Polyarylene ether ketone resin, its manufacturing method, and molded product

Abstract

To provide a polyarylene ether ketone resin that uses recyclable resources, has excellent heat resistance, and allows for control of molding temperature.SOLUTION: A polyarylene ether ketone resin meets the following (A)-(C). (A) It contains a repeat unit (1-1) represented by a general formula (1-1); (B) the melting point is 250°C or higher and lower than 400°C; and (C) the 5% mass reduction temperature is 450°C or higher as measured by TGA.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyarylene ether ketone resin, a method for producing the same, and a molded article thereof. [Background technology]

[0002] Polyarylene ether ketone resins (hereinafter sometimes abbreviated as "PAEK resins") are super engineering plastics with excellent thermal stability and toughness, allowing for continuous use in high-temperature environments. They have a proven track record in a wide range of applications, including transportation equipment such as automobile and aircraft components, as well as medical parts and textiles. Their particularly excellent chemical resistance makes them suitable for use in the semiconductor industry, which requires many cleaning processes. Furthermore, their excellent self-extinguishing properties and flame retardancy (equivalent to V-0) even in their neat resin state make them widely used in electrical and electronic materials. In recent years, they have also attracted attention as materials suitable for use in harsh environments such as high temperatures, humidity, and high pressures, such as cable coatings in oil and gas fields and pipes for transporting chemicals.

[0003] It is known that conventional methods for producing polyarylene ether ketone resins such as PAEK resins can be roughly divided into (a) polymerization using an aromatic nucleophilic substitution reaction and (b) polymerization using an aromatic electrophilic substitution reaction. When (a) is used, for example, a polyether ether ketone resin (hereinafter sometimes abbreviated as "PEEK resin") is produced by an aromatic nucleophilic substitution type polycondensation reaction in which potassium carbonate is reacted with two types of monomers, 4,4'-difluorobenzophenone and hydroquinone, in diphenyl sulfone. When (b) is used, for example, two monomers, terephthalic acid dichloride and diphenyl ether (DPE), are used, and an inorganic Lewis acid is allowed to act on them to cause an aromatic electrophilic substitution polycondensation reaction, thereby producing a polyether ketone ketone resin (hereinafter sometimes abbreviated as "PEKK resin").

[0004] PEEK resin produced by the above-mentioned process (a) requires expensive 4,4'-difluorobenzophenone as a monomer, resulting in high raw material costs. Furthermore, the production process requires a reaction temperature of 300°C or higher, resulting in high production costs. On the other hand, PEKK resin produced by the above-mentioned process (b) generally uses terephthalic acid dichloride, which is derived and activated from terephthalic acid, and a solid inorganic Lewis acid such as anhydrous aluminum chloride or iron chloride. This results in relatively low raw material costs. However, the homopolymer of terephthalic acid dichloride and DPE has a melting point exceeding 400°C, resulting in poor processability and limited applications. Therefore, the majority of PEKK resins currently produced are copolymers of terephthalic acid dichloride / isophthalic acid dichloride / DPE (hereinafter sometimes referred to as "T / I-PEKK") (Patent Document 1). T / I-PEKK is a resin in which part of the terephthalic acid (TPA) structure in the polymer chain is replaced with an isophthalic acid (IPA) structure, intentionally bending the polymer chain and lowering its alignment and melting point.It exhibits the excellent property of being able to control the melting point within a certain range by changing the TPA / IPA ratio depending on the application.

[0005] In recent years, there has been an accelerating trend toward replacing exhaustible fossil fuels as raw materials for plastics with renewable plant-derived raw materials in an effort to realize a sustainable society. However, the only known examples of renewable resource PEKK resin raw materials are Patent Document 2 and Non-Patent Document 1, which focus on furandicarboxylic acid (FDCA) as a plant-derived raw material, and it cannot be said that sufficient development has progressed.

[0006] Patent Document 2 and Non-Patent Document 1 disclose a method for producing F-PEKK by an aromatic electrophilic substitution reaction using 2,5-furandicarboxylic acid chloride and diphenyl ether. However, the maximum melting points of the disclosed resins were 179°C and 236°C, respectively, which did not provide sufficient heat resistance for a super engineering plastic. Compared to a homopolymer of terephthalic acid dichloride and DPE (commonly known as T10-PEKK), the lower melting point of the homopolymer of furandicarboxylic acid dichloride and DPE is due to the curved molecular structure of furandicarboxylic acid (the two carbonyl groups are not aligned in a straight line) as well as structural defects in the resin that arise during production. Regarding structural defects in particular, Non-Patent Document 1 describes that in addition to the main backbone repeating unit A formed by the formation of a carbon-carbon bond with 2,5-furandicarboxylic acid chloride at the para-position relative to the oxygen atom of the ether moiety of diphenyl ether during polymerization, a non-negligible amount of repeating unit B formed by the formation of a carbon-carbon bond at the ortho-position is also produced. Both factors are thought to act in a direction that reduces the polymer chain alignment and stability in the solid state compared to T10-PEKK, causing a decrease in the melting point. [ka] [ka]

[0007] Non-Patent Document 2 and Patent Document 3 describe methods for producing polyarylene ether ketones by aromatic nucleophilic substitution reaction using aromatic fluorinated compounds derived from 2,5-furandicarboxylic acid as a constituent raw material. This method requires harsh reaction conditions of 150°C or higher for polymerization to proceed, and consumes a large amount of energy, making it undesirable from the standpoints of economics and environmental impact. Furthermore, the production of resins having a PEKK skeleton, which exhibit a particularly high melting point among polyarylene ether ketones, using this method requires complicated monomer synthesis. As a result, raw material procurement costs are higher compared to the aromatic electrophilic substitution method, and neither document discloses an example of the synthesis of a resin having a PEKK skeleton. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Patent No. 3,516,966 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-88480 [Patent Document 3] Special Publication No. 2021-513586 [Non-patent literature]

[0009] [Non-Patent Document 1] Macromolecules,2016,49,4,1252-1258 [Non-patent document 2] Journal of Polymer Science Part A Polymer Chemistry,2016,54,3094-3101 Summary of the Invention [Problem to be solved by the invention]

[0010] Therefore, an object of the present invention is to provide a polyarylene ether ketone resin that is made from renewable resources, has excellent heat resistance, and allows adjustment of the molding temperature. [Means for solving the problem]

[0011] That is, the present invention is as follows. [1] Satisfy the following (A) to (C), (A) containing a repeating unit (1-1) represented by general formula (1-1); (B) Melting point 300 ℃ or more but less than 400℃; (C) 5% mass loss temperature measured by TGA is 450°C or higher 、 Further containing a repeating unit (1-2) represented by general formula (1-2) different from the repeating unit (1-1), the molar fraction of the repeating unit (1-2) is 1% or more and less than 100% relative to 100% in total moles of the repeating unit (1-1) and the repeating unit (1-2), It is a polyaryletherketoneketone resin. A polyarylene ether ketone resin characterized by: [ka] (In formula (1-1), A is a divalent aromatic group represented by the following structural formula: [ka] (In the formula, J and J' are divalent aromatic groups and may be the same or different. X is an oxygen atom or a sulfur atom. The aromatic groups J and J' may be bonded via a bond other than an -X- bond.) [ka] In formula (1-2), B and C are divalent aromatic groups, and may be the same or different. C is a group represented by the following structural formula: [ka] (In the formula, J and J' are divalent aromatic groups and may be the same or different. X is selected from oxygen atoms and sulfur atoms. The aromatic groups J and J' may be bonded via a bond other than an -X- bond.) It is expressed as [2] The A and C are each independently [ka] (wherein X is an oxygen atom or a sulfur atom) wherein B is selected from [ka] (wherein X is an oxygen atom or a sulfur atom) Selected from [1] The polyarylene ether ketone resin according to claim 1. [3] The above B [ka] Selected from [1] or [2] The polyarylene ether ketone resin according to claim 1. [4] The polyarylene ether ketone resin has the following formula: [ka] (In the formula, X represents a structure of the polyarylene ether ketone resin excluding the terminal groups, and each E independently represents an terminal group selected from the group consisting of hydrogen, a hydroxyl group, an alkyl group, an alkynyl group, an alkenyl group, an aryl group, an amino group, an amide group, an imide group, a nitro group, a cyano group, an ether group, a sulfanyl group, a carboxylic acid group, an ester group, an acyl group, a sulfonic acid group, a sulfone group, a sulfonate group, and a quaternary ammonium group.) is expressed as [1] wherein the chemical formula molecular weight of the terminal group E is 1 to 600 g / mol. [3] 1. The polyarylene ether ketone resin according to any one of claims 1 to 9. [5] [1] ~ The number average molecular weight Mn is 4000 or more and 100,000 or less. [4] 1. The polyarylene ether ketone resin according to any one of claims 1 to 9. [6] A polymerization raw material of the following (I) or the following (II), (I) An oligomer (X) containing an aromatic dicarboxylic acid and an oligomer (X) represented by the following formula (X): [ka] (wherein A and A' are divalent aromatic groups and may be the same or different). (II) An oligomer (Y) containing 2,5-furandicarboxylic acid and the following formula (Y): [ka] (In the formula, B, C, and C' are divalent aromatic groups and may be the same or different.) a protic solvent as a solvent; a sulfonic acid anhydride or a carboxylic acid anhydride as a reaction accelerator; [1] to [5]10. A method for producing the polyarylene ether ketone resin according to claim 9, wherein the polyarylene ether ketone resin is [7] [1]~ [5] 10. A polyarylene ether ketone resin composition comprising the polyarylene ether ketone resin according to any one of claims 1 to 9. [8] [7] A molded article comprising the polyarylene ether ketone resin composition according to claim 1. [9] An oligomer represented by any one of the following formulas (Z): [ka] (wherein X represents an oxygen atom or a sulfur atom) [Effects of the Invention]

[0012] The present invention can provide a polyarylene ether ketone resin that is made from renewable resources, has excellent thermal stability, and allows adjustment of the molding temperature. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. Note that the present invention is not limited to the following embodiment, and various modifications can be made within the scope of the gist of the present invention.

