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

Abstract

To provide a polyarylene ether ketone resin which has a high glass-transition temperature for excellent heat resistance and a low crystalline melting point for excellent moldability.SOLUTION: The polyarylene ether ketone resin has repeating units represented by general formulas (1-1), (2-1) and (3-1).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 various fields such as electrical and electronic parts, automotive parts, medical parts, fibers, and film applications.

[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 (see, for example, Patent Document 1) using two monomers, 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 also exist.

[0004] However, the aromatic nucleophilic substitution type solution polycondensation reaction used for producing these PAEK resins has the disadvantages that the raw material cost is high because the expensive 4,4'-difluorobenzophenone is used as a monomer, and the reaction temperature is 300 °C or higher, so the manufacturing process cost is also high, and the price of the resin tends to be high. In addition, inorganic bases are by-produced, which imposes a large burden on the environment.

[0005] Therefore, an aromatic electrophilic substitution type solution polycondensation reaction for producing a PAEK resin is known, which uses no 4,4'-difluorobenzophenone in the monomer and has mild polymerization conditions. As an example of using the aromatic electrophilic substitution type solution polycondensation reaction, there is a method for producing a PEK resin by reacting 4-phenoxybenzoic acid chloride in the presence of hydrogen fluoride - boron trifluoride (see, for example, Patent Document 2), a method for producing a PEKK resin by reacting terephthalic acid chloride and diphenyl ether in the presence of a Lewis acid (see, for example, Patent Document 3), a method for producing a PEK resin by reacting 4-phenoxybenzoic acid in the presence of a mixture of methanesulfonic acid and diphosphorus pentoxide (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. Their glass transition temperatures are as high as 140°C or more, and they have excellent heat resistance. However, their crystal melting points are also higher than 340°C, and they require high temperatures and pressures for molding processing, which has the drawback 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 excellent in heat resistance and a low crystal melting point excellent in moldability. Another object of the present invention is to provide a production method suitable for producing this polyarylene ether ketone resin.

Means for Solving the Problems

[0009] For super engineering plastics such as PAEK resin, in order to achieve high heat resistance, a polymer with a uniform structure as free of impurities as possible has been desired. Therefore, conventionally, the development of polymers having a single repeating unit has been the center as PAEK resin. However, with a single repeating unit structure, it has been difficult to adjust thermal physical 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 inventor has 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, with the following repeating unit (2-1), which is a flexible component, can lower the crystal melting point and exhibit good moldability, and thus has 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

[0013]

Chemical formula

[0014]

Chemical formula

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

[0016] [Chemical formula] (In the formula, m2 is an integer of any one of 1 to 2.)

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

[0019] [Chemical formula]

[0020]

Chem.

Advantages of the Invention

[0021] The present invention can provide a polyarylene ether ketone resin having a high glass transition temperature excellent in heat resistance and a low crystal melting point excellent in moldability. Further, the present invention can provide a production method suitable for the production of this polyarylene ether ketone resin.

Modes 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]

Chem.

[0025]

Chem.

[0026]

Chem.

[0027] The PAEK resin of the present invention has repeating units (1-1) and (3-1), which are rigid and tough components, and repeating unit (2-1), which is a flexible component. Therefore, by adjusting the ratio of repeating unit (3-1) to repeating unit (2-1), the crystal melting point can be controlled. The PAEK resin of the present invention can lower the crystal melting point. As shown also from the results of the following examples, the PAEK resin of the present invention can exhibit a high glass transition temperature (Tg) of 140°C or higher and a low crystal melting point (Tm) of 340°C or lower.

