Polyarylene ether ketone resin, method for producing the same, and molded article

Abstract

To provide a polyarylene ether ketone resin which is excellent in heat resistance and has high glass transition temperature, enables a low melting point, and has good moldability.SOLUTION: A polyarylene ether ketone resin has a repeating unit represented by polyether ketone and polyphenylene ether.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.

Background Art

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

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

[0004] However, the aromatic nucleophilic substitution type solution polycondensation reaction used for the production of these PAEK resins has the disadvantages that the raw material cost is high because the monomer uses expensive 4,4'-difluorobenzophenone, and the reaction temperature is 300 ° C or higher and the production process cost is also high, and the price of the resin tends to be high.

[0005] Therefore, an aromatic electrophilic substitution type solution polycondensation reaction for producing PAEK resin without using 4,4'-difluorobenzophenone as a monomer and under mild polymerization conditions is known. As an example using an aromatic electron-seeking substitution type solution polycondensation reaction, there is a method of reacting 4-phenoxybenzoic acid chloride in the presence of hydrogen fluoride-boron trifluoride to obtain a PEK resin (see, for example, Patent Document 2), a method of reacting terephthalic acid chloride and diphenyl ether in the presence of a Lewis acid to obtain a PEKK resin (see, for example, Patent Document 3), a method of reacting 4-phenoxybenzoic acid in the presence of a mixture of methanesulfonic acid and diphosphorus pentoxide to obtain a PEK resin (see, for example, Patent Document 4), and the like.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0007] The above-mentioned conventional PAEK resins such as PEEK resin, PEK resin, and PEKK resin are semi-crystalline polymers. Although their glass transition temperatures are high and they have excellent heat resistance, their crystal melting points are also high, and they require high temperatures and pressures for molding processing, resulting in poor molding processability.

[0008] Therefore, an object of the present invention is to provide a polyarylene ether ketone resin that has excellent heat resistance, a high glass transition temperature, can be low-melting-point, and has good molding processability. Another object of the present invention is to provide a manufacturing method suitable for manufacturing this polyarylene ether ketone resin.

Means for Solving the Problems

[0009] In order to achieve high heat resistance, super engineering plastics such as PAEK resins have been desired to be polymers with a uniform structure as free of impurities as possible. Therefore, conventionally, the development of polymers having a single repeating unit has been the center as PAEK resins. However, with a single repeating unit structure, it has been difficult to adjust thermal properties such as the crystal melting point, and it has been difficult to improve the moldability.

[0010] As a result of intensive studies to solve the above problems, the present inventors have found that a PAEK resin obtained by copolymerizing the following repeating unit (1-1) and the following repeating unit (3-1), which are rigid and tough components, and the following repeating unit (2-1), which is a flexible component, can lower the crystal melting point and exhibit good heat resistance and moldability, and have completed 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] [Chemical formula] (In the formula, k is an integer of 1 to 3.)

[0013] [Chemical formula] (In the formula, m is an integer of 1 to 3.)

[0014] [Chemical formula] (In the formula, n is an integer of 0 to 2.) [2] The polyarylene ether ketone resin according to [1] above, 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 the range of (1-1)+(3-1):(2-1)=95:5 to 40:60 in terms of molar ratio. [3] The method for producing the polyarylene ether ketone resin according to [1] or [2] above, wherein the monomer (1-2) represented by the following general formula (1-2), the monomer (2-2) represented by the following general formula (2-2), and the monomer (3-2) represented by the following general formula (3-2) are reacted in the presence of an organic sulfonic acid and phosphorus pentoxide.

[0015]

Chemical formula

[0016]

Chemical formula

[0017]

Chemical formula

[0018]

Chemical formula

[0019]

Chemical formula

[0020]

Chemical formula

Advantages of the Invention

[0021] The present invention can provide a polyarylene ether ketone resin that has excellent heat resistance and a high glass transition temperature, can be made to have a low melting point, and has good moldability. Further, the present invention can provide a production method suitable for producing this polyarylene ether ketone resin.

