Composition for producing aromatic polyether, and method for producing aromatic polyether

Abstract

Provided is a composition for producing an aromatic polyether. The composition contains an aromatic chlorine compound, and the content of a metal species constituting a Lewis acid or a hydroxide thereof is at least 2.0 ppm.

Description

Composition for producing aromatic polyether, and method for producing aromatic polyether

[0001] The present invention relates to a novel composition for producing aromatic polyethers and a method for producing aromatic polyethers. Specifically, the present invention relates to a composition for producing aromatic polyethers that can produce aromatic polyethers having high molecular weights, and a method for producing aromatic polyethers.

[0002] Aromatic polyethers have excellent heat resistance and mechanical strength, and are used as metal replacement materials due to these characteristics. In recent years, their applications have expanded to include automobiles, aircraft, and the medical field. Among them, polyether ether ketone (abbreviated as "PEEK"), a type of aromatic polyether, is produced in the presence of carbonate, with hydroquinone and aromatic halogen compounds as the main components.

[0003] For example, Patent Document 1 discloses a method for producing an aromatic polyether by reacting dichlorobenzophenone, which is an aromatic chlorine compound, with hydroquinone under specific conditions.

[0004] JP 2023-87073 A

[0005] The present inventors have found that conventional methods for producing aromatic polyethers using aromatic chlorine compounds have room for improvement in terms of suppressing side reactions and the molecular weight of the aromatic polyethers produced.

[0006] Therefore, the present inventors conducted extensive research and found that by using a composition for producing an aromatic polyether, which contains an aromatic chlorine compound and has a content of metal species constituting a Lewis acid or a hydroxide thereof of 2 ppm or more, side reactions can be suppressed and a high molecular weight aromatic polyether can be obtained, and thus completed the present invention. Furthermore, the present inventors conducted extensive research and found that by using a method for producing an aromatic polyether, which includes a reaction step of reacting a raw material mixture containing an aromatic chlorine compound, in which the total content of metal species constituting a Lewis acid or a hydroxide thereof contained in the raw material mixture is 0.4 ppm or more, side reactions can be suppressed and a high molecular weight aromatic polyether can be obtained, and thus completed the present invention.

[0007] An object of the present invention is to provide a high molecular weight aromatic polyether. Specifically, an object of the present invention is to provide a composition for producing an aromatic polyether, which can suppress side reactions and produce a high molecular weight aromatic polyether, and to provide a method for producing an aromatic polyether, which can suppress side reactions and produce a high molecular weight aromatic polyether.

[0008] According to the present invention, the following compositions for use in the production of aromatic polyethers are provided. 1. A composition for use in the production of aromatic polyethers, comprising an aromatic chlorine compound, wherein the content of a metal species constituting a Lewis acid or a hydroxide thereof is 2.0 ppm or more. 2. The composition for use in the production of aromatic polyethers as described in 1 above, wherein the aromatic chlorine compound comprises 4,4'-dichlorobenzophenone. 3. The composition for use in the production of aromatic polyethers as described in 2 above, wherein the aromatic chlorine compound further comprises 2,4'-dichlorobenzophenone, and the content of the 2,4'-dichlorobenzophenone is 0.003 to 0.9 mass% relative to 100 mass% of the composition. 4. The composition for use in the production of aromatic polyethers as described in any one of 1 to 3 above, wherein the metal species constituting the Lewis acid or a hydroxide thereof is Al or Fe. 5. A method for producing an aromatic polyether, wherein an aromatic polyether is produced using the composition for use in the production of aromatic polyethers as described in any one of 1 to 4 above. 6. A method for producing an aromatic polyether, comprising a reaction step of reacting a raw material mixture containing an aromatic chlorine compound-containing composition with an aromatic diol compound, wherein the raw material mixture contains 0.4 ppm or more of a metal species constituting a Lewis acid or a hydroxide thereof. 7. The method according to 6 above, wherein the aromatic chlorine compound contains 4,4'-dichlorobenzophenone. 8. The method according to 7 above, wherein the aromatic chlorine compound further contains 2,4'-dichlorobenzophenone, and the content of the 2,4'-dichlorobenzophenone is 0.003 to 0.9 mass% relative to 100 mass% of the aromatic chlorine compound-containing composition. 9. The method according to any one of 6 to 8 above, wherein the metal species constituting the Lewis acid or a hydroxide thereof is Al or Fe. 10. The method according to any one of 6 to 9 above, comprising a step of mixing a metal species constituting a Lewis acid or a hydroxide thereof with the raw material mixture before the reaction step. 11. 11. The method for producing a polymerizable composition according to any one of 6 to 10 above, wherein the aromatic polyether has a melt flow index of 100 g / 10 min or less. 12. The method for producing a polymerizable composition according to any one of 6 to 11 above, wherein the aromatic polyether is polyether ether ketone (PEEK).13. Use of a composition used for producing an aromatic polyether, the composition comprising an aromatic chlorine compound and having a content of a metal species constituting a Lewis acid or a hydroxide thereof of 2.0 ppm or more.

[0009] According to the present invention, side reactions can be suppressed in the production of aromatic polyethers, and high-molecular-weight aromatic polyethers can be provided.

[0010] The composition for producing an aromatic polyether and the method for producing an aromatic polyether of the present invention will be described in detail below. In this specification, "x to y" represents a numerical range of "x or more and y or less." The upper and lower limits described for the numerical ranges can be combined in any combination.

[0011] 1. Composition for producing aromatic polyethers A composition for producing aromatic polyethers according to one embodiment of the present invention (hereinafter also referred to as the "composition of the present invention") contains an aromatic chlorine compound and has a content of metal species constituting a Lewis acid or a hydroxide thereof of 2.0 ppm or more.

[0012] The compositions of the present invention can be used to prepare aromatic polyethers.

[0013]

[0013] By virtue of the above-mentioned constitution, when the composition of the present invention is used for the production of aromatic polyethers, side reactions can be suppressed and high molecular weight aromatic polyethers can be obtained. Generally, it is considered that the higher the purity of the aromatic halogen compound to be subjected to the condensation reaction, the more preferable the composition to be used for the production of aromatic polyethers. However, the present inventors have surprisingly found that when the content of metal species constituting Lewis acids or their hydroxides is 2.0 ppm or more, when the composition is used for the production of aromatic polyethers, side reactions can be suppressed and high molecular weight aromatic polyethers can be obtained.

[0014] [Aromatic Chlorine Compound] The composition of the present invention contains an aromatic chlorine compound.

[0015] In this specification, the term "aromatic chlorine compound" refers to an aromatic compound having at least one (preferably two or more, more preferably two or three, more preferably two) chloro group. Here, the term "aromatic compound" refers to a compound having an aromatic ring. The aromatic ring is a conjugated unsaturated ring structure having (4n+2) π electrons.

