Aromatic polyethers and composite materials

Abstract

The present invention provides aromatic polyethers and composite materials with excellent moldability. [Solution] An aromatic polyether comprising a structural unit represented by the following formula (a) and a structural unit represented by the following formula (b). TIFF2026113019000006.tif41170

Description

[Technical Field]

[0001] This invention relates to aromatic polyethers and composite materials. Specifically, the present invention relates to aromatic polyethers and composite materials with excellent moldability. [Background technology]

[0002] Patent Document 1 discloses a specific aromatic polyether produced by including a component having a specific polymerization catalytic activity in the reaction system. It also discloses the use of this aromatic polyether mixed with reinforcing materials or fillers such as glass fibers, carbon fibers, aramid fibers, calcium carbonate, and calcium silicate. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 64-065129 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, conventional aromatic polyethers, including those described in Patent Document 1, have room for further improvement in terms of moldability.

[0005] One of the objectives of the present invention is to provide aromatic polyethers and composite materials that exhibit excellent moldability. [Means for solving the problem]

[0006] As a result of diligent research, the inventors discovered that aromatic polyethers containing a specific combination of structural units exhibit excellent moldability, thus completing the present invention. According to the present invention, the following aromatic polyethers and the like can be provided. 1. An aromatic polyether comprising a structural unit represented by the following formula (a) and a structural unit represented by the following formula (b). [Chemical formula] 2. The aromatic polyether according to 1, wherein the radical amount at 25 °C measured with the standard substance being TEMPOL and the solvent of the standard substance being benzene is 6.5×10 15 ~9.0×10 17 (spin / g). 3. The aromatic polyether according to 1 or 2, wherein the mol ratio of the structural unit represented by the formula (b) to the total amount of the structural unit represented by the formula (a) and the structural unit represented by the formula (b) ((b) / ((a)+(b))) is 5 to 40 (mol%). 4. The aromatic polyether according to any one of 1 to 3, wherein the glass transition temperature (Tg) is 140 °C or higher. 5. The aromatic polyether according to any one of 1 to 4, wherein the melting point (Tm) is 330 °C or lower. 6. The aromatic polyether according to any one of 1 to 5, wherein the crystallinity (%) is 33% or lower. 7. The aromatic polyether according to any one of 1 to 6, which is a copolymer of 4,4'-dihalogenobenzophenone, 1,3-bis(4'-halogenobenzoyl)benzene and hydroquinone. 8. The aromatic polyether according to 7, wherein the 4,4'-dihalogenobenzophenone contains 4,4'-dichlorobenzophenone. 9. The aromatic polyether according to 7 or 8, wherein the 1,3-bis(4'-halogenobenzoyl)benzene contains 1,3-bis(4'-chlorobenzoyl)benzene. 10. The mol ratio of the 1,3-bis(4'-halogenobenzoyl)benzene (m-diketone) to the total amount of the 4,4'-dihalogenobenzophenone (DHBP) and the 1,3-bis(4'-halogenobenzoyl)benzene (m-diketone) (m-diketone / (DHBP + m-diketone)) is 5 to 40 (mol%), and the aromatic polyether according to any one of 7 to 9. 11. The aromatic polyether according to any one of 1 to 10, and 0.01 to 500 parts by mass of reinforcing fibers with respect to 100 parts by mass of the aromatic polyether and A composite material containing. 12. The composite material according to 11, wherein the reinforcing fiber contains one or more selected from the group consisting of carbon fiber, glass fiber, and aramid fiber.

Advantages of the Invention

[0007] According to the present invention, it is possible to provide an aromatic polyether and a composite material having excellent molding processability.

Modes for Carrying Out the Invention

[0008] Hereinafter, the aromatic polyether and the composite material of the present invention will be described in detail. In this specification, "x to y" represents a numerical range of "x or more and y or less". The upper limit value and the lower limit value described for the numerical range can be arbitrarily combined. In addition, among the individual embodiments of the aspects according to the present invention described below, those that do not contradict each other can be combined with two or more, and the embodiments obtained by combining two or more embodiments are also embodiments of the aspects according to the present invention.

[0009] 1. Aromatic polyether The aromatic polyether according to one aspect of the present invention includes a structural unit represented by the following formula (a) and a structural unit represented by the following formula (b).

