Polyarylene ether ketone resin, its production method, resin composition, and molded article

Abstract

To provide a polyarylene ether ketone resin (PAEK resin) that is obtained using aromatic electrophilic substitution type solution polycondensation reaction under a mild polymerization condition which is excellent in mechanical strength because of PAEK resin having a high molecular weight while having excellent characteristics inherent to the PAEK resin.SOLUTION: A branched polyarylene ether ketone resin (PAEK resin) contains a polyether ketone structural unit, a polyphenylene ether structural unit, and a triaryl ether structural unit.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Polyarylene ether ketone resin (hereinafter sometimes abbreviated as "PAEK resin") is a crystalline super engineering plastic that has excellent heat resistance, chemical resistance, toughness, etc. and can be used continuously at high temperatures. It is widely used in electrical and electronic components, automotive parts, medical parts, fibers, films, etc.

[0003] Conventionally, a well-known PAEK resin is a polyether ether ketone resin (hereinafter sometimes abbreviated as "PEEK resin") having two ether groups and one ketone group in one repeating unit, which is produced by an aromatic nucleophilic substitution solution polycondensation reaction of two monomers, 4,4'-difluorobenzophenone and hydroquinone, in diphenyl sulfone using potassium carbonate (see, for example, Patent Document 1). In addition, there are also polyetherketone resins (hereinafter sometimes abbreviated as "PEK resins") that have one ether group and one ketone group in one repeating unit, and polyetherketoneketone resins (hereinafter sometimes abbreviated as "PEKK resins") that have one ether group and two ketone groups in one repeating unit, which are manufactured by using 4,4'-dihydroxybenzophenone instead of hydroquinone.

[0004] However, the aromatic nucleophilic substitution solution polycondensation reaction used to produce these PAEK resins has the disadvantages of high raw material costs because it uses expensive 4,4'-difluorobenzophenone as a monomer, and high production process costs because the reaction temperature is 300°C or higher, which tends to increase the price of the resin.

[0005] Therefore, an aromatic electrophilic substitution type solution polycondensation reaction has been known that produces PAEK resins under mild polymerization conditions without using 4,4'-difluorobenzophenone as a monomer. Examples of the use of an aromatic electrophilic substitution solution polycondensation reaction include a PEK resin obtained by reacting 4-phenoxybenzoic acid chloride in the presence of hydrogen fluoride and boron trifluoride (see, for example, Patent Document 2), a PEKK resin obtained by reacting terephthalic acid chloride with diphenyl ether in the presence of a Lewis acid (see, for example, Patent Document 3), and a PEK resin obtained by reacting 4-phenoxybenzoic acid in the presence of a mixture of methanesulfonic acid and diphosphorus pentoxide (see, for example, Patent Document 4). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Patent No. 4,320,224 [Patent Document 2] U.S. Patent No. 3,953,400 [Patent Document 3] U.S. Patent No. 3,065,205 [Patent Document 4] Japanese Patent Application Publication No. 61-247731 Summary of the Invention [Problem to be solved by the invention]

[0007] However, aromatic electrophilic substitution solution polycondensation reactions are prone to side reactions other than the main polycondensation reaction, and it tends to be more difficult to obtain PAEK resins with a higher degree of polymerization than aromatic nucleophilic substitution solution polycondensation reactions, making it difficult to obtain PAEK resins with sufficient molecular weights.

[0008] Therefore, an object of the present invention is to provide a polyarylene ether ketone resin (PAEK resin) obtained by using an aromatic electrophilic substitution-type solution polycondensation reaction under mild polymerization conditions, which has excellent mechanical strength because it is a high-molecular-weight PAEK resin while retaining the inherent excellent properties of PAEK resins. [Means for solving the problem]

[0009] As a result of intensive research to solve the above problems, the present inventors have found that a high molecular weight PAEK resin can be obtained by adding a branching agent represented by a specific structural formula when producing a PAEK resin in an aromatic electrophilic substitution solution polycondensation reaction under mild polymerization conditions, and have thus completed the present invention.