[0028] Repeating unit (2-1) in the PAEK resin of the present invention has a role of imparting a suitable bending structure to the molecular chain of the PAEK resin, and is considered to cause a decrease in the associativity of the resulting polymer. By containing repeating unit (2-1) containing an ether bond at a specific ratio, it is considered that the resulting polymer remains in the solution while maintaining solubility, and the growth of molecules due to precipitation is prevented. As a result, the PAEK resin of the present invention exhibits a high molecular weight and good moldability. Also, repeating unit (2-1) has a role of imparting a bending structure to the molecular chain of the PAEK resin as described above, and is considered to be effectively working to lower the crystal melting point of the PAEK resin. Furthermore, the repeating unit (2-1) has a biphenyl (or terphenyl) structure, which is considered to effectively contribute to exhibiting good mechanical properties while showing a high Tg. Note that 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) in which a dicarboxyl group is substituted on the biphenyl skeleton is used as the repeating unit (2-1), the carboxylic acid, which is the reaction point with the biphenyl skeleton, forms a conjugated system, resulting in a decrease in the reactivity of the carboxylic acid. When the addition amount of diphenic acid is increased, there is a problem that the molecular weight decreases. On the other hand, since the conjugated system of the repeating unit (2-1) according to the PAEK resin of the present invention is cleaved by an ether bond, it is considered that, unlike diphenic acid or the like, the reactivity does not decrease. Therefore, it is considered that the repeating unit (2-1) according to the PAEK resin of the present invention effectively contributes to the formation of a PAEK resin having a large molecular weight without decreasing the molecular weight of the PAEK resin.

[0029] In the PAEK resin of the present invention, the ratio of the molar amount of the repeating unit (2-1) to the molar amount of the repeating unit (3-1) is preferably in the range of 65:35 to 3:97, more preferably in the range of 63:37 to 7:93, even more preferably in the range of 60:40 to 10:90, and even more preferably in the range of 55:45 to 20:80, in terms of molar ratio. Within this ratio range, by increasing the value of the ratio of the molar amount of the repeating unit (2-1) to the molar amount of the repeating unit (3-1), the crystal melting point (Tm) can be made relatively low, and a PAEK resin excellent in moldability can be obtained. Also, within this ratio range, by increasing the value of the ratio of the molar amount of the repeating unit (3-1) to the molar amount of the repeating unit (2-1), the glass transition temperature (Tg) can be adjusted to be high, and the crystallinity and the crystal melting point (Tm) can be increased, and a PAEK resin excellent in heat resistance 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 145°C or higher. More specifically, it can be adjusted to 140 to 160°C, preferably 145 to 155°C. In addition, the crystal 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 260 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 excellent in heat resistance and moldability can be obtained.

[0030] (Method for producing polyarylene ether ketone resin (PAEK resin)) One aspect of the method for producing the 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.

[0031]

Chemical formula

[0032]

Chemical formula

[0033]

Chemical formula

[0034] Examples of the above 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).

[0035] The above monomer (2-2) is diphenoxybiphenyl or diphenoxytriphenyl in which the phenoxy group can be substituted at any position of each phenyl group in biphenyl or terphenyl. The bonding position of the phenoxy group may be any of the ortho, meta, and para positions of each phenyl group in biphenyl or terphenyl. More specifically, examples of the monomer (2-2) include 2,2'-diphenoxy-1,1'-biphenyl, 2,3'-diphenoxy-1,1'-biphenyl, 2,4'-diphenoxy-1,1'-biphenyl, 3,3'-diphenoxy-1,1'-biphenyl, 3,4'-diphenoxy-1,1'-biphenyl, 4,4'-diphenoxy-1,1'-biphenyl, 2,2''-diphenoxy-1,1':4',1''-terphenyl, 2,3''-diphenoxy-1,1':4',1''-terphenyl, 2,4''-diphenoxy-1,1':4',1''-terphenyl, 3,3''-diphenoxy-1,1':4',1''-terphenyl, 3,4''-diphenoxy-1,1':4',1''-terphenyl, 4,4''-diphenoxy-1,1':4',1''-terphenyl, etc. Among these, 2,2'-diphenoxy-1,1'-biphenyl (m2 = 1) and 2,2''-diphenoxy-1,1':4',1''-terphenyl (m2 = 2) are preferred.

[0036] Examples of the above monomer (3-2) include diphenyl ether (n = 0), 1,4'-diphenoxybenzene (n = 1), and 4,4'-oxybis(phenoxybenzene) (n = 2).

[0037] 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 m2 = 1, 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.

[0038] [Chemical formula]

[0039] [Chemical formula]

[0040] [Chemical formula]

[0041] 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. For example, organic sulfonic acid and phosphorus pentoxide are mixed at 20 to 100°C for 1 to 40 hours, and then the monomers (1-2), (2-2), and (3-2) are added to this mixed solution, mixed, and the temperature is raised. Then, for example, the PAEK resin can be produced by reacting all at once at 40 to 100°C for 1 to 100 hours.