[0010]

Chemical formula

[0011] The aromatic polyether according to this embodiment provides excellent moldability. In particular, it allows for lower processing temperatures and improved dimensional stability. Furthermore, the aromatic polyether of this embodiment can maintain a high glass transition temperature (Tg) by including the structural unit represented by formula (a). This maintains heat resistance. Moreover, by including the structural unit represented by formula (b), the melting point (Tm) can be lowered without lowering the glass transition temperature. This allows for lower processing temperatures during molding while maintaining heat resistance. The fact that the melting point (Tm) is lowered by including the structural unit represented by formula (b) is thought to be largely due to the fact that the two ketone groups in this structural unit are bonded to the benzene ring at the meta position. That is, because they are at the meta position rather than the para position, the linearity of the polymer chain is reduced, and excessive crystallization is avoided. This is thought to contribute to the reduction in the melting point (Tm). Furthermore, the aromatic polyether of this embodiment can have its crystallinity reduced by including the structural unit represented by formula (b). As mentioned above, this reduction in crystallinity is largely attributed to the fact that the two ketone groups in the structural unit represented by formula (b) are bonded to the benzene ring at the meta position. This prevents warping of the molded product when subjected to press molding, etc. It also suppresses shrinkage during the cooling process during molding (improves dimensional stability) and prevents the formation of cavities inside the molded product. 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) (increasing the ratio can further reduce the crystallinity).

[0012] In one embodiment, the aromatic polyether measured the amount of radicals at 25°C, with TEMPOL as the standard substance and benzene as the solvent for the standard substance, and the amount of radicals was 6.5 × 10⁻⁶. 15 spin / g or more, 7.0×10 15spin / g or more, 8.0×10 15 spin / g or more, 9.0×10 15 spin / g or more or 1.0×10 16 spin / g or more, and also 9.0×10 17 spin / g or less, 7.0×10 17 spin / g or less, 5.0×10 17 spin / g or less or 3.0×10 17 spin / g or less. In one embodiment, the aromatic polyether has a radical amount at 25 °C, measured with the standard substance being TEMPOL and the solvent of the standard substance being benzene, of 6.5×10 15 spin / g or more and 9.0×10 17 spin / g or less, 7.0×10 15 spin / g or more and 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 1.0×10 16 spin / g or more, 3.0×10 17 spin / g or less. When the radical amount of the aromatic polyether is 6.5×10 15 spin / g or more, excellent adhesion to the reinforcing fiber is exhibited. The reason for obtaining such an effect is not necessarily clear, but it is presumed that due to the effect of the high-concentration radicals of the aromatic polyether, a structure having an adhesion effect to the reinforcing fiber is newly formed. On the other hand, when the radical amount of the aromatic polyether is 9.0×10 17 spin / g or less, the thermal stability becomes better, and better mechanical properties are exhibited as a molded product. Note that the radical amount of the aromatic polyether is a value measured by the method described in the examples.

[0013] 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.

[0014] 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 is the structural unit represented by formula (a) and the structural unit represented by formula (b).

[0015] In one embodiment, the glass transition temperature (Tg) of the aromatic polyether is 140°C or higher, 141°C or higher, 142°C or higher, or 143°C or higher. The upper limit is not particularly limited and may be, for example, 165°C or lower, 160°C or lower, 155°C or lower, 150°C or lower, or 148°C or lower. In one embodiment, the glass transition temperature (Tg) of the aromatic polyether is 140°C to 165°C, 141°C to 160°C, 142°C to 155°C, or 143°C to 148°C. Aromatic polyethers exhibit good heat resistance in various applications due to their glass transition temperature (Tg) of 140°C or higher. The glass transition temperature (Tg) of the aromatic polyether is the value measured by the method described in the examples.