[0014] In the present application, the polyarylene ketone resin refers to an aromatic polymer containing a ketone group in the repeating unit of the polymer main chain, and is preferably an aromatic polymer containing an ether group and a ketone group. The polyarylene ether ketone resin may be a polyether ketone ketone resin. Polyether ketone ketone (PEKK) refers to the polyarylene ketones described above, in which the molar ratio of the total of ether groups and thioether groups in the main chain to the ketone groups is 1:2. However, the ether groups or thioether groups in the heteroaromatic rings of the dicarboxylic acid monomers are not included in the calculation of the ratio. Among PEKK resins, resins that contain only the 2,5-furandicarbonyl structure and DPE skeleton in the repeating unit are sometimes called "F-PEKK."

[0015] [Polyarylene ether ketone resin] The polyarylene ether ketone resin of the present embodiment satisfies at least the following (A), (B), and (C). (A) containing a repeating unit (1-1) represented by general formula (1-1) (B) The melting point is 250°C or more and less than 400°C. (C) 5% mass loss temperature measured by TGA is 450°C or higher [ka] (In formula (1-1), A is a divalent aromatic group represented by the following structural formula: [ka] (In the formula, J and J' are divalent aromatic groups and may be the same or different. X is an oxygen atom or a sulfur atom. The aromatic groups J and J' may be bonded via a bond other than an -X- bond.) Examples of the bond between J and J′ other than the —X— bond include a bond in which J and J′ form a fused ring (for example, dibenzofuran, etc.), and the fused ring may contain an oxygen atom or a sulfur atom between J and J′.

[0016] The polyarylene ether ketone resin preferably contains a repeating unit (1-2) represented by the following general formula (1-2), which is different from the repeating unit (1-1), in a molar fraction of 1% or more but less than 100%, where the total number of moles of the repeating unit (1-1) and the repeating unit (1-2) in the resin is taken as 100%. [ka] In formula (1-2), B and C are divalent aromatic groups, and may be the same or different. C represents a group represented by the following structural formula: [ka] (wherein J and J' are divalent aromatic groups and may be the same or different; X is selected from oxygen atoms or sulfur atoms; and the aromatic groups J and J' may be bonded via a bond other than an -X- bond). It is expressed as Examples of the bond between J and J′ other than the —X— bond include a bond in which J and J′ form a fused ring (for example, dibenzofuran, etc.), and the fused ring may contain an oxygen atom or a sulfur atom between J and J′.

[0017] The polyarylene ether ketone resin may further contain other repeating units (for example, the following repeating unit (1-3) which is an aliphatic chain G having 1 to 20 carbon atoms (e.g., -CH2-CH2-, -CH2-CH(CH3)-, etc.)). The polyarylene ether ketone resin may be a resin consisting only of the repeating unit (1-1), or may be a resin consisting only of the repeating unit (1-1) and the repeating unit (1-2). The total mass proportion of the repeating unit (1-1) and the repeating unit (1-2) relative to 100% by mass of the polyarylene ether ketone resin is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. [ka] (wherein G represents an aliphatic chain having 1 to 20 carbon atoms)

[0018] The partial structure A in the repeating unit (1-1) and the partial structure C in the repeating unit (1-2) are each independently [ka] (wherein X is an oxygen atom or a sulfur atom) In the above formula, X is preferably an oxygen atom. The repeating units (1-1) and (1-2) preferably have an ether group, and are preferably a diphenylene ether structure in which X is an oxygen atom. X in the repeating unit (1-1) and the repeating unit (1-2) may be the same or different.

[0019] The above J and J' in A and C are each independently [ka] (wherein X is an oxygen atom or a sulfur atom) Preferably, it is selected from [ka] It is more preferable to select from:

[0020] In the repeating unit (1-2), B is [ka] (wherein X is an oxygen atom or a sulfur atom) Preferably, it is selected from [ka] It is more preferable to select from: In the above structure, the substitution positions of naphthalene include 1,4-, 1,5-, 2,6-, and 2,7-.

[0021] The repeating unit (1-1) and the repeating unit (1-2) contained in the polyarylene ether ketone resin may each be one type or multiple types.

[0022] The molar fraction of the repeating unit (1-1) relative to all repeating units constituting the polyarylene ether ketone resin is 1% or more but less than 100%, and in consideration of the balance between the molding temperature and thermal stability, which is determined based on the melting point of the resin, it is preferably 5 to 95%, more preferably 10 to 70%, and even more preferably 20 to 60%. In order to reduce the environmental impact, it is preferable to increase the proportion of biomass-derived monomers. When using biomass-derived 2,5-furandicarboxylic acid, in order to achieve a high degree of biomass conversion, the molar fraction of the repeating unit (1-1) is 1% or more and less than 100%, preferably 5% or more and less than 100%, more preferably 10% or more and less than 100%, and even more preferably 20% or more and less than 100%. The molar fraction of the repeating unit (1-1) can be calculated, for example, from the total moles of the repeating unit (1-1) and the repeating unit (1-2) contained in the polyarylene ether ketone resin.

[0023] The degree of biomass conversion is calculated from the proportion of carbon atoms derived from biomass among all carbon atoms constituting the resin. For example, in a resin consisting only of repeating units (1-1) (e.g., the unit on the left side in formula (P-1) below) and repeating units (1-2) (e.g., the repeating unit on the right side in formula (P-1) below) shown in structural formula (P-1) below, if n = m in the structural formula and only the furandicarboxylic acid moiety is derived from biomass raw material, the degree of biomass conversion is calculated to be 6 / 38 = 16%. [ka]

[0024] The polyarylene ether ketone resin (for example, polyaryl ether ketone ketone resin) of this embodiment preferably has the following structure. [ka] (wherein X represents a structure of the polyarylene ether ketone resin excluding the terminal groups, E and E' represent terminal groups, and E and E' may be the same or different.) Examples of the terminal group include hydrogen, hydroxyl, alkyl, alkynyl, alkenyl, aryl, amino, amide, imide, nitro, cyano, ether, sulfanyl, carboxylic, ester, acyl, sulfonic, sulfone, sulfonate, and quaternary ammonium groups. The alkyl, alkynyl, and alkenyl groups preferably have 0 to 40 carbon atoms, more preferably 0 to 20 carbon atoms, and even more preferably 0 to 15 carbon atoms. Examples of the alkyl, alkynyl, and alkenyl groups include methyl, ethyl, dodecyl, and ethynyl groups. Examples of the aryl group include aryl groups having 2 to 30 carbon atoms, such as phenyl, thienyl, and triazinyl groups. Among these, hydrogen atoms and aromatic substituents are preferred for the terminal group from the viewpoint of chemical stability during polymerization and melt processing. Furthermore, it is preferable to appropriately select from the above-mentioned terminal groups in terms of chemical conversion modification utilizing the reactivity of the terminal groups, attempts to change affinity such as adhesion to different materials or substances or ease of peeling, ease of addition or removal when prepared as a composition, and adjustment of the solvent resistance of the polyarylene ether ketone resin, but this is not intended to limit the uses. The chemical formula molecular weight of the terminal group E is preferably 1 to 600 g / mol, more preferably 1 to 300 g / mol, and even more preferably 1 to 200 g / mol. The form of the terminal group E is 1 It can be measured by H-NMR.

