JP2024038822A - Polyaryletherketone resin, composition containing the resin, molded article, method for producing the resin - Google Patents

Abstract

[Problem] To provide a polyaryl ether ketone resin that has good moldability and crystallinity and is excellent in productivity. [Solution] A polyaryl ether ketone resin that has repeating units (A) having a structural unit (A1) derived from an aromatic diol and a structural unit (A2) derived from 2,5-furan dicarboxylic acid, and repeating units (B) having a structural unit (B1) derived from an aromatic diol and a structural unit (B2) derived from an aromatic dicarboxylic acid, wherein at least either (B1) or (B2) is a structural unit different from (A1) and (A2), respectively. [Selected Figure] None

Description

The present invention relates to a polyaryletherketone resin having structural units derived from furandicarboxylic acid and having excellent moldability and crystallinity, a composition containing the resin, a molded article, and a method for producing the resin.

Polyaryletherketone (PAEK) resin has excellent heat resistance, chemical resistance, flame retardance, mechanical properties, and electrical properties, and is widely applied as an engineering plastic in many technical fields such as aviation, electronic information, and implants. Currently, polyetheretherketone (PEEK) resins are mainly used for these applications. For example, Patent Document 1 discloses a PEEK resin having excellent thermal and mechanical properties. However, PEEK resin tends to have a higher melting point than other thermoplastic resins. Due to its high melting point, there is a problem that the processing temperature when processing PEEK in a molten state, such as injection molding or extrusion molding, becomes high (see Patent Document 2). Therefore, there are restrictions on the molding machines that can be used for processing.

In order to solve this problem, a polyaryletherketone resin has been proposed in which the melting point is lowered by copolymerizing hydroquinone, which has conventionally been used in the polymerization of PEEK resin, and a specific aromatic diol. For example, Patent Document 3 reports that by using 4,4'-dihydroxybiphenyl as a copolymerization component, a crystalline polyaryletherketone resin with a lower melting point than conventional PEEK resin was obtained. There is. However, it has been reported that the crystallinity of this PAEK resin, that is, the value of the enthalpy of fusion during the temperature rising process of a differential scanning calorimeter, decreases compared to conventional PEEK resins due to the addition of copolymer components (patent (See reference 4).

On the other hand, a method is disclosed in which the skeleton is polyetherketoneketone (PEKK) and a part of the diketone skeleton derived from terephthalic acid is used as a skeleton derived from isophthalic acid to lower the melting point (see Patent Document 5). However, as the proportion of skeletons derived from isophthalic acid increases, crystallinity decreases and mechanical properties such as elastic modulus at high temperatures are impaired, so the problems faced by PEEK resins have not been completely solved.

Furthermore, a polyaryletherketone resin has been proposed in which the melting point is lowered by using a skeleton derived from furandicarboxylic acid (FDCA) having a bent structure. For example, Non-Patent Document 1 discloses a polyaryletherketone resin having a skeleton derived from FDCA by derivatizing FDCA and aromatic nucleophilic substitution reaction. Some skeletons have melting points of less than 300°C, which is significantly lower than the melting point of existing PEEK resins (343°C), improving moldability. However, the crystallinity was not sufficient, and there was room for improvement in achieving both moldability and crystallinity.

US Patent No. 4,320,224 JP 2021-50314 Publication International publication WO2014/207458 specification European Patent No. 3783047 European Patent No. 3783047

Y. Kanetaka; S. Yamazaki; K. Kunio, Polymer Chemistry, 2016, 54, 3094-3101. ``Preparation of Poly(ether ketone)s Derived from 2,5-Furandicarboxylic Acid via Nucleophilic Aromatic Substitution Polymerization.''

Conventional PAEK resins have high melting points, so improvements are needed from the viewpoints of moldability and productivity. However, if the melting point is lowered by introducing a copolymer component, crystallinity etc. It has been extremely difficult to achieve both of these physical properties. The present inventors investigated polyetheretherketoneketone (PEEKK) resin using a skeleton derived from furandicarboxylic acid (FDCA), which has a bent structure, and found that the melting point was lower than that of PEEK resin. At the same time, it was found that the crystallinity (that is, the enthalpy of fusion during the heating process in a differential scanning calorimeter is small) is poor. Even when such resins are made into molded products such as films or composite materials, the molecular state of the entire molded product is not uniform, making it difficult for the resin to exhibit sufficient physical properties, and the mechanical properties suddenly deteriorate in high temperature regions. Problems arise due to crystallinity, such as a tendency for crystallinity to decrease. In addition, if a long crystallization time is ensured in the molding process in order to increase the crystallinity of a resin with poor crystallinity, the process of cooling the molten resin becomes long, resulting in a high cost and inefficient process, resulting in poor moldability. The result is a resin with poor productivity.

The present invention has been made in view of the problems of the prior art described above. That is, an object of the present invention is to provide a polyaryletherketone resin having good moldability and crystallinity and excellent productivity.

The present inventors conducted extensive studies to solve the above problems. As a result, it is possible to obtain a polyaryletherketone resin that contains a structural unit derived from FDCA and has two or more types of repeating units, has good crystallinity and moldability, and has excellent productivity. We have found that the above problems can be solved.

That is, the gist of the present invention resides in the following [1] to [12].

[1] A repeating unit (A) having a structural unit (A1) derived from an aromatic diol and a structural unit (A2) derived from 2,5-furandicarboxylic acid, and a structural unit (B1) derived from an aromatic diol. ) and a repeating unit (B) having a structural unit (B2) derived from an aromatic dicarboxylic acid, and at least one of (B1) and (B2) is compatible with (A1) and (A2), respectively. A polyaryletherketone resin characterized by different constituent units.

[2] The polyaryletherketone resin according to [1], wherein the repeating unit (A) is represented by the following formula (1).

(However, Ar ¹ is a divalent aromatic group, and m is a positive integer.)

[3] The polyaryletherketone resin according to [1] or [2], wherein the repeating unit (B) is represented by the following formula (2).

(However, Ar ² is a divalent aromatic group, and n is a positive integer.)

[4] The polyaryletherketone resin according to any one of [1] to [3], which contains the repeating unit (A) in an amount of 0.1 to 30 mol% or 70 to 99.9 mol%.

[5] The polyaryletherketone resin according to any one of [1] to [4], wherein in the repeating unit (A), Ar ¹ contains 4 to 30 carbon atoms.

[6] The polyaryletherketone resin according to any one of [1] to [5], wherein in the repeating unit (B), the number of carbon atoms contained in Ar ² is 4 to 30.

[7] In the repeating unit (A), Ar ¹ is a phenylene group, a naphthylene group, a biphenylene group, which may have a substituent, or the following formula (3)

(However, X is any divalent linking group)
The polyaryletherketone resin according to any one of [1] to [6].

