JP2022165147A - Polyarylene ether ketone resin, method for producing the same, and molded article - Google Patents

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 The present invention relates to a polyarylene ether ketone resin, a method for producing the same, and a molded article.

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 used continuously at high temperatures. Widely used for parts, medical parts, fibers, films, etc.

Conventionally, as a PAEK resin, two monomers, 4,4'-difluorobenzophenone and hydroquinone, are subjected to an aromatic nucleophilic substitution type solution polycondensation reaction using potassium carbonate in diphenylsulfone (see, for example, Patent Document 1). Polyether ether ketone resins having two ether groups and one ketone group in one repeating unit (hereinafter sometimes abbreviated as "PEEK resin") are well known.
In addition, instead of hydroquinone, a polyether ketone resin having one ether group and one ketone group in one repeating unit (hereinafter referred to as "PEK resin") is produced by using 4,4'-dihydroxybenzophenone. ) and polyether ketone ketone resin (hereinafter sometimes abbreviated as "PEKK resin") having one ether group and two ketone groups in one repeating unit.

However, the aromatic nucleophilic substitution type solution polycondensation reaction used in the production of these PAEK resins uses expensive 4,4'-difluorobenzophenone as a monomer, so the raw material cost is high and the reaction temperature is high. There is a drawback that the manufacturing process cost is high at 300° C. or higher, and the price of the resin tends to be high. In addition, an inorganic base is produced as a by-product, and the burden on the environment is large.

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

U.S. Pat. No. 4,320,224 U.S. Pat. No. 3,953,400 U.S. Pat. No. 3,065,205 JP-A-61-247731

PAEK resins such as the conventional PEEK resin, PEK resin, and PEKK resin described above are partially crystalline polymers, and their glass transition temperature is as high as 140°C or higher, and although they are excellent in heat resistance, they also have a crystal melting point higher than 340°C. However, it requires high temperature and pressure for molding, and has a disadvantage of poor moldability.

Accordingly, 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, which is excellent in moldability. Another object of the present invention is to provide a production method suitable for producing this polyarylene ether ketone resin.

For super engineering plastics such as PAEK resin, it has been considered desirable to use a polymer having a uniform structure with as little impurities as possible in order to achieve high heat resistance. Therefore, conventionally, the development of polymers having a single repeating unit has focused on PAEK resins. However, with a single repeating unit structure, it is difficult to control thermophysical properties such as the crystal melting point, and it is difficult to improve moldability.

As a result of intensive research to solve the above problems, the present inventors have found that the following repeating unit (1-1) and repeating unit (3-1), which are rigid and tough components, and the following repeating unit, which is a flexible component The inventors have found that the PAEK resin copolymerized with the unit (2-1) can lower the crystalline melting point and exhibit good moldability, and have completed the present invention.

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).

（式中、ｋは１～３のいずれかの整数である。）

(In the formula, k is any integer from 1 to 3.)

（式中、ｍ１、ｍ２及びｍ３は１～２のいずれかの整数である。）

(Wherein, m1, m2 and m3 are any integers from 1 to 2.)

（式中、ｎは０～２のいずれかの整数である。）
［２］前記繰り返し単位（２－１）のモル量と、前記繰り返し単位（３－１）のモル量との割合が、モル比で、６５：３５～３：９７の範囲である、［１］に記載のポリアリーレンエーテルケトン樹脂。
［３］下記一般式（１－２）で表されるモノマー（１－２）と、下記一般式（２－２）で表されるモノマー（２－２）と、下記一般式（３－２）で表されるモノマー（３－２）とを、有機スルホン酸及び五酸化二リンの存在下で反応させる、［１］または［２］に記載のポリアリーレンエーテルケトン樹脂の製造方法。

(Wherein, n is any integer from 0 to 2.)
[2] The molar ratio of the repeating unit (2-1) to the repeating unit (3-1) is in the range of 65:35 to 3:97. ] The polyarylene ether ketone resin according to .
[3] 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 the following general formula (3-2) ) and the monomer (3-2) represented by ) in the presence of an organic sulfonic acid and diphosphorus pentoxide.

（式中、ｋは１～３のいずれかの整数である。）

(In the formula, k is any integer from 1 to 3.)

（式中、ｍ２は１～２のいずれかの整数である。）

(Wherein, m2 is an integer from 1 to 2.)