[0025] In the polyarylene ether ketone resin (e.g., polyaryl ether ketone ketone resin) of this embodiment, by appropriately selecting the ratio (e.g., molar ratio) of the two repeating units (1-2) and (1-1) having different flexibility, it is possible to control the flexibility of the polymer chain and adjust the melting point (Tm), and good moldability can be achieved. For example, when a paraphenylene skeleton, which is more symmetrical and rigid than a furan skeleton, is used as B in the repeating unit (1-2), the melting point and heat resistance improve as the molar proportion of the repeating unit (1-2) increases, but high-temperature heating close to the decomposition temperature of the resin is required during molding processing. The molar ratio of repeating units (1-1) to repeating units (1-2) (the ratio of repeating units (1-1) when the total number of moles of repeating units (1-1) and repeating units (1-2) is taken as 100%) is 1% or more and less than 100%. In consideration of the balance between the molding temperature and thermal stability, which is determined based on the melting point of the resin, the ratio is preferably 5 to 95%, more preferably 10 to 70%, and even more preferably 20 to 60%. By increasing the molar ratio of repeating units (1-2) relative to the molar amount of repeating units (1-1) within this molar ratio range, it is possible to increase the crystalline melting enthalpy and melting point (Tm), and to obtain a polyarylene ether ketone resin with excellent solvent resistance and heat resistance. Furthermore, by decreasing the molar ratio of repeating units (1-2) relative to the molar amount of repeating units (1-1) within this molar ratio range, it is possible to adjust the melting point (Tm) to a relatively low value, and to obtain a polyarylene ether ketone resin with excellent molding processability. Furthermore, when a repeating unit containing a skeleton more flexible than a furan skeleton, such as a 4,4'-oxydiphenyl skeleton shown in the following structural formula, is used as B in the repeating unit (1-2), the melting point and the molding temperature decrease as the proportion of the repeating unit (1-2) increases. [ka] The polyarylene ether ketone resin can be made into a resin excellent in heat resistance, moldability, and strength of molded bodies by appropriately optimizing the ratio of the repeating unit (1-1) and the repeating unit (1-2) and by appropriately adjusting the degree of polymerization to an optimal number-average molecular weight Mn.

[0026] The number average molecular weight Mn of the polyarylene ether ketone resin (for example, polyaryl ether ketone ketone resin) of this embodiment is preferably 3,500 or more, more preferably 4,000 to 100,000, even more preferably 4,000 to 50,000, still more preferably 4,500 to 30,000, and particularly preferably 5,000 to 15,000. By having the number average molecular weight of the copolymer be equal to or less than the upper limit, excellent moldability can be obtained, and by having the number average molecular weight be equal to or greater than the lower limit, molded articles having excellent strength can be obtained. The number average molecular weight can be measured by the method described in the Examples below.

[0027] The crystalline melting enthalpy change (ΔH) of the polyarylene ether ketone resin (for example, polyaryl ether ketone ketone resin) of this embodiment is preferably 10 to 100 J / g, more preferably 12 to 90 J / g, and even more preferably 15 to 80 J / g. The crystalline melting enthalpy change can be adjusted, for example, by appropriately selecting the ratio of the repeating unit (1-1) to the repeating unit (1-2). When the enthalpy change of crystal fusion is equal to or less than the upper limit, excellent moldability and toughness can be obtained, and when it is equal to or greater than the lower limit, a molded article having excellent chemical resistance can be obtained.

[0028] The glass transition temperature of the polyarylene ether ketone resin (for example, polyaryl ether ketone ketone resin) of this embodiment is preferably 100 to 210°C, more preferably 110 to 180°C, still more preferably 120 to 175°C, and particularly preferably 125 to 170°C. The glass transition temperature can be adjusted, for example, by appropriately selecting the ratio of the repeating unit (1-1) to the repeating unit (1-2). When the glass transition temperature is equal to or higher than the above lower limit, a molded article having excellent heat resistance can be obtained.

[0029] The melting point (Tm) of the polyarylene ether ketone resin (for example, polyaryl ether ketone ketone resin) of this embodiment is preferably 250 to 400°C, more preferably 250 to less than 400°C, still more preferably 260 to 390°C, and particularly preferably 270 to 380°C. Also, it is preferably 300 to less than 400°C. The melting point can be adjusted, for example, by appropriately selecting the ratio of the repeating unit (1-1) to the repeating unit (1-2). By having a melting point equal to or lower than the upper limit, excellent moldability and thermal stability during melting can be achieved, while by having a melting point equal to or higher than the lower limit, a molded article having excellent heat resistance and rigidity when heated can be obtained.

[0030] The 10% mass loss temperature of the polyarylene ether ketone resin (e.g., polyaryl ether ketone ketone resin) of this embodiment is preferably 450°C or higher, more preferably 470°C or higher, and even more preferably 480°C or higher, and the 5% mass loss temperature is preferably 400°C or higher, more preferably 430°C or higher, and even more preferably 450°C or higher. When the 5% mass loss temperature and the 10% mass loss temperature are equal to or higher than the lower limit values, a resin having excellent heat resistance, rigidity when heated, and the like can be obtained. The 5% mass loss temperature and 10% mass loss temperature can be measured by the method described in the Examples below.

[0031] Among the polyarylene ether ketone resins of the present embodiment (for example, polyaryl ether ketone ketone resins), those containing a DPE skeleton (excluding those that are part of a fused ring structure such as dibenzofuran) preferably have a para ratio, which is the ratio of the number of phenylene moieties in which a furandicarbonyl moiety is bonded to the para position of the phenylene moiety relative to the oxygen derived from the ether group, to the total number of phenylene moieties bonded to the furandicarbonyl moiety and the ether group, of 96% or more, more preferably 98% or more, and even more preferably more than 99%. In this specification, a phenylene moiety in which a furandicarbonyl moiety is bonded to the para-position of the phenylene moiety relative to the oxygen atom derived from the ether group may be referred to as a "para isomer," and a phenylene moiety in which a furandicarbonyl moiety is bonded to the ortho-position of the phenylene moiety relative to the oxygen atom derived from the ether group may be referred to as an "ortho isomer." Depending on the conditions, the "ortho-isomer" in PEKK may cyclize to form a six-membered ring, forming a 9-xanthenol skeleton, which may adversely affect melt stability. The following reaction formula (C) shows an example of an ortho-isomer (left) and a 9-xanthenol skeleton (right) that may be by-produced during the polymerization of 2,5-furandicarboxylic acid and DPE (an example of R in the reaction formula below is a hydroxyl group). Among the polyarylene ether ketone resins of this embodiment (e.g., polyaryl ether ketone ketone resins), those containing a DPE skeleton preferably have a molar ratio of the structural unit represented by formula (C) below of less than 1 mol % relative to 100 mol % of the total number of moles of repeating units in the resin. Note that in all of the examples of this embodiment described below, the content of the ortho-isomer and the 9-xanthenol skeleton in the resulting polyarylene ether ketone resin was less than 1 mol % relative to the total number of moles of repeating units. [ka] (In the formula, R is selected from the group consisting of a hydroxyl group, hydrogen, an alkyl group, an aryl group, a carboxylic acid ester structure represented by the general formula -OCOR', and a sulfonic acid ester structure represented by the general formula -OSO2R'. Here, R' is an alkyl group or an aryl group.)

[0032] The p / o ratio (molar number of para isomers:molar number of ortho isomers) in the main chain structure of the polyarylene ether ketone resin (e.g., polyaryl ether ketone ketone resin) is preferably 96:4 to 100:0, more preferably 97:3 to 100:0, even more preferably 98:2 to 100:0, and particularly preferably 99:1 to 100:0. When the p / o ratio is equal to or greater than the above lower limit, a resin having excellent melt stability can be obtained. The number and moles of para and ortho isomers can be measured by the method described in the Examples below.

[0033] The halogen element content (total mass ratio of chlorine and bromine elements) of the polyarylene ether ketone resin (e.g., polyaryl ether ketone ketone resin) of this embodiment is preferably 900 ppm or less, more preferably less than 100 ppm, even more preferably less than 50 ppm, and particularly preferably less than 10 ppm, relative to 100 mass% of the resin. By ensuring that the halogen element content is equal to or less than the above lower limit, generation of halogen-based harmful gases during combustion can be significantly suppressed, and a molded article can be obtained that can solve the problem of corrosion of surrounding metal parts caused by halogen residues when used as an electronic material. The halogen element content can be measured by the method described in the Examples below.

[0034] (Manufacturing method) The method for producing the polyarylene ether ketone resin of the present embodiment is not particularly limited as long as it is a method that can produce the polyarylene ether ketone resin of the present embodiment described above. The method for producing a polyarylene ketone resin of the present embodiment includes at least a step of adding a polymerization raw material (I) or (II) described below, a protic solvent as a solvent, and a sulfonic acid anhydride or a carboxylic acid anhydride as a reaction accelerator (sometimes referred to as production method (I) in this specification). (I) An oligomer (X) containing an aromatic dicarboxylic acid and an oligomer (X) represented by the following formula (X): [ka] (wherein A and A' are divalent aromatic groups and may be the same or different). (II) An oligomer (Y) containing 2,5-furandicarboxylic acid and the following formula (Y): [ka] (In the formula, B, C, and C' are divalent aromatic groups and may be the same or different.) In the above (I), the aromatic dicarboxylic acid may be 2,5-furandicarboxylic acid. In the above (I), an oligomer (Y) may be further contained, and in the above (II), an oligomer (X) may be further contained. The oligomer (X) and the oligomer (Y) have different structures. In addition, even when the method for producing a polyarylene ether ketone resin of the present embodiment does not use the oligomer (X), it is possible to produce a polyarylene ether ketone resin containing the repeating unit (1-1) by using, for example, 2,5-furandicarboxylic acid as a monomer component. The method for producing the polyarylene ether ketone resin of the present embodiment may be a production method including a step of reacting at least a dicarboxylic acid, a divalent aromatic compound, a protic solvent, and a carboxylic acid anhydride or a sulfonic acid anhydride.