[0010] That is, the present invention includes the following aspects. [1] A polyarylene ether ketone resin having repeating units represented by the following general formulas (1-1), (2-1), and (3-1): [ka] (In the formula, k is an integer of 0 to 2.) [ka] (In the formula, n is an integer of 0 to 1.) [ka] (In the formula, Ar1, Ar2, and Ar3 are divalent organic groups represented by the following general formula (4-1). The values ​​of m in Ar1, Ar2, and Ar3 may be the same or different. [ka] (wherein m is an integer of 0 to 2.) [2] The polyarylene ether ketone resin according to [1], wherein the polyarylene ether ketone resin has a main chain structure represented by the following general formula (5): [ka] (In the formula, X is represented by the following general formula (5-1), and Y is represented by the following general formula (5-2). [ka] (In the formula, n is an integer of 0 to 1.) [ka] (wherein k is an integer of 0 to 2.) [3] The polyarylene ether ketone resin according to [1] or [2], wherein the repeating unit represented by the general formula (3-1) is a repeating unit represented by the following general formula (6): [ka] (In the formula, Ar4 is a divalent organic group represented by the following general formula (4-1). [ka] (wherein m is an integer of 0 to 2.) [4] The polyarylene ether ketone resin according to any one of [1] to [3], wherein the content of the repeating unit represented by the general formula (3-1) relative to the polyarylene ether ketone resin is 0.01 to 100 mmol / kg. [5] A polyarylene ether ketone resin having a branched structure with a structural unit represented by the following general formula (3-1): A polyarylene ether ketone resin, wherein the content of the branched structure represented by the general formula (3-1) relative to the polyarylene ether ketone resin is 0.01 to 100 mmol / kg. [ka] (In the formula, Ar1, Ar2, and Ar3 are divalent organic groups represented by the following general formula (4-1). The values ​​of m in Ar1, Ar2, and Ar3 may be the same or different. [ka] (wherein m is an integer of 0 to 2.) [6] The polyarylene ether ketone resin according to [5], wherein the repeating unit represented by the general formula (3-1) is a repeating unit represented by the following general formula (6): [ka] (In the formula, Ar4 is a divalent organic group represented by the following general formula (4-1). [ka] (wherein m is an integer of 0 to 2.) [7] A method for producing a polyarylene ether ketone resin according to any one of [1] to [4], comprising reacting a monomer (1-2) represented by the following general formula (1-2), a monomer (2-2) represented by the following general formula (2-2), and a monomer (3-2) represented by the following general formula (3-2) in the presence of an organic sulfonic acid and diphosphorus pentoxide. [ka] (In the formula, k is an integer of 0 to 2.) [ka] (In the formula, n is an integer of 0 to 1.) [ka] (In the formula, Ar1, Ar2, and Ar3 are represented by the following general formula (4-2). The values ​​of m in Ar1, Ar2, and Ar3 may be the same or different. [ka] (wherein m is an integer of 0 to 2.) [8] The method for producing a polyarylene ether ketone resin according to [7], wherein the monomer (1-2) is the following monomer (1-2-A), the monomer (2-2) is the following monomer (2-2-A), and the monomer (3-2) is the following monomer (3-2-A). [ka] [ka] [ka] (In the formula, Ar5 is represented by the following general formula (3-2-B).) [ka] [9] The method for producing a polyarylene ether ketone resin according to [7] or [8], comprising adding the monomer (1-2) and the monomer (2-2) to a mixed solution of an organic sulfonic acid and diphosphorus pentoxide, mixing and reacting them, and then adding the monomer (3-2), mixing and reacting them.

[10] A resin composition containing the polyarylene ether ketone resin according to any one of [1] to [6].

[11] The resin composition according to

[10] , further comprising reinforcing fibers.

[12] A molded article obtained by molding the resin composition according to

[10] or

[11] . [Effects of the Invention]

[0011] The present invention provides a polyarylene ether ketone resin (PAEK resin) obtained by using an aromatic electrophilic substitution-type solution polycondensation reaction under mild polymerization conditions, which has excellent mechanical strength because it is a high-molecular-weight PAEK resin while retaining the inherent excellent properties of PAEK resins. DETAILED DESCRIPTION OF THE INVENTION

[0012] The PAEK resin of the present invention and the method for producing the PAEK resin will be described in detail below. However, the description of the constituent elements described below is an example of one embodiment of the present invention, and the present invention is not limited to these contents.

[0013] (Polyarylene ether ketone resin (PAEK resin)) One of the characteristics of the PAEK resin of the present invention is that it has a branched structure having a structural unit represented by the following general formula (3-1). When producing a PAEK resin using an aromatic electrophilic substitution type solution polycondensation reaction, a high molecular weight PAEK resin can be produced by introducing the branched structure represented by general formula (3-1) into the main chain of the PAEK resin.

[0014] [ka] (In the formula, Ar1, Ar2, and Ar3 are divalent organic groups represented by the following general formula (4-1). The values ​​of m in Ar1, Ar2, and Ar3 may be the same or different.

[0015] [ka] (wherein m is an integer of 0 to 2.)

