阅读说明：本技术 聚亚芳基醚酮树脂及其制造方法、以及成形品 (Polyarylene ether ketone resin, method for producing same, and molded article ) 是由 松冈龙一 西田祥子 桝本雅也 前山胜也 于 2019-01-22 设计创作，主要内容包括：一种具有下述通式(1-1)所示的重复单元(1-1)和下述通式(2-1)所示的重复单元(2-1)的聚亚芳基醚酮树脂。式中,R为氢原子或碳数1～4的烷基,Ar<Sub>1</Sub>和Ar<Sub>2</Sub>为下述通式(3-1)所示的2价有机基团(3-1),n为0或1。<Image he="390" wi="700" file="DDA0002553617460000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(A polyarylene ether ketone resin having a repeating unit (1-1) represented by the following general formula (1-1) and a repeating unit (2-1) represented by the following general formula (2-1). Wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Ar 1 And Ar 2 Is a 2-valent organic group (3-1) represented by the following general formula (3-1), and n is 0 or 1.)

1. A polyarylene ether ketone resin having a repeating unit (1-1) represented by the following general formula (1-1) and a repeating unit (2-1) represented by the following general formula (2-1),

in the formulas (1-1) and (2-1), R is hydrogen atom or alkyl with 1-4 carbon atoms, Ar₁And Ar₂Is a 2-valent organic group (3-1) represented by the following general formula (3-1),

in the formula (3-1), n is 0 or 1.

2. The polyarylene ether ketone resin according to claim 1, wherein the ratio of the repeating unit (1-1) to the repeating unit (2-1) is in a range of 95: 5 to 50: 50 in terms of a molar ratio.

3. The method for producing a polyarylene ether ketone resin according to claim 1 or 2, wherein a monomer (1-2) represented by the following formula (1-2), a monomer (2-2) represented by the following formula (2-2), and a monomer (3-2) represented by the following formula (3-2) are reacted in the presence of an organic sulfonic acid and phosphorus pentoxide,

in the formula (2-2), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

in the formula (3-2), n is 0 or 1.

4. The method for producing a polyarylene ether ketone resin according to claim 1 or 2, wherein a reaction product (2-3) represented by the following general formula (2-3) is synthesized by reacting a monomer (2-2) represented by the following general formula (2-2) with a monomer (3-2) represented by the following general formula (3-2), and the reaction product (2-3) is reacted with a monomer (1-2) represented by the following general formula (1-2),

in the formula (2-2), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

in the formula (3-2), n is 0 or 1,

in the formula (2-3), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m is an integer of 0 or more, Ar₃Is a 2-valent organic group (3-3) represented by the following general formula (3-3), Ar₄Is a 1-valent organic group (3-4) represented by the following general formula (3-4),

in the formula (3-3), n is 0 or 1,

in the formula (3-4), n is 0 or 1.

5. The method for producing a polyarylene ether ketone resin according to claim 3 or 4, wherein the ratio of the amount of the monomer (2-2) to the amount of the monomer (3-2) is in the range of 5: 100 to 50: 100 in terms of a molar ratio.

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

Technical Field

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

The present application claims priority based on japanese patent application No. 2018-008442, filed in japan on 22/1/2018, and the contents thereof are incorporated herein.

Background

Polyarylene ether ketone resins (hereinafter, also referred to simply as "PAEK resins") are widely used in applications such as electric and electronic parts, automobile parts, medical parts, fibers, and films as crystalline super engineering plastics which are excellent in heat resistance, chemical resistance, toughness, and the like and can be continuously used at high temperatures.