[0035] In the step of adding, the dicarboxylic acid (for example, aromatic dicarboxylic acid) is a compound represented by the following formula: [ka] (wherein X is an oxygen atom or a sulfur atom) A compound represented by the formula: [ka] The substitution positions of naphthalenedicarboxylic acid include 1,4-, 1,5-, 2,6-, and 2,7-. Alternatively, an aromatic carboxylic acid dichloride which can be derived from the above aromatic dicarboxylic acid may be used in place of the aromatic carboxylic acid in the polymerization.

[0036] The dicarboxylic acid or divalent aromatic compound (e.g., oligomer (X) or oligomer (Y) described below) may be substituted with functional groups selected from the group consisting of hydroxyl, alkyl, alkynyl, alkenyl, aryl, amino, amide, imide, nitro, cyano, ether, sulfanyl, carboxylic acid, ester, sulfonic acid, sulfone, sulfonate, and quaternary ammonium in any proportion of C—H bonds in the dicarboxylic acid or divalent aromatic compound, provided that the substitution does not interfere with the polymerization reaction. Any C—H bonds in the aromatic ring in the polymer main chain may be converted to the functional groups in any proportion.

[0037] The dicarboxylic acids, such as 2,5-furandicarboxylic acid, terephthalic acid, and isophthalic acid, and the divalent aromatic compounds, such as diphenyl ether and the oligomers, can be derived from biomass materials or from materials derived from biomass materials, or from petrochemical materials, such as sugars, lignin, and bioiophenols.

[0038] In the above-mentioned addition step, it is preferable to add the following aromatic nucleophiles as divalent aromatic compounds, taking into consideration the reactivity during polymerization and the rigidity of the resulting resin structure. The divalent aromatic compound may be an oligomer (X) represented by the following formula (X): [ka] (wherein A and A' are divalent aromatic groups and may be the same or different); Or an oligomer (Y) represented by the following formula (Y): [ka] (wherein B, C, and C' are divalent aromatic groups and may be the same or different); Alternatively, it is preferable to use both the oligomer (X) and the oligomer (Y), but the present invention is not limited thereto.

[0039] In the above steps, A, A', C, and C' in the oligomer (X) and the oligomer (Y) are each independently [ka] (wherein X is an oxygen atom or a sulfur atom) In the above formula, X is preferably an oxygen atom. The oligomer (X) preferably has an ether group, and is preferably a diphenylene ether structure in which X is an oxygen atom. The A, A', C and C' in the oligomer (X) and the oligomer (Y) may be the same or different. The oligomer (X) and the oligomer (Y) may be of one type or of multiple types.

[0040] In the oligomer (Y), B is [ka] (wherein X is an oxygen atom or a sulfur atom) Preferably, it is selected from [ka] It is more preferable to select from: In the above structure, the substitution positions of naphthalene include 1,4-, 1,5-, 2,6-, and 2,7-.

[0041] In the adding step, only the oligomer (X) or only the oligomer (Y) may be added, but it is more preferable to add both the oligomer (X) and the oligomer (Y). When the oligomer (X) and the oligomer (Y) are used, the molar ratio of the oligomer (X) is preferably 1 to 100 mol %, more preferably 5 to 95 mol %, based on the total number of moles of the oligomer (X) and the oligomer (Y). When the divalent aromatic compound contains the oligomer (X), the oligomer (Y), or both, it is possible to obtain a resin that is excellent in the position selectivity of bond formation in the polymerization reaction and has few structural defects.

[0042] In the step of adding, in addition to the oligomer (X) and the oligomer (Y), for example, diphenyl ether, dibenzofuran, diphenyl sulfide, dibenzothiophene, etc. may be used as the divalent aromatic compound. In order to achieve a sufficient degree of polymerization, the amount of the divalent aromatic compound added is preferably 80 to 120 mol %, more preferably 90 to 110 mol %, and even more preferably 95 to 105 mol %, relative to the total number of moles of dicarboxylic acid. The divalent aromatic compound to be added during polymerization may be one type or two or more types.

[0043] When producing the polyarylene ether ketone resin of this embodiment, which contains the repeating units (1-1) and (1-2) in a certain ratio, there is a certain degree of discretion in the selection of raw materials. For example, the following formula (2-1) [ka] A resin containing repeating units (1-1) and (1-2) in a molar ratio of 40:60, as represented by the formula (2-2), (2-3), or (2-4), can be achieved by combining any of the raw materials and ratios shown below. [ka] [ka] [ka] As mentioned above, although the overall composition of the polymer is the same, the structure that can become the terminal group in the resin and the randomness of the monomer arrangement in the resin are greatly affected by the choice of raw materials. For example, when the raw material of formula (2-4) is used, the 2,5-furandicarboxylic acid moiety cannot become a terminal group, but when the raw material of formula (2-3) is used, it can become a terminal group. Furthermore, when the raw material of formula (2-3) is used, the repeating unit (1-1) cannot, in principle, be continuous, but when the raw material of formula (2-2) is used, the repeating unit (1-1) can be continuous. In order to avoid undesired side reactions during polymerization and reduced stability during melting due to 2,5-furandicarboxylic acid or the 2,5-furandicarboxylic acid terminal, it is preferable to introduce a furandicarbonyl skeleton into the resin as an oligomer (X) rather than using 2,5-furandicarboxylic acid itself. Furthermore, by using oligomer (X) or oligomer (Y), it is possible to impart a certain degree of order to the arrangement of repeating units in the resin, as described above, which is preferable because it leads to an improvement in the stability and melting point of the crystalline state of the resin.

[0044] The molar ratio of 2,5-furandicarboxylic acid to all dicarboxylic acids used in the above-mentioned adding step is preferably 0 mol % or more, more preferably 30 to 90 mol %, and even more preferably 50 to 90 mol %. However, when the molar proportion of the 2,5-furandicarboxylic acid is 20 mol % or less, it is preferable to carry out polymerization using an oligomer (X) containing a 2,5-furandicarbonyl skeleton so that the molar fraction of the repeating unit (1-1) in the produced resin is 1% or more but less than 100%, preferably 5 to 95%, more preferably 30 to 90%, and even more preferably 50 to 90%.

[0045] In the above-mentioned adding step, it is preferable to add a protic solvent as the solvent, more specifically, a sulfonic acid or a carboxylic acid, or a mixture of a sulfonic acid and a carboxylic acid. Examples of the protic solvent include trifluoromethanesulfonic acid, methanesulfonic acid, trifluoroacetic acid, and trichloroacetic acid. In view of concerns about residual ionic impurities and production efficiency, it is preferable that the above process does not include an ionic liquid, which is generally known as a highly viscous solvent.

[0046] The protic solvent may be a fluorosulfonic acid having a longer chain than trifluoromethanesulfonic acid, such as trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, or heptadecafluorooctanesulfonic acid, or a chlorodifluoromethanesulfonic acid, methanesulfonic acid, trifluoroacetic acid, or trichloroacetic acid. Among these, trifluoromethanesulfonic acid is preferred from the viewpoint of polymerization rate and resin solubility, but the protic solvent is not limited to the above solvent. The solvent may be one type or multiple types, or a mixed solvent further containing an aprotic solvent may be used. The molar ratio of the solvent to the dicarboxylic acid monomer component is preferably 100 to 10,000 mol %, more preferably 150 to 1,000 mol %, and even more preferably 200 to 1,000 mol %.

[0047] In the above-mentioned adding step, it is preferable to add a sulfonic acid anhydride or a carboxylic acid anhydride as a reaction accelerator. Examples of the reaction accelerator include trifluoromethanesulfonic anhydride, methanesulfonic anhydride, paratoluenesulfonic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, pentafluoropropionic anhydride, heptafluorobutyric anhydride, and chlorodifluoroacetic anhydride. Among these, trifluoroacetic anhydride is preferred because it exhibits a high polymerization promoting ability. The reaction promoter may be one kind or multiple kinds. The stoichiometric ratio of the reaction accelerator to the dicarboxylic acid monomer component is preferably 200 to 1000 mol %, more preferably 210 to 500 mol %, and even more preferably 210 to 300 mol %, in order to obtain a resin with a sufficient molecular weight.

[0048] In the above production method, it is preferable to carry out a polymerization reaction after the adding step. For example, it is preferable to carry out an aromatic electrophilic substitution polycondensation reaction of the Friedel-Crafts reaction type in the solution obtained in the adding step. By carrying out the aromatic electrophilic substitution polycondensation reaction, the reaction can be carried out under polymerization conditions that are relatively milder than those of other polymerizations. In the above production method, the above solvent and the above reaction accelerator are added to the above monomer / oligomer components (e.g., a mixture containing the above dicarboxylic acid and the above divalent aromatic compound), and the mixture is heated and stirred to produce a polyarylene ether ketone resin.

[0049] In the above production method, the reaction temperature in the step of starting the reaction of the monomer / oligomer components in the presence of the solvent and the reaction accelerator (sometimes referred to herein as the reaction initiation step) is preferably −40 to 80°C, and after a certain period of time, the temperature is preferably raised to 20 to 120°C and the mixture is stirred for a certain period of time.

