stirred at room temperature for another 30 minutes to dissolve the sample and prepare it as the NMR measurement sample. If undissolved material was observed visually, the filtered filtrate was used as the NMR measurement sample. ・Observation range: 236.7 ppm ・Observation center: 100.0 ppm １３ C) Decoupling center: 4.0 ppm ( １ H) Decoupling ( １ H): Flip angle using 3,125Hz Waltz16 ( １３ C): 30° • Number of data points: 64kB • Pulse repetition time: 10 seconds • Number of integrations: 4,096 • Measurement temperature: 25°C • Chemical shift reference: Deuterated dichloromethane １３ The central peak of the five C-NMR peaks was set to 54.0 ppm. Process: An exponential function was used, the line broadening value was set to 1.00, a Fourier transform was performed, and then phase correction was applied. Baseline correction was then performed using the absn command.

[0143] [Analysis Method] Chain fraction R of BHN ＢＨＮ As shown in equation (I') below, １３ The peak area of ​​the quaternary carbon of hydroquinone was obtained from the C-NMR chart, and the ratio of the peak area of ​​BHN to the sum of the peak areas of BHB, BHN, and NHN was calculated and expressed as a percentage. ＢＨＮ [%]=B' / (A'+B'+C')×100...(I')

[0144] R ｒａｎｄｏｍ As shown in equation (II') below, １３ The peak area of ​​the quaternary carbon of hydroquinone was obtained from the C-NMR chart, and the peak areas of BHB, BHN, and NHN were used to determine the R. ｒａｎｄｏｍ =(A'+B' / 2)×(C'+B' / 2) / 50...(II')

[0145] In the above formulas (I') and (II'), the integral value A' is derived from the quaternary carbon of the hydroquinone of BHB represented by formula (E'1) and was obtained as the value integrated over the chemical shift range of 151.3 ppm to 151.8 ppm. The integral value B' is derived from the quaternary carbon of the hydroquinone of BHN represented by formula (E'2) and was obtained as the sum of the value integrated over the chemical shift range of 152.4 ppm to 152.8 ppm (benzophenone side) and the value integrated over the chemical shift range of 150.8 ppm to 151.1 ppm (benzonitrile side). The integral value C' is derived from the quaternary carbon of the hydroquinone of NHN represented by formula (E'3) and was obtained as the value integrated over the chemical shift range of 151.8 ppm to 152.2 ppm. As an example, Figure 4 shows the aromatic polyether of Example 1. １３ The C-NMR spectrum is shown. The horizontal axis represents "ppm".

[0146] (6) Warpage Measurement Sample: 8 g of aromatic polyether was placed in a SUS mold measuring 110 mm x 110 mm x 0.5 mm thickness, and pressed at a temperature of 350°C (Examples 1, 2, 4-8, Comparative Examples 1, 2) or 380°C (Comparative Examples 3-5) using a vacuum press (IMC-6215 manufactured by Imoto Seisakusho Co., Ltd.). Next, the mold filled with aromatic polyether was transferred to a benchtop test press (Shinto Metal Industry Co., Ltd.) and annealed at 210°C for 30 minutes. Then, the molded body (square plate shape) was removed from the mold. [Method for measuring warpage] The molded body was placed on a flat stage, and using two C-clamps with a contact diameter of 20 mm with the molded body, both ends of one side of the molded body were pressed toward the stage, and the distance between the stage and the point furthest from the stage on the side opposite the aforementioned side (warpage) was measured with a caliper. Here, as the aforementioned side, the side with the maximum amount of warping was selected from among the four sides of the molded body.

[0147] (7) Measurement of fracture strain (resin alone) For the molded body obtained in the same manner as in “(6) Warpage measurement”, using a lever-type cutter (Dumel Co., Ltd.), it was cut into the shape defined in ISO527-2 Type 5A (however, the thickness was changed to 0.5 mm) to prepare test pieces. For the obtained test pieces, a tensile test was conducted at a test speed of 20 mm / min and a chuck distance of 50 mm, and the fracture strain (tensile elongation) was measured.

[0148]

[0149] From Table 1, it was confirmed that the aromatic polyethers (or resin compositions) of Examples 1 to 8 did not crystallize in the first temperature drop process of cooling the molten aromatic polyether (or resin composition), and crystallized in the isothermal holding process of holding the molten aromatic polyether (or resin composition) at 210 °C for 5 minutes or more and 120 minutes or less. According to Examples 1 to 8, aromatic polyethers and resin compositions capable of forming a molded body that has fluidity during molding and excellent molding processability, and after molding, has heat resistance by being crystallized to restrict the molecular mobility below the melting point were obtained. In addition, it was found that a molded body containing an aromatic polyether having the above specific crystallinity (crystallization behavior) has excellent molding processability because the warpage is small. Furthermore, from the values of the fracture strain, it can be seen that the aromatic polyethers of Examples 2, 4, and 5 have excellent mechanical properties.