（式中、ｎは０～２のいずれかの整数である。）
［４］前記モノマー（１－２）が下記モノマー（１－２－Ａ）であり、前記モノマー（２－２）が下記モノマー（２－２－Ａ）であり、前記モノマー（３－２）が下記モノマー（３－２－Ａ）である、請求項３に記載のポリアリーレンエーテルケトン樹脂の製造方法。

(Wherein, n is any integer from 0 to 2.)
[4] 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), the method for producing a polyarylene ether ketone resin according to claim 3.

［５］［１］または［２］に記載のポリアリーレンエーテルケトン樹脂を含む成形体。

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

INDUSTRIAL APPLICABILITY 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, which is excellent in moldability. Moreover, the present invention can provide a production method suitable for producing this polyarylene ether ketone resin.

The PAEK resin of the present invention and the method for producing the PAEK resin will be described in detail below. not something.

(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).

（式中、ｋは１～３のいずれかの整数である。）

(In the formula, k is any integer from 1 to 3.)

（式中、ｍ１、ｍ２及びｍ３は１～２のいずれかの整数である。）

(Wherein, m1, m2 and m3 are any integers from 1 to 2.)

（式中、ｎは０～２のいずれかの整数である。）

(Wherein, n is any integer from 0 to 2.)

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 repeating unit (3- The crystalline melting point can be controlled by adjusting the ratio of 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 glass transition point (Tg) of 140°C or higher, and a low crystalline melting point (Tm) of 340°C or lower, as shown by the results of the following examples. can be shown.

The repeating unit (2-1) in the PAEK resin of the present invention has a role of imparting an appropriate bending structure to the molecular chain of the PAEK resin, and is thought to reduce the associativity of the resulting polymer. It is believed that by incorporating repeating units (2-1) containing an ether bond in a specific ratio, the resulting polymer remains in solution while maintaining its solubility, preventing the termination of molecular growth due to precipitation. be done. As a result, the PAEK resin of the present invention exhibits a high molecular weight and good moldability.
Further, the repeating unit (2-1) has a role of giving a curved structure to the molecular chain of the PAEK resin as described above, and is considered to work effectively to lower the crystalline melting point of the PAEK resin.
Furthermore, the repeating unit (2-1) has a biphenyl (or terphenyl) structure, which is believed to effectively contribute to exhibiting good mechanical properties while exhibiting a high Tg. 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 biphenyl skeleton is substituted with a dicarboxyl group is used as the repeating unit (2-1), the biphenyl skeleton and the carboxylic acid that is the reaction point are conjugated. In order to form the system, the reactivity of the carboxylic acid is lowered, and there is a problem that the molecular weight is lowered when the amount of diphenic acid added is increased. On the other hand, in the repeating unit (2-1) of the PAEK resin of the present invention, the conjugated system is cleaved by an ether bond, so unlike diphenic acid and the like, it is thought that reactivity does not decrease. Therefore, it is considered that the repeating unit (2-1) in the PAEK resin of the present invention effectively contributes to the formation of a PAEK resin having a large molecular weight without lowering the molecular weight of the PAEK resin.

In the PAEK resin of the present invention, the molar ratio of the repeating unit (2-1) to the repeating unit (3-1) should be in the range of 65:35 to 3:97. It is preferably in the range of 63:37 to 7:93, more preferably in the range of 60:40 to 10:90, and preferably in the range of 55:45 to 20:80. More preferred.
By increasing the ratio of the molar amount of the repeating unit (2-1) to the molar amount of the repeating unit (3-1) within this ratio range, the crystal melting point (Tm) can be made relatively low. Thus, a PAEK resin having excellent moldability can be obtained. Further, by increasing the ratio of the molar amount of the repeating unit (3-1) to the molar amount of the repeating unit (2-1) within this ratio range, the glass transition temperature (Tg) is adjusted to be high. It is possible to increase the degree of crystallinity and crystal melting point (Tm), and it is possible to obtain a PAEK resin having excellent heat resistance.
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.
Also, the crystalline melting point (Tm) of the PAEK resin of the present invention can be adjusted to 350° C. or less, more preferably 340° C. or less. 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 having excellent heat resistance and moldability can be obtained.

(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 monomer (1-2) represented by the following general formula (1-2) and a monomer (2-) represented by the following general formula (2-2) 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 to produce a PAEK resin.