[8] In the repeating unit (B), Ar ² is a phenylene group, a naphthylene group, a biphenylene group, which may have a substituent, or the following formula (4)

(However, X is any divalent linking group)
The polyaryletherketone resin according to any one of [1] to [7].

[9] A composition comprising the polyaryletherketone resin described in [1] to [8].

[10] A molded article containing the polyaryletherketone resin according to [1] to [9].

[11] The molded article according to [10], wherein the molded article is a film.

[12] The method for producing a polyaryletherketone resin according to any one of [1] to [8], characterized in that bisfluorobenzoylfuran is used as a raw material.

According to the present invention, it is possible to obtain a polyaryletherketone resin that can use raw materials derived from biomass, has good moldability and crystallinity, and has excellent productivity.

Embodiments of the present invention will be described in detail below. Note that the following explanation is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to these contents unless it exceeds the gist thereof. In the present invention, "aromatic" includes "heteroaromatic" and does not include bonds or substituents consisting of carbon, hydrogen, or hetero atoms that do not partially constitute an aromatic ring in the main chain or side chain. It's okay to stay.

[Polyaryletherketone resin]
The polyaryletherketone resin of the present invention (hereinafter sometimes referred to as "PAEK resin of the present invention" or simply "resin of the present invention") has a structural unit (A1) derived from an aromatic diol and 2,5 - A repeating unit (A) having a constituent unit (A2) derived from furandicarboxylic acid, and a repeating unit having a constituent unit (B1) originating from an aromatic diol and a constituent unit (B2) originating from an aromatic dicarboxylic acid. unit (B), and at least one of (B1) and (B2) is a structural unit different from (A1) and (A2), respectively.

Moreover, PAEK is PAEK in a broad sense, and it is sufficient that it has at least one ether bond and at least one carbonyl bond in its molecular skeleton. That is, it includes polyetheretherketone (PEEK), polyetheretherketoneketone (PEEKK), polyetherketoneketone (PEKK), and the like. Among these, resin species containing two or more ether bonds in the repeating unit of the resin are preferred, and polyether ether ketone ketones (PEEKK) are particularly preferred.

<Repeat unit (A)>
The repeating unit (A) in the polyaryletherketone resin of the present invention includes a structural unit (A1) derived from an aromatic diol (hereinafter sometimes referred to as "aromatic diol unit (A1)") and 2 , 5-furandicarboxylic acid (hereinafter sometimes referred to as "2,5-furandicarboxylic acid unit (A2)").

(Structural unit (A1) derived from aromatic diol)
The structural unit (A1) derived from an aromatic diol refers to a structural unit derived from a compound having two phenolic hydroxy groups. It may also contain bonds or substituents made of carbon, hydrogen, or heteroatoms that do not constitute an aromatic ring. Examples of the aromatic diol that can be used for the structural unit (A1) derived from an aromatic diol include the aromatic diols listed below.
The structural units derived from aromatic diols may be used singly or in combination of two or more. The proportion of structural units derived from the aromatic diol of the present invention is preferably large from the viewpoint of heat resistance and mechanical properties of the resin. Specifically, the total of these structural units is preferably 51 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, based on all the structural units derived from diol in the repeating unit (A). It is mol% or more, particularly preferably 90 mol% or more. Moreover, the upper limit is 100 mol%.

(Structural units derived from other diols)
The structural units derived from diols in the polyaryletherketone resin of the present invention include structural units other than the structural unit (A1) derived from aromatic diols (hereinafter referred to as "structural units derived from other diols"). ) may be included. Other structural units derived from diols include structural units derived from aliphatic diols and structural units derived from diols having one aliphatic hydroxyl group and one aromatic hydroxyl group. Regarding the structural units derived from other diols of the present invention, one type may be used alone, or two or more types may be used in combination. The proportion of structural units derived from other diols of the present invention is preferably small from the viewpoint of heat resistance and mechanical properties of the resin. Specifically, the total of these structural units is 49 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less, particularly preferably 10 mol% or less, based on the total structural units derived from the diol. It is less than mol%. Moreover, the lower limit is 0 mol%.

(Structural unit (A2) derived from 2,5-furandicarboxylic acid)
The proportion of 2,5-furandicarboxylic acid units (A2) is preferably large from the viewpoint of heat resistance, crystallinity, mechanical properties, moldability, etc. of the polyaryletherketone resin. It is more preferable to have as the main dicarboxylic acid unit. Specifically, in the repeating unit (A), it is 51 mol% or more, more preferably 55 mol% or more, still more preferably 60 mol% or more, and particularly preferably It is 65 mol% or more, particularly preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more. Moreover, the upper limit is 100 mol%.

(components derived from biomass)
The units constituting the polyaryletherketone resin are preferably units derived from biomass from the viewpoint of reducing environmental load. Among these, the unit (A2) derived from 2,5-furandicarboxylic acid is preferably a unit derived from 2,5-furandicarboxylic acid derived from biomass.

(Specific structural example of repeating unit (A))
The repeating unit (A) is preferably a structural unit represented by the following formula (1).

(However, Ar ¹ is a divalent aromatic hydrocarbon group, and m is a positive integer.)
In the repeating unit (A), the number of carbon atoms contained in Ar ¹ is preferably 4 to 30, more preferably 4 to 25, even more preferably 4 to 20, and The number of carbon atoms is particularly preferably 4 to 18, and most preferably 4 to 15.

In the repeating unit (A), Ar ¹ is preferably a phenylene group, a naphthylene group, a biphenylene group, which may have a substituent, or the following formula (3).

(However, X is any divalent linking group)
Examples of the substituent that Ar ¹ may have include methyl group, ethyl group, propyl group, isopropyl group, cyclopentyl group, cyclohexyl group, norbornyl group, vinyl group, allyl group, benzyl group, phenyl group, naphthyl group. Hydrocarbon groups such as groups, substituents containing ether bonds such as methoxy groups, ethoxy groups, phenoxy groups, substituents containing carbonyl groups such as acetyl groups and benzoyl groups, substituents containing ester bonds of acetoxy groups, acetamide groups , a substituent containing an amide group such as a benzamide group, a nitro group, an amino group, an aldehyde group, a cyano group, a perfluoroalkyl group such as chlorine, bromine, iodine, and a perfluoromethyl group.

Examples of the divalent linking group X include ether, carbonyl group, dimethylmethylene group, methylphenylmethylene group, bis(fluoromethyl)methylene group, ethylmethylmethylene group, diphenylmethylene group, methylmethylene group, methylene group , a sulfonyl group, a cyclohexylidene group, a cyclohexylene group, and the linking groups shown below.