[0150] 3. Production of composite material (Example 9) 100 parts by mass of water was mixed with 100 parts by mass of the aromatic polyether obtained in Example 2. Next, a metal salt (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., “Na ２ HPO ４ ” and Fuji Film Wako Pure Chemical Industries, Ltd., “NaH ２ PO ４ ” and the mass ratio (Na ２ HPO ４ : NaH ２ PO ４0.10 parts by mass of (2:3) was added and mixed at 25°C for 30 minutes. After mixing, the mixture was dried at 140°C for 24 hours. Next, 43 parts by mass of discontinuous carbon fiber (TR06U, manufactured by Mitsubishi Engineering Plastics, chopped carbon fiber, average fiber length 6 mm, filament diameter 7 μm) was melt-kneaded at a set temperature of 350°C using a twin-screw kneader with a cylinder diameter of 11 mm (Process-11, manufactured by Termo Fisher Scientific, cylinder volume 20 cc) to obtain a composite material (pellets). [Measurement Method for Tensile Strength and Fracture Strain] The obtained composite material was dried at 140°C for more than 2 hours, and injection molded using a small molding machine (Haake MiniJet-Pro) at a cylinder temperature of 350°C and a mold temperature of 170°C to produce a 4 mm thick test specimen as specified in ISO 527-2-1BA. The test specimen was sandwiched between 5 mm thick SUS plates and annealed in an oven at 210°C for 2 hours. Tensile tests were performed on the obtained test specimens at a test speed of 1 mm / min and a chuck distance of 50 mm to measure the tensile strength and fracture strain (tensile elongation). The results are shown in Table 2.

[0151]

[0152] Table 2 shows that the composite material of Example 9 exhibits excellent mechanical properties, as evidenced by its tensile strength and fracture strain values, and also has excellent moldability due to the use of an aromatic polyether that exhibits specific crystallization behavior. Therefore, it can be widely applied to applications where molding was previously difficult.

[0153] Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will find it easy to make many modifications to these exemplary embodiments and / or examples without substantially departing from the novel teachings and effects of the present invention. Accordingly, many of these modifications fall within the scope of the present invention. All references to the documents described in this specification and the contents of the application on which the priority claim under the Paris Convention of this application is based are incorporated herein by reference.

Claims

1. An aromatic polyether that, in differential scanning calorimetry (DSC), does not crystallize during the first cooling process in which the molten aromatic polyether is cooled, but crystallizes during the isothermal holding process in which the molten aromatic polyether is held at 210°C for 5 minutes or more and 120 minutes or less.

2. The aromatic polyether according to claim 1, wherein the differential scanning calorimetry (DSC) comprises, in this order, a first heating step of heating up to 360°C to melt the aromatic polyether, and the first cooling step.

3. The aromatic polyether according to claim 2, wherein in the first heating step, the aromatic polyether is heated from 50°C at a rate of 20°C / min.

4. The aromatic polyether according to any one of claims 1 to 3, wherein in the first cooling process, the molten aromatic polyether is cooled to the glass transition temperature (Tg) of the aromatic polyether.

5. The aromatic polyether according to any one of claims 1 to 4, wherein in the first cooling process, the aromatic polyether is cooled at a rate of 20°C / min.

6. The aromatic polyether according to any one of claims 1 to 5, wherein the melting is by heating.

7. The aromatic polyether according to any one of claims 1 to 6, wherein the enthalpy change ΔH in the first cooling process is 13 J / g or less.

8. The aromatic polyether according to any one of claims 1 to 7, wherein the enthalpy change ΔH in the first cooling process is 0 J / g.

9. The aromatic polyether according to any one of claims 1 to 8, wherein the enthalpy change ΔH during the isothermal holding process is greater than 13 J / g.