[0016] In one embodiment, the melting point (Tm) of the aromatic polyether is 330°C or lower, 325°C or lower, 320°C or lower, 315°C or lower, 310°C or lower, 305°C or lower, 300°C or lower, 295°C or lower, 290°C or lower, 285°C or lower, 280°C or lower, 275°C or lower, 270°C or lower, or 265°C or lower. The lower limit is not particularly limited and may be, for example, 250°C or higher. In one embodiment, the melting point (Tm) of the aromatic polyether is 250°C to 330°C, 250°C to 310°C, 250°C to 290°C, 250°C to 270°C, or 250°C to 265°C. Because the melting point (Tm) of the aromatic polyether is 330°C or lower, the processing temperature during molding can be reduced, which prevents thermal degradation of the aromatic polyether and improves energy efficiency during molding. As a result, the suitability of the aromatic polyether for molding is improved. The melting point (Tm) of the aromatic polyether is the value measured by the method described in the examples.

[0017] In one embodiment, the difference between the melting point (Tm) and the glass transition temperature (Tg) (Δ(Tm-Tg)) of an 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 in this range indicates a significant effect of "lowering the melting point (Tm) without lowering the glass transition temperature (Tg)" as described above. For example, Δ(Tm-Tg) can be reduced by increasing the ratio of structural units represented by formula (b) to structural units represented by formula (a) in the aromatic polyether. The lower limit of Δ(Tm-Tg) is not particularly limited and is, for example, 100°C or higher or 110°C or higher. In one embodiment, Δ(Tm-Tg) is 100°C to 185°C, 100°C to 150°C, or 100°C to 120°C.

[0018] In one embodiment, the degree of crystallinity of the aromatic polyether is 33% or less, 32% or less, 31% or less, 30% or less, 29% or less, 28% or less, 27% or less, 26% or less, or 25% or less. The lower limit is not particularly limited and may be, for example, 5% or more, 10% or more, 15% or more, or 20% or more. In one embodiment, the degree of crystallinity of the aromatic polyether is 5% to 33%, 10% to 30%, 15% to 28%, or 20% to 25%. By having an aromatic polyether crystallinity of 33% or less, warping of the molded product during press molding and other processes can be prevented. Furthermore, shrinkage during the cooling process during molding is suppressed, preventing the formation of voids inside the molded product. If the aromatic polyether crystallinity is 5% or higher, chemical resistance is more easily obtained. The degree of crystallinity (%) of the aromatic polyether is the value measured by the method described in the examples.

[0019] 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 also 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, 2800 Pa·s or less, 2500 Pa·s or less, 2000 Pa·s or less, or 1500 Pa·s or less. In one embodiment, the complex viscosity of the aromatic polyether at 360°C is 450 Pa·s to 7000 Pa·s, 700 Pa·s to 4000 Pa·s, 900 Pa·s to 3000 Pa·s, 1100 Pa·s to 2800 Pa·s, or 1200 Pa·s to 1500 Pa·s. From a certain perspective, complex viscosity can be considered an indicator of the molecular weight of an aromatic polyether. If the complex viscosity of an aromatic polyether at 360°C is 450 Pa·s or higher, the aromatic polyether has a sufficiently high molecular weight. Furthermore, even with such a high molecular weight aromatic polyether, as described above, by including the structural unit represented by formula (b), 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. In addition, if the complex viscosity of an aromatic polyether at 360°C is 7000 Pa·s or lower, the fluidity of the aromatic polyether during melting is favorably exhibited, improving its suitability for various molding processes. The complex viscosity of the aromatic polyether at 360°C is the value measured by the method described in the examples.

[0020] The method for producing the aromatic polyether according to one aspect of the present invention described above is not particularly limited, but for example, it can be produced by the method described in the examples.

[0021] In one embodiment, the aromatic polyether is a copolymer of 4,4'-dihalogenobenzophenone, 1,3-bis(4'-halogenobenzoyl)benzene, and hydroquinone. In one embodiment, the aromatic polyether is a copolymer containing 4,4'-dihalogenobenzophenone, 1,3-bis(4'-halogenobenzoyl)benzene, and hydroquinone as monomer components. Furthermore, the structural unit represented by formula (a) may be a conjugation of 4,4'-dihalogenobenzophenone and hydroquinone. Also, the structural unit represented by formula (b) may be a conjugation of 1,3-bis(4'-halogenobenzoyl)benzene and hydroquinone.