（式中、ｋは１～３のいずれかの整数である。）

(In the formula, k is any integer from 1 to 3.)

（式中、ｍ２は１～２のいずれかの整数である。）

(Wherein, m2 is an integer from 1 to 2.)

（式中、ｎは０～２のいずれかの整数である。）

(Wherein, n is any integer from 0 to 2.)

Examples of the monomer (1-2) include 4,4′-oxybisbenzoic acid (k=1), 1,4-bis(4-carboxyphenoxy)benzene (k=2), 4,4′-bis(p -carboxyphenoxy)diphenyl ether (k=3).

The above monomer (2-2) is diphenoxybiphenyl or diphenoxyterphenyl in which a 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 and the like. Among these, 2,2′-diphenoxy-1,1′-biphenyl (m2=1), 2,2″-diphenoxy-1,1′:4′,1″-terphenyl (m2=2) is preferred.

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

In a preferred embodiment of the method for producing a PAEK resin of the present invention, the above monomer (1-2) is the following monomer (1-2-A) when k = 1, and the above 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. method.

Since the method for producing the PAEK resin of the present invention is an aromatic electrophilic substitution type solution polycondensation reaction, it can be reacted under mild polymerization conditions. After mixing for 1 to 40 hours, the monomer (1-2), the monomer (2-2) and the monomer (3-2) are added to the mixture, mixed, and heated to From, for example, PAEK resin can be produced by collectively reacting at 40 to 100° C. for 1 to 100 hours.

As shown in the examples below, the method for producing the PAEK resin of the present invention can be carried out under mild conditions in which the polymerization step is carried out at 100° C. or lower. Moreover, the only by-product is water, which is not harmful to 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 must be used in the reaction process, a gas containing fluorine ions is generated during waste disposal, which has a large environmental impact. However, as long as methanesulfonic acid is used, for example, in the reaction step, the problem of environmental load does not arise.

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

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. is more preferred, and a range of 100:25 to 100:5 is even more preferred.

The ratio of the total amount of the monomer (1-2), the monomer (2-2) and the monomer (3-2) added to the total amount of the organic sulfonic acid and diphosphorus pentoxide is the mass ratio. , preferably in the range of 1:100 to 40:100, more preferably in the range of 2:100 to 30:100, even more preferably in the range of 5:100 to 25:100.
By using an organic sulfonic acid (e.g., especially methanesulfonic acid) and diphosphorus pentoxide in the production of the PAEK resin of the present invention, a PAEK resin exhibiting good properties can be produced. For example, if anhydrous aluminum chloride is used to produce PAEK resin instead of organic sulfonic acid and diphosphorus pentoxide, the polymerization rate is too fast and the polymer sequence is difficult to control.

The molar ratio of the amount of the monomer (2-2) added to the amount of the monomer (3-2) added in the reaction step is preferably in the range of 65:35 to 3:97, A range of 63:37 to 7:93 is more preferred, a range of 60:40 to 10:90 is particularly preferred, and a range of 55:45 to 20:80 is even more preferred. Further, in the present invention, a terminal blocking step of reacting the terminal carboxyl group with (3-2) may be further provided for the purpose of reducing the carboxyl group at the terminal of the polymer after the above reaction step. The ratio of the addition amount of (3-2) added in the terminal blocking step separately from (3-2) added in the reaction step is, (1-2) added in the reaction step, (2-2) , (3-2) in terms of molar ratio is preferably in the range of 30:100 to 0.1:100, more preferably in the range of 20:100 to 0.5:100, More preferably 15:100 to 1:100. Furthermore, it is also possible to use (2-2) instead of (3-2). The ratio of the amount of (2-2) to be added is 30:100 to 0.30 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. It is preferably in the range of 1:100, more preferably in the range of 20:100 to 0.5:100, even more preferably in the range of 15:100 to 1:100.

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

<Resin composition containing polyarylene ether ketone resin (PAEK resin)>
The PAEK resins of the present invention can be combined with other formulations to form resin compositions.
Other compounds are not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof 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.
A resin composition containing a PAEK resin more preferably contains a fibrous filler as a filler. Among fibrous fillers, carbon fiber and glass fiber are preferable because of their wide industrial application.