[0016] In one embodiment, the aromatic chlorine compound includes one or more selected from the group consisting of compounds represented by the following formulas (A1) to (A3): (In formula (A1), X Ａ１ is -C(=O)- or -S(=O) ２ In formula (A2), X Ａ２ and X Ａ３ are each independently -C(=O)- or -S(=O) ２ - indicates.)

[0017] In formulae (A1) to (A3), the bond that crosses the skeleton that constitutes the benzene ring means that the bond is made to a bondable position among the carbon atoms that constitute the benzene ring.

[0018] For example, formula (A1) includes all of the following structures:

[0019] In one embodiment, the aromatic chlorine compound includes a compound represented by formula (A1). Ａ１ is —C(═O)—.

[0020] In one embodiment, the aromatic chlorine compound includes a compound represented by the following formula (A1-1):

[0021] In one embodiment, the aromatic chlorine compound comprises 4,4'-dichlorobenzophenone.

[0022] In one embodiment, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, 99.5% by mass or more, or substantially 100% by mass of the aromatic chlorinated compounds is 4,4'-dichlorobenzophenone. Note that "substantially 100% by mass" may include inevitable impurities.

[0023] When 4,4'-dichlorobenzophenone is contained in the above range, the adhesion between the aromatic polyether produced using the composition of the present invention and the carbon fiber is increased, and the adhesive strength is likely to increase, which is preferable when used as a carbon fiber reinforced plastic.

[0024] In one embodiment, the aromatic chlorine compound includes 4,4'-dichlorobenzophenone and 2,4'-dichlorobenzophenone. In one embodiment, the content of 2,4'-dichlorobenzophenone is 0.003 to 0.9 mass%, 0.03 to 0.9 mass%, 0.3 to 0.5 mass%, or 0.1 to 0.5 mass%, relative to 100 mass% of the composition for producing aromatic polyethers.

[0025] When the aromatic chlorine compound contains 4,4'-dichlorobenzophenone and 2,4'-dichlorobenzophenone and the content of 2,4'-dichlorobenzophenone is within the above range, when the composition of the present invention is used to produce an aromatic polyether, a higher molecular weight aromatic polyether is more likely to be obtained. Without being bound by theory, it is believed that by containing 2,4'-dichlorobenzophenone in the above range relative to 4,4'-dichlorobenzophenone, the 2,4'-dichlorobenzophenone incorporated into the aromatic polyether disrupts the structure of the aromatic polyether containing 4,4'-dichlorobenzophenone as a main structural unit, making it difficult for the aromatic polyether to precipitate, thereby resulting in a higher molecular weight aromatic polyether.

[0026] In one embodiment, the composition for producing an aromatic polyether comprises 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, 98% by mass or more, or 99% by mass or more of the aromatic chlorinated compound.

[0027] [Metal Species Constituting Lewis Acid or Hydroxide Thereof] The composition of the present invention contains 2.0 ppm or more of a metal species constituting Lewis acid or hydroxide thereof relative to the entire composition.

[0028] As used herein, a Lewis acid refers to a substance that can accept an electron pair. As used herein, a hydroxide of a Lewis acid refers to a substance in which a hydroxide ion is bound to the above-mentioned Lewis acid. As used herein, a metal species that constitutes a Lewis acid or its hydroxide refers to a metal species that can become a metal ion that accepts an electron pair, or a metal species that can become a metal ion that accepts the electron pair of a hydroxide ion.

[0029] The metal species constituting the Lewis acid or its hydroxide is not particularly limited as long as it is a metal species capable of becoming a metal ion that accepts an electron pair or a metal species capable of becoming a metal ion that accepts an electron pair of a hydroxide ion, and examples thereof include aluminum (Al), iron (Fe), etc. These metal species constituting the Lewis acid or its hydroxide may be used alone or in combination of two or more.

[0030] The metal species constituting the Lewis acid or its hydroxide may be contained in the composition as a free component, or in the form of a compound (for example, chloride, hydroxide, etc.).

[0031] The content of the metal species constituting the Lewis acid or its hydroxide is 2.0 ppm or more. The lower limit of the content of the metal species constituting the Lewis acid or its hydroxide may be, for example, 4.0 ppm, 6.0 ppm, 8.0 ppm, 10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 100 ppm, 120 ppm, or 150 ppm in terms of the metal species. The upper limit of the content of the metal species constituting the Lewis acid or its hydroxide is not particularly limited, but may be, for example, 500 ppm, 400 ppm, 300 ppm, or 200 ppm in terms of the metal species. When two or more metal species constituting the Lewis acid or its hydroxide are contained, the content refers to the total of the two or more metal species.

[0032] In one embodiment, the content of metal species constituting the Lewis acid or its hydroxide is 2.0 ppm or more and 500 ppm or less, 2.0 ppm or more and 400 ppm or less, 2.0 ppm or more and 300 ppm or less, 2.0 ppm or more and 200 ppm or less, 4.0 ppm or more and 500 ppm or less, 4.0 ppm or more and 400 ppm or less, 4.0 ppm or more and 300 ppm or less, 4.0 ppm or more and 200 ppm or less, 6. 0 ppm to 500 ppm, 8.0 ppm to 400 ppm, 10 ppm to 400 ppm, 20 ppm to 400 ppm, 30 ppm to 300 ppm, 40 ppm to 300 ppm, 50 ppm to 300 ppm, 100 ppm to 200 ppm, 120 ppm to 200 ppm, or 150 ppm to 200 ppm.

[0033] When the content of the metal species constituting the Lewis acid or its hydroxide is within the above range, when the composition of the present invention is used for producing an aromatic polyether, a high molecular weight aromatic polyether is easily obtained. Without being bound by theory, it is thought that the Lewis acid or its hydroxide constituting these metal species activates the aromatic chlorine compound, thereby activating the polymerization reaction of the aromatic polyether and relatively suppressing side reactions, resulting in the production of a high molecular weight aromatic polyether.

[0034] The content of the metal species constituting the Lewis acid or its hydroxide in the composition can be increased by adding a Lewis acid compound containing the metal species or its hydroxide to the composition. Examples of the Lewis acid compound or its hydroxide to be added include, but are not limited to, aluminum chloride, iron(II) chloride, iron(III) chloride, aluminum hydroxide, iron(II) hydroxide, iron(III) hydroxide, etc., and any substance known in the art can be used.

[0035] The content of metal species constituting the Lewis acid or its hydroxide in the composition can be reduced by purifying the composition by a recrystallization method, etc. As the recrystallization method, a known method can be used, and for example, the method described in the Examples can be used.