[0016] Preferred embodiments of the PAEK resin of the present invention include PAEK resins having repeating units represented by the following general formulae (1-1), (2-1), and (3-1).

[0017] [ka] (In the formula, k is an integer of 0 to 2.)

[0018] [ka] (In the formula, n is an integer of 0 to 1.)

[0019] [ka] (In the formula, Ar1, Ar2, and Ar3 are divalent organic groups represented by the following general formula (4-1). The values ​​of m in Ar1, Ar2, and Ar3 may be the same or different.

[0020] [ka] (wherein m is an integer of 0 to 2.)

[0021] A more preferred embodiment of the PAEK resin of the present invention is a PAEK resin having, as a main chain structure, a structure represented by the following general formula (5) consisting of the above general formulas (1-1) and (2-1), and having a branched structure having the above general formula (3-1) as a constituent unit.

[0022] [ka] (In the formula, X is represented by the following general formula (5-1), and Y is represented by the following general formula (5-2).

[0023] [ka] (In the formula, n is an integer of 0 to 1.)

[0024] [ka] (wherein k is an integer of 0 to 2.)

[0025] The PAEK resin of the present invention has a structure represented by the above general formula (5) consisting of repeating units (1-1) and (2-1), which are rigid and tough components, as a main chain structure, and also has a structure in which a branched structure represented by the above general formula (3-1) is introduced into the main chain. By having such a structure, the PAEK resin of the present invention has a high glass transition temperature (Tg) and excellent heat resistance, and while retaining the inherent excellent properties of PAEK resins, it is possible to make the crystalline melting point (Tm) relatively low, resulting in excellent moldability and processability, and furthermore, due to its high degree of polymerization (high molecular weight), it is a PAEK resin with excellent mechanical strength. Furthermore, generally, attempts to increase the molecular weight of a resin result in an increase in the heat melt viscosity, which causes a problem of reduced moldability. However, in the present invention, the molecular weight of the PAEK resin is increased by using the branched structure represented by the above general formula (3-1). Since the increased molecular weight due to this branched structure has a smaller hydrodynamic radius than the increased molecular weight due to a linear structure, a decrease in melt viscosity is expected. This allows the PAEK resin of the present invention to maintain good moldability.

[0026] The glass transition temperature (Tg) of the PAEK resin of the present invention is, for example, preferably from 120 to 180°C, and more preferably from 130 to 170°C. The crystalline melting point (Tm) of the PAEK resin of the present invention is, for example, preferably 250 to 400°C, and more preferably 270 to 370°C. The weight average molecular weight (Mw) of the PAEK resin of the present invention can be 20,000 or more, and more preferably 25,000 or more.

[0027] One of the characteristics of the PAEK resin of the present invention is that it contains a small amount of a branched structure having the structural unit of the above general formula (3-1) relative to the entire PAEK resin. This allows for the production of PAEK resins that have a high glass transition temperature (Tg) and excellent heat resistance, while retaining the excellent properties inherent to PAEK resins, and that have a relatively low crystalline melting point (Tm) for excellent moldability and processability, and that also have excellent mechanical strength due to their high degree of polymerization (high molecular weight).

[0028] A preferred embodiment of the PAEK resin of the present invention is a PAEK resin containing the branched structure represented by the general formula (3-1) in an amount of 0.01 to 100 mmol / kg relative to the PAEK resin. A more preferred embodiment of the PAEK resin of the present invention is a PAEK resin having repeating units represented by the above general formulas (1-1), (2-1), and (3-1), and the branched structure represented by the above general formula (3-1) is contained in an amount of 0.01 to 100 mmol / kg.

[0029] <Branched structure having general formula (3-1) as a structural unit> The branched structure contained in the PAEK resin of the present invention is represented by the following general formula (3-1) as described above.

[0030] [ka] In general formula (3-1), Ar1, Ar2, and Ar3 are each a divalent organic group represented by the following general formula (4-1), and the groups Ar1, Ar2, and Ar3 may be groups represented by the same structural formula or different structural formulas.

[0031] [ka] However, in consideration of availability and cost, it is more preferable that the groups Ar1, Ar2, and Ar3 are groups represented by the same structural formula. In order to fully exert the effects of the present invention, m in general formula (4-1) is more preferably 1.

[0032] A more preferred embodiment of the branched structure having the general formula (3-1) as a constituent unit is a branched structure represented by the following general formula (6).

[0033] [ka] (In the formula, Ar4 is a divalent organic group represented by the following general formula (4-1).

[0034] [ka] (wherein m is an integer of 0 to 2.)