[0022] In one embodiment, the molar ratio of 1,3-bis(4'-halogenobenzoyl)benzene (m-diketone) to the total amount of 4,4'-dihalogenobenzophenone (DHBP) and 1,3-bis(4'-halogenobenzoyl)benzene (m-diketone) (m-diketone / (DHBP + m-diketone)) is 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more, 5 mol% or more, 6 mol% or more, 7 mol% or more, 8 mol% or more, 9 mol% or more, 10 mol% or more, 11 mol% or more, 12 mol% or more, 13 mol% or more, 14 mol% or more, or 15 mol% or more, and also 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. The higher the molar ratio (m-diketone / (DHBP+m-diketone)) is above 5 mol%, the more pronounced the effect of lowering the melting point (Tm) without lowering the glass transition temperature (Tg). Furthermore, improving chemical resistance is possible when the molar ratio (m-diketone / (DHBP+m-diketone)) is 40 mol% or less. Therefore, a molar ratio of 5-40 mol%, 15-40 mol%, and especially 30-40 mol% is particularly preferable. This molar ratio (m-diketone / (DHBP+m-diketone)) can correspond to the molar ratio of each monomer component in aromatic polyethers. Furthermore, this molar ratio (m-diketone / (DHBP+m-diketone)) can correspond to the molar ratio of the structural unit represented by formula (b) to the total amount of structural units represented by formula (a) and formula (b) ((b) / ((a)+(b))). In addition, this molar ratio (m-diketone / (DHBP+m-diketone)) can correspond to the molar ratio of the amount of each monomer charged in the copolymerization reaction to produce aromatic polyethers.

[0023] In one embodiment, the two halogen atoms in 4,4'-dihalogenobenzophenone are, independently, a chlorine atom, a fluorine atom, an iodine atom, or a bromine atom. In one embodiment, 4,4'-dihalogenobenzophenone includes 4,4'-dichlorobenzophenone. 4,4'-Dichlorobenzophenone increased the amount of radicals in the resulting aromatic polyether by 6.5 × 10⁻⁶. 15 ~9.0×10 17 This contributes to improving the (spin / g) ratio. As a result, the adhesion of aromatic polyethers to reinforcing fibers can be improved. In one embodiment, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, 97 mol% or more, 99 mol% or more, 99.5 mol% or more, or 100 mol% of 4,4'-dichlorobenzophenone is 4,4'-dichlorobenzophenone.

[0024] In one embodiment, the two halogen atoms in 1,3-bis(4'-halogenobenzoyl)benzene are, independently, a chlorine atom, a fluorine atom, an iodine atom, or a bromine atom. In one embodiment, 1,3-bis(4'-halogenobenzoyl)benzene includes 1,3-bis(4'-chlorobenzoyl)benzene. In one embodiment, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, 97 mol% or more, 99 mol% or more, 99.5 mol% or more, or 100 mol% of 1,3-bis(4'-chlorobenzoyl)benzene is 1,3-bis(4'-chlorobenzoyl)benzene.

[0025] 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, Nn-propyl-2-pyrrolidone, Nn-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, 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.

[0026] 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.

[0027] In one embodiment, the reaction mixture contains a base. The presence of the base in the reaction mixture promotes the reaction. The base is not particularly limited and can be any alkali metal salt. 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.

[0028] 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.

[0029] The aromatic polyether of this embodiment may be used as a resin component in various applications such as composite materials and molded articles described later, either mixed with other resins (resins other than the aromatic polyether of this embodiment) or used alone. When the aromatic polyether of this embodiment is used in mixture with other resins, the ratio of the mass of the aromatic polyether of this embodiment to the total mass of all resins (total mass of resin components) may be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, 99.5% by mass or more, or substantially 100% by mass (equivalent to the use of the aromatic polyether of this embodiment alone). In the case of "substantially 100% by mass", other resins as unavoidable impurities may be included. In one embodiment, the aromatic polyether of this embodiment is not mixed with other resins and is used alone as a resin for various applications. It is presumed that the effect of reducing the degree of crystallinity is better exhibited because the aromatic polyether of this embodiment is not mixed with other resins.