10. An aromatic polyether according to any one of claims 1 to 9, comprising a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). [In formula (1), A includes one or more selected from the group consisting of structural units represented by the following formulas (A1) and (A2). (In formula (A1), X Ａ１ is -C (=O)- or -S (=O) ２ This indicates that X Ａ２ and X Ａ３ These are, independently, -C (=O)- or -S (=O) ２ - indicates.) B includes one or more selected from the group consisting of structural units represented by the following formulas (B1) to (B3). (In formula (B1), R Ｂ (where * represents a hydrogen atom or a phenyl group.) n is an integer from 0 to 2. When n is 0, the oxygen atom in formula (1) is directly bonded to an adjacent structural unit. When n is 1, *1 of B represents a bond with the oxygen atom in formula (1), and *2 of B represents a bond with an adjacent structural unit. When n is 2, of the two Bs, *1 of B adjacent to the oxygen atom in formula (1) represents a bond with the oxygen atom in formula (1), and *2 of B furthest from the oxygen atom in formula (1) represents a bond with an adjacent structural unit. [In formula (2), B is as defined in formula (1). B in formula (1) and B in formula (2) may be the same or different. m is an integer from 0 to 2. When m is 0, the oxygen atom in formula (1) is directly bonded to an adjacent structural unit. When m is 1, *1 of B represents a bond with the oxygen atom in formula (2), and *2 of B represents a bond with an adjacent structural unit. When m is 2, of the two Bs, *1 of B adjacent to the oxygen atom in formula (2) represents a bond with the oxygen atom in formula (2), and *2 of B furthest from the oxygen atom in formula (2) represents a bond with an adjacent structural unit.] 11. The aromatic polyether according to claim 10, wherein the mol ratio of the structural unit represented by formula (2) to the sum of the structural units represented by formula (1) and the structural unit represented by formula (2) ((2) / ((1) + (2))) is 23 to 43%.

12. The aromatic polyether according to claim 10 or 11, which is a random copolymer comprising a structural unit represented by formula (1) and a structural unit represented by formula (2).

13. The aromatic polyether according to any one of claims 10 to 12, wherein formula (1) is a structural unit represented by the following formula (a), and formula (2) is a structural unit represented by the following formula (b).

14. An aromatic polyether according to any one of claims 1 to 13, wherein the melting point is 320°C or lower.

15. An aromatic polyether according to any one of claims 1 to 14, wherein the molecular weight distribution (Mw / Mn) is 2.0 to 3.

0.

16. An aromatic polyether according to any one of claims 1 to 15, comprising benzophenone, benzonitrile, and hydroquinone as monomer units.

17. The fraction R of the total number of chained BHNs in the sum of the total number of chained BHBs consisting of benzophenone-hydroquinone-benzophenone, the total number of chained BHNs consisting of benzophenone-hydroquinone-benzonitrile, and the total number of chained NHNs consisting of benzonitrile-hydroquinone-benzonitrile. ＢＨＮ The aromatic polyether according to claim 16, wherein the content is 30-45%.

18. The fraction R of the total number of chains BHN consisting of benzophenone-hydroquinone-benzonitrile in the sum of the total number of chains BHB consisting of benzophenone-hydroquinone-benzophenone, the total number of chains BHN consisting of benzophenone-hydroquinone-benzonitrile, and the total number of chains NHN consisting of benzonitrile-hydroquinone-benzonitrile ＢＨＮ is divided by the chain fraction R of statistically random chains BHN ｒａｎｄｏｍ to obtain a value (R ＢＨＮ / R ｒａｎｄｏｍ ) of 0.8 or more, and the aromatic polyether according to claim 16 or 17 19. An aromatic polyether according to any one of claims 1 to 18, wherein it is a copolymer of dihalogenobenzophenone, dihalogenobenzonitrile, and hydroquinone.

20. The aromatic polyether according to claim 19, wherein the dihalogenobenzonitrile is 2,6-dichlorobenzonitrile.

21. The aromatic polyether according to claim 19 or 20, wherein the dihalogenobenzophenone is 4,4'-difluorobenzophenone.

22. A resin composition comprising an aromatic polyether according to any one of claims 1 to 21 and an amorphous resin.

23. The resin composition according to claim 22, wherein the amorphous resin comprises one or more selected from the group consisting of polyetherimide (PEI), polyethersulfone (PES), polyphenylene ether (PPE), polysulfone (PSU), and polyimide (PI).

24. The resin composition according to claim 22, wherein the amorphous resin comprises polyetherimide (PEI).

25. The resin composition according to any one of claims 22 to 24, wherein the content of the amorphous resin is 10 to 300 parts by mass per 100 parts by mass of the aromatic polyether.

26. A resin composition that, in differential scanning calorimetry (DSC), does not crystallize during the first cooling process in which the molten resin composition is cooled, but crystallizes during the isothermal holding process in which the molten resin composition is held at 210°C for 5 minutes or more and 120 minutes or less.

27. A composite material comprising an aromatic polyether according to any one of claims 1 to 21 or a resin composition according to any one of claims 22 to 26, and reinforcing fibers.

28. The composite material according to claim 27, wherein the content of the reinforcing fibers is 10 to 500 parts by mass per 100 parts by mass of the aromatic polyether or resin composition.

29. A molded article comprising an aromatic polyether according to any one of claims 1 to 21 or a resin composition according to any one of claims 22 to 26.

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