Aromatic polyether, resin composition, and composite material

Abstract

This aromatic polyether comprises a structural unit represented by formula (a) and a structural unit represented by formula (b), and has a radical content of 6.5 × 1015 to 9.0 × 1017 (spin / g) at 25℃ as measured using TEMPOL as the standard substance and benzene as the solvent of the standard substance.

Description

Aromatic polyether, resin composition, and composite material

[0001] The present invention relates to an aromatic polyether, a resin composition, and a composite material. Specifically, the present invention relates to an aromatic polyether, a resin composition, and a composite material that exhibit excellent adhesion to reinforcing fibers and have excellent moldability.

[0002] Patent Document 1 discloses a specific aromatic polyether produced by adding a component having a specific polymerization catalytic activity to a reaction system, and also discloses the use of this aromatic polyether mixed with a reinforcing material or filler such as glass fiber, carbon fiber, aramid fiber, calcium carbonate, or calcium silicate.

[0003] Non-Patent Document 1 discloses the introduction of a specific removable bulky substituent during the synthesis of an aromatic polyether, which suppresses the crystallinity of the aromatic polyether during synthesis, improves its solubility in organic solvents, and produces a high-molecular-weight aromatic polyether, after which the substituent can be removed from the aromatic polyether.

[0004] Japanese Unexamined Patent Publication No. 64-065129

[0005] Wilhelm Risse and Dotsevi Y. Sogah, "Synthesis of Soluble High Molecular Weight Poly (aryl ether ketones) Containing Bulky Substituents", Macromolecules, American Chemical Society, September 3 (1990), Volume 23, Number 18, 4029-4033

[0006] However, it has been found that there is room for further improvement in conventional aromatic polyethers such as those described in Patent Document 1 and Non-Patent Document 1 from the viewpoint of improving adhesion to reinforcing fibers and molding processability.

[0007] An object of the present invention is to provide an aromatic polyether, a resin composition, and a composite material that can exhibit excellent adhesion to reinforcing fibers and also have excellent moldability.

[0008] As a result of extensive research, the present inventors have found that aromatic polyethers containing a specific structure have excellent adhesion to reinforcing fibers and can improve molding processability, and have thus completed the present invention. According to the present invention, the following aromatic polyethers and the like can be provided: 1. An aromatic polyether containing a structural unit represented by the following formula (a) and a structural unit represented by the following formula (b), which has a radical content of 6.5 x 10 at 25°C, measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance: １５ ~9.0 x 10 １７ (spin / g) of an aromatic polyether. 2. The aromatic polyether according to 1, wherein the molar ratio ((b) / ((a)+(b))) of the structural units represented by formula (b) to the total amount of the structural units represented by formula (a) and formula (b) is 5 to 40 (mol %). 3. The aromatic polyether according to 1 or 2, wherein the glass transition temperature (Tg) is 140°C or higher. 4. The aromatic polyether according to any one of 1 to 3, wherein the melting point (Tm) is 330°C or lower. 5. The aromatic polyether according to any one of 1 to 4, wherein the melting point (Tm) is 250°C or higher. 6. The aromatic polyether according to any one of 1 to 5, wherein the melting point (Tm) is 255°C or higher and 315°C or lower. 7. The aromatic polyether according to any one of 1 to 6, wherein the difference (Δ(Tm-Tg)) between the melting point (Tm) and the glass transition temperature (Tg) is 185°C or lower. 8. 8. The aromatic polyether according to any one of 1 to 7, having a crystallinity (%) of 33% or less. 9. The aromatic polyether according to any one of 1 to 8, having a crystallinity (%) of 5% or more and 30% or less. 10. The aromatic polyether according to any one of 1 to 9, which is a copolymer of 4,4'-dichlorobenzophenone (DCBP), hydroquinone (HQ), and 2-phenylhydroquinone (Ph-HQ). 11. The aromatic polyether according to 10, wherein the molar ratio of the 2-phenylhydroquinone (Ph-HQ) to the total amount of the hydroquinone (HQ) and the 2-phenylhydroquinone (Ph-HQ) (Ph-HQ / (HQ+Ph-HQ)) is 5 to 40 (mol%). 12. The aromatic polyether according to any one of 1 to 11, wherein 50% by mass or more of the aromatic polyether is the structural unit represented by formula (a) and the structural unit represented by formula (b). 13. 13. An amorphous resin comprising an aromatic polyether according to any one of 1 to 12, and an amorphous resin, or an aromatic polyether comprising a structural unit represented by the following formula (a) and a structural unit represented by the following formula (b), and an amorphous resin, wherein the amount of radicals at 25°C measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance is 6.5 × 10 １５ ~9.0 x 10 １７ (spin / g). 14. A composite material comprising the aromatic polyether according to any one of 1 to 12 or the resin composition according to 13, and 0.01 to 500 parts by mass of reinforcing fibers relative to 100 parts by mass of the aromatic polyether. 15. The composite material according to 14, wherein the reinforcing fibers comprise one or more fibers selected from the group consisting of carbon fibers, glass fibers, and aramid fibers.

[0009] According to the present invention, it is possible to provide an aromatic polyether, a resin composition, and a composite material that can exhibit excellent adhesion to reinforcing fibers and have excellent moldability.

[0010] The aromatic polyether, resin composition, and composite material of the present invention are described in detail below. In this specification, "x to y" represents a numerical range of "x or more and y or less." The upper and lower limits of the numerical ranges can be combined arbitrarily. Furthermore, among the individual embodiments of the aspects of the present invention described below, two or more embodiments that are not mutually contradictory can be combined, and an embodiment combining two or more embodiments is also an embodiment of the aspects of the present invention.