A specific structure of the repeating unit (A) is illustrated below.

<Repeat unit (B)>
The repeating unit (B) in the polyaryletherketone resin of the present invention is a structural unit (B1) derived from an aromatic diol (hereinafter sometimes referred to as "aromatic diol unit (B1)") and an aromatic Contains a structural unit (B2) derived from dicarboxylic acid (hereinafter sometimes referred to as "aromatic dicarboxylic acid unit (B2)"). The above-described repeating unit (A) and repeating unit (B) are in a relationship such that at least one of (B1) and (B2) is a structural unit different from (A1) and (A2), respectively.

(Structural unit (B1) derived from aromatic diol)
The structural unit (A1) derived from the above-mentioned aromatic diol can also be used as the structural unit (B1) derived from an aromatic diol. Furthermore, the same applies to the structural units derived from diols other than aromatic diols.

(Structural unit (B2) derived from aromatic dicarboxylic acid)
The structural unit derived from an aromatic dicarboxylic acid refers to a structural unit derived from a compound having two carboxyl groups directly connected to an aromatic ring. It may also contain bonds or substituents made of carbon, hydrogen, or heteroatoms that do not constitute an aromatic ring.
The proportion of units derived from aromatic dicarboxylic acid is preferably large from the viewpoint of heat resistance, crystallinity, mechanical properties, moldability, etc. of the polyaryletherketone resin. Specifically, it is 51 mol% or more, more preferably 55 mol% or more, even more preferably 60 mol% or more, particularly preferably 65 mol% or more, based on all dicarboxylic acid units. It is particularly preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more. Moreover, the upper limit is 100 mol%.
As the aromatic dicarboxylic acid used for the structural unit (B2) derived from aromatic dicarboxylic acid, aromatic dicarboxylic acids described below can be used. However, only when the structural unit (A1) derived from aromatic diol and the structural unit (B1) derived from aromatic diol are the same, the structural unit (B2) derived from aromatic dicarboxylic acid may include 2, It does not contain structural units derived from 5-furandicarboxylic acid.

(components derived from biomass)
As mentioned above, the units constituting the polyaryletherketone resin are preferably units derived from biomass from the viewpoint of reducing environmental impact, but among them, 2,5-furandicarboxylic acid as the structural unit (B2) is preferable. When using a unit derived from 2,5-furandicarboxylic acid derived from biomass, the unit is preferably a unit derived from 2,5-furandicarboxylic acid derived from biomass.

(Specific structural example of repeating unit (B))
The repeating unit (B) is preferably a structural unit represented by the following formula (2).

(However, Ar ² is a divalent aromatic hydrocarbon group, and n is a positive integer.)

In the repeating unit (B), the number of carbon atoms contained in Ar ² is preferably 4 to 30, more preferably 4 to 25, even more preferably 4 to 20, and The number of carbon atoms is particularly preferably 4 to 18, and most preferably 4 to 15. It is more preferable that

In the repeating unit (B), Ar ² is preferably a phenylene group, a naphthylene group, a biphenylene group, which may have a substituent, or the following formula (4).

(However, X is any divalent linking group)
Examples of the substituents that Ar ² may have include the same substituents as the substituents that Ar ¹ may have.

Examples of the divalent linking group X include ether, carbonyl group, dimethylmethylene group, methylphenylmethylene group, difluoromethylmethylene group, ethylmethylmethylene group, diphenylmethylene group, methylmethylene group, methylene group, and sulfonyl group. , cyclohexylene group and the linking group shown below.

A specific structure of the repeating unit (B) is illustrated below.

In the repeating unit (A) and the repeating unit (B), m and n are not particularly limited as long as they are positive integers. The sum of m and n is preferably 5 or more, more preferably 10 or more, particularly preferably 20 or more, and most preferably 30 or more. The sum of m and n is preferably 10,000 or less, more preferably 1,000 or less, particularly preferably 500 or less, particularly preferably 300 or less, and most preferably 200 or less. By setting the sum of m and n within the above-mentioned preferred range, the polyaryl ether ketone resin has a suitable melt viscosity, and molded products with excellent moldability and high mechanical strength can be produced. In addition, molded products with excellent crystallinity and heat resistance can be produced.

In the polyaryletherketone resin of the present invention, based on all the repeating units including the repeating unit (A) and repeating unit (B) described above, the larger of repeating unit (A) and repeating unit (B) is 70 mol. % or more, more preferably 75 mol% or more, particularly preferably 80% or more, particularly preferably 83% or more, and most preferably 85% or more. Also, based on all the repeating units including repeating unit (A) and repeating unit (B) described above, the larger one of repeating unit (A) and repeating unit (B) is usually contained at 99.9 mol% or less, and 99 The content is preferably mol % or less, more preferably 98 mol % or less, even more preferably 97 mol % or less, even more preferably 96 mol % or less, and most preferably 95 mol % or less. By setting it as the said range, the crystallinity of polyaryletherketone resin improves.

<Structural units derived from aromatic diols (structural units (A1), structural units (B1))>
When two or more types of aromatic diols are used together in the polyaryletherketone resin of the present invention, they can be used in combination in any ratio, but the melting point, glass transition temperature, and crystallinity of the resin tend to increase. From this point of view, it is preferable to contain a large amount of a specific component, and from the point of view that the melting point of the resin is low and molding is easy, it is preferable not to be biased toward specific components. Therefore, specifically, the lower limit of the structural unit having the highest proportion among the structural units derived from aromatic diols is preferably 51 mol% or more based on the total of all structural units derived from aromatic diols. is 60 mol% or more, more preferably 70 mol% or more, particularly preferably 80 mol% or more, particularly preferably 90 mol% or more, and most preferably 95 mol% or more. The upper limit is 100 mol% or less, preferably 98 mol% or less, more preferably 95 mol% or less, particularly preferably 93 mol%, based on the total of all structural units derived from aromatic diols. % or less, particularly preferably 91 mol% or less, and most preferably 90 mol% or less.

<Structural units derived from other dicarboxylic acids>
The polyaryletherketone resin of the present invention has structural units derived from dicarboxylic acids (hereinafter referred to as , sometimes referred to as "a structural unit derived from other dicarboxylic acids"). Other dicarboxylic acid units are not limited as long as they do not impair the properties of the polyaryletherketone resin of the present invention, and include structural units derived from aliphatic dicarboxylic acids and both aliphatic carboxyl groups and aromatic carboxyl groups. Examples include those having the following. Regarding the structural units derived from other dicarboxylic acids of the present invention, one type may be used alone, or two or more types may be used in combination. The proportion of structural units derived from other dicarboxylic acids of the present invention is preferably small from the viewpoint of heat resistance and mechanical properties of the resin. Specifically, the total of these structural units is 49 mol% or less, preferably 40 mol% or less, more preferably 40 mol% or less based on the total dicarboxylic acid units in the repeating unit (A) or the repeating unit (B). is 30 mol% or less, particularly preferably 10 mol% or less. Moreover, the lower limit is 0 mol%.