[0036] The content of the metal species constituting the Lewis acid or its hydroxide in the composition can be measured by the method described in the Examples.

[0037] 2. First Production Method of Aromatic Polyether A first production method of an aromatic polyether according to one aspect of the present invention (hereinafter also referred to as "first production method of the present invention") includes a reaction step of reacting a raw material mixture containing an aromatic chlorine compound-containing composition and an aromatic diol compound, in which the raw material mixture contains 0.4 ppm or more of a metal species constituting a Lewis acid or a hydroxide thereof.

[0038] According to the first method for producing an aromatic polyether according to one aspect of the present invention, side reactions can be suppressed and a high molecular weight aromatic polyether can be obtained. Without being bound by theory, it is believed that the Lewis acid or hydroxide thereof constituted by the above-mentioned metal species activates the aromatic chlorine compound, thereby activating the polymerization reaction of the aromatic polyether, and as a result, a high molecular weight aromatic polyether can be obtained.

[0039] [Raw material mixture] The raw material mixture contains an aromatic chlorine compound-containing composition and an aromatic diol compound. In the following description, the "raw material mixture" refers to the reaction system from the start of the reaction to the completion of the reaction in the reaction step. The composition of the raw material mixture may change as the reaction progresses. Usually, as the reaction progresses, the concentration of the reactants (aromatic chlorine compounds, etc.) in the raw material mixture decreases, and the concentration of the product (aromatic polyether) increases.

[0040] (Aromatic Chlorine Compound-Containing Composition) The raw material mixture contains an aromatic chlorine compound-containing composition. The aromatic chlorine compound-containing composition contains an aromatic chlorine compound and a metal species that constitutes a Lewis acid or a hydroxide thereof.

[0041] In one embodiment, the aromatic chlorine compound-containing composition comprises 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, 98% by mass or more, 99% by mass or more, 99.5% by mass or more, or substantially 100% of the aromatic chlorine compound-containing composition is composed of metal species constituting the Lewis acid or its hydroxide. Note that "substantially 100% by mass" may contain inevitable impurities.

[0042] (Aromatic Chlorine Compound) With regard to the aromatic chlorine compound, the matters explained in relation to the composition for producing an aromatic polyether according to one embodiment of the present invention can be applied.

[0043] In one embodiment, the aromatic chlorine compound-containing 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, 98% by weight or more, or 99% by weight or more of the aromatic chlorine compound.

[0044] In one embodiment, the aromatic chlorine compound comprises 4,4'-dichlorobenzophenone.

[0045] In one embodiment, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, 99.5% by mass or more, or substantially 100% by mass or more of the aromatic chlorine compounds in the aromatic chlorine compound-containing composition is 4,4'-dichlorobenzophenone. Note that "substantially 100% by mass" may include inevitable impurities.

[0046] When 4,4'-dichlorobenzophenone is contained in the above range, the adhesion between the aromatic polyether produced by the production method of the present invention and the carbon fiber is increased, and the adhesive strength is likely to increase, which is preferable when used as a carbon fiber reinforced plastic.

[0047] In one embodiment, the aromatic chlorine compound includes 4,4'-dichlorobenzophenone and 2,4'-dichlorobenzophenone. In one embodiment, the content of 2,4'-dichlorobenzophenone is 0.003 to 0.9 mass%, 0.03 to 0.9 mass%, 0.3 to 0.5 mass%, or 0.1 to 0.5 mass%, relative to 100 mass% of the aromatic chlorine compound-containing composition.

[0048] (Metal Species Constituting Lewis Acid or Hydroxide Thereof) The raw material mixture contains 0.4 ppm or more of metal species constituting Lewis acid or hydroxide thereof relative to the entire raw material mixture. With regard to the metal species constituting Lewis acid or hydroxide thereof, the matters described for the composition for producing aromatic polyethers according to one embodiment of the present invention can be applied.

[0049] The lower limit of the content of the metal species constituting the Lewis acid or its hydroxide in the raw material mixture may be, for example, 0.6 ppm, 0.8 ppm, 1.0 ppm, 1.5 ppm, 2.0 ppm, 5.0 ppm, 8.0 ppm, 10 ppm, 20 ppm, or 30 ppm in terms of the metal species. The upper limit of the content of the metal species constituting the Lewis acid or its hydroxide is not particularly limited, but may be, for example, 300 ppm, 200 ppm, 100 ppm, 80 ppm, 60 ppm, 50 ppm, or 30 ppm in terms of the metal species. When two or more metal species constituting the Lewis acid or its hydroxide are contained, the content refers to the total of the two or more metal species.

[0050] In one embodiment, the content of metal species constituting the Lewis acid or hydroxide thereof in the raw material mixture is, in terms of the metal species, 0.6 ppm to 300 ppm, 0.6 ppm to 200 ppm, 0.6 ppm to 100 ppm, 0.6 ppm to 80 ppm, 0.6 ppm to 60 ppm, 0.6 ppm to 50 ppm, 0.6 ppm to 30 ppm, 0.8 ppm to 300 ppm, 1.0 ppm to 200 ppm, 1.5 ppm to 200 ppm, or 2.0 ppm to 100 ppm. ppm or less, 5.0 ppm to 100 ppm, 8.0 ppm to 80 ppm, 10 ppm to 80 ppm, 10 ppm to 60 ppm, 10 ppm to 50 ppm, 10 ppm to 30 ppm, 20 ppm to 60 ppm, 20 ppm to 50 ppm, 20 ppm to 30 ppm, 30 ppm to 300 ppm, 30 ppm to 200 ppm, 30 ppm to 100 ppm, 30 ppm to 80 ppm, 30 ppm to 60 ppm, or 30 ppm to 50 ppm.

[0051] In one embodiment, the metal species that constitutes the Lewis acid or its hydroxide is Al or Fe.

[0052] In one embodiment, the production method of the present invention includes a step of mixing a metal species constituting a Lewis acid or a hydroxide thereof with the raw material mixture before the reaction step. The mixing method is not limited as long as the content of the metal species constituting the Lewis acid or the hydroxide thereof contained in the raw material mixture before the reaction step can be 0.4 ppm or more.

[0053] For example, when the raw material mixture does not contain the above-mentioned metal species, a Lewis acid of the metal species or its hydroxide (e.g., AlCl ３ , Al(OH) ３ , FeCl ３ , Fe(OH) ３ etc.) may be mixed into the raw material mixture in an amount of 0.4 ppm or more in terms of the metal species.

[0054] In one embodiment, the metal species that constitutes the Lewis acid or its hydroxide is Al or Fe.