[0050] The reaction time at the temperature at the reaction initiation stage is preferably 0 to 10 hours, and the total reaction time is preferably 1 to 100 hours. Furthermore, the reaction time at the temperature at the reaction initiation stage is preferably shorter than the total reaction time. The reaction accelerator, the solvent, and the divalent aromatic compound may be added to the dicarboxylic acid in a sequential stepwise manner. However, it is preferable to dissolve them in a solvent in advance and add them as a solution. However, the order and manner of adding the reactants (e.g., preparing a solution, adding dropwise to the reaction mixture, or adding all at once) are not limited to the above order and manner, and any order and manner of addition can be used. The reactants may be added during or after the polymerization to modify the terminals of unreacted polymers or oligomers, thereby imparting functionality or improving chemical stability. Furthermore, the resin obtained by removing the solvent is preferably subjected to purification procedures such as washing, reprecipitation, and drying.

[0051] (oligomer) The oligomer of this embodiment is an oligomer represented by any one of the following formulas (Z). [ka] (wherein X represents an oxygen atom or a sulfur atom) In formula (Z), X is preferably an oxygen atom.

[0052] The oligomer (Z) can be used to produce the polyarylene ether ketone resin of the present embodiment using the above-mentioned production method. The oligomer (Z) has excellent regioselectivity during bond formation in polymerization, and therefore provides a resin with few structural defects and excellent thermal stability.

[0053] The oligomer (Z) of the present embodiment may be, for example, a dicarboxylic acid such as 2,5-furandicarboxylic acid, a divalent aromatic compound represented by the following formula, [ka] (wherein X represents an oxygen atom or a sulfur atom) It can be produced by reacting a protic solvent with at least a carboxylic acid anhydride or a sulfonic acid anhydride.

[0054] The amount of the divalent aromatic compound added is preferably 210 to 500 mol %, more preferably 210 to 400 mol %, and even more preferably 210 to 300 mol %, relative to the total number of moles of dicarboxylic acid, in order to prevent undesired polymerization.

[0055] Examples of the carboxylic acid anhydride or sulfonic acid anhydride include trifluoromethanesulfonic acid anhydride, methanesulfonic acid anhydride, paratoluenesulfonic acid anhydride, difluoroacetic acid anhydride, trifluoroacetic acid anhydride, pentafluoropropionic acid anhydride, heptafluorobutyric acid anhydride, and chlorodifluoroacetic acid anhydride. Among these, trifluoroacetic anhydride is preferred because it exhibits a high polymerization-promoting ability. The carboxylic acid anhydride or sulfonic acid anhydride may be one kind or a plurality of kinds. In the above step, the amount of carboxylic acid anhydride or sulfonic acid anhydride added is preferably 200 to 1000 mol %, more preferably 210 to 400 mol %, and even more preferably 220 to 300 mol %, based on the total number of moles of dicarboxylic acid, in order to obtain the oligomer (Z) in good yield.

[0056] Examples of the protic solvent include fluorosulfonic acids with longer chains than trifluoromethanesulfonic acid, such as trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, and heptadecafluorooctanesulfonic acid, as well as chlorodifluoromethanesulfonic acid, methanesulfonic acid, trifluoroacetic acid, and trichloroacetic acid. Among these, trifluoromethanesulfonic acid is preferred from the viewpoints of polymerization rate and resin solubility. The protic solvent may be one type or multiple types, and a mixed solvent further containing an aprotic solvent may be used. The molar ratio of the protic solvent to the dicarboxylic acid monomer component is preferably 100 to 5000 mol %, more preferably 100 to 1000 mol %, and even more preferably 200 to 500 mol %.

[0057] The protic solvent and the carboxylic acid anhydride or sulfonic acid anhydride are added to the dicarboxylic acid and divalent aromatic compound component, and the mixture is heated and stirred to produce the oligomer (Z).

[0058] In the above production method, the reaction temperature in the step of starting the reaction of the dicarboxylic acid, the divalent aromatic compound, the protic solvent, and the carboxylic acid anhydride or sulfonic acid anhydride in the presence of the dicarboxylic acid anhydride or the divalent aromatic compound (sometimes referred to as the reaction initiation step in this specification) is preferably −40 to 80° C., and the temperature is preferably raised to 20 to 80° C. after a certain time period, and the mixture is stirred for a certain time period.

[0059] The reaction time at the temperature at the initial stage of the reaction is preferably 0 to 10 hours, and the total reaction time is preferably 1 to 100 hours. Furthermore, the reaction time at the temperature at the initial stage of the reaction is preferably shorter than the total reaction time. The carboxylic acid anhydride or sulfonic acid anhydride, the protic solvent, and the divalent aromatic compound may be added to the dicarboxylic acid component in a sequential stepwise manner, or may be added to a single reactor in any order. This arbitrary order is not limited to the above order. Furthermore, when adding the dicarboxylic acid and the divalent aromatic compound to the reactor, it is preferable to dissolve them in the protic solvent in advance and add them as a solution. Furthermore, after the reaction, the oligomer (Z) obtained by removing the solvent is preferably subjected to purification procedures such as washing, recrystallization, and drying.

[0060] The divalent aromatic compound-derived moiety in the oligomer (Z) has a slightly reduced reactivity to electrophilic aromatic substitution reactions compared to the starting divalent aromatic compound due to the introduction of an electron-withdrawing carbonyl group. Generally, reactivity and reaction regioselectivity are trade-offs. Therefore, rather than directly using the starting divalent aromatic compound in polymerization, oligomer (Z) is first synthesized, and the by-product regioisomers are removed by recrystallization or other procedures. Polymerization using oligomer (Z) improves reaction regioselectivity and suppresses the formation of ortho-isomers. This leads to an increase in the para ratio, suppresses the formation of structural defects, and contributes to an increase in melting point and thermal stability.

[0061] [Polyarylene ether ketone resin composition] The polyarylene ether ketone resin composition of the present embodiment may contain, in addition to the polyarylene ether ketone resin of the present embodiment described above, for example, polyarylene ether ketones (PAEKs) such as polyaryl ether ether ketone (PEKK), aromatic polyamide (PPA), polyphenylene sulfide (PPS), polysulfone (PSU), polyethersulfone (PES), polyetherimide (PEI), fluororesin resins such as polytetrafluoroethylene (PTFE), and the like. The resin composition of this embodiment may further contain an additive, such as 2,4,8,10-tetra(tert-butyl)-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocin. 6-oxide sodium salt (CAS number: 85209-91-2), tetrakis(2,4-di-tert-butylphenyl)[1,1'-biphenyl]-4,4'-diylbisphosphonite (119345-01-6), 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (35948-25-5), 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene (1709-70-2), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (27676-62-6), and the like, but the present invention is not limited thereto. The mass proportion of the polyarylene ether ketone resin of the present embodiment in 100 mass% of the resin composition of the present embodiment is preferably 50 mass% or more, more preferably 70 mass% or more, even more preferably 80 mass% or more, and particularly preferably 90 mass% or more. The polyarylene ether ketone resin composition may consist solely of the polyarylene ether ketone resin.

[0062] [Molded products] The molded article of the present embodiment preferably contains the polyarylene ether ketone resin composition of the present embodiment described above, and may consist solely of the polyarylene ether ketone resin composition. The molded products include composite materials compounded with glass fiber, carbon fiber, cellulose fiber, fluororesin, etc., primary processed products such as pellets, films, rods, boards, and filaments, and secondary processed products such as gears, composites, implants, and 3D printed molded products made from various injection-molded or machined products. Applications include components for transporting automobiles, aircraft, and chemical substances, as well as electrical and electronic materials subject to elemental content restrictions and medical components where health and safety considerations are particularly important. [Example]

[0063] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0064] Example 1 A three-neck flask equipped with a nitrogen inlet tube and a stirrer was charged with 8.31 g of terephthalic acid, 22.5 g of trifluoromethanesulfonic acid, and 26.3 g of trifluoroacetic anhydride, and the mixture was stirred at 25°C under a nitrogen atmosphere for 5 hours (first reaction). A four-neck flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer was charged with 21.2 g of oligomer (O-1) represented by the following structural formula, 2.30 g of oligomer (O-2), and 45.0 g of trifluoromethanesulfonic acid, and the mixture was stirred at 25°C under a nitrogen atmosphere for 2 hours (second reaction). A second reaction compound was added to the first reaction mixture at 25°C. The mixture was then heated to 50°C and stirred for 6 hours (third reaction). After cooling to 25°C, the reaction solution was poured into vigorously stirred distilled water, and the resin was precipitated. The mixture was stirred for 1 hour and filtered. The filtered resin was washed twice with 1N aqueous sodium hydroxide, twice with distilled water, and twice with ethanol. The resin was then air-dried overnight at room temperature and then dried under vacuum at 170°C for 8 hours (yield: 29.1 g). The molecular weight was measured using GPC, revealing that Mn was 7543, confirming that PAEK resin (P-1) (n:m = 5:95) had been obtained. [ka] [ka] [ka]

[0065] Example 2 A three-neck flask equipped with a nitrogen inlet tube and a stirrer was charged with 8.31 g of terephthalic acid, 22.5 g of trifluoromethanesulfonic acid, and 26.3 g of trifluoroacetic anhydride, and the mixture was stirred at 25°C under a nitrogen atmosphere for 5 hours (first reaction). A four-neck flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer was charged with 9.41 g of oligomer (O-1), 13.8 g of oligomer (O-2), and 45.0 g of trifluoromethanesulfonic acid, and the mixture was stirred at 25°C under a nitrogen atmosphere for 2 hours (second reaction). A second reaction compound was added to the first reaction mixture at 25°C. The mixture was then heated to 70°C and stirred for 6 hours (third reaction). After cooling to 25°C, the reaction solution was poured into vigorously stirred distilled water, and the resin was precipitated. The resin was stirred for 1 hour and then filtered. The filtered resin was washed twice with 1N aqueous sodium hydroxide solution, twice with distilled water, and twice with ethanol. The resin was then air-dried overnight at room temperature and then dried under vacuum at 170°C for 8 hours (yield: 28.2 g). When the molecular weight was measured using GPC, Mn was found to be 24002, confirming that PAEK resin (P-1) (n:m = 3:7) was obtained.