Conventionally, as PAEK resins, polyether ether ketone resins (hereinafter, also referred to simply as "PEEK resins") having 2 ether groups and 1 ketone group in 1 repeating unit, which are produced by an aromatic nucleophilic substitution solution polycondensation reaction using potassium carbonate in diphenyl sulfone (see patent document 1), using two monomers, 4' -difluorobenzophenone and hydroquinone, have been known. Further, there are polyether ketone resins having 1 ether group and 1 ketone group in each repeating unit (hereinafter, may be abbreviated as "PEK resin") and polyether ketone resins having 1 ether group and 2 ketone groups in each repeating unit (hereinafter, may be abbreviated as "PEKK resin") which are produced by using 4, 4' -dihydroxybenzophenone instead of hydroquinone.

However, the aromatic nucleophilic substitution solution polycondensation reaction used for producing these PAEK resins has disadvantages that the raw material cost is high because expensive 4, 4' -difluorobenzophenone is used as a monomer, and the production process cost is high because the reaction temperature is 300 ℃ or higher, and the price of the resin tends to be high.

Thus, it is known that: aromatic electrophilic substitution solution polycondensation reaction for preparing PAEK resin under mild polymerization condition without using 4, 4' -difluorobenzophenone as monomer. As examples of the polycondensation reaction using an aromatic electrophilic substitution type solution, there are: a PEK resin obtained by a method of reacting 4-phenoxybenzoyl chloride in the presence of hydrofluoric acid/boron trifluoride (patent document 2), a PEKK resin obtained by a method of reacting terephthaloyl chloride and diphenyl ether in the presence of a lewis acid (patent document 3), a PEK resin obtained by a method of reacting 4-phenoxybenzoic acid in the presence of a mixture of methanesulfonic acid and phosphorus pentoxide (patent document 4), and the like.

Disclosure of Invention

Problems to be solved by the invention

The PAEK resin such as the conventional PEEK resin, PEK resin, PEKK resin, etc. is a partially crystalline polymer, and has a high glass transition temperature of 140 ℃ or higher and excellent heat resistance, but has a crystal melting point of 340 ℃ or higher, and requires a high temperature and pressure for molding, resulting in poor moldability.

The purpose of the present invention is to provide a polyarylene ether ketone resin which has excellent heat resistance, has a high glass transition temperature, and can control the crystal melting point while maintaining high crystallinity, and has good molding processability. Another object of the present invention is to provide a production method suitable for producing the polyarylene ether ketone resin.

Means for solving the problems

For super engineering plastics such as PAEK resins, polymers having a uniform structure and containing as little impurities as possible are desired in order to achieve high heat resistance. Therefore, in the past, the development of a polymer having a single repeating unit has been centered as a PAEK resin. However, it is difficult to adjust the thermal properties such as the crystal melting point of a single repeating unit structure, and it is difficult to improve the molding processability.

The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that a PAEK resin obtained by copolymerizing a repeating unit (1-1) described below as a rigid and tough component and a repeating unit (2-1) described below as a soft component can control the crystal melting point while maintaining high crystallinity by adjusting the ratio of the repeating unit (1-1) to the repeating unit (2-1), and exhibits good moldability, and have completed the present invention.

That is, the present invention includes the following aspects.

[1] A polyarylene ether ketone resin having a repeating unit (1-1) represented by the following general formula (1-1) and a repeating unit (2-1) represented by the following general formula (2-1).

(wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Ar₁And Ar₂Is a 2-valent organic group (3-1) represented by the following general formula (3-1). )

(wherein n is 0 or 1.)

[2] The polyarylene ether ketone resin according to [1], wherein the ratio of the repeating unit (1-1) to the repeating unit (2-1) is in a range of 95: 5 to 50: 50 in terms of a molar ratio.

[3] The method for producing a polyarylene ether ketone resin according to [1] or [2], wherein a monomer (1-2) represented by the following formula (1-2), a monomer (2-2) represented by the following formula (2-2), and a monomer (3-2) represented by the following formula (3-2) are reacted in the presence of an organic sulfonic acid and phosphorus pentoxide.

(wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

(wherein n is 0 or 1.)