[0042] As shown in the following examples, the production method of the PAEK resin of the present invention can be carried out under mild conditions where the polymerization step is 100°C or lower. Moreover, the by-product is only water that does not burden the environment. The production method of the PAEK resin of the present invention does not contain fluorine in the reaction monomers or solvents. For example, in the reaction process, if trifluoromethanesulfonic acid must be used, in waste treatment, a gas containing fluoride ions is generated, resulting in 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.

[0043] There are no particular restrictions on the organic sulfonic acid, and it 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.

[0044] 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.

[0045] The ratio of the total addition amount of the above monomers (1-2), (2-2), and (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.

[0046] The ratio of the addition amount of the monomer (2-2) to the addition amount of the monomer (3-2) in the above reaction step is preferably in the range of 65:35 to 3:97, more preferably in the range of 63:37 to 7:93, particularly preferably in the range of 60:40 to 10:90, and even more preferably in the range of 55:45 to 20:80 in terms of molar ratio. Further, in the present invention, after the above reaction step, a terminal capping step of reacting the terminal carboxyl group with (3-2) can be further provided for the purpose of reducing the carboxyl group at the polymer terminal. The ratio of the addition amount of (3-2) added in the terminal capping step separately from (3-2) added in the above 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 with respect to the total amount of (1-2), (2-2), and (3-2) added in the above reaction step. Further, it is also possible to use (2-2) instead of (3-2). The ratio of the addition amount of (2-2) 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 with respect to the total amount of (1-2), (2-2), and (3-2) added in the above reaction step.

[0047] The ratio of the addition amount of the monomer (2-2), the total addition amount of the monomer (3-2), and the addition amount of the monomer (1-2) is preferably in the range of (2-2)+(3-2):(1-1)=85:100 to 115:100, more preferably in the range of 90:100 to 110:100, particularly preferably in the range of 92:100 to 108:100, and especially preferably in the range of 98:100 to 105:100 from the viewpoint of tensile strength in terms of molar ratio.

[0048] <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. Other formulations are not particularly limited and can be appropriately selected according to the purpose. Examples include inorganic fillers, organic fillers, and the like. The shape of the filler is not particularly limited. Examples include particulate, plate-like, fibrous fillers, and the like. 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.

[0049] <Molded article containing polyarylene ether ketone resin (PAEK resin)> The PAEK resin according to the present invention is excellent in heat resistance and has a high glass transition temperature (Tg). It can also be made to have a low melting point, and has good molding processability 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, 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. The molded articles formed by molding the PAEK resin according to the present invention can be used in automobiles, aircraft, electric and electronic products, medical members, etc.

Examples

[0050] (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 determine the glass transition point (Tg) and the crystal melting point (Tm).

[0051] (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.

[0052] (Reduced viscosity (equivalent to the molecular weight of the PAEK resin) dL / g) Using a Cannon-Fenske viscometer (manufactured by Shibata Kagaku Co., Ltd.), at 25 °C, the flow times of the solvent and a polymer solution prepared by dissolving 0.3 g of the polymer in 100 mL of the solvent were measured, and the reduced viscosity was calculated using the following formula. As the solvent, a solution prepared 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 flow time of the solvent, t represents the flow time of the polymer solution, and c represents the polymer concentration (g / dL) in the polymer solution.

[0053] (Tensile strength) The tensile strength was measured using a Tensilon universal material testing machine RTG-1310 manufactured by A&D Company, Ltd.

[0054] (Example 1) 136.41 g of methanesulfonic acid and 32.74 g of diphosphorus pentoxide were charged into a four-necked separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, heated to 100 °C, and stirred for 4 hours. Then, after cooling to 60 °C, 14.85 g of 4,4'-oxybisbenzoic acid, 11.68 g of 2,2'-diphenoxy-biphenyl, and 6.03 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. Then, after cooling to room temperature, the reaction solution was poured into vigorously stirred methanol to precipitate the polymer. And the precipitated polymer was filtered. Furthermore, the precipitated polymer was washed twice with methanol. Next, it was washed twice with ion-exchanged water. Then, solid-liquid separation was performed, and the washed cake obtained by filtration was dried at 180 °C under vacuum for 4 hours to obtain the polymer.