[0011] 1. Aromatic Polyether The aromatic polyether according to one embodiment of the present invention comprises a structural unit represented by the following formula (a) and a structural unit represented by the following formula (b), and has a radical amount of 6.5 × 10 at 25°C, measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance: １５ ~9.0 x 10 １７ (spin / g).

[0012]

[0013] The aromatic polyether according to this embodiment can exhibit excellent adhesion to reinforcing fibers and also exhibit excellent molding processability. Regarding molding processability, in particular, the processing temperature can be lowered and dimensional stability can be improved. While the reason for such effects is not entirely clear, it is presumed that a new structure with adhesive properties to reinforcing fibers is formed due to the effect of the high concentration of radicals in the aromatic polyether. Furthermore, the aromatic polyether according to this embodiment can maintain its glass transition temperature (Tg) by including a structural unit represented by formula (a). This maintains heat resistance. Furthermore, the aromatic polyether according to this embodiment can lower its melting point (Tm) without lowering its glass transition temperature by including a structural unit represented by formula (b). This allows the processing temperature during molding to be lowered while maintaining heat resistance. Furthermore, the aromatic polyether according to this embodiment can reduce its crystallinity by including a structural unit represented by formula (b). This prevents warping of molded articles when subjected to press molding, etc. Furthermore, shrinkage during the cooling process during molding can be suppressed (dimensional stability can be improved), preventing the formation of voids inside the molded article. This crystallinity can also be controlled by adjusting the ratio of the structural unit represented by formula (b) to the structural unit represented by formula (a) (by increasing this ratio, the crystallinity can be further reduced. Conversely, by decreasing this ratio, the crystallinity can be improved).

[0014] In one embodiment, the radical content of the aromatic polyether is 6.5×10 １５ spin / g or more, 7.0×10 １５ spin / g or more, 8.0×10 １５ spin / g or more, 9.0×10 １５ spin / g or more or 1.0 x 10 １６ spin / g or more, and １７ spin / g or less, 7.0×10 １７ spin / g or less, 5.0×10 １７ spin / g or less or 3.0 x 10 １７ The amount of radicals in the aromatic polyether is 6.5×10 １５If the amount of radicals in the aromatic polyether is less than 9.0×10 １７ If the value exceeds 10 ...

[0015] In one embodiment, the radical content of the aromatic polyether is 6.5×10 １５ spin / g or more 9.0×10 １７ spin / g or less, 7.0×10 １５ spin / g or more 9.0×10 １７ spin / g or less, 8.0×10 １５ spin / g or more 7.0×10 １７ spin / g or less, 9.0×10 １５ spin / g or more 5.0×10 １７ spin / g or less or 1.0 x 10 １６ spin / g or more 3.0×10 １７ spin / g or less.

[0016] The aromatic polyether can also be said to be a copolymer of a structural unit represented by formula (a) and a structural unit represented by formula (b). In one embodiment, the copolymer is a random copolymer, an alternating copolymer, or a block copolymer, and is preferably a random copolymer.

[0017] In aromatic polyethers, the substitution position (bonding position) of the phenyl group in the structural unit represented by formula (b) may be any position on the benzene ring constituting the main chain, which is shown on the far right in formula (b) (the phenyl group is introduced so as to substitute one of the four hydrogen atoms on the benzene ring). When two or more structural units represented by formula (b) are adjacent in an aromatic polyether, the aromatic polyether may contain one or more structures selected from the group consisting of a structure represented by the following (b1), a structure represented by the following (b2), and a structure represented by the following (b3):

[0018] In each of the structures represented by the above formulas (b1) to (b3), the substitution positions of the phenyl groups in the two structural units represented by formula (b) 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 where two or more structural units represented by formula (b) are adjacent has been described. However, even in the case where two or more structural units represented by formula (b) 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 (b) may be the same or different from each other. In either case, the effects of the present invention are well exhibited.

[0019] In one embodiment, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, 97% by weight or more, 99% by weight or more, 99.5% by weight or more, or substantially 100% by weight of the aromatic polyether are structural units represented by formula (a) and structural units represented by formula (b).

[0020] In one embodiment, the glass transition temperature (Tg) of the aromatic polyether is 140°C or higher, 145°C or higher, or 150°C or higher. The upper limit is not particularly limited, and may be, for example, 165°C or lower, 153°C or lower, or 152°C or lower. When the aromatic polyether has a glass transition temperature (Tg) of 140°C or higher, it can exhibit good heat resistance in various applications. The glass transition temperature (Tg) of the aromatic polyether is a value measured by the method described in the examples.

[0021] In one embodiment, the glass transition temperature (Tg) of the aromatic polyether is 140°C or more and 165°C or less, 145°C or more and 153°C or less, or 150°C or more and 152°C or less.

[0022] In one embodiment, the melting point (Tm) of the aromatic polyether is 330°C or less, 325°C or less, 320°C or less, 315°C or less, 310°C or less, 305°C or less, 300°C or less, 295°C or less, 290°C or less, 285°C or less, 280°C or less, 275°C or less, 270°C or less, or 265°C or less. The lower limit is not particularly limited, and may be, for example, 250°C or more or 255°C or more. When the melting point (Tm) of the aromatic polyether is 330°C or less, the processing temperature during molding can be lowered, thereby preventing thermal degradation of the aromatic polyether and improving energy efficiency during molding. As a result, the suitability of the aromatic polyether for molding processing is improved. The melting point (Tm) of the aromatic polyether is a value measured by the method described in the examples.

[0023] In one embodiment, the aromatic polyether has a melting point (Tm) of 250°C or more and 330°C or less, 250°C or more and 325°C or less, 255°C or more and 320°C or less, or 255°C or more and 315°C or less.