[0066] Example 3 A three-neck flask equipped with a nitrogen inlet tube and a stirrer was charged with 4.15 g of terephthalic acid, 3.90 g of 2,5-furandicarboxylic acid, 22.5 g of trifluoromethanesulfonic acid, and 26.3 g of trifluoroacetic anhydride, and the mixture was stirred at 25°C under a nitrogen atmosphere for 5 hours (first reaction). A four-neck flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer was charged with 11.8 g of oligomer (O-1), 11.5 g of oligomer (O-2), and 45.0 g of trifluoromethanesulfonic acid, and the mixture was stirred at 25°C under a nitrogen atmosphere for 2 hours (second reaction). A second reaction compound was added to the first reaction mixture at 25°C. The mixture was then heated to 50°C and stirred for 6 hours (third reaction). After cooling to 25°C, the reaction solution was poured into vigorously stirred distilled water, and the resin was precipitated. The mixture was stirred for 1 hour and filtered. The filtered resin was washed twice with 1N aqueous sodium hydroxide, twice with distilled water, and twice with ethanol. The resin was then air-dried at room temperature overnight and then dried under vacuum at 170°C for 8 hours (yield: 27.5 g). The molecular weight was measured using GPC, revealing that Mn was 7312, confirming that PAEK resin (P-1) (n:m = 5:5) had been obtained.

[0067] Example 4 A three-neck flask equipped with a nitrogen inlet tube and a stirrer was charged with 8.31 g of terephthalic acid, 22.5 g of trifluoromethanesulfonic acid, and 26.3 g of trifluoroacetic anhydride, and the mixture was stirred at 25°C under a nitrogen atmosphere for 5 hours (first reaction). A four-neck flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer was charged with 23.0 g of oligomer (O-2) and 45.0 g of trifluoromethanesulfonic acid, and the mixture was stirred at 25°C under a nitrogen atmosphere for 2 hours (second reaction). A second reaction compound was added to the first reaction mixture at 25°C. The mixture was then heated to 60°C and stirred for 6 hours (third reaction). After cooling to 25°C, the reaction solution was poured into vigorously stirred distilled water, and the resin was precipitated. The resin was stirred for 1 hour and filtered. The filtered resin was washed twice with 1N aqueous sodium hydroxide solution, twice with distilled water, and twice with ethanol. The resin was then air-dried at room temperature overnight and then dried under vacuum at 170°C for 8 hours (yield: 28.3 g). When the molecular weight was measured using GPC, Mn was found to be 11007, confirming that a resin (P-2) was obtained in which two repeating units of the PAEK resin (P-1) were arranged alternately. [ka]

[0068] Example 5 A three-neck flask equipped with a nitrogen inlet tube and a stirrer was charged with 7.80 g of 2,5-furandicarboxylic acid, 22.5 g of trifluoromethanesulfonic acid, and 26.3 g of trifluoroacetic anhydride, and the mixture was stirred at 25°C under a nitrogen atmosphere for 5 hours (first reaction). A four-neck flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer was charged with 14.1 g of oligomer (O-1), 9.21 g of oligomer (O-2), and 45.0 g of trifluoromethanesulfonic acid, and the mixture was stirred at 25°C under a nitrogen atmosphere for 2 hours (second reaction). A second reaction compound was added to the first reaction mixture at 25°C. The mixture was then heated to 50°C and stirred for 6 hours (third reaction). After cooling to 25°C, the reaction solution was poured into vigorously stirred distilled water, and the resin was precipitated. The resin was stirred for 1 hour and filtered. The filtered resin was washed twice with 1N aqueous sodium hydroxide solution, twice with distilled water, and twice with ethanol. The resin was then air-dried overnight at room temperature and then dried under vacuum at 170°C for 8 hours (yield: 28.7 g). When the molecular weight was measured using GPC, Mn was found to be 6468, confirming that PAEK resin (P-1) (n:m = 7:3) was obtained.

[0069] Example 6 A three-neck flask equipped with a nitrogen inlet tube and a stirrer was charged with 7.80 g of 2,5-furandicarboxylic acid, 22.5 g of trifluoromethanesulfonic acid, and 26.3 g of trifluoroacetic anhydride, and the mixture was stirred at 25°C under a nitrogen atmosphere for 5 hours (first reaction). A four-neck flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer was charged with 2.35 g of oligomer (O-1), 20.72 g of oligomer (O-2), and 45.0 g of trifluoromethanesulfonic acid, and the mixture was stirred at 25°C under a nitrogen atmosphere for 2 hours (second reaction). A second reaction compound was added to the first reaction mixture at 25°C. The mixture was then heated to 60°C and stirred for 6 hours (third reaction). After cooling to 25°C, the reaction solution was poured into vigorously stirred distilled water, and the resin was precipitated. The mixture was stirred for 1 hour and filtered. The filtered resin was washed twice with 1N aqueous sodium hydroxide, twice with distilled water, and twice with ethanol. The resin was then air-dried at room temperature overnight and then dried under vacuum at 170°C for 8 hours (yield: 27.9 g). The molecular weight was measured using GPC, revealing that Mn was 8213, confirming the formation of PAEK resin (P-1) (n:m = 95:5).

[0070] Example 7 A three-neck flask equipped with a nitrogen inlet tube and a stirrer was charged with 7.80 g of 2,5-furandicarboxylic acid, 22.5 g of trifluoromethanesulfonic acid, and 26.3 g of trifluoroacetic anhydride, and the mixture was stirred at 25°C under a nitrogen atmosphere for 5 hours (first reaction). A four-neck flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer was charged with 23.0 g of oligomer (O-1) and 45.0 g of trifluoromethanesulfonic acid, and the mixture was stirred at 25°C under a nitrogen atmosphere for 2 hours (second reaction). A second reaction compound was added to the first reaction mixture at 25°C. The mixture was then heated to 60°C and stirred for 6 hours (third reaction). After cooling to 25°C, the reaction solution was poured into vigorously stirred distilled water, and the resin was precipitated. The resin was stirred for 1 hour and filtered. The filtered resin was washed twice with 1N aqueous sodium hydroxide solution, twice with distilled water, and twice with ethanol. The resin was then air-dried overnight at room temperature and then dried under vacuum at 170°C for 8 hours (yield: 27.9 g). When the molecular weight was measured using GPC, Mn was found to be 14030, confirming that a PAEK resin (P-3) had been obtained. [ka]

[0071] Example 8 A three-neck flask equipped with a nitrogen inlet tube and a stirrer was charged with 8.31 g of terephthalic acid, 22.5 g of trifluoromethanesulfonic acid, and 26.3 g of trifluoroacetic anhydride, and the mixture was stirred at 25°C under a nitrogen atmosphere for 5 hours (first reaction). A four-neck flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer was charged with 22.8 g of oligomer (O-3) represented by the following structural formula and 45.0 g of trifluoromethanesulfonic acid, and the mixture was stirred at 25°C under a nitrogen atmosphere for 2 hours (second reaction). A second reaction compound was added to the first reaction mixture at 25°C. The mixture was then heated to 70°C and stirred for 6 hours (third reaction). After cooling to 25°C, the reaction solution was poured into vigorously stirred distilled water, and the resin was precipitated. The resin was stirred for 1 hour and then filtered. The filtered resin was washed twice with 1N aqueous sodium hydroxide solution, twice with distilled water, and twice with ethanol. The resin was then air-dried overnight at room temperature and then dried under vacuum at 170°C for 8 hours (yield: 28.3 g). When the molecular weight was measured using GPC, Mn was found to be 8800, confirming that a PAEK resin (P-4) represented by the following structural formula had been obtained. [ka] [ka]

[0072] The following comparative example illustrates the synthesis of F-PEKK by a known synthesis method. In accordance with the method described in Patent Document 2, the 2,5-furandicarboxylic acid used in the polymerization was recrystallized and then purified by sublimation, the DPE was distilled, and the 1-butyl-3-methylimidazolium chloride was dried by heating under 0.2 mmHg. In Non-Patent Document 1, it is believed that the number average molecular weight of the resin obtained was calculated using NMR, but the calculation method was not sufficiently described and was not reproducible. Therefore, Table 1 lists the relative number average molecular weight calculated as PMMA using GPC, as in the Examples.

