Polyether ether ketone and method for producing same

Abstract

A polyether ether ketone which comprises a repeating unit represented by formula (1) and a terminal structure represented by formula (2).

Description

Polyether ether ketone and its manufacturing method

[0001] The present invention relates to a polyether ether ketone and a method for producing the same, and more particularly to a polyether ether ketone having excellent processability and a method for producing the same.

[0002] Polyether ether ketone (abbreviated as "PEEK"), a type of crystalline aromatic polyether, is known. PEEK has excellent heat resistance and mechanical strength, and is used as a metal replacement material due to these characteristics. In recent years, its applications have expanded to include automobiles, aircraft, and the medical field.

[0003] Patent Document 1 describes that PEEK having an ionic group (-AX; A is an anion and X is a metal cation) at the end of the molecular chain has a high crystallization temperature T ｃ It is disclosed that

[0004] Japanese Unexamined Patent Publication No. 163926 / 1986

[0005] When PEEK is processed (e.g., molded), it must be processed under high-temperature conditions due to its excellent heat resistance. In this case, in order to effectively impart the characteristics of PEEK as a crystalline resin to the processed product (e.g., molded body), it is necessary to lower the temperature over a long period of time so that the PEEK is sufficiently crystallized, which makes it difficult to obtain processability (e.g., a balance between production efficiency and crystallinity).

[0006] Crystallization temperature T of PEEK ｃ is increased to the crystallization temperature T ｃ and melting point T ｍ If the difference between the melting point T ｍ Since crystallization can be promoted at temperatures close to this range, there is a possibility that processability can be improved.

[0007] However, the crystallization temperature T ｃ As a technique for increasing the resistance to heat and chemicals, the method of introducing a specific ionic group into the terminal as described in Patent Document 1 has limitations.

[0008] An object of the present invention is to provide a PEEK having excellent processability and a method for producing the same.

[0009] As a result of extensive research, the present inventors have found that a specific PEEK has the above-mentioned excellent processability, and have completed the present invention. According to the present invention, the following PEEK and the like can be provided: 1. A polyether ether ketone containing a repeating unit represented by the following formula (1) and a terminal structure represented by the following formula (2). 2. １ 2. The polyether ether ketone according to 1 or 2, having a ratio of the phenoxyphenol unit peak intensity to the main chain peak intensity in H-NMR measurement of 0.0150% or more. 3. The polyether ether ketone according to 1 or 2, having a melt flow rate of 200 g / 10 min or less. 4. The polyether ether ketone according to 1 or 2, having a crystallization temperature T ｃ 4. The polyether ether ketone according to any one of 1 to 3, having a melting point T ｍ 5. The polyether ether ketone according to any one of 1 to 4, wherein the temperature at which the repeating unit represented by formula (6) is 300°C or higher. 6. The polyether ether ketone according to any one of 1 to 5, wherein the width of the exothermic peak due to crystallization observed in differential scanning calorimetry is 23.7°C or lower. 7. The polyether ether ketone according to any one of 1 to 6, which does not contain a repeating unit represented by formula (6) below, or contains a repeating unit represented by formula (6), and when it contains a repeating unit represented by formula (6), the molar ratio of the repeating unit represented by formula (6) to the total of the repeating unit represented by formula (1) and the repeating unit represented by formula (6) is less than 25 mol%: (In formula (6), three R １are each independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium. The three a's are each independently selected from the group consisting of integers of 0 to 4. 8. The polyether ether ketone according to any one of 1 to 7, having a chlorine atom content of 2 mg / kg or more. 9. The polyether ether ketone according to any one of 1 to 8, produced using at least hydroquinone and 4,4'-dichlorobenzophenone as monomers. 10. A method for producing a polyether ether ketone according to any one of 1 to 9, comprising reacting hydroquinone with 4,4'-dihalogenobenzophenone, wherein, when the amount of molar fractions of the hydroquinone used in the reaction is a mol and the amount of molar fractions of the 4,4'-dihalogenobenzophenone is b mol, the condition b / a < 1.00 is satisfied. 11. A method for producing a polyether ether ketone according to 10, wherein the condition b / a ≦ 0.99 is satisfied. 12. A method for producing a polyether ether ketone according to any one of 1 to 9, comprising reacting hydroquinone, 4,4'-dihalogenobenzophenone, and one or more members selected from the group consisting of 4-phenoxyphenol and 4-halogenodiphenyl ether. 13. 13. The method for producing polyether ether ketone according to any one of 10 to 12, wherein the 4,4'-dihalogenobenzophenone is one or more selected from the group consisting of 4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone. 14. The method for producing polyether ether ketone according to any one of 10 to 13, comprising heating a reaction mixture at a temperature of 250°C or higher for 3 hours or longer.