[0055] (Aromatic Diol Compound) The raw material mixture contains an aromatic diol compound. In this specification, the aromatic diol compound refers to a compound having a structure in which hydrogen atoms bonded to two carbon atoms of an aromatic hydrocarbon are substituted with hydroxy groups, one by one.

[0056] In one embodiment, the raw material mixture contains one or more aromatic diol compounds selected from the group consisting of compounds represented by the following formulas (B1) to (B3): (In formula (B1), R Ｂ represents a hydrogen atom or a phenyl group.

[0057] In formulas (B1) and (B2), the bond crossing the skeleton constituting the benzene ring means bonding to a bondable position of the carbon atoms constituting the benzene ring. In formula (B3), the bond crossing the skeleton constituting the naphthalene ring means bonding to a bondable position of the carbon atoms constituting the naphthalene ring.

[0058] In one embodiment, the raw material mixture contains a compound represented by formula (B1) or formula (B2). Ｂ is a hydrogen atom.

[0059] In one embodiment, the raw material mixture includes hydroquinone.

[0060] In one embodiment, the molar ratio of the aromatic chlorine compound to the aromatic diol compound (aromatic chlorine compound:aromatic diol compound) in the raw material mixture is 47.5:52.5 to 52.5:47.5, 48.0:52.0 to 52.0:48.0, 48.5:51.5 to 51.5:48.5, 49.0:51.0 to 51.0:49.0, or 49.5:50.5 to 50.5:49.5. The number of moles of the aromatic chlorine compound may be greater than, smaller than, or the same as the number of moles of the aromatic diol compound.

[0061] Alkali Metal Salt In one embodiment, the raw material mixture includes an alkali metal salt.

[0062] In the reaction step, the alkali metal salt is a solid and is unlikely to react (neutralize) with a Lewis acid or its hydroxide even when the latter is present, resulting in a synergistic effect between the alkali metal salt's effect of improving the reaction efficiency (reducing the reaction time) and the Lewis acid's or its hydroxide's effect of increasing the molecular weight.

[0063] Examples of the alkali metal salt include alkali metal carbonates and alkali metal hydrogen carbonates.

[0064] Examples of alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, etc. Examples of alkali metal hydrogen carbonates include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate, etc. These alkali metal salts may be used alone or in combination of two or more.

[0065] The content of the alkali metal salt in the raw material mixture is not particularly limited.

[0066] In one embodiment, the content of the alkali metal salt may be 90 mol parts or more, 92 mol parts or more, 95 mol parts or more, or 100 mol parts or more, or may be 180 mol parts or less, 160 mol parts or less, 140 mol parts or less, or 120 mol parts or less, relative to 100 mol parts of the aromatic chlorine compound. When the content of the alkali metal salt is 90 mol parts or more, the reaction time in the reaction step is easily shortened. When the amount of the alkali metal salt blended is 180 mol parts or less, the formation of a gel component in the reaction step is easily suppressed. When two or more alkali metal salts are contained, the content refers to the total of the two or more alkali metal salts.

[0067] In one embodiment, the content of the alkali metal salt may be 90 mol parts or more and 180 mol parts or less, 92 mol parts or more and 160 mol parts or less, 95 mol parts or more and 140 mol parts or less, or 100 mol parts or more and 120 mol parts or less, relative to 100 mol parts of the aromatic chlorine compound.

[0068] (Other Components) The raw material mixture may contain other components used in the polymerization reaction of the aromatic polyether, such as a solvent, a catalyst, a reaction terminator, and the like.

[0069] As the solvent, for example, an aprotic polar solvent can be used, such as 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, and the like.

[0070] When the aromatic chlorine compound and the aromatic diol compound are reacted in a solvent containing an aromatic sulfone, the content of the solvent having a boiling point of 270 to 330°C is preferably 0 part by mass or more and less than 1 part by mass per 100 parts by mass of the aromatic sulfone contained in the raw material mixture.

[0071] By setting the content of the solvent having a boiling point of 270 to 330°C to 0 part by mass or more and less than 1 part by mass per 100 parts by mass of aromatic sulfone, it is easy to produce a high molecular weight aromatic polyether at low cost.

[0072] The raw material mixture may contain two or more solvents, but preferably contains only one solvent (single solvent), which can simplify the process.

[0073] [Reaction Step] The reaction step can be carried out in an inert gas atmosphere. The inert gas is not particularly limited, and examples thereof include nitrogen and argon gas.

[0074] The reaction of the raw material mixture can be carried out under heating. The reaction temperature is usually in the range of 150 to 380° C., preferably in the range of 180 to 350° C. The reaction time is usually in the range of 0.1 to 10 hours, preferably 1 to 5 hours.

[0075] The reaction of the raw material mixture may be completed in one step or in two or more steps. When the reaction is carried out in two or more steps, for example, a portion of all the monomers to be reacted may be reacted to form a prepolymer, and the remaining monomers may then be added to the prepolymer and reacted.

[0076] In one embodiment, the raw material mixture is heated to 150°C or higher and then maintained at that temperature. In one embodiment, the raw material mixture is heated to 150°C or higher and then the heating and temperature maintenance are repeated multiple times. In each of the above embodiments, the heating after heating to 150°C or higher may be performed at a rate of 10°C / min or less. This allows the rate-determining step in the reaction of the raw material mixture to proceed smoothly, making it easier to obtain a high molecular weight aromatic polyether.

[0077] The reaction of the raw material mixture may include, for example, (i) a step of increasing the temperature to 180 to 220°C and maintaining the increased temperature for 0.5 to 2 hours, (ii) a step of increasing the temperature to 230 to 270°C and maintaining the increased temperature for 0.5 to 2 hours, and (iii) a step of increasing the temperature to 280 to 320°C and maintaining the increased temperature for 1 to 8 hours.

[0078] The temperature increase in (i) to (iii) can be carried out at a rate of, for example, 10°C / min or less, 5°C / min or less, or 3°C / min or less. The temperature increase in (i) to (iii) is preferably, for example, 0.1 to 10°C / min or less. This allows the rate-determining step in the reaction of the raw material mixture to proceed smoothly, and makes it easier to obtain a high molecular weight aromatic polyether.

[0079] In one embodiment, the reaction of the raw material mixture can include at least one step selected from the group consisting of the above-mentioned steps (i) to (iii). When two or three steps are included, the steps are preferably performed in order from lowest to highest temperature. Between two or three steps, the raw material mixture can be heated.

[0080] In one embodiment, the reaction of the raw material mixture is carried out under conditions in which the maximum temperature of the raw material mixture is 280 to 320° C., more preferably higher than 290° C. and not higher than 320° C. In this specification, the "maximum temperature" of the raw material mixture refers to the maximum temperature (maximum reached temperature) that the raw material mixture reaches during the process from the start of the reaction of the raw material mixture to the completion of the reaction.