[0024] In one embodiment, the difference (Δ(Tm-Tg)) between the melting point (Tm) and the glass transition temperature (Tg) of the aromatic polyether is 185°C or less, 180°C or less, 170°C or less, 165°C or less, 160°C or less, 155°C or less, 150°C or less, 145°C or less, 140°C or less, 135°C or less, 130°C or less, 125°C or less, or 120°C or less. A small difference means that the above-mentioned effect of "lowering the melting point (Tm) without lowering the glass transition temperature (Tg)" is large. The lower limit of Δ(Tm-Tg) is not particularly limited, and is, for example, 100°C or more or 110°C or more.

[0025] In one embodiment, the Δ(Tm-Tg) of the aromatic polyether is 100°C or more and 185°C or less, 100°C or more and 180°C or less, 100°C or more and 170°C or less, 110°C or more and 170°C or less, 110°C or more and 165°C or less, 110°C or more and 150°C or less, 110°C or more and 130°C or less, or 110°C or more and 120°C or less.

[0026] In one embodiment, the crystallinity of the aromatic polyether is 33% or less, 30% or less, 25% or less, 20% or less, or 15% or less. The lower limit is not particularly limited and may be, for example, 5% or more. When the crystallinity of the aromatic polyether is 33% or less, it is possible to prevent warping of the molded article when subjected to press molding or the like. In addition, shrinkage during the temperature drop process during molding is suppressed, and it is possible to prevent the formation of cavities inside the molded article. When the crystallinity of the aromatic polyether is 5% or more, chemical resistance is easily obtained. The crystallinity (%) of the aromatic polyether is a value measured by the method described in the examples.

[0027] In one embodiment, the crystallinity of the aromatic polyether is 5% or more and 33% or less, or 5% or more and 30% or less.

[0028] In one embodiment, the complex viscosity of the aromatic polyether at 360 ° C. is 450 Pa s or more, 500 Pa s or more, 600 Pa s or more, 700 Pa s or more, 800 Pa s or more, 900 Pa s or more, 1000 Pa s or more, 1100 Pa s or more, or 1200 Pa s or more, and is 7000 Pa s or less, 6000 Pa s or less, 5000 Pa s or less, 4500 Pa s or less, 4000 Pa s or less, 3500 Pa s or less, 3000 Pa s or less, or 2800 Pa s or less. From one perspective, the complex viscosity can be said to be an indicator of the molecular weight of the aromatic polyether. If the complex viscosity of the aromatic polyether at 360 ° C. is 450 Pa s or more, the aromatic polyether has a sufficiently high molecular weight. Furthermore, even in such highly molecular weight aromatic polyethers, by including the structural unit represented by formula (b) as described above, the melting point (Tm) can be lowered without lowering the glass transition temperature (Tg). Therefore, the processing temperature during molding can be lowered while maintaining heat resistance. Furthermore, if the complex viscosity of the aromatic polyether at 360°C is 7000 Pa s or less, the aromatic polyether will exhibit favorable fluidity when melted, improving its suitability for various moldings. The complex viscosity of the aromatic polyether at 360°C is a value measured by the method described in the Examples.

[0029] In one embodiment, the complex viscosity of the aromatic polyether at 360°C is 500 Pa·s or more and 7000 Pa·s or less, 700 Pa·s or more and 7000 Pa·s or less, 800 Pa·s or more and 6000 Pa·s or less, 1000 Pa·s or more and 5000 Pa·s or less, or 1200 Pa·s or more and 4500 Pa·s or less.

[0030] The method for producing the aromatic polyether according to one embodiment of the present invention described above is not particularly limited, and it can be produced, for example, by the method described in the Examples.

[0031] In one embodiment, the aromatic polyether is a copolymer of 4,4'-dichlorobenzophenone, hydroquinone, and 2-phenylhydroquinone. In one embodiment, the aromatic polyether is a copolymer containing 4,4'-dichlorobenzophenone, hydroquinone, and 2-phenylhydroquinone as monomer components. The structural unit represented by formula (a) may be a linkage of 4,4'-dichlorobenzophenone and hydroquinone. The structural unit represented by formula (b) may be a linkage of 4,4'-dichlorobenzophenone and 2-phenylhydroquinone.

[0032] 4,4'-Dichlorobenzophenone reduces the radical amount of the resulting aromatic polyether to 6.5 x 10 １５ ~9.0 x 10 １７ As a result, the adhesiveness of the aromatic polyether to the reinforcing fibers can be improved.

[0033] In one embodiment, the molar ratio of the 2-phenylhydroquinone to the total amount of the hydroquinone (HQ) and the 2-phenylhydroquinone (Ph-HQ) (Ph-HQ / (HQ+Ph-HQ)) is 5 mol% or more, 6 mol% or more, 7 mol% or more, 8 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and is 99 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, or 40 mol% or less. When the molar ratio (Ph-HQ / (HQ+Ph-HQ)) is 5 mol% or more, the effect of lowering the melting point (Tm) without lowering the glass transition temperature (Tg) is significantly exhibited. Furthermore, by having the molar ratio (Ph-HQ / (HQ+Ph-HQ)) be 40 mol% or less, chemical resistance can be improved. Therefore, it is particularly preferable that the molar ratio (Ph-HQ / (HQ+Ph-HQ)) be 5 to 40 mol%. This molar ratio (Ph-HQ / (HQ+Ph-HQ)) can be measured by the method described in the Examples. This molar ratio (Ph-HQ / (HQ+Ph-HQ)) can correspond to the molar ratio of each monomer component in the aromatic polyether. Furthermore, this molar ratio (Ph-HQ / (HQ+Ph-HQ)) can correspond to the molar ratio of the structural unit represented by formula (b) relative to the total amount of the structural unit represented by formula (a) and the structural unit represented by formula (b). Furthermore, this molar ratio (Ph-HQ / (HQ+Ph-HQ)) can correspond to the molar ratio of the amounts of each monomer charged in a copolymerization reaction for producing an aromatic polyether.