[0030] 2.Composite materials A composite material according to one aspect of the present invention comprises an 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. According to the composite material of this embodiment, the aromatic polyether exhibits excellent moldability, resulting in superior molding accuracy. Furthermore, the amount of radicals in aromatic polyethers is 6.5 × 10⁻⁶. 15 ~9.0×10 17 When the value is (spin / g), the adhesion between the aromatic polyether and the reinforcing fiber is excellent, resulting in superior mechanical strength (e.g., tensile strength) as a composite material.

[0031] In one embodiment, the content of reinforcing fibers in the composite material is 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 aromatic polyether, and also 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. In one embodiment, the content of reinforcing fibers in the composite material is 0.01 parts by mass or more and 500 parts by mass or less, 0.05 parts by mass or more and 500 parts by mass or less, 0.1 parts by mass or more and 500 parts by mass or less, 0.5 parts by mass or more and 500 parts by mass or less, 1 part by mass or more and 500 parts by mass or less, 10 parts by mass or more and 500 parts by mass or less, 20 parts by mass or more and 40 parts by mass or less, 30 parts by mass or more and 300 parts by mass or less, or 40 parts by mass or more and 200 parts by mass or less, per 100 parts by mass of aromatic polyether.

[0032] In one embodiment, the reinforcing fiber includes one or more selected from the group consisting of carbon fiber, glass fiber, and aramid fiber. In one embodiment, 50% or more by mass of the reinforcing fibers 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 carbon fibers, glass fibers, and aramid fibers.

[0033] 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).

[0034] 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.

[0035] In one embodiment, from the viewpoint of mechanical properties such as strength, elastic modulus, and impact resistance of a molded product 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 calculated by the arithmetic mean of the values ​​measured with calipers.

[0036] In one embodiment, 50% or more by mass of the composite material, 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 aromatic polyether and reinforcing fibers.

[0037] 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 referred to as "UD materials").

[0038] 3. Molded body A molded article according to one aspect of the present invention contains an aromatic polyether according to one aspect of the present invention. Therefore, it exhibits excellent moldability. A molded article according to another aspect of the present invention includes a composite material according to one aspect of the present invention. Therefore, moldability can be improved. In particular, the amount of aromatic polyether radicals is 6.5 × 10 15 ~9.0×10 17 When the value is (spin / g), the adhesion between the aromatic polyether and the reinforcing fiber is excellent, resulting in superior mechanical strength (e.g., tensile strength) as a composite material.

[0039] The form of the molded article according to one aspect of the present invention and other aspects is not particularly limited. In one embodiment, the molded body is either an injection-molded body, an extruded body, or a compression-molded body (also referred to as a "press-molded body").

[0040] The applications of aromatic polyethers, composite materials, and molded articles described above are not particularly limited and can be broadly applied to various applications requiring dimensional stability and strength. Aromatic polyethers, 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 applications such as aerospace components, automotive components, sliding components such as gears and bearings, 3D printer filaments, and semiconductor manufacturing equipment components. [Examples]

[0041] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments.

[0042] 1. Production of aromatic polyethers (Example 1) In a 2L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and water recovery container connected to a condenser, 230.80 g (0.91 mol) of 4,4'-dichlorobenzophenone (Sino-High), 124.63 g (1.13 mol) of hydroquinone (Fujifilm Wako Pure Chemical Industries, Ltd.), 81.62 g (0.23 mol) of 1,4-bis(4'-chlorobenzoyl)benzene, 179.89 g (1.30 mol) of potassium carbonate (AGC Inc., fine powder), and 980 g of diphenyl sulfone (Sino-High) were added, and nitrogen was circulated. After the reaction was carried out under the following temperature control, 22.74 g (0.09 mol) of 4,4'-dichlorobenzophenone was added as a reaction stopper. <Temperature control> (1) After raising the temperature to 150°C, increase the stirring speed to 250 rpm over 30 minutes to raise the temperature to 200°C. (2) Hold at 200°C for 60 minutes (3) Increase the temperature from 200°C to 250°C over 70 minutes. (4) Hold at 250°C for 60 minutes (5) Increase the temperature from 250°C to 300°C over 155 minutes. (6) After reaching 300°C, add the reaction stopper and maintain a stirring speed of 250 rpm for 60 minutes.