[0035] Among the branched structures represented by general formula (6), it is more preferable that m in general formula (4-1) is 1 in order to fully exert the effects of the present invention.

[0036] (Manufacturing method of polyarylene ether ketone resin (PAEK resin)) One embodiment of the method for producing a PAEK resin of the present invention is a method for producing a PAEK resin, comprising reacting a monomer (1-2) represented by the following general formula (1-2), a monomer (2-2) represented by the following general formula (2-2), and a monomer (3-2) represented by the following general formula (3-2) in the presence of an organic sulfonic acid and diphosphorus pentoxide.

[0037] [ka] (In the formula, k is an integer of 0 to 2.)

[0038] [ka] (In the formula, n is an integer of 0 to 1.)

[0039] [ka] (In the formula, Ar1, Ar2, and Ar3 are represented by the following general formula (4-2). The values ​​of m in Ar1, Ar2, and Ar3 may be the same or different.

[0040] [ka] (wherein m is an integer of 0 to 2.)

[0041] Examples of the monomer (1-2) include 1,4-cyclohexanedicarboxylic acid (k=0), 4,4'-oxybisbenzoic acid (k=1), and 1,4-bis(4-carboxyphenoxy)benzene (k=2). Examples of the monomer (2-2) include diphenyl ether (n=0), 1,4-diphenoxybenzene (n=1), and 4,4'-oxybis(phenoxybenzene) (n=2). Examples of the monomer (3-2) include 1,3,5-triphenoxybenzene, 1,2,4-triphenoxybenzene, 1,3,5-tri(4-phenoxyphenoxy)benzene, 1,2,4-tri(4-phenoxyphenoxy)benzene, 1,3,5-tri(4-(4-phenoxyphenoxy)phenoxy)benzene, and 1,2,4-tri(4-(4-phenoxyphenoxy)phenoxy)benzene.

[0042] A preferred embodiment of the method for producing a PAEK resin of the present invention is a method for producing a PAEK resin in which the above monomer (1-2) is the following monomer (1-2-A) when k=1, the above monomer (2-2) is the following monomer (2-2-A) when n=1, and the above monomer (3-2) is the following monomer (3-2-A).

[0043] [ka]

[0044] [ka]

[0045] [ka] (In the formula, Ar5 is represented by the following general formula (3-2-B).)

[0046] [ka]

[0047] The method for producing a PAEK resin of the present invention is an aromatic electrophilic substitution type solution polycondensation reaction, and therefore the reaction can be carried out under mild polymerization conditions. Specifically, an organic sulfonic acid and diphosphorus pentoxide are mixed at 20 to 100°C for 1 to 40 hours, and the temperature is once adjusted to a predetermined temperature. Then, the above-mentioned monomer (1-2), the above-mentioned monomer (2-2), and the above-mentioned monomer (3-2) are added to this mixed liquid.

[0048] One embodiment of the method for producing the PAEK resin of the present invention includes a production method in which the above-mentioned monomer (1-2), the above-mentioned monomer (2-2), and the above-mentioned monomer (3-2) are added to a mixed solution of an organic sulfonic acid and diphosphorus pentoxide, and these monomers are mixed and reacted all at once. In this case, for example, a mixed solution of an organic sulfonic acid and diphosphorus pentoxide is mixed at 20 to 100°C for 1 to 40 hours, and then the temperature is adjusted to 40 to 80°C. After that, the above-mentioned monomer (1-2), monomer (2-2), and monomer (3-2) are added, mixed, and reacted for 1 to 100 hours, thereby producing a PAEK resin.

[0049] Another embodiment of the method for producing a PAEK resin of the present invention is a production method in which the above-mentioned monomer (1-2) and the above-mentioned monomer (2-2) are added to a mixed solution of an organic sulfonic acid and diphosphorus pentoxide, mixed, and reacted, and then the above-mentioned monomer (3-2) is added, mixed, and reacted. In this case, for example, a PAEK resin can be produced by mixing a mixed solution of an organic sulfonic acid and diphosphorus pentoxide at 20 to 100°C for 1 to 40 hours, then adjusting the temperature to 40 to 80°C, adding the monomer (1-2) and the monomer (2-2), mixing, and reacting for 1 to 50 hours, and then adding the monomer (3-2), mixing, and reacting for 1 to 50 hours. From the viewpoint of facilitating the production of a high molecular weight PAEK resin, a method of producing a PAEK resin by reacting the monomer (1-2) with the monomer (2-2) and then adding and reacting the monomer (3-2) is preferred.