<Other units>
The polyaryletherketone resin of the present invention has a unit derived from the above-mentioned 2,5-furandicarboxylic acid (A2), a structural unit derived from an aromatic diol (A1), and a structural unit derived from an aromatic diol (B1). and a structural unit other than the structural unit (B2) derived from an aromatic dicarboxylic acid (hereinafter, may be simply referred to as "other units"). Moreover, when having other units, it may have only one type or two or more types of units. Other units include structural units having only one hydroxyl group or carboxyl group, and structural units having three or more hydroxyl groups and/or carboxyl groups in any combination. Specific examples of compounds constituting other units include phenol, methanol, ethanol, benzoic acid, acetic acid, propionic acid, 1,3,5-trihydroxybenzene, trimethylolethane, 1,3,5-tricarboxybenzene. etc. These components can be used in small amounts for the purpose of controlling the molecular weight and physical properties, and are also useful in making it easy to obtain a resin with a molecular weight sufficient for practical use, and in preventing problems such as the formation of excessive cross-linked structures and the generation of foreign substances. Therefore, it is preferable to keep the amount to the minimum necessary. Specifically, the total of these structural units is 49 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less, particularly preferably is 5 mol% or less, particularly preferably 2 mol% or less, particularly preferably 1 mol% or less, particularly preferably 0.8 mol% or less, and most preferably 0.5 mol% or less. Moreover, the lower limit is 0 mol%.

<Metal component>
The polyaryletherketone resin of the present invention contains metal impurities contained in the above biomass-derived components and metal components derived from the base used in the polymerization reaction. In this case, metal impurities derived from biomass raw materials include alkali metals such as Na and K, and alkaline earth metals such as Mg and Ca. It is preferable that these components be contained in a small amount from the viewpoints that the color tone of the resin tends to be good and that side reactions during the reaction are easily suppressed. Specifically, the amount of alkali metal is preferably 1000 ppm or less, more preferably 500 ppm or less, even more preferably 300 ppm or less, particularly preferably 250 ppm or less, and 200 ppm or less. is most preferable. Further, the amount of alkaline earth metal is preferably 1000 ppm or less, more preferably 500 ppm or less, even more preferably 300 ppm or less, particularly preferably 250 ppm or less, and 200 ppm or less. is most preferred.

[Production method of polyaryletherketone resin]
The polyaryletherketone resin of the present invention can be produced by a known polyaryletherketone resin production method by selecting raw materials and additives so that each constituent unit has the above-mentioned proportions and composition. For example, acid chloridation of a dicarboxylic acid followed by a Friedel-Crafts acylation reaction with an aromatic compound followed by a polycondensation reaction, or acid chloridation of a dicarboxylic acid followed by a Friedel-Crafts acylation reaction with an aromatic halide. It can be produced by any of the following methods: a dihalo compound is synthesized by a chemical reaction, followed by a nucleophilic substitution reaction with a diol in the presence of a base, followed by a polycondensation reaction.

Among these, it is known that multiple positional isomers are generated in the Friedel-Crafts acylation reaction, and if these are used as a mixture for resin synthesis, the resulting resin will have poor thermophysical properties. There are concerns. In addition, in the Friedel-Crafts acylation reaction, aluminum chloride is used as a catalyst in an amount equal to or more than the same mole relative to the substrate, so it is known that a large amount of residual aluminum hydroxide is produced as a by-product. If the resin is turned into a resin, its removal requires a large amount of cost and labor, and productivity is significantly reduced. On the other hand, by performing appropriate purification at the stage of low molecular weight intermediates immediately after Friedel-Crafts acylation reaction, deterioration of resin physical properties due to incorporation of isomers and catalyst residues can be easily removed. As the production method, aromatic nucleophilic substitution reaction is more preferable because it can be carried out efficiently.

When producing the polyaryletherketone resin of the present invention by an aromatic nucleophilic substitution reaction, an oligomerization reaction is performed using a unit derived from a diol and a dicarboxylic acid, and a base, and then a polycondensation reaction is performed at a high temperature. It can be produced by a general solution polymerization method such as The synthesis method using an aromatic nucleophilic substitution reaction will be described in detail below, but other production methods may be used as long as they do not depart from the spirit of the present invention.
The ratio of each structural unit contained in the polyaryletherketone resin can be adjusted to an arbitrary ratio by adjusting the molar ratio of the raw materials.

<Aromatic diol>
The raw material forming the structural unit derived from an aromatic diol is not particularly limited, but aromatic diols having 4 to 30 carbon atoms are preferred, aromatic diols having 4 to 25 carbon atoms are more preferred, and aromatic diols having 4 to 20 carbon atoms are preferred. Aromatic diols are more preferred, aromatic diols having 4 to 18 carbon atoms are particularly preferred, and aromatic diols having 4 to 15 carbon atoms are most preferred.
Specifically, substituted benzene derivatives such as hydroquinone (HQ), resorcinol, and catechol; diphenyl ether derivatives such as 4,4'-dihydroxydiphenyl ether, 2,2'-dihydroxydiphenyl ether, and 2,4'-dihydroxydiphenyl ether; 4,4' - Benzophenone derivatives such as dihydroxybenzophenone (DHBP), 2,2'-dihydroxybenzophenone, 2,4'-dihydroxybenzophenone;4,4'-dihydroxybiphenyl,2,2'-dihydroxybiphenyl,2,4'-dihydroxybiphenyl Biphenyl derivatives such as; 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8 - Naphthalene derivatives such as dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene; bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, Examples include bisphenols such as bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z, and may further have any functional group other than a hydroxyl group. Among these, substituted benzene derivatives, diphenyl ether derivatives, benzophenone derivatives, biphenyl derivatives, naphthalene derivatives, and bisphenol S are preferred. Particularly preferred are hydroquinone, 4,4'-dihydroxydiphenyl ether (DHDPE), 4,4'-dihydroxybenzophenone, 4,4'-dihydroxybiphenyl, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and bisphenol S. The raw materials for the aromatic diol unit may be used alone or in combination of two or more.