[0081] After the reaction of the raw material mixture is completed, the produced aromatic polyether can be separated, washed or purified according to known methods.

[0082] 3. Second Production Method of Aromatic Polyether The second production method of aromatic polyether according to one embodiment of the present invention (hereinafter also referred to as "second production method of the present invention") produces an aromatic polyether using the composition of the present invention described above. Conventionally known production methods of aromatic polyethers can be applied, except that the composition of the present invention described above is used.

[0083] According to the second method for producing an aromatic polyether according to one aspect of the present invention, side reactions can be suppressed and a high molecular weight aromatic polyether can be obtained. Without being bound by theory, it is believed that the Lewis acid or hydroxide thereof constituted by the metal species contained in the composition of the present invention activates the aromatic chlorine compound, thereby activating the polymerization reaction of the aromatic polyether, resulting in the production of a high molecular weight aromatic polyether.

[0084] 4. Aromatic Polyether The aromatic polyether according to one aspect of the present invention (hereinafter also referred to as "the aromatic polyether of the present invention") is produced by the first production method of the present invention or the second production method of the present invention described above.

[0085] In one embodiment, the aromatic polyether of the present invention comprises a structural unit represented by the following formula (100): In formula (100), A includes one or more structural units selected from the group consisting of structural units represented by the following formulae (A11) to (A13): (In formula (A11), X Ａ１ is -C(=O)- or -S(=O) ２ In formula (A12), X Ａ２ and X Ａ３ are each independently -C(=O)- or -S(=O) ２ In formula (A13), R Ａ represents a cyano group. B includes at least one structural unit selected from the group consisting of structural units represented by the following formulae (B11) to (B13). (In formula (B11), R Ｂ represents a hydrogen atom or a phenyl group.) n is an integer of 0 to 2. When n is 0, the oxygen atom is directly bonded to the adjacent unit structure. When n is 1, B is directly bonded to the adjacent unit structure. When n is 2, of the two Bs, the B farthest from A is directly bonded to the adjacent unit structure.]

[0086] When two or more structural units represented by formulae (A11) to (A13) are present, the two or more structural units represented by formulae (A11) to (A13) may be the same as or different from each other. When two or more structural units represented by formulae (B11) to (B13) are present, the two or more structural units represented by formulae (B11) to (B13) may be the same as or different from each other.

[0087] In formulae (A11) to (A13) and (B11) to (B12), the bond crossing the skeleton constituting the benzene ring means bonding to a bondable position among the carbon atoms constituting the benzene ring. In formula (B13), the bond crossing the skeleton constituting the naphthalene ring means bonding to a bondable position among the carbon atoms constituting the naphthalene ring.

[0088] For example, formula (A11) includes all of the following structures:

[0089] In one embodiment, in the aromatic polyether containing the structural unit represented by formula (100), the molar ratio of the structural unit represented by A to the structural unit represented by B (structural unit represented by A:structural unit represented by B) is 47.5:52.5 to 52.5:47.5, 48.0:52.0 to 52.0:48.0, 48.5:51.5 to 51.5:48.5, 49.0:51.0 to 51.0:49.0, or 49.5:50.5 to 50.5:49.5. The number of moles of the structural unit represented by A may be greater than, smaller than, or the same as the number of moles of the structural unit represented by B.

[0090] In one embodiment, A in formula (100) is a structure represented by formula (A11) or formula (A13). Ａ１ is —C(═O)—.

[0091] In one embodiment, A in formula (100) is a structure represented by the following formula (A11-1):

[0092] In one embodiment, B in formula (100) is a structure represented by formula (B11) or formula (B12). Ｂ is a hydrogen atom.

[0093] In one embodiment, the aromatic polyether of the present invention comprises a structural unit represented by the following formula (100-1):

[0094] In one embodiment, the aromatic polyether of the present invention contains a structural unit (hereinafter also referred to as a "repeating unit") represented by the following formula (1) and a structural unit represented by the following formula (2):

[0095] In the aromatic polyether of the present invention, the molar ratio ([1]:[2]) of the structural unit represented by formula (1) to the structural unit represented by formula (2) is not particularly limited. In one embodiment, the molar ratio ([1]:[2]) is 47.5:52.5 to 52.5:47.5, 48.0:52.0 to 52.0:48.0, 48.5:51.5 to 51.5:48.5, 49.0:51.0 to 51.0:49.0, or 49.5:50.5 to 50.5:49.5. The number of moles of the structural unit represented by formula (1) may be greater than, smaller than, or the same as the number of moles of the structural unit represented by formula (2).

[0096] In the aromatic polyether according to one embodiment, the structural unit represented by formula (1) is linked to the structural unit represented by formula (2).

[0097] The aromatic polyether according to one embodiment includes a structural unit represented by the following formula (3):

[0098] The structural unit represented by formula (3) is a structural unit formed by linking a structural unit represented by formula (1) and a structural unit represented by formula (2).

[0099] In one embodiment, the aromatic polyether does not contain any structural units other than the structural units represented by formulas (1) and (2). However, the molecular chain may have a terminal structure as described above. In one embodiment, the aromatic polyether contains structural units other than the structural units represented by formulas (1) and (2) to the extent that the effects of the present invention are not impaired.

[0100] In one embodiment, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, 99.5% by mass or more, or substantially 100% by mass of the aromatic polyether are structural units represented by formula (1) and structural units represented by formula (2).

[0101] In one embodiment, the aromatic polyether has a Cl (chlorine) atom at the end of the main chain. In the aromatic polyether according to one embodiment, the structural unit represented by A or the structural unit represented by formula (1) is disposed at one or more ends of the main chain. In this case, the end structure bonded to the structural unit may be a chlorine atom (Cl).

[0102] In an aromatic polyether according to one embodiment, a terminal structure is bonded to the structural unit represented by B or the structural unit represented by formula (2) and is arranged at one or more ends of the main chain. The terminal structure may be, for example, a hydrogen atom (H) or the like (when the terminal structure is a hydrogen atom (H), a hydroxyl group is formed together with the oxygen atom (O) in the structural unit). The terminal structure of the aromatic polyether may be, for example, a structure in which the above-mentioned chlorine atom (Cl) or hydroxyl group is replaced with a hydrogen atom (H). The terminal structure may have a structure other than those exemplified above.

[0103] Examples of monomers containing a structural unit represented by A include halogenated diphenyl ketones, halogenated benzonitriles, and halogenated diphenyl sulfones. Examples of monomers containing a structural unit represented by formula (1) include halogenated diphenyl ketones. Examples of halogenated diphenyl ketones include 4,4'-dichlorobenzophenone and 2,4'-dichlorobenzophenone. 4,4'-Dichlorobenzophenone can be easily synthesized and is also commercially available.