[0050] As shown in the examples below, the method for producing a PAEK resin of the present invention can be carried out under mild conditions, with the polymerization step being carried out at 100°C or less. Furthermore, the only by-product is water, which is environmentally friendly. In the method for producing a PAEK resin of the present invention, the reaction monomers and solvents do not contain fluorine. For example, if trifluoromethanesulfonic acid must be used in the reaction step, a gas containing fluorine ions will be generated during waste disposal, resulting in a significant environmental impact. However, as long as methanesulfonic acid is used in the reaction step, such environmental impact issues will not arise.

[0051] The organic sulfonic acid is not particularly limited and can be appropriately selected depending on the purpose, but examples thereof include aliphatic sulfonic acids and aromatic sulfonic acids. Among these, aliphatic sulfonic acids are preferred. More specifically, examples of the organic sulfonic acid include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid (tosylic acid), and the like.

[0052] The ratio of the amount of organic sulfonic acid added to the amount of diphosphorus pentoxide added is preferably in the range of 100:35 to 100:1, more preferably in the range of 100:30 to 100:5, and even more preferably in the range of 100:25 to 100:5, by mass.

[0053] The ratio of the total amount of the monomer (1-2), the monomer (2-2), and the monomer (3-2) added to the total amount of the organic sulfonic acid and diphosphorus pentoxide added is preferably in the range of 1:100 to 50:100 by mass, more preferably in the range of 2:100 to 45:100, and even more preferably in the range of 5:100 to 40:100. In the production of the PAEK resin of the present invention, an organic sulfonic acid (e.g., particularly methanesulfonic acid) and diphosphorus pentoxide can be used to produce a PAEK resin exhibiting good properties. For example, if an attempt is made to produce a PAEK resin using anhydrous aluminum chloride instead of using an organic sulfonic acid and diphosphorus pentoxide, the polymerization rate is too fast, making it difficult to control the polymer sequence.

[0054] The molar ratio of the amount of the monomer (1-2) added to the amount of the monomer (2-2) added in the reaction step is preferably in the range of 100:90 to 100:110, more preferably in the range of 100:92 to 100:108.

[0055] As described above, the amount of the monomer (3-2) added is set so that the proportion of the monomer (3-2) relative to the PAEK resin is 0.01 to 100 mmol / kg, preferably 0.1 to 50 mmol / kg.

[0056] <Resin composition containing polyarylene ether ketone resin (PAEK resin)> The PAEK resins of the present invention can be combined with other ingredients to form resin compositions. The other ingredients are not particularly limited and can be selected appropriately depending on the purpose, but preferred embodiments of the other ingredients include fillers such as inorganic fillers and organic fillers. The shape of the filler is not particularly limited, and examples thereof include particulate, plate-like, and fibrous fillers.

[0057] Furthermore, a preferred embodiment of the resin composition containing the PAEK resin according to the present invention is a resin composition containing the PAEK resin of the present invention and reinforcing fibers. Here, examples of reinforcing fibers include inorganic fibers such as carbon fibers, glass fibers, boron fibers, alumina fibers, silicon carbide fibers, potassium titanate fibers, stainless steel fibers, glass cloth, glass nonwoven fabric, glass mat, and glass roving fabric, as well as organic fibers such as plant fibers such as paper, aramid paper, aramid cloth, aramid fibers, and aromatic ester fibers. Of these, carbon fibers and glass fibers are preferred because of their wide range of industrial applications. Of these, only one type may be used, or multiple types may be used simultaneously. The reinforcing fibers may be an aggregate of fibers, in the form of a woven fabric or a nonwoven fabric. They may also be fiber bundles in which fibers are aligned in one direction, or in the form of a sheet in which fiber bundles are arranged. They may also be a three-dimensional shape in which a thickness is added to an aggregate of fibers.

[0058] <Molded body containing polyarylene ether ketone resin (PAEK resin)> The PAEK resin according to the present invention has excellent heat resistance and a high glass transition temperature (Tg), and can be reduced in melting point and has good moldability. Furthermore, due to its high molecular weight, it also has excellent mechanical strength. Therefore, it can be used as a neat resin or as a compound with glass fiber, carbon fiber, fluororesin, and the like. Furthermore, by molding the PAEK resin according to the present invention or a resin composition containing the PAEK resin, primary processed products such as rods, boards, films, and filaments can be produced, as well as secondary processed products such as various injection-molded products, various machined products, gears, bearings, composites, implants, and 3D molded products. These molded products obtained by molding the PAEK resin according to the present invention can be used in automobiles, aircraft, electrical and electronic equipment, medical components, and the like. [Example]

[0059] (glass transition temperature (Tg) and crystalline melting temperature (Tm)) Using a PerkinElmer DSC device (Pyris Diamond), measurements were carried out under nitrogen flow at 50 mL / min with a temperature increase rate of 20°C / min from 40 to 400°C to determine the glass transition point (Tg) and crystalline melting point (Tm).