<2,5-bis(fluorobenzoyl)furan (BFBF)>
In the polyaryletherketone resin of the present invention, as a method for introducing a structural unit derived from 2,5-furandicarboxylic acid, not only 2,5-furandicarboxylic acid derived from biomass is used, but also 2,5-furandicarboxylic acid derived from biomass is used. Bis(fluorobenzoyl)furan (hereinafter sometimes referred to as "BFBF") can be used. BFBF can be manufactured by a known manufacturing method. For example, BFBF is produced by converting 2,5-furandicarboxylic acid into 2,5-furandicarboxylic acid dichloride with a suitable chlorinating agent and subjecting it to a Friedel-Crafts acylation reaction with fluorobenzene catalyzed by Lewis acid. be able to. BFBF produced by this method has three positional isomers in which the two fluorine substitution positions relative to the carbonyl group are the 2,2', 2,4', and 4,4' positions, and usually, The reaction product is obtained as a mixture of these. Although the obtained BFBF can be used for polymerization as a mixture of positional isomers, from the viewpoint of the heat resistance and mechanical properties of the resin, it is preferable to use one at the 4,4' position for polymerization. Any known method can be used to isolate the 4,4'-position component from the positional isomer, but recrystallization and the like are particularly preferred.

<Other aromatic dicarboxylic acids>
The raw material that becomes the constituent unit derived from the aromatic dicarboxylic acid other than BFBF is not particularly limited, but is preferably an aromatic dicarboxylic acid having 4 to 30 carbon atoms, more preferably an aromatic dicarboxylic acid having 4 to 25 carbon atoms, even more preferably an aromatic dicarboxylic acid having 4 to 20 carbon atoms, particularly preferably an aromatic dicarboxylic acid having 4 to 18 carbon atoms, and most preferably an aromatic dicarboxylic acid having 4 to 15 carbon atoms.
Specific examples of raw materials that can be used as structural units derived from other aromatic dicarboxylic acid units include substituted benzene derivatives such as terephthalic acid, isophthalic acid, and phthalic acid; substituted heterocyclic derivatives such as thiophenedicarboxylic acid and pyridinedicarboxylic acid; diphenyl ether derivatives such as 4,4'-dicarboxydiphenyl ether, 2,2'-dicarboxydiphenyl ether, and 2,4'-dicarboxydiphenyl ether; benzophenone derivatives such as 4,4'-dicarboxydiphenyl ether, 2,2'-dicarboxybenzophenone, and 2,4'-dicarboxybenzophenone; ... Biphenyl derivatives such as carboxybiphenyl, 2,2'-dicarboxybiphenyl, and 2,4'-dicarboxybiphenyl; naphthalene derivatives such as 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, and 2,7-dicarboxynaphthalene; and the like, which may further have any functional group other than the carboxy group. Among them, terephthalic acid, isophthalic acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxybiphenyl, 2,6-dicarboxynaphthalene, and 2,7-dicarboxynaphthalene are preferred from the viewpoint of easiness in increasing the melting point, glass transition temperature, and crystallinity of the resin. The raw materials for the other aromatic dicarboxylic acid units may be used alone or in combination of two or more.

The proportion of the structural units derived from the other aromatic dicarboxylic acids described above is preferably small from the viewpoint of the heat resistance and mechanical properties of the resin. Specifically, the total of these structural units is 49 mol% or less, preferably 40 mol% or less, more preferably 40 mol% or less based on the total dicarboxylic acid units in the repeating unit (A) or the repeating unit (B). is 30 mol% or less, particularly preferably 10 mol% or less. Moreover, the lower limit is 0 mol%.

<Raw material charging molar ratio>
In producing the polyaryletherketone resin of the present invention, the molar ratio of the monomers used for polymerization is not particularly limited as long as the polyaryletherketone of the present invention can be produced. The molar ratio of diol to dicarboxylic acid derivative is usually 0.90 or more, preferably 0.95 or more, more preferably 0.97 or more, from the viewpoint of obtaining a polymer with a high degree of polymerization. More preferably, it is 0.99 or more. Further, it is usually 1.10 or less, preferably 1.05 or less, more preferably 1.03 or less, still more preferably 1.01 or less.

<Base>
When producing the polyaryletherketone resin of the present invention by aromatic nucleophilic substitution reaction, the polymerization reaction is usually carried out in the presence of a base. As bases, carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate; carbonates of alkaline earth metals such as calcium carbonate, strontium carbonate, and barium carbonate; lithium hydrogen carbonate, hydrogen carbonate Alkali metal bicarbonates such as sodium, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate; alkaline earth metal bicarbonates such as calcium bicarbonate, strontium bicarbonate, barium bicarbonate; lithium hydroxide, hydroxide Examples include hydroxides of alkali metals such as sodium, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide, strontium hydroxide, and barium hydroxide. Among these, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate are particularly preferred from the viewpoint of ease of handling and reactivity. One type of base may be used alone, or two or more types may be used in combination. From the viewpoint of converting all the hydroxy groups involved in the reaction into alkali metal salts, the molar ratio of alkali metal to hydroxy groups is usually 1.00 equivalent or more, preferably 1.01 equivalent or more, and more preferably 1. It is .02 equivalent or more, more preferably 1.03 equivalent or more, and most preferably 1.05 equivalent or more. In addition, from the viewpoint of resin quality and electrical properties, the amount is usually 2.00 equivalents or less, preferably 1.50 equivalents or less, more preferably 1.30 equivalents or less, and even more preferably 1.20 equivalents. or less, most preferably 1.10 equivalent or less.

<Solvent>
When carrying out the present invention by aromatic nucleophilic substitution reaction, it is preferable to carry out the reaction in an aprotic polar solvent. Specific examples of aprotic polar solvents include N-methylpyrrolidone, N,N-dimethylformamide, N-methylcaprolactam, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and hexamethyl. Compounds containing amide groups such as phosphoramide and tetramethylurea; Compounds containing sulfonyl groups such as dimethylsulfone, sulfolane, diphenylsulfone, dibenzothiophene-5,5'-dioxide, and 4-phenylsulfonylbiphenyl; Sulfinyl groups such as dimethylsulfoxide Containing compounds; nitrile group-containing compounds such as benzonitrile; ether bond-containing compounds such as diphenyl ether; ketone group-containing compounds such as benzophenone and acetophenone; chlorine-containing compounds such as chlorobenzene; and the like. Those having a sulfonyl group are preferred because they have a high boiling point and can be reacted at high temperatures, and have high solubility in monomers, and among them, diphenyl sulfone is particularly preferred. The number of solvents may be one, or two or more solvents may be used in combination. If the amount of the solvent is too small, the polymer will not be sufficiently dissolved and the time required for the reaction will become longer, so it is preferably 0.1 L or more, more preferably 0.15 L per 1 mole of the total amount of monomers. Above, it is more preferably 0.2 L or more, particularly preferably 0.25 L or more. There is no particular upper limit to the amount of solvent, but if the amount of solvent used is large, economic efficiency will deteriorate, and the concentration of functional groups that contribute to the reaction in the reaction system will decrease, resulting in an increase in the time required for the reaction. Therefore, it is preferably 10 L or less, more preferably 5 L or less, even more preferably 3 L or less, particularly preferably 2 L or less, particularly preferably 1.5 L or less, and most preferably 1 L, based on 1 mole of the total amount of monomers. It is as follows.
In addition to the above solvents, high boiling point solvents may be used to suppress sublimation of the monomers. Examples of high boiling point solvents include alkyl ethers such as triglyme and tetraglyme.