Embodiments for Carrying Out the Invention

[0022] Hereinafter, the PAEK resin of the present invention and the production method of the PAEK resin will be described in detail. However, the description of the constituent elements described below is an example as one embodiment of the present invention and 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]

Chemical formula

[0025]

Chemical formula

[0026]

Chemical formula

[0027] Since the PAEK resin of the present invention has the repeating units (1-1) and (3-1) which are rigid and tough components and the repeating unit (2-1) which is a flexible component, the crystal 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 lower the crystal melting point. In addition, in all of the repeating units (1-1), (2-1), and (3-1), the substituents are arranged in the para position. As shown in the following examples, the PAEK resin of the present invention having such repeating units (1-1), (2-1), and (3-1) can shorten the crystallization time. By the way, generally in the case of a crystalline thermoplastic resin, even if it is not cooled to the glass transition temperature, if the resin crystallizes and solidifies, it can be demolded. Therefore, the crystallization rate from the molten state to the crystalline state affects the productivity. For example, when the crystallization rate is slow (= it takes a long time to solidify), in addition to the deterioration of the mold release property from the mold, a long molding cycle time is required, resulting in poor productivity. For this reason, in the molding of thermoplastic resins (especially injection molding), there is a great demand for shortening the molding cycle by improving the crystallization rate (shortening the crystallization time). According to the present invention, the crystallization time of the PAEK resin can be shortened. If the crystallization time is shortened, the cooling time is shortened and the molding processability is improved. Therefore, according to the present invention, it is possible to provide a PAEK resin with improved molding processability. The crystallization time can be determined, for example, by measuring the isothermal crystallization time using a differential scanning calorimeter (Flash DSC). Specifically, for example, after melting the resin, it is rapidly cooled (several 1000 K / s) to a predetermined temperature, and the time required for crystallization when it is isothermally held at that temperature is measured.

[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 a molar ratio [(molar amount of repeating unit (1-1) + molar amount of repeating unit (3-1)): molar amount of repeating unit (2-1)], preferably in the range of 95:5 to 40:60, and more preferably in the range of 90:10 to 60:40. Within this ratio range, by increasing the value of 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), the glass transition temperature (Tg) can be adjusted to be higher, the crystallinity and the crystal melting point (Tm) can be increased, and a PAEK resin with excellent heat resistance can be obtained. Also, within this ratio range, by decreasing the value of 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), the crystal melting point (Tm) can be made relatively low, and a PAEK resin with excellent moldability can be obtained. By adjusting this ratio, the glass transition temperature (Tg) of the PAEK resin of the present invention can be adjusted to 120 °C or higher, more preferably 140 °C or higher. More specifically, it can be adjusted to 120 to 165 °C, preferably 125 to 160 °C, and more preferably 140 to 155 °C. Also, the crystal melting point (Tm) of the PAEK resin of the present invention can be adjusted to 350 °C or lower. More specifically, it can be adjusted to 280 to 350 °C, preferably 300 to 350 °C, and more preferably 310 to 349 °C. By optimizing the ratio of the repeating units (1-1) and (3-1) to the repeating unit (2-1), a PAEK resin excellent in heat resistance and moldability can be obtained.

[0029] (Method for producing polyarylene ether ketone resin (PAEK resin)) One aspect of the method for producing a PAEK resin of the present invention is a method for producing a PAEK resin, in which 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) are reacted in the presence of an organic sulfonic acid and diphosphorus pentoxide.

[0030]

Chemical formula

[0031]

Chemical formula

[0032]

Chemical formula

[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-phenoxybenzoic acid (ma = 0), 4-(4-phenoxyphenoxy)benzoic acid (ma = 1), and 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid (ma = 2). Examples of the monomer (3-2) include diphenyl ether (n = 0), 1,4-diphenoxybenzene (n = 1), and 4,4'-oxybis(phenoxybenzene) (n = 2).

[0034] As a preferred embodiment of the method for producing the PAEK resin of the present invention, the monomer (1-2) is the following monomer (1-2-A) when k = 1, the monomer (2-2) is the following monomer (2-2-A) when ma = 2, and the monomer (3-2) is the following monomer (3-2-A) when n = 1. Examples of the method for producing the PAEK resin include those described above.

[0035]

Chemical formula

[0036]

Chemical formula

[0037]

Chemical formula

[0038] Since the method for producing the PAEK resin of the present invention is an aromatic electrophilic substitution type solution polycondensation reaction, the reaction can be carried out under mild polymerization conditions. Specifically, an organic sulfonic acid and phosphorus pentoxide are mixed at 20 to 100 °C for 1 to 40 hours, and then the monomer (1-2), the monomer (2-2), and the monomer (3-2) are added to this mixed solution.