[0060] (GPC molecular weight) The molecular weight was determined under the following measurement conditions. Apparatus: Waters 2695 (manufactured by Waters) Column: TSKgel GMHHR-N (Tosoh), two columns connected in series Column temperature: 30℃ Eluent: hexafluoroisopropyl alcohol Detector: Waters2414 (RI detector) Sample concentration: 0.2% (wt / wt) Sample injection volume: 30 μL Calibration curve: Standard polystyrene (PS)

[0061] Example 1 Methanesulfonic acid (13.8 mL, 212 mmol) and diphosphorus pentoxide (2.04 g, 14.3 mmol) were charged into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, and the mixture was heated to 100 °C and stirred for 4 hours. After cooling to 60 °C, 4,4'-oxybisbenzoic acid (OBBA) (0.914 g, 3.54 mmol), 1,4-diphenoxybenzene (DPOB) (0.979 g, 3.73 mmol), and 1,3,5-tri(4-phenoxyphenoxy)benzene (TPOPOB) (0.034 g, 0.054 mmol) were charged and reacted for 22 hours. After cooling to room temperature, the reaction solution was poured into vigorously stirred methanol to precipitate the polymer, which was then filtered. The filtered polymer was washed twice with methanol and twice with ion-exchanged water. The polymer was then dried under vacuum at 180°C for 10 hours. This resulted in a PAEK resin yield of 1.25 g, 2.59 mmol, and 73%.

[0062] Example 2 Methanesulfonic acid (13.8 mL, 212 mmol) and diphosphorus pentoxide (2.04 g, 14.3 mmol) were charged into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, and the mixture was heated to 100°C and stirred for 4 hours. After cooling to 60°C, 4,4'-oxybisbenzoic acid (0.914 g, 3.54 mmol), 1,4-diphenoxybenzene (0.979 g, 3.73 mmol), and 1,3,5-tri(4-phenoxyphenoxy)benzene (0.045 g, 0.070 mmol) were charged and reacted for 22 hours. After cooling to room temperature, the reaction solution was poured into vigorously stirred methanol to precipitate the polymer, which was then filtered. The filtered polymer was washed twice with methanol and twice with ion-exchanged water. The polymer was then dried under vacuum at 180°C for 10 hours. This resulted in a PAEK resin yield of 1.16 g, 2.40 mmol, and 68%.

[0063] Example 3 Methanesulfonic acid (13.8 mL, 212 mmol) and diphosphorus pentoxide (2.04 g, 14.3 mmol) were charged into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, and the mixture was heated to 100°C and stirred for 4 hours. After cooling to 60°C, 4,4'-oxybisbenzoic acid (0.964 g, 3.68 mmol), 1,4-diphenoxybenzene (0.964 g, 3.68 mmol), and 1,3,5-tri(4-phenoxyphenoxy)benzene (0.056 g, 0.089 mmol) were charged and reacted for 22 hours. After cooling to room temperature, the reaction solution was poured into vigorously stirred methanol to precipitate the polymer, which was then filtered. The filtered polymer was washed twice with methanol and twice with ion-exchanged water. The polymer was then dried under vacuum at 180°C for 10 hours. This resulted in a PAEK resin yield of 1.34 g, 2.76 mmol, and 78%.

[0064] Example 4 A four-neck separable flask equipped with a nitrogen inlet tube, thermometer, reflux condenser, and stirrer was charged with methanesulfonic acid (13.8 mL, 212 mmol) and diphosphorus pentoxide (2.04 g, 14.3 mmol). The mixture was heated to 100°C and stirred for 4 hours. After cooling to 60°C, 4,4'-oxybisbenzoic acid (0.912 g, 3.53 mmol) and 1,4-diphenoxybenzene (0.926 g, 3.53 mmol) were added and reacted for 1 hour. 1,3,5-tri(4-phenoxyphenoxy)benzene (0.033 g, 0.053 mmol) was then added and reacted for 21 hours. After cooling to room temperature, the reaction solution was poured into vigorously stirred methanol to precipitate the polymer, which was then filtered. The filtered polymer was washed twice with methanol and twice with ion-exchanged water. The polymer was then dried under vacuum at 180°C for 10 hours. This resulted in a PAEK resin yield of 1.39 g, 2.86 mmol, and 81%.

