Polyarylene ether ketone resin, its production method, and molded body

Abstract

To provide a polyarylene ether ketone resin that has a high glass transition temperature with excellent heat resistance and a low crystalline melting point, which is excellent in moldability.SOLUTION: Provided is a polyarylene ether ketone resin that has a repeating unit represented by the following general formula (1-1). (In the formula, k is any integer from 1 to 3.).SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Polyarylene ether ketone resin (hereinafter sometimes referred to 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 subjecting two monomers, 4,4'-difluorobenzophenone and hydroquinone, to an aromatic nucleophilic substitution type solution polycondensation reaction using potassium carbonate in diphenyl sulfone (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 produced by using 4,4'-dihydroxybenzophenone instead of hydroquinone.

[0004] However, the aromatic nucleophilic substitution type solution polycondensation reaction used in the production of these PAEK resins has the disadvantages of high raw material costs due to the use of expensive 4,4'-difluorobenzophenone as a monomer, and high manufacturing process costs due to the reaction temperature of 300°C or higher, which tends to increase the price of the resin. In addition, inorganic bases are produced as by-products, which places a heavy burden on the environment.

[0005] Therefore, an aromatic electrophilic substitution type solution polycondensation reaction is known that produces PAEK resins without using 4,4'-difluorobenzophenone as a monomer and under mild polymerization conditions. Examples of the use of an aromatic electrophilic substitution type solution polycondensation reaction include a PEK resin produced by reacting 4-phenoxybenzoic acid chloride in the presence of hydrogen fluoride-boron trifluoride (see, for example, Patent Document 2), a PEKK resin produced 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 produced 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. Pat. 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] The conventional PAEK resins, such as the PEEK resin, PEK resin, and PEKK resin described above, are partially crystalline polymers. Their glass transition temperatures are high, at 140°C or higher, and they have excellent heat resistance. However, their crystalline melting points are also higher than 340°C, and they require high temperatures and pressures for molding, which means they have the disadvantage of poor moldability.

[0008] Therefore, an object of the present invention is to provide a polyarylene ether ketone resin having a high glass transition temperature with excellent heat resistance and a low crystalline melting point with excellent moldability, and to provide a production method suitable for producing the polyarylene ether ketone resin. [Means for solving the problem]

[0009] In order to achieve high heat resistance, it is desirable for super engineering plastics such as PAEK resins to be polymers with as few impurities as possible and with a uniform structure. Therefore, the development of PAEK resins has traditionally focused on polymers with a single repeating unit. However, with a single repeating unit structure, it is difficult to adjust thermal properties such as the crystalline melting point, and it has been difficult to improve molding processability.

[0010] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems and have found that a PAEK resin obtained by copolymerizing the following repeating units (1-1) and (3-1), which are rigid and tough components, with the following repeating unit (2-1), which is a soft component, can lower the crystalline melting point and exhibit good moldability, thereby completing the present invention.

[0011] 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).

[0012] [ka] (In the formula, k is an integer of 1 to 3.)

[0013] [ka] (In the formula, m1 and m2 are integers of 1 or 2.)

[0014] [ka] (In the formula, n is an integer of 0 to 2.) [2] The polyarylene ether ketone resin according to [1], wherein the ratio of the total molar amount of the repeating units (1-1) and (3-1) to the molar amount of the repeating unit (2-1) is, in terms of molar ratio, (1-1)+(3-1):(2-1)=95:5 to 60:40. [3] A method for producing the polyarylene ether ketone resin according to [1] or [2] above, 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.

[0015] [ka] (In the formula, k is an integer of 1 to 3.)

[0016] [ka] (In the formula, m2 is an integer of 1 or 2.)

[0017] [ka] (In the formula, n is an integer of 0 to 2.) [4] The method for producing a polyarylene ether ketone resin according to [3] above, 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).