[0034] In one embodiment, the reaction system (also referred to as "reaction mixture") for producing the aromatic polyether contains a solvent in addition to the above-mentioned monomers. The solvent is not particularly limited, and for example, an aprotic polar solvent can be used. Examples of the aprotic polar solvent 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.

[0035] 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.

[0036] In one embodiment, the reaction mixture contains a base. The reaction is promoted by including a base in the reaction mixture. The base is not particularly limited, and examples thereof 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 alone or in combination of two or more.

[0037] In one embodiment, the reaction mixture is heated. The maximum temperature (maximum temperature reached) of the reaction mixture during the reaction is not particularly limited as long as it is a temperature at which an aromatic polyether is produced, and may be, for example, 250 to 350°C.

[0038] 2. Resin Composition A resin composition (also referred to as "alloy") according to one aspect of the present invention comprises an aromatic polyether according to one aspect of the present invention and an amorphous resin (first embodiment), or an aromatic polyether comprising a structural unit represented by formula (a) and a structural unit represented by formula (b), and an amorphous resin, and has a radical amount of 6.5 x 10 at 25°C measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance. １５ ~9.0 x 10 １７ (spin / g) (Second embodiment). In the second embodiment, it is sufficient that the resin composition satisfies the radical amount condition. Here, the aromatic polyether itself may or may not satisfy the radical amount condition. For the aromatic polyether of the second embodiment, the explanation given for the aromatic polyether according to one aspect of the present invention is applicable, except that the radical amount condition is not essential. Furthermore, for the radical amount of the resin composition, the explanation given for the radical amount of the aromatic polyether according to one aspect of the present invention is applicable.

[0039] The resin composition according to this embodiment can exhibit excellent adhesion to reinforcing fibers and also has excellent molding processability, particularly allowing the processing temperature to be lowered and improving dimensional stability.

[0040] Examples of amorphous resins include resins that do not show a clear endothermic peak but show a stepwise endothermic change in differential scanning calorimetry (DSC).

[0041] 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).

[0042] In one embodiment, the amorphous resin comprises polyetherimide (PEI).

[0043] In one embodiment, the content of the amorphous resin in the resin composition is 5 to 300 parts by mass relative to 100 parts by mass of the aromatic polyether, and may be 5 to 200 parts by mass, 5 to 100 parts by mass, 5 to 50 parts by mass, 5 to 25 parts by mass, 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.

[0044] The content of the 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, relative to 100 parts by mass of the aromatic polyether. Furthermore, the content of the 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, 50 parts by mass or less, or 25 parts by mass, relative to 100 parts by mass of the aromatic polyether.

[0045] In one embodiment, the resin composition comprises 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, 97% by weight or more, 99% by weight or more, 99.5% by weight or more, or substantially 100% by weight of the aromatic polyether and the amorphous resin.

[0046] 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.

[0047] 3. Composite Material A composite material according to one aspect of the present invention comprises the aromatic polyether according to one aspect of the present invention and 0.01 to 500 parts by mass of reinforcing fibers per 100 parts by mass of the aromatic polyether. A composite material according to another aspect of the present invention comprises the resin composition according to one aspect of the present invention and 0.01 to 500 parts by mass of reinforcing fibers per 100 parts by mass of the aromatic polyether in the resin composition. The composite material according to this aspect exhibits excellent adhesion between the aromatic polyether or resin composition and the reinforcing fibers, resulting in excellent mechanical strength (e.g., tensile strength) as a composite material.

[0048] In one embodiment, the content of the reinforcing fibers in the composite material is, relative to 100 parts by mass of the aromatic polyether, 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, and is 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.

[0049] In one embodiment, the content of the reinforcing fibers in the composite material is, relative to 100 parts by mass of the aromatic polyether, 0.01 parts by mass to 500 parts by mass, 0.05 parts by mass to 500 parts by mass, 0.1 parts by mass to 500 parts by mass, 0.5 parts by mass to 400 parts by mass, 1 part by mass to 400 parts by mass, 5 parts by mass to 400 parts by mass, 10 parts by mass to 300 parts by mass, 15 parts by mass to 300 parts by mass, 20 parts by mass to 300 parts by mass, 30 parts by mass to 200 parts by mass, or 40 parts by mass to 200 parts by mass.

[0050] 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 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 substantially 100 mass% of the reinforcing fibers are one or more selected from the group consisting of carbon fibers, glass fibers, and aramid fibers.

[0051] In one embodiment, the carbon fiber comprises one or more selected from the group consisting of PAN-based carbon fiber, pitch-based carbon fiber, thermosetting carbon fiber, phenolic carbon fiber, vapor-grown carbon fiber, and recycled carbon fiber (RCF). In one embodiment, 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 substantially 100 mass% of the carbon fiber is one or more selected from the group consisting of PAN-based carbon fiber, pitch-based carbon fiber, thermosetting carbon fiber, phenolic carbon fiber, vapor-grown carbon fiber, and recycled carbon fiber (RCF).

[0052] The types of glass fibers and aramid fibers are 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.

[0053] In one embodiment, from the viewpoint of mechanical properties such as strength, elastic modulus, and impact resistance of a molded article formed using the 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 as the arithmetic mean of values ​​measured with a vernier caliper.

[0054] In one embodiment, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 97%, at least 99%, at least 99.5%, or substantially 100% by weight of the composite material is the aromatic polyether or resin composition and reinforcing fibers.