[0104] Examples of monomers containing the structural unit represented by B include hydroquinone and biphenol. Examples of monomers containing the structural unit represented by formula (2) include hydroquinone. Hydroquinone can be easily synthesized and is also commercially available.

[0105] In one embodiment, the aromatic polyether has a melt flow index (abbreviated as "MI", which is synonymous with the melt flow rate (abbreviated as "MFR") described in ASTM D 1238-13) of 100 g / 10 min or less, 90 g / 10 min or less, 80 g / 10 min or less, 40 g / 10 min or less, 30 g / 10 min or less, or 20 g / 10 min or less, and is 0.01 g / 10 min or more, 0.05 g / 10 min or more, 0.1 g / 10 min or more, 0.3 g / 10 min or more, 0.5 g / 10 min or more, 1.0 g / 10 min or more, 1.5 g / 10 min or more, or 1.7 g / 10 min or more.

[0106] In one embodiment, the melt flow index of the aromatic polyether is 0.01 g / 10 min to 100 g / 10 min, 0.1 g / 10 min to 90 g / 10 min, 0.5 g / 10 min to 80 g / 10 min, 1.0 g / 10 min to 40 g / 10 min, 1.5 g / 10 min to 30 g / 10 min, or 1.7 g / 10 min to 20 g / 10 min.

[0107] Furthermore, in one embodiment, the melt flow index of the aromatic polyether is preferably 1.0 to 100 g / 10 min, more preferably 1.0 to 90 g / 10 min, more preferably 1.5 to 70 g / 10 min, more preferably 1.0 to 50 g / 10 min, more preferably 1.5 to 50 g / 10 min, and most preferably 1.7 to 50 g / 10 min. This provides the effect of allowing the aromatic polyether to have a viscosity range suitable for extrusion molding, injection molding, and the like. The melt flow index of the aromatic polyether is preferably 50 g / 10 min or less. Aromatic polyethers with a melt flow index of 50 g / 10 min or less have a sufficiently high molecular weight, and are preferably suitable for pelletization using an extruder, for example. The melt flow index of the aromatic polyether is a value measured by the method described in the Examples. The melt flow index of the aromatic polyether can be adjusted by the temperature conditions of the raw material mixture (maximum temperature, temperature holding time, temperature rise rate, etc.) and the ratio of raw materials (4,4'-dichlorobenzophenone and hydroquinone, etc.) in the raw material mixture.

[0108] The melt flow index of an aromatic polyether can also be measured by the following measurement method, and even when measured by this measurement method, the preferred ranges etc. are as described above. The melt flow index of an aromatic polyether is measured using a melt indexer (L-220) manufactured by Tateyama Scientific High-Technologies Co., Ltd. in accordance with JIS K 7210-1:2014 (ISO 1133-1:2011) under the following measurement conditions. [Measurement Conditions] Measurement temperature (resin temperature): 380°C Measurement load: 2.16 kg Cylinder inner diameter: 9.550 mm Die inner diameter: 2.095 mm Die length: 8.000 mm Piston head length: 6.35 mm Piston head diameter: 9.474 mm Piston weight: 110.0 g (the above measurement load includes the piston weight) Procedure: The sample is dried in advance at 150°C for at least 2 hours. The sample is placed in the cylinder, the piston is inserted, and preheated for 6 minutes. A load is applied, the piston guide is removed, and the molten sample is extruded from the die. A sample is cut out at a specified range of piston movement and a specified time (t [s]), and its weight is measured (m [g]). MI is calculated using the following formula: MI [g / 10 min] = 600 / t x m

[0109] In one embodiment, the aromatic polyether of the present invention is polyetheretherketone (PEEK).

[0110] (Applications) The aromatic polyether according to this embodiment can be used to produce, for example, pellets containing the aromatic polyether. These pellets can be used as various molding materials requiring heat resistance, solvent resistance, insulating properties, etc. These pellets can be used to produce molded articles by molding methods such as injection molding using a mold. These pellets can also be used to produce molded articles by molding methods such as extrusion molding, press molding, sheet molding, and film molding. The applications of the aromatic polyether according to one embodiment of the present invention are not particularly limited. The aromatic polyether is suitable, for example, for aerospace applications, sliding members such as gears and bearings, and various resin compositions. The molded article containing the aromatic polyether according to one embodiment of the present invention is suitable, for example, as aerospace molded articles, molded articles for sliding members, and filaments for 3D printers. The molded article containing the aromatic polyether is also suitable, for example, as aerospace injection molded articles and injection molded articles for sliding members.

[0111] The present invention will be explained in more detail below by showing examples, but the scope of the present invention is not limited to the descriptions of these examples in any way.

[0112] Five samples (DCBP1-5, DCBP1') of 4,4'-dichlorobenzophenone (composition for producing aromatic polyethers) with different Al and Fe contents were prepared. DCBP1' was obtained by subjecting DCBP1 to the following recrystallization method. <Recrystallization Method> 50 g of DCBP1 and 650 g of acetone were placed in a 1 L round-bottom flask along with a stirrer, and the water bath temperature was raised to 60°C, followed by heating and stirring to dissolve all of the DCBP1. 80 g of acetone was removed from the solution using a rotary evaporator, and the contents were transferred to a 1 L Erlenmeyer flask and allowed to stand at room temperature for two days. After two days, crystals precipitated. The acetone was removed by filtration, and the crystals were recovered. The same recrystallization procedure was repeated four times to obtain the amount required for polymerization evaluation. The recovered crystals were completely dissolved in 650 g of acetone per 50 g of crystals, and trace amounts of insoluble matter were removed by filtration. Acetone was removed from the recovered solution using a rotary evaporator, and the solution was dried in a vacuum dryer for 10 hours at 60° C. A total of 200 g of DCBP1 was used in four recrystallization operations, and 76 g of purified DCBP1′ was obtained by recrystallization.

[0113] The Al and Fe contents and the 2,4'-dichlorobenzophenone (2,4'-DCBP) content in each of the prepared DCBPs (DCBP1 to 5, DCBP1') were measured by the following methods. The results are shown in Tables 1 to 3.

[0114] (Measurement of Al and Fe Contents) Each sample was dissolved under the following pretreatment conditions, and the Al and Fe contents were measured by ICP emission spectrometry under the following measurement conditions.

[0115] <Pretreatment conditions> 0.1 to 1 g of sample was placed on a platinum dish, concentrated sulfuric acid was added, and the sample was heated to carbonize, then placed in an electric furnace and incinerated for 12 hours at 550°C. After that, hydrochloric acid was added to the sample, which was then heated, allowed to cool, and then made up to a constant volume with ultrapure water.