[4] The method for producing a polyarylene ether ketone resin according to [1] or [2], which comprises reacting a monomer (2-2) represented by the following general formula (2-2) with a monomer (3-2) represented by the following general formula (3-2) to synthesize a reaction product (2-3) represented by the following general formula (2-3), and reacting the reaction product (2-3) with the monomer (1-2) represented by the following general formula (1-2).

(wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

(wherein n is 0 or 1.)

(wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m is an integer of 0 or more, Ar₃Is a 2-valent organic group (3-3) represented by the following general formula (3-3), Ar₄Is a 1-valent organic group (3-4) represented by the following general formula (3-4). )

(wherein n is 0 or 1.)

(wherein n is 0 or 1.)

[5] The method for producing a polyarylene ether ketone resin according to [3] or [4], wherein a ratio of an amount of the monomer (2-2) to an amount of the monomer (3-2) is in a range of 5: 100 to 50: 100 in terms of a molar ratio.

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

Effects of the invention

The polyarylene ether ketone resin of the present invention has excellent heat resistance, a high glass transition temperature, and good moldability, and can control the crystal melting point while maintaining high crystallinity. The method for producing a polyarylene ether ketone resin of the present invention is suitable for producing the polyarylene ether ketone resin of the present invention.

Detailed Description

(polyarylene ether ketone resin (PAEK resin))

The PAEK resin of the present invention has a repeating unit (1-1) represented by the following general formula (1-1) and a repeating unit (2-1) represented by the following general formula (2-1).

(wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Ar₁And Ar₂Is a 2-valent organic group (3-1) represented by the following general formula (3-1). )

(wherein n is 0 or 1.)

Since the PAEK resin of the present invention has repeating units (1-1) as rigid and tough components and repeating units (2-1) as soft components, the crystal melting point (Tm) can be controlled while maintaining high crystallinity by adjusting the ratio of the repeating units (1-1) to the repeating units (2-1), and good molding processability can be exhibited.

In the PAEK resin of the present invention, the molar ratio of the repeating unit (1-1) to the repeating unit (2-1) is preferably in the range of 95: 5 to 50: 50, more preferably in the range of 92: 8 to 53: 48, and particularly preferably in the range of 90: 10 to 55: 45. Within the range of the ratio, by increasing the value of the ratio of the molar amount of the repeating unit (1-1) to the molar amount of the repeating unit (2-1), the glass transition temperature (Tg) can be adjusted to be high, the crystallinity and the crystal melting point (Tm) can be increased, and a PAEK resin having excellent heat resistance can be produced. In addition, within the range of the ratio, by decreasing the value of the ratio of the molar amount of the repeating unit (1-1) to the molar amount of the repeating unit (2-1), the crystal melting point (Tm) can be lowered, and a PAEK resin having excellent moldability can be produced. By adjusting the ratio, the glass transition temperature (Tg) of the PAEK resin of the present invention can be adjusted to 120 to 150 ℃, preferably 125 to 150 ℃, more preferably 130 to 148 ℃, the crystal melting point (Tm) can be adjusted to 260 to 340 ℃, preferably 285-338 ℃, more preferably 290 to 336 ℃, the crystallinity can be adjusted to 26 to 40%, preferably 28 to 39%, more preferably 30 to 38%, the 5% weight loss temperature (Td5) can be adjusted to 500 to 550 ℃, preferably 510 to 545 ℃, more preferably 525 to 540 ℃, and the ratio of the repeating unit (1-1) to the repeating unit (2-1) is optimized, thereby enabling the production of a PAEK resin having both excellent heat resistance and moldability.

(method for producing polyarylene Ether Ketone resin (PAEK resin))

One embodiment of the method for producing a PAEK resin of the present invention is a method for producing a PAEK resin, in which a monomer (1-2) represented by the following formula (1-2), a monomer (2-2) represented by the following formula (2-2), and a monomer (3-2) represented by the following formula (3-2) are reacted in the presence of an organic sulfonic acid and phosphorus pentoxide.

(wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

(wherein n is 0 or 1.)