[0055] The method for producing the composite material (composite method) is not particularly limited. For example, a method of melt-kneading an aromatic polyether or resin composition with reinforcing fibers, or a method of melting and impregnating an aggregate of reinforcing fibers with one or more forms of an aromatic polyether or resin composition selected from the group consisting of powder, film, and pellets, can be used. A composite material containing continuous reinforcing fibers with an average fiber length of 5 mm or more can be in one or more forms selected from the group consisting of a woven fabric, a nonwoven fabric, and a unidirectional material (also called a "UD material").

[0056] 4. Molded Article A molded article according to one aspect of the present invention contains the aromatic polyether according to one aspect of the present invention. Therefore, it has excellent molding processability. A molded article according to another aspect of the present invention contains the resin composition according to one aspect of the present invention. Therefore, it is possible to improve the molding processability. A molded article according to another aspect of the present invention contains the composite material according to one aspect of the present invention. Therefore, it is possible to improve the molding processability. Furthermore, since the interfacial shear strength between the aromatic polyether or resin composition and the reinforcing fibers in the composite material is excellent, it is also possible to obtain the effect of excellent mechanical strength (e.g., tensile strength).

[0057] The shape of the molded body according to one aspect and another aspect of the present invention is not particularly limited. In one embodiment, the molded body is an injection molded body, an extrusion molded body, or a compression molded body (also referred to as a "press molded body").

[0058] The uses of the aromatic polyethers, resin compositions, composite materials, and molded articles described above are not particularly limited, and can be widely applied to various applications requiring dimensional stability and strength. The aromatic polyethers, resin compositions, composite materials, and molded articles are suitable, for example, as metal replacement materials, particularly for applications requiring heat resistance, solvent resistance, and durability. More specifically, they can be used suitably for aerospace components, automotive components, sliding components such as gears and bearings, 3D printer filaments, and semiconductor manufacturing equipment components.

[0059] Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0060] 1. Production of Aromatic Polyether (Example 1) 288.49 g (1.15 mol) of 4,4'-dichlorobenzophenone (manufactured by Sino-High Corporation), 112.17 g (1.02 mol) of hydroquinone (Fujifilm Wako Pure Chemical Industries, Ltd.), 21.08 g (0.11 mol) of 2-phenylhydroquinone (manufactured by Shinko Corporation), 164.25 g (1.19 mol) of potassium carbonate (AGC Corporation, fine powder), and 980 g of diphenyl sulfone (manufactured by Sino-High Corporation) were placed in a 2 L four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a water collection container connected to a condenser, and nitrogen was circulated. After the reaction was carried out under the following temperature control, 45.48 g (0.18 mol) of 4,4'-dichlorobenzophenone was added as a reaction terminator.

[0061] <Temperature control> (1) After heating to 150°C, the temperature was raised to 200°C over 30 minutes at a stirring speed of 250 rpm. (2) The temperature was maintained at 200°C for 60 minutes. (3) The temperature was raised from 200°C to 250°C over 70 minutes. (4) The temperature was maintained at 250°C for 60 minutes. (5) The temperature was raised from 250°C to 300°C over 155 minutes. (6) The temperature was maintained at 300°C for 47 minutes. (7) A reaction terminator was added and the temperature was maintained at a stirring speed of 250 rpm for 60 minutes.

[0062] After the reaction was completed, the contents were transferred to a stainless steel tray and cooled to room temperature for solidification. The product was pulverized in a blender (7010HS manufactured by Waring Co.), washed with acetone, an aqueous oxalic acid solution, and water in that order, and dried in a dryer at 180°C to obtain a powdery aromatic polyether.

[0063] Example 2 A powdery aromatic polyether was obtained in the same manner as in Example 1, except that the amounts of hydroquinone and 2-phenylhydroquinone in the reaction mixture were changed to 105.94 g (0.96 mol) and 31.62 g (0.17 mol), respectively, and the retention time in the temperature control (6) was set to 0 minutes.

[0064] Example 3 A powdery aromatic polyether was obtained in the same manner as in Example 2, except that the amounts of hydroquinone and 2-phenylhydroquinone in the reaction mixture were changed to 99.71 g (0.91 mol) and 42.15 g (0.23 mol), respectively.

[0065] Example 4 A powdery aromatic polyether was obtained in the same manner as in Example 1, except that the amounts of hydroquinone and 2-phenylhydroquinone in the reaction mixture were changed to 87.24 g (0.79 mol) and 63.23 g (0.34 mol), respectively, and the reaction was carried out under the following temperature control.

[0066] <Temperature control> (1) to (4) were the same as in Example 1. (5) The temperature was raised from 250°C to 280°C over 93 minutes. (6) The temperature was maintained at 280°C for 62 minutes. (7) A reaction terminator was added and the temperature was maintained at 250 rpm for 59 minutes.

[0067] Example 5 A powdery aromatic polyether was obtained in the same manner as in Example 4, except that the amount of 4,4'-dichlorobenzophenone used in Example 4 was changed to 289.92 g (1.15 mol) and the reaction was carried out under the following temperature control.

[0068] <Temperature control> (1) to (4) were the same as in Example 4. (5) The temperature was raised from 250°C to 280°C over 93 minutes. When the temperature reached 270°C, the stirring speed was changed to 150 rpm. (6) The temperature was maintained at 280°C for 73 minutes. (7) A reaction terminator was added, and the temperature was maintained at 250 rpm for 36 minutes.

[0069] Example 6 A powdery aromatic polyether was obtained in the same manner as in Example 5, except that the reaction was carried out under the following temperature control.

[0070] <Temperature control> (1) to (5) were the same as in Example 5. (6) The temperature was maintained at 280°C for 107 minutes. (7) A reaction stopper was added, and the temperature was maintained at 250 rpm for 26 minutes.