[0018] [ka]

[0019] [ka]

[0020] [ka] [5] A molded article comprising the polyarylene ether ketone resin according to [1] or [2] above. Effect of the Invention

[0021] The present invention can provide a polyarylene ether ketone resin having a high glass transition temperature with excellent heat resistance and a low crystalline melting point with excellent moldability. The present invention can also provide a production method suitable for producing the polyarylene ether ketone resin. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] The PAEK resin of the present invention and the method for producing the PAEK resin are 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.

[0023] (Polyarylene ether ketone resin (PAEK resin)) The PAEK resin of the present invention has repeating units represented by the following general formulas (1-1), (2-1) and (3-1).

[0024] [ka] (In the formula, k is an integer of 1 to 3.)

[0025] [ka] (In the formula, m1 and m2 are integers of 1 or 2.)

[0026] [ka] (In the formula, n is an integer of 0 to 2.)

[0027] The PAEK resin of the present invention has repeating units (1-1) and (3-1), which are rigid and tough components, and a repeating unit (2-1) that breaks the repeating units (1-1) and (3-1) and reduces the crystallinity, so that the crystalline melting point can be controlled by adjusting the ratio of the repeating units (1-1) and (3-1) to the repeating unit (2-1). The PAEK resin of the present invention can have a low crystalline melting point. The PAEK resin of the present invention has a high molecular weight and good moldability. As shown by the results of the following examples, the PAEK resin of the present invention can exhibit a high glass transition point (Tg) of 150°C or higher, while exhibiting a low crystalline melting point (Tm) of 340°C or lower. In addition, the repeating unit (2-1) has a biphenyl (or terphenyl) structure, which is considered to effectively contribute to the high Tg and good mechanical properties. The repeating unit (2-1) has a biphenyl (or terphenyl) skeleton, and the biphenyl skeleton is bonded to a functional group via an ether bond. Here, when diphenic acid (2,2'-biphenyldicarboxylic acid) or the like in which a dicarboxyl group is substituted on a biphenyl skeleton is used as the repeating unit (2-1), the reactivity of the carboxylic acid, which is the reaction point, decreases because the biphenyl skeleton and the carboxylic acid form a conjugated system, and when the amount of diphenic acid added is increased, there is a problem that the molecular weight decreases. On the other hand, the repeating unit (2-1) of the PAEK resin of the present invention is considered not to cause a decrease in reactivity, unlike diphenic acid, because the conjugated system is cut by the ether bond. Therefore, the repeating unit (2-1) of the PAEK resin of the present invention is considered to effectively contribute to the formation of a PAEK resin with a large molecular weight without decreasing the molecular weight of the PAEK resin.

[0028] In the PAEK resin of the present invention, the ratio of the total molar amount of the repeating units (1-1) and (3-1) to the molar amount of the repeating unit (2-1) is preferably in the range of 95:5 to 60:40, more preferably in the range of 93:7 to 75:25, and even more preferably in the range of 90:10 to 85:15, in terms of molar ratio [(molar amount of repeating unit (1-1)+molar amount of repeating unit (3-1)):molar amount of repeating unit (2-1)]. By increasing the ratio of the total molar amount of the repeating unit (1-1) and the repeating unit (3-1) to the molar amount of the repeating unit (2-1) within the above ratio range, the glass transition temperature (Tg) can be adjusted to a high value, and the crystallinity and crystalline melting point (Tm) can be increased to obtain a PAEK resin with excellent heat resistance. By decreasing the ratio of the total molar amount of the repeating unit (1-1) and the repeating unit (3-1) to the molar amount of the repeating unit (2-1) within the above ratio range, the crystalline melting point (Tm) can be made relatively low, and a PAEK resin with excellent moldability can be obtained. By adjusting the above ratio, the glass transition temperature (Tg) of the PAEK resin of the present invention can be adjusted to 140° C. or higher, more preferably 150° C. or higher. More specifically, it can be adjusted to 140 to 170° C., preferably 150 to 165° C. The crystalline melting point (Tm) of the PAEK resin of the present invention can be adjusted to 350° C. or lower, more preferably 340° C. or lower. More specifically, it can be adjusted to 250 to 350° C., preferably 280 to 340° C. By optimizing the ratio of the repeating units (1-1) and (3-1) to the repeating unit (2-1), a PAEK resin having excellent heat resistance and moldability can be obtained.