[0055] (Example 2) Into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 136.41 g of methanesulfonic acid and 32.74 g of diphosphorus pentoxide were charged, heated to 100 °C, and stirred for 4 hours. Then, after cooling to 60 °C, 14.85 g of 4,4'-oxybisbenzoic acid, 11.97 g of 2,2'-diphenoxy-biphenyl, and 6.03 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. Then, it was cooled to room temperature, and the reaction solution was poured into vigorously stirred methanol to precipitate the polymer. And the precipitated polymer was filtered. Furthermore, the precipitated polymer was washed twice with methanol. Next, it was washed twice with ion-exchanged water. Then, solid-liquid separation was performed, and the washed cake obtained by filtration was dried at 180 °C under vacuum for 4 hours to obtain the polymer.

[0056] (Example 3) Into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 136.41 g of methanesulfonic acid and 32.74 g of diphosphorus pentoxide were charged, heated to 80 °C, and stirred for 4 hours. Then, after cooling to 80 °C, 14.85 g of 4,4'-oxybisbenzoic acid, 11.95 g of 2,2'-diphenoxy-biphenyl, and 6.35 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. Then, it was cooled to room temperature, and the reaction solution was poured into vigorously stirred methanol to precipitate the polymer. And the precipitated polymer was filtered. Furthermore, the precipitated polymer was washed twice with methanol. Next, it was washed twice with ion-exchanged water. Then, solid-liquid separation was performed, and the washed cake obtained by filtration was dried at 180 °C under vacuum for 4 hours to obtain the polymer.

[0057] (Example 4) Into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 136.41 g of methanesulfonic acid and 32.74 g of diphosphorus pentoxide were charged, the temperature was raised to 100 °C, and the mixture was stirred for 4 hours. Then, after cooling to 60 °C, 14.85 g of 4,4'-oxybisbenzoic acid, 9.73 g of 2,2'-diphenoxy-biphenyl, and 7.54 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. Then, after cooling to room temperature, the reaction solution was poured into vigorously stirred methanol to precipitate the polymer. And 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 carried out, and the washed cake obtained by filtration was dried at 180 °C under vacuum for 4 hours to obtain the polymer.

[0058] (Example 5) Into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 136.41 g of methanesulfonic acid and 32.74 g of diphosphorus pentoxide were charged, the temperature was raised to 100 °C, and the mixture was stirred for 4 hours. Then, after cooling to 60 °C, 14.85 g of 4,4'-oxybisbenzoic acid, 9.73 g of 2,2'-diphenoxy-biphenyl, and 7.54 g of 1,4-diphenoxybenzene were charged and reacted for 48 hours. Then, after cooling to room temperature, the reaction solution was poured into vigorously stirred methanol to precipitate the polymer. And 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 carried out, and the washed cake obtained by filtration was dried at 180 °C under vacuum for 4 hours to obtain the polymer.

[0059] (Example 6) Into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 136.41 g of methanesulfonic acid and 32.74 g of diphosphorus pentoxide were charged, heated to 100 °C, and stirred for 4 hours. Then, after cooling to 80 °C, 14.85 g of 4,4'-oxybisbenzoic acid, 9.73 g of 2,2'-diphenoxy-biphenyl, and 7.54 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. Then, it was cooled to room temperature, and the reaction solution was poured into vigorously stirred methanol to precipitate the polymer. And the precipitated polymer was filtered. Furthermore, the precipitated polymer was washed twice with methanol. Next, it was washed twice with ion-exchanged water. Then, solid-liquid separation was performed, and the washed cake obtained by filtration was dried at 180 °C under vacuum for 4 hours to obtain the polymer.

[0060] (Example 7) Into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 136.41 g of methanesulfonic acid and 32.74 g of diphosphorus pentoxide were charged, heated to 100 °C, and stirred for 4 hours. Then, 14.85 g of 4,4'-oxybisbenzoic acid, 9.73 g of 2,2'-diphenoxy-biphenyl, and 7.54 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. Then, it was cooled to room temperature, and the reaction solution was poured into vigorously stirred methanol to precipitate the polymer. And the precipitated polymer was filtered. Furthermore, the precipitated polymer was washed twice with methanol. Next, it was washed twice with ion-exchanged water. Then, solid-liquid separation was performed, and the washed cake obtained by filtration was dried at 180 °C under vacuum for 4 hours to obtain the polymer.