[0043] (Example 2) In Example 1, powdered aromatic polyether was obtained in the same manner as in Example 1, except that the amounts of the reaction mixture were changed to 216.37 g (0.86 mol) of 1,4-dichlorobenzophenone, 102.02 g (0.29 mol) of 1,4-bis(4'-chlorobenzoyl)benzene, and 164.25 g (1.19 mol) of potassium carbonate, and the amount of reaction stopper was set to 45.48 g (0.18 mol).

[0044] (Example 3) Powdered aromatic polyether was obtained in the same manner as in Example 1, except that the amounts of the reaction mixture were changed to 1,4-dichlorobenzophenone 201.95 g (0.80 mol) and 1,4-bis(4'-chlorobenzoyl)benzene 122.43 g (0.34 mol).

[0045] (Example 4) In Example 1, powdered aromatic polyethers were obtained in the same manner as in Example 1, except that the amounts of the reaction mixture were changed to 173.10 g (0.69 mol) of 1,4-dichlorobenzophenone and 163.24 g (0.46 mol) of 1,4-bis(4'-chlorobenzoyl)benzene, and the reaction was carried out under the following temperature control conditions. <Temperature control> (1) to (4) are the same as in Example 1. (5) Increase the temperature from 250°C to 290°C over 124 minutes. (6) Hold at 290°C for 49 minutes (7) Add the reaction stopper and hold at a stirring speed of 250 rpm for 15 minutes.

[0046] (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). Furthermore, this PEEK is produced by polymerizing difluorobenzophenone and hydroquinone as monomers, and dichlorobenzophenone is not used.

[0047] (Comparative Example 2) Nitrogen gas was circulated through a 240L reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube, and water recovery container connected to a condenser. 137.37 kg of diphenyl sulfone was added in stages, 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 order. After the reaction was carried out under the following temperature control, 6.15 kg (25 mol) of 4,4'-dichlorobenzophenone was added as a reaction stopper.

[0048] <Temperature control> (1) Heat from 160°C to 200°C over 90 minutes at a stirring speed of 100 rpm. (2) Hold at 200°C for 60 minutes (3) Increase the temperature from 200°C to 250°C over 90 minutes. (4) Hold at 250°C for 60 minutes (5) Increase the temperature from 250°C to 300°C over 150 minutes. (6) Hold at 300°C for 171 minutes (7) Add the reaction stopper and hold at a stirring speed of 100 rpm for 60 minutes.

[0049] After the reaction was complete, the contents were transferred to a stainless steel tray and allowed to cool and solidify at room temperature. The product was pulverized in a blender (Waring 7010HS), washed in acetone, oxalic acid aqueous solution, and water in that order, and dried in a 180°C dryer to obtain powdered aromatic polyether.

[0050] 2. Measurement Method and Evaluation Method The following measurements and evaluations were performed on the aromatic polyethers of the examples and comparative examples. (1) Measurement of the molar ratio of structural units For the obtained aromatic polyether, the molar ratio of the structural unit represented by formula (b) to the total amount of structural units represented by formula (a) and formula (b) is ((b) / ((a)+(b))), 1 The measurement was performed using the 1H-NMR method under the following conditions and procedure. [ka]

[0051] The structural unit represented by formula (a) corresponds to a conjugate of 4,4'-dihalogenobenzophenone and hydroquinone. The structural unit represented by formula (b) corresponds to a conjugate of 1,3-bis(4'-halogenobenzoyl)benzene and hydroquinone.

[0052] [NMR analysis conditions] • Magnet: Ascend500 ·Spectrometer: AVANCE III HD • Probe: 5mm diameter TCI cryopreole · 1 H resonance frequency: 500MHz • Total number of times: 256 • Waiting time: 10 seconds Sample preparation: Approximately 20 mg of the 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 sample for measurement. • Chemical shift correction: Of the three peaks for heavy dichloromethane, the middle peak was set to 5.32 ppm.