[0071] Example 7 A powdery aromatic polyether was obtained in the same manner as in Example 4, except that the amounts of hydroquinone and 2-phenylhydroquinone in the reaction mixture were changed to 81.01 g (0.74 mol) and 73.77 g (0.40 mol), respectively, and the reaction was carried out under the following temperature control.

[0072] <Temperature control> (1) to (5) were the same as in Example 4. (6) The temperature was maintained at 280°C for 87 minutes. (7) A reaction stopper was added and the temperature was maintained at 250 rpm for 30 minutes.

[0073] Example 8 A powdery aromatic polyether was obtained in the same manner as in Example 4, except that the amounts of hydroquinone and 2-phenylhydroquinone in the reaction mixture were changed to 74.78 g (0.68 mol) and 84.31 g (0.45 mol), respectively, and the reaction was carried out under the following temperature control.

[0074] <Temperature control> (1) to (5) were the same as in Example 4. (6) The temperature was maintained at 280°C for 103 minutes. (7) A reaction stopper was added and the temperature was maintained at 250 rpm for 26 minutes.

[0075] Comparative Example 1: Commercially available polyether ether ketone (abbreviated as PEEK) (151G) manufactured by Victrex was used. This PEEK is composed of structural units represented by formula (a) and does not contain structural units represented by formula (b). This PEEK is obtained by polymerizing difluorobenzophenone and hydroquinone as monomers, and does not contain dichlorobenzophenone.

[0076] Comparative Example 2 Nitrogen gas was circulated through a 240 L reactor equipped with a stirrer, thermometer, nitrogen inlet pipe, and a water collection vessel connected to a cooling pipe. 137.37 kg of diphenyl sulfone was added stepwise, and the temperature was raised to 160°C. Once melting was confirmed, 39.00 kg (155 mol) of 4,4'-dichlorobenzophenone, 16.85 kg (153 mol) of hydroquinone, and 21.78 kg (158 mol) of potassium carbonate were added in that order. After the reaction was allowed to proceed under the temperature control described below, 6.15 kg (25 mol) of 4,4'-dichlorobenzophenone was added as a reaction terminator.

[0077] <Temperature control> (1) At a stirring speed of 100 rpm, the temperature was raised from 160°C to 200°C over 90 minutes. (2) The temperature was maintained at 200°C for 60 minutes. (3) The temperature was raised from 200°C to 250°C over 90 minutes. (4) The temperature was maintained at 250°C for 60 minutes. (5) The temperature was raised from 250°C to 300°C over 150 minutes. (6) The temperature was maintained at 300°C for 171 minutes. (7) The reaction stopper was added and the temperature was maintained at 100 rpm for 60 minutes.

[0078] 2. Production of Alloy (Example 9) 93 parts by mass of the aromatic polyether obtained in Example 4 and 7 parts by mass of polyetherimide (1000P, manufactured by Saudi Basic Industries Corporation (SABIC)) were dry-blended to obtain a dry-blend raw material, which was melt-kneaded using a twin-screw extruder having a cylinder diameter of 11 mm at a screw rotation speed of 200 rpm and a set temperature of 350°C. The dry-blend raw material was fed from the base of the twin-screw extruder (upstream side of the screw) at a rate of 6 g per minute. The residence time in the twin-screw extruder was 3.5 minutes. The strands discharged from the twin-screw extruder were cooled in water and then pelletized using a pelletizer to obtain a pelletized aromatic polyether composition.

[0079] 3. Measurement and Evaluation Methods The following measurements and evaluations were carried out on the aromatic polyethers of Examples 1 to 8 and Comparative Examples 1 and 2, and the alloy of Example 9. The results are shown in Tables 1 and 2.

[0080] (1) Measurement of the molar ratio of structural units For the obtained aromatic polyether, the molar ratio ((b) / ((a)+(b))) of the structural unit represented by formula (b) to the total amount of the structural unit represented by formula (a) and the structural unit represented by formula (b) was determined as follows: １ Measurement was carried out by H-NMR under the following conditions and procedures. The molar ratio of the structural units of the alloy was not measured.

[0081] The structural unit represented by formula (a) corresponds to a linked compound of 4,4'-dichlorobenzophenone and hydroquinone, and the structural unit represented by formula (b) corresponds to a linked compound of 4,4'-dichlorobenzophenone and 2-phenylhydroquinone.

[0082] [NMR measurement conditions] Magnet: Ascend 500 Spectrometer: AVANCE III HD Probe: 5 mm diameter TCI cryoprobe １H resonance frequency: 500 MHz; Number of accumulations: 256; Waiting time: 10 seconds; Sample preparation: 0.6 mL of methanesulfonic acid was added to approximately 20 mg of sample and stirred at room temperature for 1 hour. 0.4 mL of deuterated dichloromethane was added to the sample to prepare the measurement sample. Chemical shift correction: The central peak of the three peaks of deuterated dichloromethane was set to 5.32 ppm.

[0083] [Procedure] An integral value A of a peak detected at a chemical shift of 7.10 ppm to 7.54 ppm, an integral value B of a peak detected at a chemical shift of 7.45 ppm to 7.52 ppm, and an integral value C of a peak detected at a chemical shift of 7.85 ppm to 8.32 ppm were obtained, and an integral value D was calculated according to the following formula (1): D=A-C-4×B (1)

[0084] Here, integral value A corresponds to the hydrogen atoms possessed by the benzene ring of the hydroquinone-derived moiety in the structural unit represented by formula (a), the hydrogen atoms located in the ortho position relative to the ether group in the 4,4'-dichlorobenzophenone-derived moiety, and the hydrogen atoms possessed by the 2-phenylhydroquinone-derived moiety in the structural unit represented by formula (b). Integral value B corresponds to the hydrogen atoms possessed by the ortho positions (2nd and 5th positions) of the phenyl group in the 2-phenylhydroquinone-derived moiety in the structural unit represented by formula (b). Integral value C corresponds to the hydrogen atoms possessed by the 4,4'-dichlorobenzophenone-derived moiety in the structural unit represented by formula (a) and (b), the ortho positions relative to the ketone group. The integral value D corresponds to the hydrogen atom of the benzene ring of the hydroquinone-derived moiety in the structural unit represented by formula (a).