[0061] (Example 8) Into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 136.41 g of methanesulfonic acid and 32.74 g of diphosphorus pentoxide were charged, heated to 100 °C, and stirred for 4 hours. Then, after cooling to 80 °C, 14.85 g of 4,4'-oxybisbenzoic acid, 9.92 g of 2,2'-diphenoxy-biphenyl, and 7.69 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. Then, after cooling to room temperature, the reaction solution was poured into vigorously stirred methanol to precipitate the polymer. And 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 washed cake obtained by filtration was dried at 180 °C under vacuum for 4 hours to obtain the polymer.

[0062] (Example 9) Into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 136.41 g of methanesulfonic acid and 32.74 g of diphosphorus pentoxide were charged, heated to 100 °C, and stirred for 4 hours. Then, after cooling to 60 °C, 14.85 g of 4,4'-oxybisbenzoic acid, 7.78 g of 2,2'-diphenoxy-biphenyl, and 9.05 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. Then, after cooling to room temperature, the reaction solution was poured into vigorously stirred methanol to precipitate the polymer. And 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 washed cake obtained by filtration was dried at 180 °C under vacuum for 4 hours to obtain the polymer.

[0063] (Example 10) Into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 136.41 g of methanesulfonic acid and 32.74 g of diphosphorus pentoxide were charged, heated to 100 °C, and stirred for 4 hours. Then, after cooling to 60 °C, 14.85 g of 4,4'-oxybisbenzoic acid, 7.78 g of 2,2'-diphenoxy-biphenyl, and 9.23 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. Then, it was cooled to room temperature, and the reaction solution was poured into vigorously stirred methanol to precipitate the polymer. And the precipitated polymer was filtered. Furthermore, the precipitated polymer was washed twice with methanol. Next, it was washed twice with ion-exchanged water. Then, solid-liquid separation was carried out, and the washed cake obtained by filtration was dried at 180 °C under vacuum for 4 hours to obtain the polymer.

[0064] (Example 11) Into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 136.41 g of methanesulfonic acid and 32.74 g of diphosphorus pentoxide were charged, heated to 100 °C, and stirred for 4 hours. Then, after cooling to 60 °C, 14.85 g of 4,4'-oxybisbenzoic acid, 3.89 g of 2,2'-diphenoxy-biphenyl, and 12.07 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. Then, it was cooled to room temperature, and the reaction solution was poured into vigorously stirred methanol to precipitate the polymer. And the precipitated polymer was filtered. Furthermore, the precipitated polymer was washed twice with methanol. Next, it was washed twice with ion-exchanged water. Then, solid-liquid separation was carried out, and the washed cake obtained by filtration was dried at 180 °C under vacuum for 4 hours to obtain the polymer.

[0065] (Example 12) Into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 136.41 g of methanesulfonic acid and 32.74 g of diphosphorus pentoxide were charged, heated to 100 °C, and stirred for 4 hours. Then, after cooling to 60 °C, 14.85 g of 4,4'-oxybisbenzoic acid, 1.95 g of 2,2'-diphenoxy-biphenyl, and 13.58 g of 1,4-diphenoxybenzene were charged and reacted for 24 hours. Then, it was cooled to room temperature, and the reaction solution was poured into vigorously stirred methanol to precipitate the polymer. And the precipitated polymer was filtered. Furthermore, the precipitated polymer was washed twice with methanol. Next, it was washed twice with ion-exchanged water. Then, solid-liquid separation was performed, and the washed cake obtained by filtration was dried at 180 °C under vacuum for 4 hours to obtain the polymer.

[0066] The glass transition temperature (Tg), crystal melting point (Tm), 5% weight loss temperature (Td5 (°C)), reduced viscosity (dL / g), and tensile strength of the PAEK resins according to Examples 1 to 12 were measured, and the results are shown in Tables 1-1 to 1-3.