[0053] [procedure] The integral value A of the peak detected at chemical shifts from 8.05 ppm to 8.17 ppm and the integral value B of the peak detected at chemical shifts from 8.23 ​​ppm to 8.33 ppm were obtained. Furthermore, the integral value C was calculated from these integral values ​​using the following equation (1). C = AB × 4 / 3 ... (1)

[0054] Here, the integral value A corresponds to the two hydrogen atoms (a total of four on both sides) located at the ortho position of each benzene ring (the first and third benzene rings from the left in formula (b)) that are bonded to both sides of the m-diketone structure in formula (b) (a structure consisting of the second benzene ring from the left in formula (b) and a total of two carbonyl groups bonded to its 1st and 3rd positions), and the two hydrogen atoms (a total of four on both sides) located at the ortho position of each benzene ring (the first and second benzene rings from the left in formula (a)) that are bonded to both sides of the carbonyl group of the benzophenone structure in formula (a). The integral value B corresponds to the three hydrogen atoms at positions 2, 4, and 6 of the benzene ring in the m-diketone structure in equation (b). The integral value C corresponds to the two hydrogen atoms (a total of four) located at the ortho position of each benzene ring (the first and second benzene rings from the left in formula (a)) bonded to the carbonyl group in the benzophenone structure in formula (a).

[0055] Using the integral values ​​B and C, the molar ratio X((b) / ((a)+(b)))[mol%] of the structural unit represented by equation (b) to the total amount of structural units represented by equation (a) and equation (b) was calculated using equation (2) below. X[%]={(B / 3) / (B / 3+C / 4)}×100 ···(2)

[0056] (2) Measurement of radical quantity The radical content of aromatic polyethers (measured at 25°C with the standard substance as TEMPOL and the standard substance's solvent as benzene) was measured by ESR (electron spin resonance) under the following conditions and procedure.

[0057] [ESR measurement conditions] • ESR device: JESFA200 model manufactured by JEOL Ltd. ·ESR sample tube diameter: 5mm • Microwave output: 0.5mW Modulated magnetic field: 0.3mT ·Time constant: 0.03 seconds • Magnetic field range: 328~344mT • Measurement time: 60 seconds ·Mn strength: 650 ·Measurement temperature: 25℃

[0058] [procedure] TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl) was dissolved in benzene at a concentration of 5 μM, and 400 μL was added to an ESR sample tube. The ESR was measured under the above measurement conditions. The integral value of the peak derived from TEMPOL was divided by the integral value of the peak derived from Mn and normalized (integral value A). Subsequently, the sample was weighed (weighed value B), filled into an ESR sample tube, and the ESR was measured under the above measurement conditions. The integral value of the peak derived from the sample was divided by the integral value of the peak derived from Mn and normalized (integral value C). Using the obtained values ​​A, B, and C, the amount of radicals per unit weight of the sample was calculated using the following formula. Radical amount per unit weight of sample [spin / g] = (5 × 10) -6 ×400×10 -6 ×6.02×10 23 ×C) / (A×B)

[0059] (3) Measurement of glass transition temperature (Tg), melting point (Tm), heat of fusion (ΔH), and degree of crystallinity A differential scanning calorimeter (DSC) (PerkinElmar DSC 8500) was used. The instrument was calibrated using indium and lead standard samples. A 5 mg test piece of aromatic polyether, formed by press molding, was placed in an aluminum pan and heated to 420°C at a heating rate of 20°C / min, and held for 1 minute. 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). Furthermore, the temperature at the peak of the endothermic peak caused by crystal melting was defined as the melting point (Tm). Furthermore, the degree of crystallinity (%) was derived by dividing the heat of fusion (ΔH) by 130 J / g. Furthermore, the "test specimens" were obtained by the following method. Aromatic polyether (powder) was filled into a mold and pressed at 350°C using a vacuum press (IMC-6215, manufactured by Imoto Seisakusho). After pressing, the material was annealed at 180°C for 1 hour while maintaining pressure to obtain a 0.5 mm thick flat plate. This flat plate was punched out using a punching machine to form a No. 6 dumbbell test specimen (JIS K-6251).

[0060] (4) Measurement of complex viscosity The complex viscosity of aromatic polyethers was measured using a viscoelasticity analyzer under the following conditions and procedure.