[0073] (Comparative Example 1) Comparative Example 1 illustrates the synthesis of F-PEKK by a known synthesis method. The F-PEKK sample was synthesized according to the example that exhibited the highest melting point and reduced viscosity among the examples described in Japanese Patent Application Publication No. 2014-88480 (Patent Document 2), filed October 29, 2012. 2.0 g of the dried 1-butyl-3-methylimidazolium chloride and 4.0 g of aluminum chloride were added to a two-neck flask equipped with a nitrogen inlet and a stirrer, and the mixture was stirred at 25°C for 24 hours to obtain a homogeneous solution. To a separate three-neck flask, 170 mg of diphenyl ether, 192 mg of 2,5-furandicarboxylic acid dichloride, and 2 mL of the ionic liquid and aluminum chloride mixture were added. The mixture was then heated to 60°C and reacted for 24 hours. The reaction mixture was then poured into methanol, and the precipitated solid was filtered. 30 mL of methanol cooled to 0°C was added to the reaction mixture to precipitate the solid. The precipitated solid was filtered and then refluxed in a Soxhlet extractor using methanol as the extraction solvent for 24 hours for washing. The mixture was then dried under vacuum at 150°C for 8 hours. The molecular weight was measured using GPC, confirming that the Mn was 4404 and that 0.35 g of PAEK resin (P-3) was obtained. The resin obtained was analyzed as described below, and the measurement results are shown in Table 1.

[0074] (Comparative Example 2) Comparative Example 2 illustrates the synthesis of F-PEKK by a known synthesis method. The F-PEKK sample was synthesized according to the example that showed the highest melting point and reduced viscosity among the examples described in Macromolecules, 2016, 49, 4, 1252-1258 (Non-Patent Document 1). 10.0 g of the dried 1-butyl-3-methylimidazolium chloride and 19.7 g of aluminum chloride were added to a two-neck flask equipped with a nitrogen inlet and a stirrer, and the mixture was stirred at 20°C for 12 hours to obtain a homogeneous solution. 0.49 g of diphenyl ether, 0.47 g of 2,5-furandicarboxylic acid dichloride, and 13.1 g of the ionic liquid and aluminum chloride mixture were added to a separate three-neck flask and stirred at 25°C for 10 minutes. After further reaction at 60°C for 24 hours, the reaction mixture was poured into methanol, and the precipitated solid was filtered and then refluxed in a Soxhlet extractor using methanol as the extraction solvent for 24 hours. The mixture was then dried under vacuum at 150°C for 8 hours. The molecular weight was measured using GPC, confirming that the Mn was 5601 and that 0.92 g of PAEK resin (P-3) had been obtained. The resulting resin was analyzed as described below, and the results are shown in Table 1.

[0075] (Comparative Example 3) In Comparative Example 3, the synthesis of a PAEK copolymer (corresponding to Example 3) polymerized with DPE so that the ratio of terephthaloyl skeletons to 2,5-furandicarbonyl skeletons in the resin was intentionally set to 7:3 was attempted using DPE and 2,5-furandicarboxylic acid as monomers without using oligomer (O-2). A three-neck flask equipped with a nitrogen inlet and a stirrer was charged with 22.5 g of trifluoromethanesulfonic acid, 2.34 g of 2,5-furandicarboxylic acid, 5.81 g of terephthalic acid, and 26.3 g of trifluoroacetic anhydride, and the mixture was stirred at 25°C for 5 hours under a nitrogen atmosphere (first reaction). After cooling the solution to 0°C, 8.51 g of diphenyl ether was added, and the mixture was heated to 70°C and stirred for 3 hours (second reaction). After cooling to 25°C, the reaction solution was poured into vigorously stirred distilled water, and the resin was precipitated. The mixture was stirred for 1 hour and then filtered. The filtered resin was washed twice with 1N aqueous sodium hydroxide, twice with distilled water, and twice with ethanol. The resin was then air-dried at room temperature overnight and then dried under vacuum at 170°C for 8 hours (yield: 13.5 g). When the molecular weight was measured using GPC, it was confirmed that Mn was 6302, and that a PAEK resin (P-1) (n:m=7:3) was obtained.

[0076] (Production of Oligomer (O-2)) The oligomer (O-2) used in the above Examples and Comparative Examples was an oligomer produced by the following method. A three-neck flask equipped with a nitrogen inlet tube and a stirrer was charged with 4.68 g of 2,5-furandicarboxylic acid, 30 g of trifluoromethanesulfonic acid, and 15.8 g of trifluoroacetic anhydride, and the mixture was stirred at 25°C for 5 hours under a nitrogen atmosphere (first reaction). After cooling the solution to 0°C, 15.3 g of diphenyl ether was added and the mixture was stirred at 0°C for an additional 2 hours. The mixture was then heated to 25°C and stirred for 6 hours (second reaction). The reaction solution was poured into vigorously stirred ethanol to precipitate the solid, which was then stirred for 1 hour and filtered (reaction termination and recovery procedure). The filtered solid was air-dried and then dried under vacuum at 100°C for 8 hours to obtain oligomer (O-2). [ka]

[0077] [evaluation] [Molecular weight] The resins obtained in the examples and comparative examples were analyzed using a Tosoh Corporation GPC system (HPLC8320) with the instrument control software HLC-83220GPC EcoSEC System Control Version 1.15. The detector was the instrument's standard RI detector. The eluent was hexafluoroisopropanol containing 0.4% sodium trifluoroacetate dissolved therein, and a Shodex KF-606M column. Polymethyl methacrylate (PMMA) was used as the standard material. A baseline was drawn from the rising baseline of the chromatographic peak to the falling baseline. The number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were calculated from the resulting peaks using a PMMA calibration curve (Agilent, EasiVial) for the standard material.

[0078] [Crystal melting enthalpy change] For the resins obtained in the examples and comparative examples, a NETZSCH DSC device (DSC3500) was used to collect 5 mg of a sample in an aluminum pan that had not been subjected to any special heat treatment after polymerization. The sample was then heated from 50°C to 400°C at a temperature increase rate of 20°C / min under a nitrogen flow of 20 mL / min, and then cooled to 50°C at a temperature decrease rate of 5°C / min. Measurements were then carried out from 50°C to 400°C at a temperature increase rate of 20°C / min to determine the enthalpy change in crystal fusion, ΔH (J / g).

[0079] [Glass transition temperature (Tg) and melting point (Tm)] For the resins obtained in the examples and comparative examples, 5 mg of a sample that had not been subjected to any special heat treatment after polymerization was collected in an aluminum pan using a NETZSCH DSC device (DSC3500), and then measured under a nitrogen flow of 20 mL / min under conditions of a temperature increase of 20°C / min from 50°C to 400°C, and a temperature decrease of 10°C / min from 400°C to 50°C. Unless otherwise specified, the glass transition temperature (Tg) and melting point (Tm) were determined as the midpoint of the glass transition temperature and the peak top temperature of the melting point peak detected in the second program cycle after the start of measurement under the above temperature increase conditions.

[0080] [10% mass reduction temperature, 5% mass reduction temperature] For the resins obtained in the examples and comparative examples, 5 mg of a sample that had not been subjected to any special heat treatment after polymerization was collected in an aluminum pan using TGA (NETZSCH TGA apparatus (TG-DTA2500 Regulus)), and the temperature was raised from room temperature to 550°C at a rate of 20°C / min in a nitrogen gas flow of 20 mL / min. The temperature at which the thermal weight loss rate (%) reached 10% or 5% was determined and used as an index of thermal stability.

[0081] [Quantitative analysis of repeating units in resins using NMR] For the resins obtained in the examples and comparative examples, PAEK resin was dissolved in a mixed solvent of CDCl3 and TFA-d at a weight ratio of 4:1, and measured using a JEOL NMR device (ECA-500) under the following conditions: 1H was used as the observation nucleus, a waiting time of 5 seconds, a measurement temperature of 25°C, an accumulation count of 128, and a standard of 7.26 ppm (CDCl3). The molar ratios of the repeating units (1-1) and (1-2) in the PAEK resins (P-1) and (P-2) were calculated using the signals derived from the repeating units observed at 7.9 to 8.0 ppm and 7.50 to 7.55 ppm, respectively. The ratios (mol %) of para- and ortho-isomers in each polymer were calculated with reference to the description in Non-Patent Document 1 using signals derived from the corresponding structures observed at 7.50 to 7.55 ppm and 7.40 to 7.45 ppm, respectively. In Table 1, ">99:1" indicates that the para isomer accounts for 99 mol % or more.

[0082] [Elemental analysis] Approximately 0.1 g of the resin samples obtained in the Examples and Comparative Examples was weighed into a tetrafluorometaxil (TFM) decomposition vessel, sulfuric acid and nitric acid were added, and pressure acid decomposition was performed using a microwave decomposition device. The resulting decomposition solution was adjusted to a constant volume of 50 mL and subjected to ICP-MS measurement. Aluminum elemental content was quantified using an Agilent Technologies (Agilent 7900) for ICP-MS measurement. Chlorine and bromine elemental content were also quantified using a Dionex ion chromatograph (ICS-1500). In the table, "less than 1" and "less than 20" indicate that the value is below the lower limit of quantification.