[0039] As an embodiment of the method for producing the PAEK resin of the present invention, there is provided a production method in which the monomer (1-2), the monomer (2-2), and the monomer (3-2) are added to a mixed solution of an organic sulfonic acid and phosphorus pentoxide, mixed, and these monomers are reacted in one batch. In this case, for example, the monomer (1-2), the monomer (2-2), and the monomer (3-2) are added to a mixed solution of an organic sulfonic acid and phosphorus pentoxide, mixed, and after raising the temperature, for example, at 40 to 100 °C, more preferably at 60 to 90 °C, still more preferably at 60 to 80 °C for 1 to 100 hours, and reacted in one batch to produce a PAEK resin.

[0040] The method for producing the PAEK resin of the present invention can be carried out under mild conditions where the polymerization temperature is 100°C or lower as shown in the following examples. Further, the by-product is only water that does not impose a burden on the environment. The method for producing the PAEK resin of the present invention does not contain fluorine in the reaction monomers or solvents. For example, if trifluoromethanesulfonic acid has to be used in the reaction process, in waste treatment, a gas containing fluoride ions will be generated, imposing a large environmental burden. However, for example, as long as methanesulfonic acid is used in the reaction process, such environmental burden problems do not occur.

[0041] The organic sulfonic acid is not particularly limited and can be appropriately selected according to the purpose. Examples include aliphatic sulfonic acids and aromatic sulfonic acids. Among them, 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.

[0042] The ratio of the addition amount of the organic sulfonic acid to the addition amount of phosphorus pentoxide 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.

[0043] The ratio of the total addition amount of the above monomers (1-2), the above monomers (2-2), and the above monomers (3-2) to the total addition amount of the organic sulfonic acid and phosphorus pentoxide 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, by using an organic sulfonic acid (for example, particularly methanesulfonic acid) and phosphorus pentoxide, a PAEK resin showing good properties can be produced. For example, if an attempt is made to produce a PAEK resin using anhydrous aluminum chloride instead of using an organic sulfonic acid and phosphorus pentoxide, the polymerization rate is too fast and it becomes difficult to control the polymer sequence.

[0044] The ratio of the addition amount of the monomer (1-2) to the addition amount of the monomer (3-2) in the above reaction step is preferably substantially equimolar because this reaction is an aromatic electrophilic substitution type polycondensation reaction. Specifically, in terms of molar ratio, it is preferably in the range of 90:100 to 110:100, more preferably in the range of 92:100 to 108:100, and particularly preferably in the range of 92:102 to 108:100.

[0045] The ratio of the total addition amount of the monomer (1-2) and the monomer (3-2) to the addition amount of the monomer (2-2) is preferably in the range of 95:5 to 40:60 in terms of molar ratio, and more preferably in the range of 90:10 to 60:40.

[0046] <Resin composition containing polyarylene ether ketone resin (PAEK resin)> The PAEK resin according to the present invention can be used in combination with other formulations to prepare a resin composition. There are no particular restrictions on other formulations, and they can be appropriately selected according to the purpose. Examples include inorganic fillers, organic fillers, and the like. There are no particular limitations on the shape of the filler. Examples include fillers such as particulate, plate-like, and fibrous fillers. The resin composition containing the PAEK resin preferably contains a fibrous filler as the filler. Among the fibrous fillers, carbon fiber and glass fiber are preferred because of their wide industrial application range.

[0047] <Molded article 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 made to have a low melting point and has good moldability. 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, etc., and secondary processed products such as various injection molded products, various machined products, gears, bearings, composites, implants, 3D molded products, etc. can be manufactured, and the molded products formed by molding these PAEK resins according to the present invention can be used in automobiles, airplanes, electric and electronic, medical members, etc.

Examples

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

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

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

[0051] (Crystallization time) Using a differential scanning calorimeter (Flash DSC1) manufactured by Mettler Toledo, the crystallization time at 200 °C was measured by one of the following two methods under a nitrogen flow of 40 mL / min. 1) After heating from 30 °C to 360 °C at 100 K / s, holding at 360 °C for 1 second to melt the sample, rapidly cooling to 200 °C at 6000 K / s, and then determining the exothermic peak due to crystallization during isothermal holding at that temperature. 2) After heating from 30 °C to 360 °C at 100 K / s, holding at 360 °C for 1 second to melt the sample, rapidly cooling to 200 °C at 6000 K / s, measuring the heat of fusion during isothermal holding at that temperature for various times, and determining it based on the degree of crystallization progress with respect to time.