[0061] [Measurement conditions] • Viscoelasticity measuring device: MCR302 (manufactured by Anton Paar) • Fixture: SHAFT FOR DISPOSABLE MEASUREING SYSTEM D-CP / PP25 • Disposable dish: Φ41mm • Disposable parallel plate: Φ25mm ·Temperature: 360℃ • Preheating time: 3 minutes Gap: 0.8mm ·Time: 300min Shear strain: 1% ·Angular frequency: 6.28rad / s

[0062] [procedure] A disc-shaped aromatic polyether was placed in a disposable dish and measured under the conditions described above. For the measurement, the sample, sandwiched between a disposable dish and a disposable plate with a 0.8 mm gap, was preheated and then trimmed to a diameter of Φ25 mm. Complex viscosity is the value obtained at 5 min in the molten state. Furthermore, the "disk" was obtained by the following method. Aromatic polyether was filled into a mold and pressed at 350°C using a vacuum press (IMC-6215, manufactured by Imoto Seisakusho Co., Ltd.). After pressing, it was rapidly cooled to 25°C to form a disc with a diameter of 25 mm and a thickness of 1.0 mm.

[0063] The results are shown in Table 1.

[0064] [Table 1]

[0065] In Table 1, "Charge Amount [mol%]" refers to the percentage of the molar ratio of 1,3-bis(4'-chlorobenzoyl)benzene to the total of 4,4'-dichlorobenzophenone and 1,3-bis(4'-chlorobenzoyl)benzene (this percentage corresponds to the charge ratio of the monomers). Also, "Molar Ratio of Structural Units (b) / ((a)+(b)) [mol%]" refers to the obtained aromatic polyether. 1 This refers to the percentage of the molar ratio ((b) / ((a)+(b))) of the structural unit represented by formula (b) to the total amount of structural units represented by formula (a) and formula (b), as measured by 1H-NMR. As is clear from Table 1, the aromatic polyether of the present invention can lower the melting point (Tm) without lowering the glass transition temperature (Tg). Therefore, it is possible to lower the processing temperature while maintaining heat resistance. Furthermore, since the degree of crystallinity can be lowered with the aromatic polyether of the present invention, shrinkage during the cooling process during molding can be suppressed, and the formation of voids inside the molded product can be prevented. As a result, the processability of the moldable product can be improved. Moreover, while exhibiting these effects, adhesion to reinforcing fibers can also be achieved by maintaining a high radical concentration.

Claims

1. An aromatic polyether comprising a structural unit represented by the following formula (a) and a structural unit represented by the following formula (b). 【Chemistry 4】

2. The radical amount at 25°C was measured using TEMPOL as the standard substance and benzene as the solvent for the standard substance, and was 6.5 × 10⁻⁶. １５ ~9.0 x 10 １７ The aromatic polyether according to claim 1, wherein the ratio is (spin / g).

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

4. An aromatic polyether according to any one of claims 1 to 3, wherein the glass transition temperature (Tg) is 140°C or higher.

5. An aromatic polyether according to any one of claims 1 to 4, wherein the melting point (Tm) is 330°C or less.

6. An aromatic polyether according to any one of claims 1 to 5, wherein the degree of crystallinity (%) is 33% or less.

7. An aromatic polyether according to any one of claims 1 to 6, which is a copolymer of 4,4'-dihalogenobenzophenone, 1,3-bis(4'-halogenobenzoyl)benzene, and hydroquinone.

8. The aromatic polyether according to claim 7, wherein the 4,4'-dihalogenobenzophenone comprises 4,4'-dichlorobenzophenone.

9. The aromatic polyether according to claim 7 or 8, wherein the 1,3-bis(4'-halogenobenzoyl)benzene comprises 1,3-bis(4'-chlorobenzoyl)benzene.

10. The aromatic polyether according to any one of claims 7 to 9, wherein the mol ratio of 1,3-bis(4'-halogenobenzoyl)benzene (m-diketone) to the total amount of 4,4'-dihalogenobenzophenone (DHBP) and 1,3-bis(4'-halogenobenzoyl)benzene (m-diketone) (m-diketone / (DHBP + m-diketone)) is 5 to 40 (mol%).

11. An aromatic polyether according to any one of claims 1 to 10, 0.01 to 500 parts by mass of reinforcing fibers per 100 parts by mass of the aromatic polyether A composite material containing [a certain component].

12. The composite material according to claim 11, wherein the reinforcing fiber comprises one or more selected from the group consisting of carbon fiber, glass fiber, and aramid fiber.

Images