Specifically, the PAEK resin can be produced by mixing an organic sulfonic acid and phosphorus pentoxide at 20 to 100 ℃ for 1 to 40 hours, adding and mixing the monomer (1-2), the monomer (2-2), and the monomer (3-2) to the mixture, heating the mixture, and then reacting the mixture at 40 to 80 ℃ for 1 to 100 hours.

Examples of the organic sulfonic acid include methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid (toluenesulfonic acid).

The weight ratio of the addition amount of the organic sulfonic acid to the addition amount of the phosphorus pentoxide is preferably 25: 100 to 1: 100, more preferably 20: 100 to 2: 100, and most preferably 15: 100 to 5: 100.

Examples of the monomer (2-2) include isophthalic acid, 5-methylisophthalic acid, 2-methylisophthalic acid, 4-methylisophthalic acid, 5-ethylisophthalic acid, 2-ethylisophthalic acid, 4-ethylisophthalic acid, 5-propylisophthalic acid, 2-propylisophthalic acid, 4-propylisophthalic acid, 5-butylisophthalic acid, 2-butylisophthalic acid, and 4-butylisophthalic acid.

Examples of the monomer (3-2) include diphenyl ether (n ═ 0) and 4-diphenoxybenzene (n ═ 1).

The ratio of the total amount of the monomer (1-2), the monomer (2-2) and the monomer (3-2) to the total amount of the organic sulfonic acid and the phosphorus pentoxide is preferably 1: 100 to 40: 100, more preferably 2: 100 to 30: 100, and most preferably 5: 100 to 20: 100, in terms of a weight ratio.

The PAEK resin of the present invention is not limited to the above-mentioned production method, and can be produced, for example, by reacting the monomer (2-2), the monomer (3-2), and the monomer (3-2) represented by the following general formula (4-2) in the presence of an organic sulfonic acid and phosphorus pentoxide.

Specifically, the PAEK resin can be produced by mixing an organic sulfonic acid and phosphorus pentoxide at 20 to 100 ℃ for 1 to 40 hours, adding and mixing the monomer (2-2), the monomer (3-2), and the monomer (4-2) to the mixture, raising the temperature of the mixture, and then reacting the mixture at 40 to 80 ℃ for 1 to 100 hours.

The PAEK resin of the present invention can also be produced, for example, by reacting the monomer (3-2), the monomer (5-2) represented by the following general formula (5-2), and the monomer (6-2) represented by the following general formula (6-2) in the presence of a Lewis acid catalyst such as anhydrous aluminum chloride.

(wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

Specifically, the PAEK resin can be produced by dissolving the monomer (3-2), the monomer (5-2) and the monomer (6-2) in a solvent such as 1, 2-dichlorobenzene, cooling the solution to, for example, -10 to 0 ℃ under a nitrogen atmosphere, adding anhydrous aluminum chloride, uniformly dissolving the solution, slowly raising the temperature of the solution, and reacting the solution at 20 to 40 ℃ for 1 to 100 hours.

Another embodiment of the method for producing a PAEK resin of the present invention is a method for producing a PAEK resin, comprising reacting the monomer (2-2) with the monomer (3-2) to synthesize a reaction product (2-3) represented by the following general formula (2-3), and reacting the reaction product (2-3) with the monomer (1-2).

(wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m is an integer of 0 or more, Ar₃Is a 2-valent organic group (3-3) represented by the following general formula (3-3), Ar₄Is a 1-valent organic group (3-4) represented by the following general formula (3-4). )

(wherein n is 0 or 1.)

(wherein n is 0 or 1.)

Specifically, the organic sulfonic acid and phosphorus pentoxide are mixed at 20 to 100 ℃ for 1 to 40 hours, the monomer (2-2) and the monomer (3-2) are added to the mixture and mixed, the mixture is heated, the mixture is reacted at 40 to 80 ℃ for 0.5 to 20 hours, more preferably 50 to 70 ℃ for 1 to 15 hours, a reaction product (2-3) is synthesized, the monomer (1-2) is added to the reaction solution and mixed, the mixture is reacted at 40 to 80 ℃ for 1 to 60 hours, more preferably 50 to 70 ℃ for 5 to 50 hours, and the PAEK resin is produced.