[0052] (Example 1) To a four-necked separable flask equipped with a nitrogen inlet tube, thermometer, reflux condenser, and stirrer, 1.93 g of diphosphorus pentoxide was gradually added to 19.24 g of methanesulfonic acid, then the temperature was raised to 40 °C and stirred for 2 hours. Thereafter, 0.762 g of 4,4'-oxybisbenzoic acid, 0.294 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid, and 0.837 g of 1,4-diphenoxybenzene were charged, the temperature was raised to 60 °C, and the reaction was carried out for 22 hours. Thereafter, after adding 4-chlorophenol, it was cooled to 65 °C and water was added. The precipitated polymer was filtered off and washed with methanol and ion-exchanged water. The obtained polymer was transferred to another container, N-methyl-2-pyrrolidone (hereinafter, NMP) was added, stirred at 150 °C for 15 minutes, and then filtered. Washing of the filtered polymer with a mixed solvent of NMP and boiling water was repeated twice. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added, stirred for 10 minutes, and then filtered. Washing of the filtered polymer with boiling water was repeated twice. Thereafter, the polymer was dried at 120 °C under vacuum for 4 hours. Thus, a PAEK resin was obtained with a yield of 1.22 g and a yield of 72%.

[0053] (Example 2) In a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 1.93 g of diphosphorus pentoxide was gradually added to 19.24 g of methanesulfonic acid, and then the temperature was raised to 40 °C and stirred for 2 hours. Then, 0.762 g of 4,4'-oxybisbenzoic acid, 0.294 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid, and 0.837 g of 1,4-diphenoxybenzene were charged, and after raising the temperature to 80 °C, the reaction was carried out for 22 hours. After that, 4-chlorophenol was added, then cooled to 65 °C, and water was added. The precipitated polymer was filtered off, washed with methanol and ion-exchanged water. The obtained polymer was transferred to another container, NMP was added and stirred at 150 °C for 15 minutes, and then filtration was carried out. The filtered polymer was washed twice with a mixed solvent of NMP and boiling water. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added and stirred for 10 minutes, and then filtration was carried out. The filtered polymer was washed twice with boiling water. Then, the polymer was dried at 120 °C under vacuum for 4 hours. As a result, a PAEK resin was obtained with a yield of 1.31 g and a yield of 77%.

[0054] (Example 3) In a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 1.93 g of diphosphorus pentoxide was gradually added to 19.24 g of methanesulfonic acid, and then the temperature was raised to 40 °C and stirred for 2 hours. Then, 0.762 g of 4,4'-oxybisbenzoic acid, 0.294 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid, and 0.837 g of 1,4-diphenoxybenzene were charged, and after raising the temperature to 90 °C, the reaction was carried out for 22 hours. Thereafter, after adding 4-chlorophenol, it was cooled to 65°C, and water was added. The precipitated polymer was filtered off and washed with methanol and ion-exchanged water. The obtained polymer was transferred to another container, N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added, and it was stirred at 150°C for 15 minutes, and then filtered. Washing of the filtered polymer with a mixed solvent of NMP and boiling water was repeated twice. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added, and it was stirred for 10 minutes, and then filtered. Washing of the filtered polymer with boiling water was repeated twice. Thereafter, the polymer was dried at 120°C under vacuum for 4 hours. Thus, PAEK resin was obtained with a yield of 1.28 g and a yield of 75%.

[0055] (Example 4) To a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 1.85 g of diphosphorus pentoxide was gradually added to 18.50 g of methanesulfonic acid, and then the temperature was raised to 40°C and stirred for 2 hours. Thereafter, 0.682 g of 4,4'-oxybisbenzoic acid, 0.45 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid, and 0.748 g of 1,4-diphenoxybenzene were charged, and after raising the temperature to 80°C, the reaction was carried out for 22 hours. Thereafter, after adding 4-chlorophenol, it was cooled to 65°C, and water was added. The precipitated polymer was filtered off and washed with methanol and ion-exchanged water. The obtained polymer was transferred to another container, NMP was added, and it was stirred at 150°C for 15 minutes, and then filtered. Washing of the filtered polymer with a mixed solvent of NMP and boiling water was repeated twice. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added, and it was stirred for 10 minutes, and then filtered. Washing of the filtered polymer with boiling water was repeated twice. Thereafter, the polymer was dried at 120°C under vacuum for 4 hours. Thus, PAEK resin was obtained with a yield of 1.31 g and a yield of 77%.