[0116] <Measurement conditions> ICP optical emission spectrometer: 5100 manufactured by Agilent Technologies, Inc. Al measurement wavelength: 396.152 nm Fe measurement wavelength: 238.204 nm

[0117] (Measurement of 2,4'-DCBP content) Each sample was dissolved under the following pretreatment conditions, and the insoluble matter was filtered off and the resulting solution was subjected to GC analysis under the following measurement conditions to measure the content of 2,4'-DCBP in the sample. The quantitative value was determined based on a calibration curve prepared from references of known concentrations, and the calibration curve solution had the same concentration as the sample solution.

[0118] <Pretreatment Conditions> Approximately 0.1 g of sample was placed in a 10 mL volumetric flask and adjusted to 10 mL with chloroform. After shaking the 10 mL volumetric flask, dissolution of the sample was visually confirmed, and the solution was then filtered using a 0.45 μm pore size polypropylene syringe filter (GL Sciences, non-aqueous) and a 2 mL luer-lock glass syringe (Tsubasa Kogyo Co., Ltd.) to remove solids. The resulting chloroform solution was subjected to the following gas chromatographic (GC) analysis.

[0119] <Measurement conditions> Gas chromatograph: 8890 Gas Chromatograph (Agilent Technologies, Inc.) Column: DB-5ms (length 30 m × film thickness 0.25 μm × inner diameter 0.25 mm) Injection port temperature: 250°C Oven temperature: 40°C (0 min) → 5°C / min → 320°C (5 min) Flow rate: 1.0 mL / min Split ratio: 10:1 Sample injection amount: 1.0 μL Detector: FID Detector temperature: 300°C

[0120] Example 1 1. Preparation of aromatic polyether A 300 mL four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a water collection container connected to a condenser was charged with 41.21 g (0.1641 mol) of DCBP1, 17.81 g (0.1617 mol) of hydroquinone (Fujifilm Wako Pure Chemical Industries, Ltd., special grade), 25.70 g (0.1860 mol) of potassium carbonate (Junsei Chemical Co., Ltd., special grade), and 140.00 g of diphenyl sulfone (Sino-high Corporation), and nitrogen gas was passed through. This raw material mixture was reacted under the following temperature control. The addition of a reaction terminator was omitted.

[0121] <Temperature Control> After heating to 150°C, the raw materials were dissolved at 150°C with a stirring speed of 30-50 rpm. The stirring speed was increased to 250 rpm, and the temperature was raised to 200°C over 30 minutes. The mixture was held at 200°C for 1 hour, and then heated from 200°C to 250°C over 30 minutes. The mixture was held at 250°C for 1 hour, then heated from 250°C to 300°C over 30 minutes, and held at 300°C for 120 minutes. The contents were then removed from an SUS tray and cooled to room temperature for solidification. After the reaction was completed, the product was pulverized in a blender (Waring 7010HS), washed with acetone, an aqueous oxalic acid solution, and water, and then dried in a dryer at 180°C to obtain a powdered aromatic polyether (PEEK).

[0122] 2. Evaluation of Melt Flow Index (MI) The melt flow index of the obtained aromatic polyether was measured using a Melt Indexer L-220 (manufactured by Tateyama Scientific High-Technologies Co., Ltd.) in accordance with JIS K 7210-1:2014 (ISO 1133-1:2011) under the following measurement conditions. The results are shown in Table 1.

[0123] <Measurement conditions> Measurement temperature (resin temperature): 380°C Measurement load: 2.16 kg Cylinder inner diameter: 9.550 mm Die inner diameter: 2.095 mm Die length: 8.000 mm Piston head length: 6.35 mm Piston head diameter: 9.474 mm Piston weight: 110.0 g (the above measurement load includes the piston weight) Procedure: The sample was dried at 150°C for at least 2 hours in advance. The sample was placed in the cylinder, and the piston was inserted and preheated for 6 minutes. A load was applied, the piston guide was removed, and the molten sample was extruded from the die. A sample was cut out at a specified range of piston movement and a specified time (t [s]), and its weight was measured (m [g]). MI was calculated using the following formula: MI [g / 10 min] = 600 / t x m

[0124] Example 2 An aromatic polyether was synthesized and evaluated in the same manner as in Example 1, except that DCBP2 was used instead of DCBP1. The results are shown in Table 1.

[0125] Comparative Example 1 An aromatic polyether was synthesized and evaluated in the same manner as in Example 1, except that DCBP1' was used instead of DCBP1. The results are shown in Table 1.

[0126]

[0127] In Table 1, "ND" means that the component was not detected. "Cl / OH" means the molar ratio of Cl monomer (DCBP) to OH monomer (hydroquinone). ２ CO ３ " / HQ" means the molar ratio of potassium carbonate to hydroquinone (HQ). "Concentration [mol / kg]" means the value obtained by multiplying the number of moles of OH monomer (hydroquinone) by two and dividing the result by the mass [kg] of the solvent (diphenyl sulfone). "Total amount of Al and Fe relative to DCBP [ppm]" can be calculated using the following formula: (amount (g) of Al and Fe contained in DCBP) ÷ (DCBP (g)) × 10 ６ The "total amount of Al and Fe [ppm] relative to the total amount of charged" can be calculated using the following formula: (amount of Al and Fe contained in DCBP (g)) ÷ (total amount of all charged components (g)) × 10 ６

[0128] As can be seen from Table 1, when the total amount of Al and Fe relative to the composition for producing aromatic polyethers (DCBP) is 2 ppm or more, the molecular weight index MI is small and the molecular weight of the resulting PEEK is large. Also, when the total amount of Al and Fe relative to the total amount charged is 0.4 ppm or more, the molecular weight index MI is small and the molecular weight of the resulting PEEK is large.

[0129] (Example 3) 1. Preparation of aromatic polyether Into a 2000 mL four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a water collection container connected to a cooling tube, 285.49 g (1.177 mol) of DCBP1, 123.40 g (1.121 mol) of hydroquinone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade), 178.12 g (1.129 mol) of potassium carbonate (FG-F20, manufactured by AGC Inc.), and 970.30 g of diphenyl sulfone (manufactured by Sino-high Corporation) were placed, and nitrogen gas was passed through.