[0083] [Table 1]

[0084] The TPA-derived skeleton / FDCA-derived skeleton (molar ratio) in the table is the molar ratio of all TPA-derived units and all FDCA-derived units in the raw materials calculated from the sum of all terephthaloyl skeletons and 2,5-furandicarbonyl skeletons contained in TPA (terephthalic acid), FDCA, oligomer (X), and oligomer (Y) used in the polymerization. The proportion of repeating units represented by formula (P-1) etc. in the resin after polymerization is as described above.

[0085] Compared with Comparative Examples 1 and 2, the degrees of polymerization of the PAEK copolymers of Examples 1 to 7 were sufficiently high regardless of composition. Furthermore, in Comparative Example 3, in which polymerization was performed without using oligomer (X) or oligomer (Y), the molecular weight of the resulting resin was insufficient, possibly due to the occurrence of side reactions. This demonstrates the importance of preparing oligomer (X) and oligomer (Y) in advance in the main polymerization. Furthermore, the use of oligomer (X) and oligomer (Y) is extremely effective in terms of para selectivity during polymerization. In all Examples, signals derived from the ortho isomer or 9-xanthenol skeleton (structural defect) accounted for less than 1 mol% of all repeating units, indicating that these are excellent resins with extremely few structural defects. A comparison of Examples 1 to 3 and 5 to 7 showed that the melting point, crystalline melting enthalpy change, and 5% and 10% mass loss temperatures, which are indicators of thermal stability, tended to improve as the ratio of repeating unit (1-2) increased. Furthermore, regardless of the composition, Examples 1 to 3 and 5 to 7 exhibited higher values ​​for the crystalline melting enthalpy change, 10% mass loss temperature, and melting point compared to Comparative Examples 1 and 2, indicating from Table 1 that these resins have high heat resistance and crystallinity. These results demonstrate that copolymerization can improve the thermal properties of the polymer chains of 2,5-furandicarboxylic acid skeleton-containing polyarylene ether ketones over a wide range of blend ratios. Although the resin compositions of Examples 3 and 4 are the same overall, the former is characterized by random bonding of repeating units (1-1) and (1-2), while the latter is characterized by alternating bonding of the two repeating units. Measurements of the resin properties revealed that the resin of Example 4 exhibited higher values ​​for the crystalline fusion enthalpy change, melting point, and glass transition temperature. This is thought to be because the resin obtained in Example 4 has a more regular main chain structure, resulting in superior polymer chain alignment and crystalline stability. Furthermore, when comparing the homopolymer F-PEKK with Comparative Examples 1 and 2, which reproduced known literature using an ionic liquid, and Example 7, in which polymerization was carried out using oligomer (X), the F-PEKK obtained in Example 7 showed a significantly higher melting point. This is thought to be due to the fact that there are fewer structural defects in the polyarylene ether ketone resin of the present embodiment.

[0086] Focusing on the crystalline melting enthalpy change in Examples 1 to 7, the crystalline melting enthalpy change was not 0 J / g at any of the compositions, indicating that the copolymer is a crystalline resin, at least within the composition range of the Examples. Furthermore, regarding the composition, a positive correlation is observed between the ratio of repeating units (1-2) and the degree of crystallinity (proportional to the crystalline melting enthalpy change), indicating that the crystallinity of the resin can be adjusted by the composition ratio. In particular, when comparing the crystalline melting enthalpy change of the resins of Examples 1 to 6, in which a terephthaloyl skeleton has been introduced, with that of Comparative Examples 1 and 2, it is found that the crystalline melting enthalpy change of Examples 1 to 6 is significantly larger. The crystalline melting enthalpy change is directly linked to the crystallinity of the resin and is generally known to be positively correlated with the high rigidity and chemical resistance characteristic of crystalline polymers. The resins of Examples 1 to 6 are expected to be resins with excellent properties in these respects.

[0087] Comparing the 5% and 10% mass loss temperatures in TGA measurements between Examples 1 to 7 and Comparative Examples 1 and 2, a positive correlation was observed between the ratio of repeating structure (1-2) and the 10% mass loss temperature, indicating that copolymerization successfully improved the thermal stability of PAEK having a 2,5-furandicarbonyl skeleton. This is thought to be due to the effect of introducing the terephthaloyl skeleton, which has high chemical stability. Furthermore, when comparing the same compositions, a comparison between Comparative Example 3 and Example 2, and between Comparative Examples 1 and 2 and Example 7, revealed that polymerization using oligomer (X) and oligomer (Y) yields a resin that is more stable even at high temperatures because it has fewer chemically unstable structural defects.

[0088] Although the glass transition temperature changes less with changes in composition than the melting point, a comparison of Examples 1 to 7 revealed that the glass transition temperature remains at around 150°C regardless of the proportion of repeating unit (1-2). Furthermore, the resin obtained in Example 8, which has a completely different structure containing a dibenzofuran skeleton, exhibited a very high glass transition temperature. Since both resins exhibit glass transition temperatures exceeding 140°C, they can be said to be resins with excellent rigidity when heated.

[0089] Furthermore, elemental analysis results showed that while nearly 1000 ppm was detected in Comparative Examples 1 and 2, which used aluminum chloride according to the conventional method, only trace amounts (<30 ppm) of aluminum and chlorine were detected in Examples 1 to 7 and Comparative Example 3. Ionic or halogen impurities are avoided in electronic material applications and in filament and powder applications for 3D printers, which have seen remarkable development in recent years, and the resin described in this application, which does not contain these elements as impurities, can be said to be an excellent resin.

Claims

1. Satisfy the following (A) to (C): (A) containing a repeating unit (1-1) represented by general formula (1-1); (B) a melting point of 300°C or higher and lower than 400°C; (C) a 5% mass loss temperature measured by TGA of 450°C or higher; Further containing a repeating unit (1-2) represented by general formula (1-2) different from the repeating unit (1-1), the molar fraction of the repeating unit (1-2) is 1% or more and less than 100% relative to 100% in total moles of the repeating unit (1-1) and the repeating unit (1-2), It is a polyaryletherketoneketone resin. A polyarylene ether ketone resin characterized by: 【Chemistry 1】 (In formula (1-1), A is a divalent aromatic group represented by the following structural formula: 【Chemistry 2】 (In the formula, J and J' are divalent aromatic groups and may be the same or different. X is an oxygen atom or a sulfur atom. The aromatic groups J and J' may be bonded via a bond other than an -X- bond.) 【Transformation 3】 In formula (1-2), B and C are divalent aromatic groups, and may be the same or different. C is a group represented by the following structural formula: 【Chemistry 4】 (In the formula, J and J' are divalent aromatic groups and may be the same or different. X is selected from an oxygen atom or a sulfur atom. The aromatic groups J and J' may be bonded via a bond other than an -X- bond.) It is expressed as

2. The A and C are each independently 【Transformation 5】 (wherein X is an oxygen atom or a sulfur atom) wherein B is selected from 【Transformation 6】 (wherein X is an oxygen atom or a sulfur atom) The polyarylene ether ketone resin according to claim 1 , selected from the group consisting of

3. The above B 【Transformation 7】 The polyarylene ether ketone resin according to claim 1 or 2, selected from the group consisting of:

4. The polyarylene ether ketone resin has the following formula: 【Transformation 8】 (In the formula, X represents a structure of the polyarylene ether ketone resin excluding the terminal groups, and each E independently represents an terminal group selected from the group consisting of hydrogen, a hydroxyl group, an alkyl group, an alkynyl group, an alkenyl group, an aryl group, an amino group, an amide group, an imide group, a nitro group, a cyano group, an ether group, a sulfanyl group, a carboxylic acid group, an ester group, an acyl group, a sulfonic acid group, a sulfone group, a sulfonate group, and a quaternary ammonium group.) is expressed as The polyarylene ether ketone resin according to any one of claims 1 to 3, wherein the end group E has a formula molecular weight of 1 to 600 g / mol.

5. The polyarylene ether ketone resin according to any one of claims 1 to 4, having a number average molecular weight Mn of 4,000 or more and 100,000 or less.

6. The following polymerization raw material (I) or the following (II) (I) An oligomer (X) containing an aromatic dicarboxylic acid and an oligomer (X) represented by the following formula (X): 【Chemistry 9】 (wherein A and A' are divalent aromatic groups and may be the same or different). (II) A polymer containing 2,5-furandicarboxylic acid and an oligomer (Y) represented by the following formula (Y): 【Chemistry 10】 (wherein B, C, and C' are divalent aromatic groups and may be the same or different.) a protic solvent as a solvent; a sulfonic acid anhydride or a carboxylic acid anhydride as a reaction accelerator; The method for producing the polyarylene ether ketone resin according to any one of claims 1 to 5, comprising adding at least

7. A polyarylene ether ketone resin composition comprising the polyarylene ether ketone resin according to any one of claims 1 to 5.

8. A molded article comprising the polyarylene ether ketone resin composition according to claim 7.

9. An oligomer represented by any one of the following formulas (Z): 【Chemistry 11】 (wherein X represents an oxygen atom or a sulfur atom)

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