The ratio of the amount of the monomer (2-2) to the amount of the monomer (3-2) is preferably 5: 100 to 50: 100, more preferably 8: 100 to 48: 100, and particularly preferably 10: 100 to 45: 100 in terms of a molar ratio.

The ratio of the total amount of the monomer (1-2) and the monomer (2-2) to the amount of the monomer (3-2) is preferably in the range of 85: 100 to 115: 100 in terms of a molar ratio, and is preferably 90: 100-110: 100, preferably 92: 100-108: 100.

Among the reaction products (2-3), m is preferably 0 or 1. The average m in the reaction solution is preferably 0 to 1, preferably 0 to 0.5, and preferably 0 to 0.2. As the average of m is closer to 0, the obtained PAEK resin has a morphology closer to that of an alternating copolymer, and the uniformity and thermal stability of the entire polymer tend to be good.

In the method of reacting the monomer (1-2), the monomer (2-2), and the monomer (3-2) together, the monomer (1-2) and the monomer (3-2) are more reactive, so that the polymerization reaction of the monomer (1-2) and the monomer (3-2) proceeds preferentially than the polymerization reaction of the monomer (2-2) and the monomer (3-2), and the polymerization reaction of the monomer (2-2) and the monomer (3-2) proceeds in the latter stage of the polymerization reaction. Therefore, the PAEK resin obtained has an uneven structure in which the segment of the repeating unit (1-1) and the segment of the repeating unit (2-1) are separated, and as a result, the repeating unit (2-1) having relatively low heat resistance is likely to be thermally decomposed, and the heat resistance of the entire PAEK resin is likely to be lowered.

When the polymerization reaction of the monomer (1-2) and the monomer (3-2) is preferentially carried out, the polymer composed only of the structural unit (1-1) obtained therefrom is insoluble in methanesulfonic acid, and therefore the reaction is stopped. Alternatively, a polymer composed only of the repeating unit (1-1) and a polymer composed only of the repeating unit (2-1) are produced separately, and phase separation occurs, whereby a polymer that cannot be molded is obtained.

In the method of using the above-mentioned anhydrous aluminum chloride instead of the mixture of methanesulfonic acid and phosphorus pentoxide, the polymerization rate is too fast, and there is a fear that it becomes difficult to control the polymer sequence.

On the other hand, the monomer (1-2) is polymerized while maintaining the solubility in methanesulfonic acid as the whole because the solubility of the reaction product (2-3) in methanesulfonic acid is relatively high by dividing the monomer feed sequence, synthesizing the reaction product (2-3) from the monomer (2-2) and the monomer (3-2), and then reacting the monomer (1-2) with the reaction product (2-3). As a result, the repeating unit (1-1) and the repeating unit (2-1) are introduced in a form close to a random copolymer or an alternating copolymer in the polymer sequence, and the uniformity and thermal stability of the entire polymer tend to be good.

(Molding product comprising polyarylene Ether ketone resin (PAEK resin))

The PAEK resin of the present invention has excellent heat resistance, has a high glass transition temperature (Tg), can control a crystal melting point (Tm) while maintaining high crystallinity, and has good molding processability, and therefore, can be used as a pure resin (ニートレジン) or as a composite material such as glass fiber, carbon fiber, and fluororesin. Further, by molding the PAEK resin of the present invention, primary processed products such as rods, plates, films, filaments, and the like, various injection/cutting processed products, gears, bearings, composite materials, implants, 3D molded products, and the like can be produced, and these molded products containing the PAEK resin of the present invention can be used for automobiles, airplanes, electric and electronic, medical members, and the like.