[0029] (Production 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.

[0030] [ka] (In the formula, k is an integer of 1 to 3.)

[0031] [ka] (In the formula, m2 is an integer of 1 or 2.)

[0032] [ka] (In the formula, n is an integer of 0 to 2.)

[0033] Examples of the monomer (1-2) include 4,4'-oxybisbenzoic acid (k=1), 1,4-bis(4-carboxyphenoxy)benzene (k=2), and 4,4'-bis(p-carboxyphenoxy)diphenyl ether (k=3). Examples of the monomer (2-2) include 4'-phenoxybiphenyl-4-carboxylic acid (m2=1), 4''-phenoxy-[1,1':4',1''-terphenyl]-4-carboxylic acid (m2=2), and the like. Examples of the monomer (3-2) include diphenyl ether (n=0), 1,4'-diphenoxybenzene (n=1), and 4,4'-oxybis(phenoxybenzene) (n=2).

[0034] A preferred embodiment of the method for producing a PAEK resin of the present invention includes 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 m2=1, and the above monomer (3-2) is the following monomer (3-2-A) when n=1.

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] 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. For example, an organic sulfonic acid and diphosphorus pentoxide are mixed at 20 to 100°C for 1 to 40 hours, and then the above-mentioned monomer (1-2), monomer (2-2) and monomer (3-2) are added to this mixed liquid, mixed, heated, and then reacted all at once at 40 to 80°C for 1 to 100 hours, for example, to produce a PAEK resin.

[0039] As shown in the following examples, the method for producing a PAEK resin of the present invention can be carried out under mild conditions, such as a polymerization step at 100°C or less. In addition, 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 is generated during waste disposal, which places a large burden on the environment. However, as long as methanesulfonic acid is used in the reaction step, such an environmental load problem does not occur.

[0040] The organic sulfonic acid is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include aliphatic sulfonic acid, aromatic sulfonic acid, etc. Among them, aliphatic sulfonic acid is preferable. More specifically, examples of the organic sulfonic acid include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid (tosylic acid), etc.

[0041] 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 ratio.

[0042] The ratio of the total amount of the above-mentioned monomer (1-2), monomer (2-2) and 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 40:100, more preferably in the range of 2:100 to 30:100, and even more preferably in the range of 5:100 to 25:100, by mass ratio. In the production of the PAEK resin of the present invention, an organic sulfonic acid (e.g., particularly methanesulfonic acid) and diphosphorus pentoxide are 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.

[0043] The ratio of the amount of the monomer (1-2) added to the amount of the monomer (3-2) added in the reaction step is preferably in the range of 85:100 to 115:100, more preferably in the range of 90:100 to 110:100, and particularly preferably in the range of 92:100 to 108:100, in terms of molar ratio. In addition, in the present invention, a terminal blocking step of reacting terminal carboxyl groups with (3-2) can be further provided after the reaction step in order to reduce the number of carboxyl groups at the polymer terminals. The ratio of the amount of (3-2) added in the terminal blocking step, separate from the (3-2) added in the reaction step, to the total amount of (1-2), (2-2), and (3-2) added in the reaction step is preferably in the range of 30:100 to 0.1:100, more preferably in the range of 20:100 to 0.5:100, and even more preferably in the range of 15:100 to 1:100, in terms of molar ratio.

[0044] The ratio of the total amount of the monomer (1-2) and the monomer (3-2) to the amount of the monomer (2-2) added is, in molar ratio, (1-1)+(3-1):(2-1)=95:5 to 60:40, preferably 93:7 to 75:25, and more preferably 90:10 to 85:15.