[0130] <Temperature Control> After heating to 150°C, the raw materials were dissolved at 150°C and a stirring speed of 110 rpm. The stirring speed was increased to 250 rpm, and the temperature was raised to 200°C over 30 minutes, held at 200°C for 1 hour, and then raised from 200°C to 250°C over 70 minutes. After holding at 250°C for 1 hour, the temperature was raised from 250°C to 300°C over 110 minutes and held at 300°C for 180 minutes. The contents were then removed from a stainless steel tray and cooled to room temperature for solidification. After the reaction was completed, the product was pulverized using a blender (Waring 7010HS), washed with acetone, an aqueous oxalic acid solution, and water, and then dried in a dryer at 180°C to obtain a powdered aromatic polyether (PEEK).

[0131] 2. Evaluation of Melt Flow Index (MI) The melt flow index of the obtained aromatic polyether was measured in the same manner as in Example 1. The results are shown in Table 2.

[0132] Examples 4 and 5 Aromatic polyethers were synthesized and evaluated in the same manner as in Example 1, except that DCBP1 was replaced with DCBPs shown in Table 1 and the reaction time at 300° C. was changed to 300 minutes. The results are shown in Table 2.

[0133] Comparative Example 2 An aromatic polyether was synthesized and evaluated in the same manner as in Example 1, except that DCBP5 was used instead of DCBP1 and the reaction time at 300° C. was changed to 300 minutes. The results are shown in Table 2.

[0134]

[0135] In Table 2, "Cl / OH" means the molar ratio of Cl monomer (DCBP) to OH monomer (hydroquinone). ２ CO ３ " / HQ" means the molar ratio of potassium carbonate to hydroquinone (HQ). "Concentration [mol / kg]" means the value obtained by multiplying the number of moles of OH monomer (hydroquinone) by two and dividing the result by the mass [kg] of the solvent (diphenyl sulfone). "Total amount of Al and Fe relative to DCBP [ppm]" can be calculated using the following formula: (amount (g) of Al and Fe contained in DCBP) ÷ (DCBP (g)) × 10 ６ The "total amount of Al and Fe [ppm] relative to the total amount of charged" can be calculated using the following formula: (amount of Al and Fe contained in DCBP (g)) ÷ (total amount of all charged components (g)) × 10 ６

[0136] As can be seen from Table 2, when the total amount of Al and Fe relative to the composition for producing aromatic polyethers (DCBP) is 2 ppm or more, the molecular weight index MI is small and the molecular weight of the resulting PEEK is large. Also, when the total amount of Al and Fe relative to the total amount charged is 0.4 ppm or more, the molecular weight index MI is small and the molecular weight of the resulting PEEK is large.

[0137] (Example 6) In Example 1, DCBP5 was used in place of DCBP1, and AlCl ３ An aromatic polyether was synthesized and evaluated in the same manner as in Example 1, except that 150 ppm in terms of Al was added. The results are shown in Table 3.

[0138] (Example 7) In Example 1, DCBP5 was used in place of DCBP1, and Al(OH) ３ An aromatic polyether was synthesized and evaluated in the same manner as in Example 1, except that 150 ppm in terms of Al was added. The results are shown in Table 3.

[0139] Comparative Example 3 An aromatic polyether was synthesized and evaluated in the same manner as in Example 1, except that DCBP5 was used instead of DCBP1. The results are shown in Table 3.

[0140]

[0141] In Table 3, "Cl / OH" means the molar ratio of Cl monomer (DCBP) to OH monomer (hydroquinone). ２ CO ３ " / HQ" means the molar ratio of potassium carbonate to hydroquinone (HQ). "Concentration [mol / kg]" means the value obtained by multiplying the number of moles of OH monomer (hydroquinone) by two and dividing the result by the mass [kg] of the solvent (diphenyl sulfone). "Total amount of Al and Fe relative to DCBP [ppm]" can be calculated using the following formula: (amount (g) of Al and Fe contained in DCBP + amount (g) of Al and Fe in added components) ÷ DCBP (g) x 10 ６ The "total amount of Al and Fe [ppm] relative to the total amount of charge" can be calculated using the following formula: (amount of Al and Fe contained in DCBP (g) + amount of Al and Fe in added components (g)) ÷ (total amount of all charge components (g)) × 10 ６

[0142] As can be seen from Table 3, even when Al is added to DCBP (DCBP5) in which the total amount of Al and Fe is less than 2 ppm, if the total amount of Al and Fe relative to the raw material mixture is 2 ppm or more, it can be confirmed that the MI (molecular weight index) is small and the molecular weight of the resulting PEEK is large. It can also be confirmed that when the total amount of Al and Fe relative to the total amount charged is 0.4 ppm or more, the MI (molecular weight index) is small and the molecular weight of the resulting PEEK is large.

[0143] 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. A composition for producing an aromatic polyether, which contains an aromatic chlorine compound and has a content of a metal species constituting a Lewis acid or its hydroxide of 2.0 ppm or more.

2. The composition for producing an aromatic polyether according to claim 1, wherein the aromatic chlorine compound contains 4,4'-dichlorobenzophenone.

3. Further, the aromatic chlorine compound contains 2,4'-dichlorobenzophenone, and the content of the 2,4'-dichlorobenzophenone is 0.003 to 0.9% by mass based on 100% by mass of the composition. The composition for producing an aromatic polyether according to claim 2.

4. The composition for producing an aromatic polyether according to any one of claims 1 to 3, wherein the metal species constituting the Lewis acid or its hydroxide is Al or Fe.

5. A method for producing an aromatic polyether, which uses the composition for producing an aromatic polyether according to any one of claims 1 to 4.

6. A method for producing an aromatic polyether, which includes a reaction step of reacting a raw material mixture containing an aromatic chlorine compound-containing composition and an aromatic diol compound, and the content of a metal species constituting a Lewis acid or its hydroxide contained in the raw material mixture is 0.4 ppm or more. The production method.

7. The production method according to claim 6, wherein the aromatic chlorine compound contains 4,4'-dichlorobenzophenone.

8. Further, the aromatic chlorine compound contains 2,4'-dichlorobenzophenone, and the content of the 2,4'-dichlorobenzophenone is 0.003 to 0.9% by mass based on 100% by mass of the aromatic chlorine compound-containing composition. The production method according to claim 7.

9. The production method according to any one of claims 6 to 8, wherein the metal species constituting the Lewis acid or its hydroxide is Al or Fe.

10. The production method according to any one of claims 6 to 9, which includes a step of mixing a metal species constituting a Lewis acid or its hydroxide into the raw material mixture before the reaction step.

11. The production method according to any one of claims 6 to 10, wherein the melt flow index of the aromatic polyether is 100 g / 10 min or less.

12. The production method according to any one of claims 6 to 11, wherein the aromatic polyether is polyether ether ketone (PEEK).

13. Use of a composition for producing an aromatic polyether, wherein the composition contains an aromatic chlorine compound and the content of the metal species constituting a Lewis acid or its hydroxide is 2.0 ppm or more.

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