<Polycondensation reaction step>
When carrying out the present invention by aromatic nucleophilic substitution reaction, polycondensation is usually carried out at a relatively low temperature and then at a relatively high temperature.
Conditions such as temperature, time, pressure, etc. in polycondensation at a relatively low temperature can be within the range of conventionally known polyaryletherketone production methods. The reaction temperature is preferably a high temperature in that it can increase the solubility of the reaction substrate, reaction product, and base as well as speed up the reaction rate, specifically 150°C or higher, more preferably 170°C. Above, the temperature is more preferably 180°C or higher, particularly preferably 190°C or higher. On the other hand, from the point of view of suppressing side reactions such as sublimation and thermal decomposition of monomers, it is preferable that the temperature is lower than 250°C, more preferably 230°C or lower, and even more preferably 220°C The temperature is preferably 210°C or lower, particularly preferably 210°C or lower. The reaction atmosphere is preferably an inert gas atmosphere such as nitrogen or argon. The reaction time is preferably long from the viewpoint of sufficiently advancing the polycondensation, and specifically, it is usually 10 minutes or more, preferably 20 minutes or more, and more preferably 30 minutes or more. , more preferably 45 minutes or more, and most preferably 1 hour or more. In addition, from the viewpoint of suppressing side reactions such as thermal decomposition, it is preferably short, and specifically, it is usually 5 hours or less, preferably 4 hours or less, more preferably 3 hours or less, and even more preferably is 2 hours and 30 minutes or less, most preferably 2 hours or less. The reaction pressure is preferably low from the viewpoint of promoting discharge of water generated during the polymerization reaction out of the reaction system and suppressing side reactions such as depolymerization, and suppressing volatilization of reaction substrates and intermediates. High pressure is preferable from the viewpoint that a polymer with a high degree of polymerization can be easily obtained by maintaining the molar balance of functional groups in the reaction system. Specifically, normal pressure is preferable.

Conditions such as temperature, time, pressure, etc. in polycondensation at a relatively high temperature can be those of conventionally known polyaryletherketone production methods. The reaction temperature is preferably 200°C or higher, more preferably 220°C or higher, and even more preferably 240°C or higher, in that it can increase the solubility of the reaction substrate, reaction product, and base, as well as speed up the reaction rate. , particularly preferably 260°C or higher. On the other hand, from the viewpoint of suppressing side reactions such as thermal decomposition, the reaction temperature is preferably 400°C or lower, more preferably 380°C or lower, even more preferably 350°C or lower, and particularly preferably 320°C or lower. be. The reaction atmosphere is preferably an inert gas atmosphere such as nitrogen or argon. The reaction time is preferably long from the viewpoint of sufficiently advancing the polycondensation to obtain a polymer, and specifically, it is usually 10 minutes or more, preferably 20 minutes or more, and more preferably It is 30 minutes or more, more preferably 45 minutes or more, and most preferably 1 hour or more. Further, from the viewpoint of suppressing side reactions such as thermal decomposition, it is preferably short, and specifically, it is usually 20 hours or less, preferably 15 hours or less, more preferably 10 hours or less, and even more preferably is 5 hours or less, particularly preferably 4 hours or less, particularly preferably 3 hours or less, and most preferably 2 hours or less. The reaction pressure is preferably low from the viewpoint of promoting discharge of water generated during the polymerization reaction out of the reaction system and suppressing side reactions such as depolymerization, and suppressing volatilization of reaction substrates and intermediates. By maintaining the molar balance of functional groups in the reaction system, it is easier to obtain a polymer with a high degree of polymerization, and the distillation of the solvent out of the reaction system is suppressed, allowing the fluidity of the reaction solution to be maintained until the final stage of the reaction. High pressure is preferable because the properties are easily maintained. Specifically, normal pressure is preferable.

Usually, after completing the polycondensation reaction step, the polymerization product in a solid state is taken out from the reaction vessel, pulverized, suspended and washed with an organic solvent, and the solid component is filtered to obtain the desired resin. Any polar solvent can be used as the organic solvent used for washing, such as aprotic polar solvents such as acetone and N-methyl-2-pyrrolidone; and alcohols such as methanol, ethanol, and isopropanol. Can be mentioned. A polyaryletherketone resin is obtained by washing the recovered solid component with water and recovering the solid component by filtration.

<Reactor>
When carrying out the present invention using an aromatic nucleophilic substitution reaction, a known vertical or horizontal stirred tank reactor can be used as the reaction apparatus for carrying out the above reaction. When carrying out the two-step process of the oligomerization reaction step and the polycondensation reaction step, the entire process may be carried out using one reaction apparatus or a plurality of reaction apparatuses. Known types of stirring blades provided in the reaction tank can be selected, and specific examples include propeller blades, screw blades, turbine blades, fan turbine blades, disk turbine blades, Faudler blades, full zone blades, max blend blades, etc. .

As the device used for cleaning, any known device can be used. As a known device, for example, a single-plate pressure filter (Nutsche filter) is known, in which a filter medium is attached to a horizontal filter plate inside a closed container.

[Physical properties of polyaryletherketone resin]
<Reduced viscosity (RV)>
The reduced viscosity of the polyaryletherketone resin of the present invention is usually 0.5 dL/g or more. Moreover, it is preferably 0.6 dL/g or more, more preferably 0.7 dL/g or more, still more preferably 0.8 dL/g or more, and particularly preferably 0.9 dL/g or more. On the other hand, the reduced viscosity of the polyaryletherketone resin of the present invention is usually 3.5 dL/g or less, preferably 3.0 dL/g or less, and more preferably 2.5 dL/g or less. , more preferably 2.0 dL/g or less, particularly preferably 1.9 dL/g or less, particularly preferably 1.8 dL/g or less, particularly preferably 1.7 dL/g or less , most preferably 1.6 dL/g or less. By setting the above-mentioned preferable reduced viscosity, the polyaryletherketone resin has an appropriate melt viscosity, and a molded article with excellent moldability and high mechanical strength can be manufactured. Furthermore, a molded article with excellent crystallinity and heat resistance can be produced. In the present invention, the reduced viscosity can be measured by the method described in the Examples below.