[0045] In addition, in the method for producing a PAEK resin of the present invention, the monomers may be charged in a divided order, and the monomer (1-2) and the monomer (2-2) may be reacted with each other, and then the monomer (3-2) may be reacted with each other. Furthermore, in the method for producing a PAEK resin of the present invention, the monomers may be charged in a divided order, and the monomer (1-2) and the monomer (3-2) may be reacted with each other, and then the monomer (2-2) may be reacted with each other. By producing the PAEK resin by dividing the order of charging the monomers, it is possible to prevent the resulting PAEK resin from having a non-uniform structure separated into segments of each monomer, and the uniformity and thermal stability of the entire PAEK resin tends to be improved, which is preferable.

[0046] <Resin composition containing polyarylene ether ketone resin (PAEK resin)> The PAEK resins of the present invention can be combined with other ingredients to make resin compositions. The other ingredients are not particularly limited and can be appropriately selected depending on the purpose. Examples of the other ingredients include inorganic fillers and organic fillers. The shape of the filler is not particularly limited, and examples thereof include particulate, plate-like, and fibrous fillers. The resin composition containing the PAEK resin more preferably contains a fibrous filler as the filler. Among the fibrous fillers, carbon fiber and glass fiber are preferred because they have a wide range of industrial applications.

[0047] <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), can have a low melting point, and has good moldability and excellent impact resistance. Therefore, it can be used as a neat resin or as a compound with glass fiber, carbon fiber, fluororesin, etc. By molding the PAEK resin according to the present invention, primary processed products such as rods, boards, films, filaments, various injection processed products, various cut processed products, secondary processed products such as gears, bearings, composites, implants, and 3D molded products can be manufactured, and these molded products obtained by molding the PAEK resin according to the present invention can be used for automobiles, aircraft, electrical and electronic equipment, medical parts, etc. EXAMPLES

[0048] (Glass transition point (Tg) and crystalline melting point (Tm)) Using a PerkinElmer DSC device (Pyris Diamond), measurements were performed under nitrogen flow of 50 mL / min and temperature increase of 20° C. / min from 40 to 400° C. to determine the glass transition point (Tg) and crystalline melting point (Tm).

[0049] (5% weight loss temperature (Td5(℃))) Using a TG-DTA device (Rigaku Corporation TG-8120), measurements were performed under a nitrogen flow of 20 mL / min at a temperature increase rate of 20° C. / min to measure the 5% weight loss temperature.

[0050] (Reduced viscosity (equivalent to molecular weight of PAEK resin) dL / g) Using a Cannon-Fenske viscometer (manufactured by Shibata Scientific Co., Ltd.), the outflow times of the solvent and the polymer solution in which 0.3 g of polymer was dissolved in 100 mL of solvent were measured at 25° C., and the reduced viscosity was calculated by the following formula: The solvent used was a solution in which chloroform and trifluoroacetic acid were mixed in a mass ratio of 4:1. Reduced viscosity (dL / g)=(t-t0) / (c×t0) Here, t0 is the outflow time of the solvent, t is the outflow time of the polymer solution, and c is the polymer concentration (g / dL) in the polymer solution.

[0051] (Linear thermal expansion coefficient (10 -6 / ℃) A thermomechanical analyzer (EXSTAR TMA / SS6100 manufactured by Hitachi High-Tech Science Corporation) was used to determine the linear thermal expansion coefficient as the average value in the range of 200 to 250°C from the elongation of the test piece at a heating rate of 3°C / min by thermomechanical analysis.

[0052] Example 1 In a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, 128.88 g of methanesulfonic acid and 30.93 g of diphosphorus pentoxide were charged, and the temperature was raised to 100°C and stirred for 4 hours. After that, after cooling to 80°C, 8.12 g of 4,4'-oxybisbenzoic acid, 10.30 g of 4'-phenoxybiphenyl-4-carboxylic acid, and 8.25 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. After that, it was cooled to room temperature, and the reaction solution was poured into methanol with strong stirring to precipitate a polymer. The precipitated polymer was then filtered. The precipitated polymer was washed twice with methanol, then twice with ion-exchanged water, and then subjected to solid-liquid separation. The washed cake was filtered and dried at 180°C under vacuum for 10 hours to obtain the polymer.