[0065] Example 5 A four-neck separable flask equipped with a nitrogen inlet tube, thermometer, reflux condenser, and stirrer was charged with methanesulfonic acid (13.8 mL, 212 mmol) and diphosphorus pentoxide (2.04 g, 14.3 mmol). The mixture was heated to 100°C and stirred for 4 hours. After cooling to 60°C, 4,4'-oxybisbenzoic acid (0.912 g, 3.53 mmol) and 1,4-diphenoxybenzene (0.926 g, 3.53 mmol) were added and reacted for 2 hours. 1,3,5-tri(4-phenoxyphenoxy)benzene (0.033 g, 0.053 mmol) was then added and reacted for 20 hours. After cooling to room temperature, the reaction solution was poured into vigorously stirred methanol to precipitate the polymer, which was then filtered. The filtered polymer was washed twice with methanol and twice with ion-exchanged water. The polymer was then dried under vacuum at 180°C for 10 hours. This resulted in a PAEK resin yield of 1.49 g, 3.08 mmol, and 87%.

[0066] Example 6 A four-neck separable flask equipped with a nitrogen inlet tube, thermometer, reflux condenser, and stirrer was charged with methanesulfonic acid (13.8 mL, 212 mmol) and diphosphorus pentoxide (2.04 g, 14.3 mmol). The mixture was heated to 100°C and stirred for 4 hours. After cooling to 60°C, 4,4'-oxybisbenzoic acid (0.912 g, 3.53 mmol) and 1,4-diphenoxybenzene (0.926 g, 3.53 mmol) were added and reacted for 3 hours. 1,3,5-tri(4-phenoxyphenoxy)benzene (0.033 g, 0.053 mmol) was then added and reacted for 19 hours. After cooling to room temperature, the reaction solution was poured into vigorously stirred methanol to precipitate the polymer, which was then filtered. The filtered polymer was washed twice with methanol and twice with ion-exchanged water. The polymer was then dried under vacuum at 180°C for 10 hours. This resulted in a PAEK resin yield of 1.33 g, 2.75 mmol, and 78%.

[0067] Example 7 A four-neck separable flask equipped with a nitrogen inlet tube, thermometer, reflux condenser, and stirrer was charged with methanesulfonic acid (13.8 mL, 212 mmol) and diphosphorus pentoxide (2.04 g, 14.3 mmol). The mixture was heated to 100°C and stirred for 4 hours. After cooling to 60°C, 4,4'-oxybisbenzoic acid (0.912 g, 3.53 mmol) and 1,4-diphenoxybenzene (0.926 g, 3.53 mmol) were added and reacted for 7 hours. 1,3,5-tri(4-phenoxyphenoxy)benzene (0.033 g, 0.053 mmol) was then added and reacted for 15 hours. After cooling to room temperature, the reaction solution was poured into vigorously stirred methanol to precipitate the polymer, which was then filtered. The filtered polymer was washed twice with methanol and twice with ion-exchanged water. The polymer was then dried under vacuum at 180°C for 10 hours. This resulted in a PAEK resin yield of 1.46 g, 3.02 mmol, and 86%.

[0068] The glass transition temperature (Tg), crystalline melting point (Tm), number average molecular weight (Mn) and weight average molecular weight (Mw) of the PAEK resins according to Examples 1 to 7 were measured, and the results are shown in Tables 1 and 2.

[0069] [Table 1]

[0070] [Table 2]

[0071] (Comparative Example 1) Methanesulfonic acid (13.8 mL, 212 mmol) and diphosphorus pentoxide (2.04 g, 14.3 mmol) were charged into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, and the mixture was heated to 100°C and stirred for 4 hours. After cooling to 60°C, 4,4'-oxybisbenzoic acid (0.914 g, 3.54 mmol) and 1,4-diphenoxybenzene (1.0 g, 3.82 mmol) were charged and reacted for 22 hours. After cooling to room temperature, the reaction solution was poured into vigorously stirred methanol to precipitate the polymer, which was then filtered. The filtered polymer was washed twice with methanol and twice with ion-exchanged water. The polymer was then dried under vacuum at 180°C for 10 hours. This resulted in a PAEK resin yield of 1.17 g, 2.40 mmol, and 68%.

[0072] The glass transition temperature (Tg), crystalline melting point (Tm), number average molecular weight (Mn) and weight average molecular weight (Mw) of the PAEK resin according to Comparative Example 1 were measured, and the results are shown in Table 1.