[0056] (Example 5) Into a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 1.78 g of diphosphorus pentoxide was gradually added to 17.76 g of methanesulfonic acid, and then the temperature was raised to 40 °C and stirred for 2 hours. Then, 0.599 g of 4,4'-oxybisbenzoic acid, 0.618 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid, and 0.658 g of 1,4-diphenoxybenzene were charged. After raising the temperature to 80 °C, the reaction was carried out for 22 hours. Then, after adding 4-chlorophenol, it was cooled to 65 °C and water was added. The precipitated polymer was filtered off and washed with methanol and ion-exchanged water. The obtained polymer was transferred to another container, NMP was added, and it was stirred at 150 °C for 15 minutes, and then filtered. The filtered polymer was washed twice with a mixed solvent of NMP and boiling water. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added, and it was stirred for 10 minutes, and then filtered. The filtered polymer was washed twice with boiling water. Then, the polymer was dried at 120 °C under vacuum for 4 hours. Thus, a PAEK resin was obtained with a yield of 1.17 g and a yield of 68%.

[0057] (Example 6) Into a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 1.71 g of diphosphorus pentoxide was gradually added to 17.02 g of methanesulfonic acid, and then the temperature was raised to 40 °C and stirred for 2 hours. Then, 0.511 g of 4,4'-oxybisbenzoic acid, 0.789 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid, and 0.561 g of 1,4-diphenoxybenzene were charged. After raising the temperature to 80 °C, the reaction was carried out for 22 hours. Thereafter, after adding 4-chlorophenol, it was cooled to 65°C, and water was added. The precipitated polymer was filtered off and washed with methanol and ion-exchanged water. The obtained polymer was transferred to another container, NMP was added, and it was stirred at 150°C for 15 minutes, followed by filtration. The filtered polymer was washed twice with a mixed solvent of NMP and boiling water. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added, and it was stirred for 10 minutes, followed by filtration. The filtered polymer was washed twice with boiling water. Thereafter, the polymer was dried at 120°C under vacuum for 4 hours. As a result, PAEK resin was obtained with a yield of 1.08 g and a yield rate of 63%.

[0058] (Example 7) To a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 1.93 g of diphosphorus pentoxide was gradually added to 19.24 g of methanesulfonic acid, and then the temperature was raised to 40°C and stirred for 2 hours. Thereafter, 0.762 g of 4,4'-oxybisbenzoic acid, 0.294 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid, and 0.837 g of 1,4-diphenoxybenzene were charged, and after raising the temperature to 100°C, the reaction was carried out for 22 hours. Thereafter, after adding 4-chlorophenol, it was cooled to 65°C, and water was added. The precipitated polymer was filtered off and washed with methanol and ion-exchanged water. The obtained polymer was transferred to another container, NMP was added, and it was stirred at 150°C for 15 minutes, followed by filtration. The filtered polymer was washed twice with a mixed solvent of NMP and boiling water. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added, and it was stirred for 10 minutes, followed by filtration. The filtered polymer was washed twice with boiling water. Thereafter, the polymer was dried at 120°C under vacuum for 4 hours. As a result, PAEK resin was obtained with a yield of 1.33 g and a yield rate of 78%.

[0059] The glass transition temperature (Tg), crystal melting point (Tm), 5% weight loss temperature (Td5 (°C)), reduced viscosity (dL / g), and crystallization time (seconds) of the PAEK resins according to Examples 1 to 7 were measured, and the results are shown in Table 1.

[0060]

Table 1

[0061] (Comparative Example 1) To a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 1.26 g of phosphorus pentoxide was gradually added to 12.58 g of methanesulfonic acid, and then the temperature was raised to 40 °C and stirred for 2 hours. Then, 1.79 g of 4-(4-(4-phenoxyphenoxy)phenoxy)benzoic acid was charged, and after raising the temperature to 80 °C, the reaction was carried out for 22 hours. Thereafter, after adding 4-chlorophenol, it was cooled to 65 °C and water was added. The precipitated polymer was filtered off and washed with methanol and ion-exchanged water. The obtained polymer was transferred to another container, NMP was added and stirred at 150 °C for 15 minutes. Thereafter, the product was completely dissolved in NMP, and the target product could not be obtained. Therefore, in Comparative Example 1, various measurements could not be performed (see Table 2 below).

[0062] (Comparative Example 2) To a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 12.29 g of methanesulfonic acid and 2.95 g of phosphorus pentoxide were charged, the temperature was raised to 100 °C, and stirred for 4 hours. Thereafter, after cooling to 80 °C, 1.17 g of 4,4'-oxybisbenzoic acid, 0.581 g of 3-phenoxybenzoic acid and 1.20 g of 1,4-diphenoxybenzene were charged, and the reaction was carried out for 24 hours. Thereafter, it was cooled to room temperature, and the reaction solution was poured into methanol with strong stirring to precipitate the polymer. Then, the precipitated polymer was filtered. Furthermore, the precipitated polymer was washed twice with methanol. Next, it was washed twice with ion-exchanged water. Thereafter, solid-liquid separation was carried out, and the washed cake obtained by filtration was dried at 180 °C under vacuum for 10 hours to obtain PAEK resin: 2.56 g of yield at a yield of 92%.