[0085] Using the integral values ​​B and D, the molar ratio of the structural units ((b) / ((a)+(b))) [mol %] was calculated according to the following formula (2): (b) / ((a)+(b))={(B / 2) / ((B / 2)+(D / 4))} (2)

[0086] (2) Measurement of Radical Amount The radical amounts of aromatic polyethers and alloys (radical amounts at 25°C measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance) were measured by ESR (electron spin resonance) under the following conditions and procedures.

[0087] [ESR measurement conditions] ESR device: JESFA200 model manufactured by JEOL Ltd. ESR sample tube diameter: 5 mm Microwave output: 0.5 mW Modulation magnetic field: 0.3 mT Time constant: 0.03 seconds Magnetic field range: 328 to 344 mT Measurement time: 60 seconds Mn intensity: 650 Measurement temperature: 25°C

[0088] [Procedure] TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl) was dissolved in benzene to a concentration of 5 μM, and 400 μL of this solution was added to an ESR sample tube. ESR was measured under the above-mentioned measurement conditions. The integral of the peak derived from TEMPOL obtained was divided by the integral of the peak of Mn for normalization (integral value A). Thereafter, the measurement sample (aromatic polyether or alloy) was weighed (weighed value B), filled into an ESR sample tube, and ESR was measured under the above-mentioned measurement conditions. The integral of the peak derived from the sample obtained was divided by the integral of the peak of Mn for normalization (integral value C). Using the obtained values ​​of A, B, and C, the amount of radicals per unit weight of the sample was calculated according to the following formula: Amount of radicals per unit weight of sample [spin / g] = (5 × 10 －６ x400 x 10 －６ x 6.02 x 10 ２３ × C) / (A × B)

[0089] (3) Measurement of Glass Transition Temperature (Tg), Melting Point (Tm), Heat of Fusion (ΔH), and Crystallinity A differential scanning calorimeter (DSC) (PerkinElmar DSC 8500) was used. The instrument was calibrated and inspected using standard samples of indium and lead. Five mg of press-molded aromatic polyether or alloy test pieces were placed in an aluminum pan, heated to 420°C at a rate of 20°C / min, and held for 1 minute. The glass transition temperature (Tg) was determined as the temperature at the point where a line equidistant along the vertical axis from the line extending the baselines of the low and high specific heat capacity sides of the specific heat capacity change intersects with the curve of the stepwise change in glass transition. The melting point (Tm) was determined as the temperature at the apex of the endothermic peak due to crystalline melting. Furthermore, the heat of fusion (ΔH) was divided by 130 J / g to derive the crystallinity (%). The "test pieces" were obtained by the following method. The aromatic polyether or alloy was filled into a mold and pressed using a vacuum press (IMC-6215 manufactured by Imoto Machinery Co., Ltd.) at a temperature of 350° C. After pressing, the mixture was annealed at 180° C. for 1 hour while maintaining pressure, to obtain a flat plate with a thickness of 0.5 mm.

[0090] (4) Measurement of Complex Viscosity The complex viscosity of the aromatic polyether and the alloy was measured using a viscoelasticity measuring device under the following conditions and procedures.

[0091] [Measurement conditions] Viscoelasticity measuring device: MCR302 (manufactured by Anton Paar) Jig: SHAFT FOR DISPOSABLE MEASUREMENT SYSTEM D-CP / PP25 Disposable dish: Φ41 mm Disposable parallel plate: Φ25 mm Temperature: 360°C Preheating time: 3 minutes Gap: 0.8 mm Time: 300 min Shear strain: 1% Angular frequency: 6.28 rad / s

[0092] [Procedure] A disk-shaped aromatic polyether or alloy was placed in a disposable dish and measured under the conditions described above. For the measurement, a sample was sandwiched between a disposable dish and a disposable plate with a gap of 0.8 mm, and then preheated and trimmed to a diameter of 25 mm. The complex viscosity is the value at 5 min in the molten state. The "disks" were obtained by the following method. The aromatic polyether or alloy was filled into a mold and pressed at a temperature of 350°C using a vacuum press (IMC-6215, manufactured by Imoto Machinery Co., Ltd.). After pressing, the sample was quenched at 25°C to form a disk with a diameter of 25 mm and a thickness of 1.0 mm.

[0093] The results are shown in Tables 1 and 2.

[0094]

[0095] In Table 1, "Charge amount [mol %]" means the percentage of the molar ratio of 2-phenylhydroquinone to the total of hydroquinone and 2-phenylhydroquinone used in "1. Production of aromatic polyether." In Table 1, "Molar ratio of structural units (b) / ((a)+(b)) [mol %]" means the molar ratio of the obtained aromatic polyether. １ It means the percentage of the molar ratio ((b) / ((a)+(b))) of the structural unit represented by formula (b) to the total amount of the structural unit represented by formula (a) and the structural unit represented by formula (b), as measured by H-NMR.

[0096] As is clear from Table 1, the aromatic polyethers of the present invention can lower the melting point (Tm) without lowering the glass transition temperature (Tg). It can also be seen that the Tg is maintained for the aromatic polyethers of Examples 7 and 8. For the aromatic polyethers of Examples 7 and 8, no melting point (Tm) was detected under the above measurement conditions.