[0073] As shown in Table 1, the glass transition temperature (Tg) of the PAEK resins of the Examples can be adjusted to 148°C or higher. Furthermore, the PAEK resins of the Examples can be adjusted to a crystalline melting point (Tm) of 354°C or lower while maintaining such excellent heat resistance, and have good moldability. Furthermore, the PAEK resins of the Examples are high-molecular-weight PAEK resins, and have excellent mechanical strength.

Claims

1. A polyarylene ether ketone resin having repeating units represented by the following general formulas (1-1), (2-1), and (3-1): The polyarylene ether ketone resin has a weight average molecular weight (Mw) of 20,000 or more. 【Chemistry 1】 (In the formula, k is an integer of 0 to 2.) 【Chemistry 2】 (In the formula, n is an integer of 0 to 1.) 【Transformation 3】 (In the formula, Ar １ , Ar ２ , and Ar ３ is a divalent organic group represented by the following general formula (4-1): １ , Ar ２ , and Ar ３ The values ​​of m may be the same or different. 【Chemistry 4】 (wherein m is an integer of 0 to 2.)

2. The polyarylene ether ketone resin according to claim 1, wherein the polyarylene ether ketone resin has a main chain structure represented by the following general formula (5): 【Transformation 5】 (In the formula, X is represented by the following general formula (5-1), and Y is represented by the following general formula (5-2). 【Transformation 6】 (In the formula, n is an integer of 0 to 1.) 【Transformation 7】 (wherein k is an integer of 0 to 2.)

3. The polyarylene ether ketone resin according to claim 1 or 2, wherein the repeating unit represented by the general formula (3-1) is a repeating unit represented by the following general formula (6): 【Transformation 8】 (In the formula, Ar ４ is a divalent organic group represented by the following general formula (4-1). 【Chemistry 9】 (wherein m is an integer of 0 to 2.)

4. The polyarylene ether ketone resin according to any one of claims 1 to 3, wherein the content of the repeating unit represented by the general formula (3-1) relative to the polyarylene ether ketone resin is 0.01 to 100 mmol / kg.

5. A polyarylene ether ketone resin having a branched structure and containing the following general formula (3-1) as a constituent unit: the content of the branched structure represented by the general formula (3-1) relative to the polyarylene ether ketone resin is 0.01 to 100 mmol / kg, The polyarylene ether ketone resin has a weight average molecular weight (Mw) of 20,000 or more. 【Chemistry 10】 (In the formula, Ar １ , Ar ２ , and Ar ３ is a divalent organic group represented by the following general formula (4-1): １ , Ar ２ , and Ar ３ The values ​​of m may be the same or different. 【Chemistry 11】 (wherein m is an integer of 0 to 2.)

6. The polyarylene ether ketone resin according to claim 5, wherein the repeating unit represented by the general formula (3-1) is a repeating unit represented by the following general formula (6): 【Chemistry 12】 (In the formula, Ar ４ is a divalent organic group represented by the following general formula (4-1). 【Chemistry 13】 (wherein m is an integer of 0 to 2.)

7. A method for producing the polyarylene ether ketone resin according to any one of claims 1 to 4, comprising reacting a monomer (1-2) represented by the following general formula (1-2), a monomer (2-2) represented by the following general formula (2-2), and a monomer (3-2) represented by the following general formula (3-2) in the presence of an organic sulfonic acid and diphosphorus pentoxide. 【Chemistry 14】 (In the formula, k is an integer of 0 to 2.) 【Chemistry 15】 (In the formula, n is an integer of 0 to 1.) 【Chemistry 16】 (In the formula, Ar １ , Ar ２ , and Ar ３ is represented by the following general formula (4-2): １ , Ar ２ , and Ar ３ The values ​​of m may be the same or different. 【Chemistry 17】 (wherein m is an integer of 0 to 2.)

8. The method for producing a polyarylene ether ketone resin according to claim 7, wherein the monomer (1-2) is the following monomer (1-2-A), the monomer (2-2) is the following monomer (2-2-A), and the monomer (3-2) is the following monomer (3-2-A). [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 (In the formula, Ar ５ is represented by the following general formula (3-2-B): 【Chemistry 21】

9. The method for producing a polyarylene ether ketone resin according to claim 7 or 8, wherein the monomer (1-2) and the monomer (2-2) are added to a mixed solution of an organic sulfonic acid and diphosphorus pentoxide, mixed and reacted, and then the monomer (3-2) is added, mixed and reacted.

10. A resin composition comprising the polyarylene ether ketone resin according to any one of claims 1 to 6.

11. The resin composition according to claim 10, further comprising reinforcing fibers.

12. A molded article obtained by molding the resin composition according to claim 10 or 11.

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