<Molded body containing polyarylene ether ketone resin (PAEK resin)>
The PAEK resin according to the present invention has excellent heat resistance, a high glass transition temperature (Tg), a low melting point, good moldability, and excellent impact resistance. Therefore, it can be used as a neat resin or as a compound of glass fiber, carbon fiber, fluororesin, or the like. By molding the PAEK resin according to the present invention, primary processed products such as rods, boards, films, and filaments, various injection processed products, various cut products, gears, bearings, composites, implants, 3D molded products, etc. can be produced, and the molded products obtained by molding these PAEK resins according to the present invention can be used for automobiles, aircraft, electric and electronic parts, medical parts, and the like.

(Glass transition point (Tg) and crystalline melting point (Tm))
Using a Perkin Elmer DSC device (Pyris Diamond), under a nitrogen flow of 50 mL / min, measurement was performed from 40 to 400 ° C. at a temperature increase of 20 ° C. / min, and the glass transition point (Tg) and crystalline melting point (Tm). asked for

(5% weight loss temperature (Td5 (°C)))
Using a TG-DTA device (Rigaku TG-8120), measurement was performed under a nitrogen flow of 20 mL/min at a heating rate of 20° C./min to measure the 5% weight loss temperature.

(Reduced viscosity (equivalent to molecular weight of PAEK resin) dL/g)
Using a Canon Fenske viscometer (manufactured by Shibata Scientific Co., Ltd.), at 25 ° C., measure the outflow time of the solvent and the polymer solution in which 0.3 g of polymer is dissolved in 100 mL of the solvent, and calculate the reduced viscosity with the following formula. Calculated. As a solvent, a mixed solution of chloroform and trifluoroacetic acid at a mass ratio of 4:1 was used.
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.

(tensile strength)
The tensile strength was measured using a Tensilon universal material testing machine RTG-1310 manufactured by A&D.

(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 stirrer, and the temperature was raised to 100°C. Stirred for 4 hours. 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. . After cooling to room temperature, the reaction solution was poured into strongly stirred methanol to precipitate a 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. Then, solid-liquid separation was performed, and the filtered washed cake was dried under vacuum at 180° C. for 4 hours to obtain a polymer.

(Example 2)
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 stirrer, and the temperature was raised to 100°C. Stirred for 4 hours. 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. . After cooling to room temperature, the reaction solution was poured into strongly stirred methanol to precipitate a 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. Then, solid-liquid separation was performed, and the filtered washed cake was dried under vacuum at 180° C. for 4 hours to obtain a polymer.

(Example 3)
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 stirrer, and the temperature was raised to 80°C. Stirred for 4 hours. 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. . After cooling to room temperature, the reaction solution was poured into strongly stirred methanol to precipitate a 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. Then, solid-liquid separation was performed, and the filtered washed cake was dried under vacuum at 180° C. for 4 hours to obtain a polymer.

(Example 4)
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 stirrer, and the temperature was raised to 100°C. Stirred for 4 hours. 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. . After cooling to room temperature, the reaction solution was poured into strongly stirred methanol to precipitate a 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. Then, solid-liquid separation was performed, and the filtered washed cake was dried under vacuum at 180° C. for 4 hours to obtain a polymer.

(Example 5)
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 stirrer, and the temperature was raised to 100°C. Stirred for 4 hours. 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. . After cooling to room temperature, the reaction solution was poured into strongly stirred methanol to precipitate a 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. Then, solid-liquid separation was performed, and the filtered washed cake was dried under vacuum at 180° C. for 4 hours to obtain a polymer.

(Example 6)
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 stirrer, and the temperature was raised to 100°C. Stirred for 4 hours. 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. . After cooling to room temperature, the reaction solution was poured into strongly stirred methanol to precipitate a 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. Then, solid-liquid separation was performed, and the filtered washed cake was dried under vacuum at 180° C. for 4 hours to obtain a polymer.

(Example 7)
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 stirrer, and the temperature was raised to 100°C. 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. After cooling to room temperature, the reaction solution was poured into strongly stirred methanol to precipitate a 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. Then, solid-liquid separation was performed, and the filtered washed cake was dried under vacuum at 180° C. for 4 hours to obtain a polymer.

(Example 8)
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 stirrer, and the temperature was raised to 100°C. 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 allowed to react for 24 hours. rice field. After cooling to room temperature, the reaction solution was poured into strongly stirred methanol to precipitate a 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. Then, solid-liquid separation was performed, and the filtered washed cake was dried under vacuum at 180°C for 4 hours to obtain a polymer.