<Melting point (Tm)>
The melting point of the polyaryletherketone resin of the present invention is not particularly limited as long as it does not impair heat resistance or mechanical properties. However, since it has excellent moldability and productivity, the temperature is usually 200°C or higher, preferably 210°C or higher, more preferably 220°C or higher, even more preferably 230°C or higher, and particularly preferably 240°C. The temperature is above, and most preferably 250°C or above. Further, the temperature is usually 400°C or lower, preferably 350°C or lower, more preferably 320°C or lower, even more preferably 310°C or lower, particularly preferably 300°C or lower, particularly preferably 290°C. It is as follows. Any method can be used to measure the melting point of the polyaryletherketone resin, and in the present invention, it is measured by the method described in the Examples below. The melting point can be measured by a thermal analysis method such as a differential thermal analysis method, or simply by a visual method (JIS K6220).

<Glass transition point (Tg)>
The glass transition point of the polyaryletherketone resin of the present invention is not particularly limited as long as it does not impair heat resistance or mechanical properties. However, since it has particularly excellent heat resistance and can be applied to engineering plastics, the temperature is usually 110°C or higher, preferably 120°C or higher, more preferably 130°C or higher, even more preferably 135°C or higher, and especially Preferably it is 140°C or higher. Further, the temperature is usually 200°C or lower, preferably 190°C or lower, more preferably 180°C or lower, even more preferably 170°C or lower, particularly preferably 160°C or lower. Any method can be used to measure the glass transition point of the polyaryletherketone resin, and in the present invention, it is measured by the method described in the Examples below. The glass transition point can be measured by a thermal analysis method such as a differential thermal analysis method.

<Enthalpy of fusion (ΔHm)>
The crystallinity of the polyaryletherketone resin of the present invention can be evaluated by enthalpy of fusion. It can be seen that the larger the melting enthalpy observed under the same measurement conditions, the higher the crystallinity. The enthalpy of melting of the polyaryletherketone resin of the present invention is preferably 24 J/g or more, more preferably 25 J/g or more, and 26 J/g or more, when measured by the method described in the Examples below. It is more preferably at least 27 J/g, particularly preferably at least 28 J/g, and most preferably at least 30 J/g. Note that there is no particular restriction on the upper limit of the enthalpy of fusion.

[Composition]
The polyaryletherketone resin of the present invention can be further mixed with resins and additives other than the polyaryletherketone resin of the present invention, depending on the intended use and required performance, and used as a composition. As components such as resins and additives other than the polyaryletherketone resin of the present invention used in the composition, one type may be used alone or two or more types may be used in combination.
The content of these components is not particularly limited, and is preferably large in that the effects of containing the additives can be easily obtained. On the other hand, it is preferable that the amount of the additive is small because it is easily dispersed, has excellent moldability and mechanical properties, and can reduce the load of the entire process.
Furthermore, from the viewpoint of reducing environmental load, these components are preferably units derived from biomass (plant raw materials).
Examples of resins other than the polyaryletherketone resin of the present invention include polyphenylene sulfide resin, polyetherimide resin, LCP (liquid crystal polymer), polyphenylsulfone resin, polyethersulfone resin, polyphthalamide resin, polysulfone resin, polyimide resin, Examples include epoxy resin. Additives include heat stabilizers, lubricants, antiblocking agents, nucleating agents, inorganic fillers, colorants, pigments, ultraviolet absorbers, light stabilizers, modifiers, crosslinking agents, etc. good. Examples of additives include carbon fibers and glass fibers.

[Molded object]
The polyaryletherketone resin of the present invention and the composition of the present invention can be molded by melt molding methods such as injection molding or extrusion molding, or by a method in which the resin is treated as a solution using an appropriate good solvent, depending on the intended use and required performance. , it can be used as a molded body. Specific examples of the shape and use of the molded article include films, fibers, pipes, rods, rings, gears, bearings, coating materials, and in-vivo implant materials. In addition, as for its form, a molded article may be composed only of the polyaryletherketone resin of the present invention or the composition of the present invention, but it may be combined with other materials in any shape as long as the properties can be exhibited. For example, it can also be used as a laminate.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
The measurement methods for each physical property and evaluation item are as follows.

<Composition of polyaryletherketone resin>
The composition of the polyaryletherketone resin was determined by measuring the ¹ H-NMR spectrum using a nuclear magnetic resonance spectrometer "AVANCENEO 400" manufactured by Bruker, and from the ratio of the integral values of the signals corresponding to each constituent unit. . For example, in the case of a polyaryletherketone resin composed of hydroquinone units, 4,4'-dihydroxybenzophenone units, and 2,5-furandicarboxylic acid units, the integral ratio of signals appearing at 8.01 ppm and 7.59 ppm indicates that hydroquinone The molar ratio of units/4,4'-dihydroxybenzophenone units/furandicarboxylic acid was determined.

<Reduced viscosity (RV) (dL/g)>
It was determined in the following manner using an Ubbelohde viscometer. That is, using concentrated sulfuric acid (>95%) as a solvent, the falling seconds of a polyaryletherketone sample solution with a concentration of 0.1 g/dL and only the solvent were measured at 25°C, and from the following formula (1) I asked for it.
RV=η _sp /C (1)
In equation (1), η _sp =η/η ₀ −1, η is the number of seconds for the sample solution to fall, η ₀ is the number of seconds for the solvent to fall, and C is the concentration (g/dL) of the sample solution.

<Melting point (Tm) (°C) of polyaryletherketone resin>
The polyaryletherketone resin was heated from 30°C to 360°C at a rate of 10°C/min using a differential scanning calorimeter "DSC7020" (manufactured by Hitachi High-Tech Science), and then from 360°C to 30°C for 10 minutes. This is carried out by cooling at a rate of .degree. C./min and further heating from 30.degree. C. to 360.degree. C. at a rate of 10.degree. C./min. At this time, the endothermic peak temperature during the second heating process was read and determined as the melting point of the polyaryletherketone resin.

<Glass transition point (Tg) (°C) of polyaryletherketone resin>
The measurement was carried out using a differential scanning calorimeter "DSC7020" (manufactured by Hitachi High-Tech Science). After increasing the temperature from 30°C to 360°C at a rate of 10°C/min, This is carried out by cooling at a rapid rate and further increasing the temperature from 30°C to 360°C at a rate of 10°C/min. At this time, the temperature at the intersection of the tangent at the first inflection point of the DSC curve during the second heating process and the baseline before the inflection point was read and determined as the glass transition point of the polyaryletherketone resin.