[0097] As can be seen from Table 2, the resin composition (alloy) of the present invention, compared with the corresponding Example 4 consisting only of an aromatic polyether, has a slightly increased glass transition temperature (Tg) (in other words, without decreasing the glass transition temperature (Tg)) due to the inclusion of polyetherimide, and the melting point (Tm) remains unchanged, resulting in a decrease in Δ(Tm-Tg).

[0098] From the above results, the polyether and resin composition of the present invention can realize a lower processing temperature while maintaining heat resistance. Furthermore, the aromatic polyether and resin composition of the present invention can also reduce the crystallinity, thereby suppressing shrinkage during the temperature drop process during molding and preventing the formation of cavities inside the molded product. As a result, molding processability can be improved. Furthermore, while exhibiting these effects, the aromatic polyether and resin composition of the present invention can maintain a high radical concentration, so that it can also achieve adhesion to reinforcing fibers.

[0099] 3. Production of Composite Material (Example 10) 100 parts by mass of the aromatic polyether obtained in Example 5 and 43 parts by mass of an inorganic filler ("T-786H" manufactured by Nippon Electric Glass Co., Ltd., chopped glass fiber, average fiber length 3 mm, filament diameter 11 μm) were melt-kneaded at a set temperature of 350° C. using a twin-screw kneader having a cylinder diameter of 11 mm ("Process-11" manufactured by Termo Fisher Scientific, cylinder volume 20 cc) to obtain a composite material (pellets).

[0100] (Example 11) A composite material (pellet) was obtained in the same manner as in Example 10, except that the inorganic filler in Example 10 was changed to discontinuous carbon fiber ("TR06U" manufactured by Mitsubishi Engineering Plastics Corporation, chopped carbon fiber, average fiber length 6 mm, filament diameter 7 μm).

[0101] 4. Measurement Method and Evaluation Method (1) Measurement of Radical Amount of Composite Material In "(2) Measurement of Radical Amount" described above for Examples 1 to 9 and Comparative Examples 1 and 2, the radical amount of the composite material of Example 10 was measured by using a composite material instead of the aromatic polyether or alloy as the measurement sample.

[0102] (2) Measurement of tensile strength and breaking strain The obtained composite material was dried at 140°C for 2 hours or more and injection molded using a small molding machine (MiniJet-Pro, manufactured by Haake Co., Ltd.) at a cylinder temperature of 370°C and a mold temperature of 180°C to prepare a 4 mm thick test piece specified in ISO527-2-1BA. The obtained test piece was subjected to a tensile test at a test speed of 1 mm / min and a chuck distance of 50 mm, and the tensile strength and breaking strain (tensile elongation) were measured.

[0103] The results are shown in Table 3.

[0104]

[0105] 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. Contains a structural unit represented by the following formula (a) and a structural unit represented by the following formula (b), and has a radical amount of 6.5 x 10 at 25°C, measured using TEMPOL as the standard substance and benzene as the solvent for the standard substance. １５ ~9.0 x 10 １７ (spin / g) of an aromatic polyether.

2. The aromatic polyether according to claim 1, wherein the molar ratio ((b) / ((a)+(b))) of the structural units represented by formula (b) to the total amount of the structural units represented by formula (a) and formula (b) is 5 to 40 (mol %).

3. The aromatic polyether according to claim 1 or 2, having a glass transition temperature (Tg) of 140°C or higher.

4. The aromatic polyether according to any one of claims 1 to 3, having a melting point (Tm) of 330°C or lower.

5. The aromatic polyether according to any one of claims 1 to 4, having a melting point (Tm) of 250°C or higher.

6. The aromatic polyether according to any one of claims 1 to 5, having a melting point (Tm) of 255°C or higher and 315°C or lower.

7. The aromatic polyether according to any one of claims 1 to 6, wherein the difference between the melting point (Tm) and the glass transition temperature (Tg) (Δ(Tm-Tg)) is 185°C or less.

8. The aromatic polyether according to any one of claims 1 to 7, having a crystallinity (%) of 33% or less.

9. The aromatic polyether according to any one of claims 1 to 8, having a crystallinity (%) of 5% or more and 30% or less.

10. The aromatic polyether according to any one of claims 1 to 9, which is a copolymer of 4,4'-dichlorobenzophenone (DCBP), hydroquinone (HQ), and 2-phenylhydroquinone (Ph-HQ).

11. The aromatic polyether according to claim 10, wherein the molar ratio of the 2-phenylhydroquinone (Ph-HQ) to the total amount of the hydroquinone (HQ) and the 2-phenylhydroquinone (Ph-HQ), (Ph-HQ / (HQ+Ph-HQ)), is 5 to 40 (mol %).

12. The aromatic polyether according to any one of claims 1 to 11, wherein 50% by mass or more of the aromatic polyether is the structural unit represented by formula (a) and the structural unit represented by formula (b).

13. A composition comprising an aromatic polyether according to any one of claims 1 to 12 and an amorphous resin, or an aromatic polyether comprising a structural unit represented by the following formula (a) and a structural unit represented by the following formula (b), and an amorphous resin, wherein the amount of radicals at 25°C measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance is 6.5 x 10 １５ ~9.0 x 10 １７ (spin / g).

14. A composite material comprising the aromatic polyether according to any one of claims 1 to 12 or the resin composition according to claim 13, and 0.01 to 500 parts by mass of reinforcing fibers per 100 parts by mass of the aromatic polyether.

15. The composite material of claim 14, wherein the reinforcing fibers comprise one or more selected from the group consisting of carbon fibers, glass fibers, and aramid fibers.

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