[0053] Example 2 In a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, 128.88 g of methanesulfonic acid and 30.93 g of diphosphorus pentoxide were charged, and the temperature was raised to 100°C and stirred for 4 hours. After that, it was cooled to 80°C, and then 9.68 g of 4,4'-oxybisbenzoic acid, 6.79 g of 4'-phenoxybiphenyl-4-carboxylic acid, and 9.83 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. After that, it was cooled to room temperature, and the reaction solution was poured into methanol with strong stirring to precipitate a polymer. The precipitated polymer was then filtered. The precipitated polymer was washed twice with methanol, then twice with ion-exchanged water, and then subjected to solid-liquid separation. The washed cake was filtered and dried at 180°C under vacuum for 10 hours to obtain the polymer.

[0054] Example 3 In a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, 128.88 g of methanesulfonic acid and 30.93 g of diphosphorus pentoxide were charged, and the temperature was raised to 100°C and stirred for 4 hours. After that, it was cooled to 80°C, and then 9.68 g of 4,4'-oxybisbenzoic acid, 6.79 g of 4'-phenoxybiphenyl-4-carboxylic acid, and 9.83 g of 1,4-diphenoxybenzene were charged and reacted for 48 hours. After that, it was cooled to room temperature, and the reaction solution was poured into methanol with strong stirring to precipitate a polymer. The precipitated polymer was then filtered. The precipitated polymer was washed twice with methanol, then twice with ion-exchanged water, and then subjected to solid-liquid separation. The washed cake was filtered and dried at 180°C under vacuum for 10 hours to obtain the polymer.

[0055] Example 4 In a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, 128.88 g of methanesulfonic acid and 30.93 g of diphosphorus pentoxide were charged, and the temperature was raised to 100°C and stirred for 4 hours. After that, it was cooled to 60°C, and then 9.68 g of 4,4'-oxybisbenzoic acid, 6.79 g of 4'-phenoxybiphenyl-4-carboxylic acid, and 9.83 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. After that, it was cooled to room temperature, and the reaction solution was poured into methanol with strong stirring to precipitate a polymer. The precipitated polymer was then filtered. The precipitated polymer was washed twice with methanol, then twice with ion-exchanged water, and then subjected to solid-liquid separation. The washed cake was filtered and dried at 180°C under vacuum for 10 hours to obtain the polymer.

[0056] Example 5 In a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, 128.88 g of methanesulfonic acid and 30.93 g of diphosphorus pentoxide were charged, and the temperature was raised to 100°C and stirred for 4 hours. Then, 9.68 g of 4,4'-oxybisbenzoic acid, 6.79 g of 4'-phenoxybiphenyl-4-carboxylic acid, and 9.83 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. Then, the mixture was cooled to room temperature, and the reaction solution was poured into vigorously stirred methanol to precipitate a polymer. The precipitated polymer was then filtered. The precipitated polymer was washed twice with methanol, then twice with ion-exchanged water, and then subjected to solid-liquid separation. The washed cake was filtered and dried at 180°C under vacuum for 10 hours to obtain the polymer.

[0057] Example 6 In a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, 128.88 g of methanesulfonic acid and 30.93 g of diphosphorus pentoxide were charged, and the temperature was raised to 100°C and stirred for 4 hours. After that, it was cooled to 80°C, and then 10.71 g of 4,4'-oxybisbenzoic acid, 4.47 g of 4'-phenoxybiphenyl-4-carboxylic acid, and 10.88 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. After that, it was cooled to room temperature, and the reaction solution was poured into methanol with strong stirring to precipitate a polymer. The precipitated polymer was then filtered. The precipitated polymer was washed twice with methanol, then twice with ion-exchanged water, and then subjected to solid-liquid separation. The washed cake was filtered and dried at 180°C under vacuum for 10 hours to obtain the polymer.