(Example 9)
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 stirrer, and the temperature was raised to 100°C. Stirred for 4 hours. 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. . After cooling to room temperature, the reaction solution was poured into strongly stirred methanol to precipitate a 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. Then, solid-liquid separation was performed, and the filtered washed cake was dried under vacuum at 180° C. for 4 hours to obtain a polymer.

(Example 10)
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 stirrer, and the temperature was raised to 100°C. Stirred for 4 hours. 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. . After cooling to room temperature, the reaction solution was poured into strongly stirred methanol to precipitate a 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. Then, solid-liquid separation was performed, and the filtered washed cake was dried under vacuum at 180° C. for 4 hours to obtain a polymer.

(Example 11)
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 stirrer, and the temperature was raised to 100°C. Stirred for 4 hours. 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. . After cooling to room temperature, the reaction solution was poured into strongly stirred methanol to precipitate a 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. Then, solid-liquid separation was performed, and the filtered washed cake was dried under vacuum at 180° C. for 4 hours to obtain a polymer.

(Example 12)
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 stirrer, and the temperature was raised to 100°C. Stirred for 4 hours. 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. . After cooling to room temperature, the reaction solution was poured into strongly stirred methanol to precipitate a 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. Then, solid-liquid separation was performed, and the filtered washed cake was dried under vacuum at 180° C. for 4 hours to obtain a polymer.

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

(Comparative example 1)
818 g of methanesulfonic acid and 82 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 stirrer, and stirred at room temperature for 20 hours under a nitrogen atmosphere. After that, 34.7 g of 2,2'-biphenyldicarboxylic acid and 40.6 g of diphenyl ether (3-2) were charged, heated to 60°C, and reacted at the same temperature for 10 hours. After that, 24.7 g (1-2) of 4,4'-oxybisbenzoic acid was added and reacted at the same temperature for 40 hours. After cooling to room temperature, the reaction solution was poured into strongly stirred methanol to precipitate a polymer. Then, the precipitated polymer was filtered. Thereafter, solid-liquid separation was performed, and the filtered washed cake was dried under vacuum at 180° C. for 10 hours to obtain a polymer.
The glass transition temperature (Tg), crystalline 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. 2-1.

(Comparative example 2)
As a PEEK resin according to Comparative Example 2, 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 tensile strength were measured, and the results are shown in Table 2-1.

(Comparative Example 3)
As a PEK resin according to Comparative Example 3, 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), the tensile strength was measured and the results are shown in Table 2-1.

As shown in Tables 1-1 to 1-3, the PAEK resins of Examples can adjust the glass transition temperature (Tg) to 140 ° C. or higher, and the commercially available PEEK resin (Comparative Example 2) and PEK It can be seen that the resin has heat resistance equal to or superior to that of the resin (Comparative Example 3). In addition, the PAEK resins of the examples can be controlled to have a crystal melting point (Tm) of 340°C or less while maintaining such excellent heat resistance. Since it is lower than the crystalline melting point (Tm) of (Comparative Example 2) and PEK resin (Comparative Example 3), it can be seen that it has good moldability. In addition, the PAEK resin of the example exhibits a reduced viscosity comparable to that of the PEEK resin (Comparative Example 2) and the PEK resin (Comparative Example 3), and exhibits excellent tensile strength despite having a bent structure in the main chain. showed strength.
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) has a glass transition point of Td5 And the reduced viscosity was low, and the heat resistance was poor.

Claims (5)

A polyarylene ether ketone resin having repeating units represented by the following general formulas (1-1), (2-1) and (3-1).

(In the formula, k is any integer from 1 to 3.)

(Wherein, m1, m2 and m3 are any integers from 1 to 2.)

(Wherein, n is any integer from 0 to 2.) 2. The method according to claim 1, wherein the molar ratio of the repeating unit (2-1) to the repeating unit (3-1) is in the range of 65:35 to 3:97. of polyarylene ether ketone resins. 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 represented by the following general formula (3-2) 3. The method for producing a polyarylene ether ketone resin according to claim 1, wherein the monomer (3-2) to be obtained is reacted in the presence of an organic sulfonic acid and diphosphorus pentoxide.

(In the formula, k is any integer from 1 to 3.)

(Wherein, m2 is an integer from 1 to 2.)

(Wherein, n is any integer from 0 to 2.) 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), the method for producing a polyarylene ether ketone resin according to claim 3.

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