[0063] (Comparative Example 3) Into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 12.29 g of methanesulfonic acid and 2.95 g of diphosphorus pentoxide were charged, heated to 100 °C, and stirred for 4 hours. After cooling to 80 °C, 1.17 g of 4,4'-oxybisbenzoic acid, 0.581 g of 3-phenoxybenzoic acid, and 1.20 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. After that, after adding 4-chlorophenol, it was cooled to 65 °C and water was added. The precipitated polymer was filtered off and washed with methanol and ion-exchanged water. The obtained polymer was transferred to another container, NMP was added, and it was stirred at 150 °C for 15 minutes and then filtered. Washing of the filtered polymer with a mixed solvent of NMP and boiling water was repeated twice. The obtained polymer was further transferred to another container, boiling water and 3N hydrochloric acid were added, stirred for 10 minutes, and then filtered. Washing of the filtered polymer with boiling water was repeated twice. Then, the polymer was dried at 120 °C under vacuum for 4 hours. As a result, PAEK resin was obtained with a yield of 2.20 g and a yield of 79%.

[0064] (Comparative Example 4) Into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 20.4 g of methanesulfonic acid and 2.04 g of diphosphorus pentoxide were charged, heated to 40 °C, and stirred for 2 hours. Then, 1.00 g of 1,4-diphenoxybenzene, 0.546 g of 4,4'-oxybisbenzoic acid, and 0.364 g of 3,4'-oxybisbenzoic acid were charged, heated to 60 °C, and reacted for 22 hours. After cooling to room temperature, the reaction solution was poured into vigorously stirred methanol to precipitate the polymer. Then, the precipitated polymer was filtered. The precipitated polymer was further washed twice with methanol. Next, it was washed twice with ion-exchanged water. Then, solid-liquid separation was performed, and the filtered washing cake was dried at 180 °C under vacuum for 10 hours to obtain a polymer.

[0065] (Comparative Example 5) As a comparative PEK resin, a commercially available VICTREX HT (manufactured by Victrex) was used as Comparative Example 5.

[0066] The glass transition temperature (Tg), crystal melting point (Tm), 5% weight loss temperature (Td5 (°C)), reduced viscosity (dL / g), and crystallization time (seconds) of the PAEK resins according to Comparative Examples 2 to 5 were measured, and the results are shown in Table 2.

[0067] [Table 2]

[0068] As shown in Table 1, the PAEK resin of the example can adjust the glass transition temperature (Tg) to 140°C or higher. Further, the PAEK resin of the example can be controlled to a crystal melting point (Tm) of 346°C or lower while maintaining such excellent heat resistance, and has good moldability. Further, since the PAEK resin of the example has a short crystallization time, the cooling time can be shortened and the moldability can be improved.

Claims

1. A method for producing a polyarylene ether ketone resin having repeating units represented by the following general formulas (1-1), (2-1), and (3-1), A method for producing a polyarylene ether ketone resin, which comprises 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 phosphorus pentoxide. 【Chemical Formula 1】 (In the formula, k is an integer of 1 to 3.) 【Chemical Formula 2】 (In the formula, m is an integer of 1 to 3.) 【Chemical Formula 3】 (In the formula, n is an integer of 0 to 2.) 【Chemical Formula 4】 (In the formula, k is an integer of 1 to 3.) 【Chemical Formula 5】 (In the formula, ma is an integer of 0 to 2.) 【Chemical Formula 6】 (In the formula, n is an integer of 0 to 2.)

2. The method for producing a polyarylene ether ketone resin according to claim 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 the range of (1-1)+(3-1):(2-1)=95:5 to 40:60 in terms of molar ratio.

3. The method for producing a polyarylene ether ketone resin according to claim 1, 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). 【Chemical Formula 7】 【Chemical Formula 8】 【Chemical Formula 9】

4. A method for manufacturing a molded article containing a polyarylene ether ketone resin, wherein the polyarylene ether ketone resin is produced by the method for producing a polyarylene ether ketone resin according to Claim 1, the method for manufacturing a molded article.

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