[0058] Example 7 In a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, 128.88 g of methanesulfonic acid and 30.93 g of diphosphorus pentoxide were charged, and the temperature was raised to 100°C and stirred for 4 hours. After that, it was cooled to 80°C, and then 11.49 g of 4,4'-oxybisbenzoic acid, 2.72 g of 4'-phenoxybiphenyl-4-carboxylic acid, and 11.67 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. After that, it was cooled to room temperature, and the reaction solution was poured into methanol with strong stirring to precipitate a polymer. The precipitated polymer was then filtered. The precipitated polymer was washed twice with methanol, then twice with ion-exchanged water, and then subjected to solid-liquid separation. The washed cake was filtered and dried at 180°C under vacuum for 10 hours to obtain the polymer.

[0059] The glass transition temperature (Tg), crystalline melting point (Tm), 5% weight loss temperature (Td5 (°C)), reduced viscosity (dL / g), and linear thermal expansion coefficient (10 -6 The results are shown in Tables 1-1 and 1-2.

[0060] Comparative Example 1 As the PEEK resin according to Comparative Example 1, VICTREX PEEK 150P manufactured by Victrex was prepared, and its glass transition temperature (Tg), crystalline melting point (Tm), 5% weight loss temperature (Td5 (°C)), reduced viscosity (dL / g), and linear thermal expansion coefficient (10 -6 / °C) and the results are shown in Table 2-1.

[0061] Comparative Example 2 As the PEK resin according to Comparative Example 2, VICTREX HT manufactured by Victrex was prepared, and its glass transition temperature (Tg), crystalline melting point (Tm), 5% weight loss temperature (Td5 (°C), reduced viscosity (dL / g), and linear thermal expansion coefficient (10 -6 / °C) and the results are shown in Table 2-1.

[0062] [Table 1-1]

[0063] [Table 1-2]

[0064] [Table 2-1]

[0065] As shown in Tables 1-1 and 1-2, the PAEK resin of the examples can be adjusted to have a glass transition temperature (Tg) of 150°C or higher, and is a resin with excellent heat resistance equivalent to or higher than that of commercially available PEEK resin (Comparative Example 1) and PEK resin (Comparative Example 2). In addition, the PAEK resin of the examples can be controlled to have a crystal melting point (Tm) of 340°C or lower while maintaining such excellent heat resistance, and since this crystal melting point (Tm) is lower than the crystal melting points (Tm) of commercially available PEEK resin (Comparative Example 1) and PEK resin (Comparative Example 2), it is found to have good moldability. In addition, the PAEK resin of the examples shows reduced viscosity and linear thermal expansion coefficient comparable to those of PEEK resin (Comparative Example 1) and PEK resin (Comparative Example 2).

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 molar ratio of (1-1)+(3-1):(2-1)=93:7 to 75:25 between the total molar amount of the repeating units (1-1) and (3-1) and the molar amount of the repeating unit (2-1). 【Chemistry 1】 (In the formula, k is an integer of 1 to 3.) 【Chemistry 2】 (In the formula, m1 and m2 are integers of 1 to 2.) 【Chemistry 3】 (In the formula, n is an integer of 0 to 2.)

2. 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): The method for producing a polyarylene ether ketone resin according to claim 1, wherein the ratio of the total molar amount of the monomers (1-2) and (3-2) to the molar amount of the monomer (2-2) is in a molar ratio range of (1-2)+(3-2):(2-2)=93:7 to 75:25, and the monomers are reacted in the presence of an organic sulfonic acid and diphosphorus pentoxide. 【Chemistry 4】 (In the formula, k is an integer of 1 to 3.) 【Chemistry 5】 (In the formula, m2 is an integer of 1 to 2.) 【Chemistry 6】 (In the formula, n is an integer of 0 to 2.)

3. The method for producing a polyarylene ether ketone resin according to claim 2, 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 7】 【Chemistry 8】 【Chemistry 9】

4. A molded body comprising the polyarylene ether ketone resin described in claim 1.

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