[0067] (Comparative Example 1) Into a four-neck separable flask equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, 818 g of methanesulfonic acid and 82 g of diphosphorus pentoxide were charged and stirred at room temperature for 20 hours under a nitrogen atmosphere. Then, 34.7 g of 2,2'-biphenyldicarboxylic acid and 40.6 g (3-2) of diphenyl ether were charged, heated to 60 °C, and reacted at the same temperature for 10 hours. Then, 24.7 g (1-2) of 4,4'-oxybisbenzoic acid was added and reacted at the same temperature for 40 hours. Then, it was cooled to room temperature, and the reaction solution was poured into vigorously stirred methanol to precipitate the polymer. And the precipitated polymer was filtered. Then, solid-liquid separation was performed, and the washed cake obtained by filtration was dried at 180 °C under vacuum for 10 hours to obtain the polymer. The glass transition temperature (Tg), crystal melting point (Tm), 5% weight loss temperature (Td5 (°C)), reduced viscosity (dL / g), and tensile strength of the PAEK resin according to Comparative Example 1 were measured, and the results are shown in Table 2-1.

[0068] (Comparative Example 2) As the PEEK resin according to Comparative Example 2, VICTREX PEEK 150P manufactured by Victrex was prepared, and its glass transition temperature (Tg), crystal melting point (Tm), 5% weight loss temperature (Td5 (°C)), reduced viscosity (dL / g), and tensile strength were measured, and the results are shown in Table 2-1.

[0069] (Comparative Example 3) As the PEK resin according to Comparative Example 3, VICTREX HT manufactured by Victrex was prepared, and its glass transition temperature (Tg), crystal melting point (Tm), 5% weight loss temperature (Td5 (°C)), reduced viscosity (dL / g), and tensile strength were measured, and the results are shown in Table 2-1.

[0070] [Table 1-1]

[0071] [Table 1-2]

[0072] [Table 1-3]

[0073] [Table 2-1]

[0074] As shown in Table 1-1 to Table 1-3, the PAEK resin of the example can adjust the glass transition temperature (Tg) to 140°C or higher, and it can be seen that it is a resin with heat resistance equivalent to or better than that of commercially available PEEK resin (Comparative Example 2) and PEK resin (Comparative Example 3). Further, the PAEK resin of the example can be controlled to have a crystal melting point (Tm) of 340°C or lower while maintaining such excellent heat resistance. Since this crystal melting point (Tm) is lower than the crystal melting points (Tm) of commercially available PEEK resin (Comparative Example 2) and PEK resin (Comparative Example 3), it can be seen that it has good moldability. Also, the PAEK resin of the example showed a reduced viscosity similar to that of PEEK resin (Comparative Example 2) and PEK resin (Comparative Example 3), and showed excellent tensile strength despite containing a bent structure in the main chain. On the other hand, the PAEK resin of Comparative Example 1 using diphenic acid (2,2'-biphenyldicarboxylic acid) instead of the repeating unit (2-1) had a lower glass transition point, Td5, and reduced viscosity and was inferior in heat resistance compared to the PAEK resin of the example.

Claims

1. A polyarylene ether ketone resin having repeating units represented by the following general formulas (1-1), (2-1), and (3-1). 【Chemical 1】 (In the formula, k is an integer of 1 to 3.) [Chemical Formula 2] (In the formula, m1, m2, and m3 are integers of 1 to 2. However, the bonding position of the phenoxy group is the ortho position of each phenyl group in biphenyl or terphenyl.) 【Chemical Formula 3】 (In the formula, n is an integer of 0 to 2.)

2. The polyarylene ether ketone resin according to Claim 1, wherein the ratio of the molar amount of the repeating unit (2-1) to the molar amount of the repeating unit (3-1) is in the range of 65:35 to 3:97 in terms of molar ratio.

3. 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), 【Chemical 4】 (In the formula, k is an integer of 1 to 3.) [Chemical Formula 5] (In the formula, m1, m2, and m3 are integers of 1 to 2.) 【Chemical Formula 6】 (In the formula, n is an integer of 0 to 2.) The method for producing a polyarylene ether ketone 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. [Chemical Formula 7] (In the formula, k is an integer of 1 to 3.) [Chemical 8] (In the formula, m2 is an integer of 1 to 2.) 【Chemical Formula 9】 (In the formula, n is an integer of 0 to 2.)

4. The method for producing a polyarylene ether ketone resin according to Claim 3, 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 10】 【Chemical 11】 【Chemical Formula 12】

5. A molded article containing the polyarylene ether ketone resin according to Claim 1 or 2.

Images