<Enthalpy of fusion (ΔHm) (J/g)>
The measurement was carried out using a differential scanning calorimeter "DSC7020" (manufactured by Hitachi High-Tech Science). After increasing the temperature from 30°C to 360°C at a rate of 10°C/min, This is carried out by cooling at a rapid rate and further increasing the temperature from 30°C to 360°C at a rate of 10°C/min. At this time, the area of the endothermic peak corresponding to the melting of the sample during the second heating process was defined as the enthalpy of fusion (ΔHm), and was used as an index of crystallinity.

[Example 1]
In a reaction vessel equipped with a stirring blade, a nitrogen inlet/decompression port, and a heating device, 22.7 parts by mass of bisfluorobenzoylfuran (BFBF), 0.80 parts by mass of hydroquinone (HQ), and 4,4'-dihydroxybenzophenone ( 14.0 parts by mass of DHBP), 10.1 parts by mass of potassium carbonate, 87.0 parts by mass of diphenylsulfone, and 4.8 parts by mass of triglyme. Here, the molar ratio of BFBF/HQ/DHBP is 100/10/90. While stirring the contents of the reaction vessel, nitrogen gas was introduced into the vessel, and the inside of the system was brought into a nitrogen atmosphere by vacuum displacement. Next, the temperature of the system was raised to 200° C. while stirring, and the reaction was carried out at this temperature for 1 hour. Thereafter, the temperature was raised to 280°C over 5 minutes, and polycondensation was continued at this temperature for 1 hour. The polymerization product was taken out from the reaction vessel and crushed with a hammer to form a powder, and then washed by solid-liquid extraction with 784 parts by mass of acetone at room temperature for 15 minutes to recover solid components. Washing with acetone was performed once again under the same conditions. Subsequently, washing was performed by solid-liquid extraction with 1000 parts by mass of water at 60° C. for 15 minutes to recover solid components. Washing with water was performed again under the same conditions. Thereafter, washing was performed by solid-liquid extraction with 309 parts by mass of N-methyl-2-pyrrolidone at 120° C. for 30 minutes to recover solid components. The solid component collected by filtration was vacuum-dried at 120° C. for 6 hours using a vacuum dryer to obtain the desired polyaryletherketone resin. It was confirmed from the ¹ H-NMR spectrum that the polyaryletherketone resin consisted of the following repeating units. The molar ratio of the structural units derived from 2,5-furandicarboxylic acid/HQ/DHBP determined from the ¹ H-NMR spectrum was 100/11/89.

Moreover, the above-mentioned evaluations were performed on the obtained resin. The results are shown in Table 1.
This polyaryletherketone resin could be molded into a film having sufficient strength by melt-molding it using a hot press machine at a temperature higher than its melting point +20°C and then cooling it using a cooling press machine.

[Example 2]
In Example 1, 4,4'-dihydroxydiphenyl ether (DHDPE) was used instead of DHBP, and the molar ratio of BFBF/HQ/DHBPE at the time of charging was 100/90/into the same reaction vessel as in Example 1. Each component was added in an amount of 10, and reacted in the same manner to obtain the desired polyaryletherketone resin.
Table 1 shows the molar ratio of each constituent unit of the obtained resin.

[Comparative example 1]
In the same reaction vessel as in Example 1, equimolar amounts of HQ and BFBF were charged, and the reaction was carried out in the same manner as in Example 1 except that the heating time at 280°C was changed to 2 hours to obtain the desired polyaryletherketone. Resin was obtained.
Table 1 shows the molar ratio of each constituent unit of the obtained resin.

[Comparative example 2]
Equimolar amounts of DHBP and BFBF were charged into the same reaction vessel as in Example 1 and reacted in the same manner to obtain the desired polyaryletherketone resin.
Table 1 shows the molar ratio of each constituent unit of the obtained resin.

FDCA: 2,5-furandicarboxylic acid HQ: Hydroquinone DHBP: 4,4'-dihydroxybenzophenone DHDPE: 4,4'-dihydroxydiphenyl ether BFBF: 4,4'-bisfluorobenzoylfuran

In Table 1, the polyaryletherketone resins of the present invention (Examples 1 and 2) are different from the polyaryletherketone resins (Comparative Examples 1 and 2) consisting of units derived from furandicarboxylic acid and one type of aromatic diol unit. It can be confirmed that the crystallinity is improved compared to . Also, is the polyaryletherketone resin of the present invention (Examples 1 and 2) equivalent to the polyaryletherketone resin (Comparative Examples 1 and 2) consisting of units derived from furandicarboxylic acid and one type of diol unit? It can be confirmed that it has a melting point slightly lower than that, and has moldability comparable to that of conventional PAEK resin.
It has been shown that the polyaryletherketone resin of the present invention has improved crystallinity, so that it is possible to obtain a film with less decrease in mechanical properties around the glass transition point.

Claims (12)

A repeating unit (A) having a structural unit (A1) derived from an aromatic diol and a structural unit (A2) derived from 2,5-furandicarboxylic acid, a structural unit (B1) derived from an aromatic diol, and an aromatic A repeating unit (B) having a structural unit (B2) derived from a group dicarboxylic acid, and at least one of (B1) and (B2) is a structural unit different from (A1) and (A2), respectively. A polyaryletherketone resin characterized by: The polyaryletherketone resin according to claim 1, wherein the repeating unit (A) is represented by the following formula (1).

(However, Ar ¹ is a divalent aromatic group, and m is a positive integer.) The polyaryletherketone resin according to claim 1 or 2, wherein the repeating unit (B) is represented by the following formula (2).

(However, Ar ² is a divalent aromatic group, and n is a positive integer.) The polyaryletherketone resin according to claim 1 or 2, which contains the repeating unit (A) in an amount of 0.1 to 30 mol% or 70 to 99.9 mol%. The polyaryletherketone resin according to claim 2, wherein in the repeating unit (A), the number of carbon atoms contained in Ar ¹ is 4 to 30. The polyaryletherketone resin according to claim 3, wherein in the repeating unit (B), the number of carbon atoms contained in Ar ² is 4 to 30. In the repeating unit (A), Ar ¹ is a phenylene group, a naphthylene group, a biphenylene group, which may have a substituent, or the following formula (3)

(However, X is any divalent linking group)
The polyaryletherketone resin according to claim 2, which is In the repeating unit (B), Ar ² is a phenylene group, a naphthylene group, a biphenylene group, which may have a substituent, or the following formula (4)

(However, X is any divalent linking group)
The polyaryletherketone resin according to claim 3, which is A composition comprising the polyaryletherketone resin according to claim 1 or 2. A molded article comprising the polyaryletherketone resin according to claim 1 or 2. The molded article according to claim 10, wherein the molded article is a film. The method for producing a polyaryletherketone resin according to claim 1 or 2, characterized in that bisfluorobenzoylfuran is used as a raw material.