[0010] According to the present invention, it is possible to provide PEEK having excellent processability and a method for producing the same.

[0011] 1 shows DSC curves measured in Examples 1 to 3 and Comparative Example 2. １ 1H-NMR spectrum measured in Comparative Example 3. １ 1 H-NMR spectrum.

[0012] The polyether ether ketone and its production method of the present invention are described in detail below. In this specification, the upper and lower limits of the numerical ranges described can be combined in any combination. Two or more of the individual embodiments of the aspects of the present invention described below that are not mutually contradictory can be combined, and a combination of two or more embodiments is also an embodiment of the aspects of the present invention.

[0013] 1. Polyether ether ketone PEEK according to one embodiment of the present invention contains a repeating unit represented by the following formula (1) and a terminal structure represented by the following formula (2).

[0014]

[0015] The PEEK according to the present embodiment has a terminal structure represented by formula (2) introduced at the end of the molecular chain composed of the repeating unit represented by formula (1), and therefore has a high crystallization temperature T ｃ In addition, the introduction of the terminal structure represented by formula (2) increases the crystallization temperature T ｃ Even if the melting point T ｍ As a result, the change in the crystallization temperature T ｃ and melting point T ｍ The difference between the melting point T ｍ For example, in processing by injection molding, the crystallization temperature T ｃ and melting point T ｍ The smaller the difference between these values, the faster the processing cycle (molding cycle) can be.

[0016] The fact that PEEK contains a repeating unit represented by formula (1) and a terminal structure represented by formula (2) is as follows: １ This can be confirmed by H-NMR measurement. １In the H-NMR measurement, when a main chain peak (chemical shift 7.34 ppm in the examples) and a phenoxyphenol (abbreviated as "PhP") unit peak (chemical shift 7.04 ppm in the examples) are observed, it is determined that the PEEK contains a repeating unit represented by formula (1) and a terminal structure represented by formula (2). Specifically, this is confirmed by the method described in the examples. The main chain peak may vary within a chemical shift range of ±0.02 ppm from 7.34 ppm. Furthermore, although the PhP unit peak may vary from the chemical shift of 7.04 ppm, it is possible to identify it as a PhP unit peak.

[0017] In one embodiment, the PEEK is １ The ratio of the intensity of the PhP unit peak to the intensity of the main chain peak in H-NMR measurement (hereinafter also referred to as "peak intensity ratio") is 0.150% or more, 0.200% or more, 0.300% or more, 0.500% or more, or 0.600% or more. The larger this peak intensity ratio, the higher the crystallization temperature T ｃ The upper limit of the peak intensity ratio is not particularly limited, and is, for example, 4.500% or less. The peak intensity ratio is a value measured by the method described in the examples.

[0018] The melt flow rate of the PEEK is not particularly limited. In one embodiment, the melt flow rate of the PEEK is 1500 g / 10 min or less, 1000 g / 10 min or less, 500 g / 10 min or less, 300 g / 10 min or less, 200 g / 10 min or less, 100 g / 10 min or less, 80 g / 10 min or less, 50 g / 10 min or less, 30 g / 10 min or less, 20 g / 10 min or less, or 15 g / 10 min or less, and is 0.0001 g / 10 min or more, 0.0005 g / 10 min or more, or 0.001 g / 10 min or more. The melt flow rate of PEEK is preferably 200 g / 10 min or less, 160 g / 10 min or less, 100 g / 10 min or less, 50 g / 10 min or less, or even 20 g / 10 min or less. PEEK with a melt flow rate of 200 g / 10 min or less has a sufficiently high molecular weight, and is therefore suitable for pelletization using, for example, an extruder. Such pellets are preferably applicable to applications such as injection molding. The melt flow rate is a value measured by the method described in the examples.

[0019] Crystallization temperature T of PEEK ｃ is not particularly limited. The crystallization temperature T ｃ shows a tendency to increase with the introduction amount of the terminal structure represented by formula (2) (the above-mentioned peak intensity ratio is one index of the introduction amount). In one embodiment, the crystallization temperature T ｃ is 257°C or more, 258°C or more, 259°C or more, or 260°C or more, and is 310°C or less, 300°C or less, 295°C or less, or 290°C or less. ｃ The crystallization temperature T is preferably 260°C or higher, 265°C or higher, 270°C or higher, 275°C or higher, or even 280°C or higher. ｃ is a value measured by the method described in the Examples.

[0020] The glass transition temperature T of PEEK ｇ is not particularly limited. In one embodiment, the glass transition temperature T ｇis 130°C or higher, 135°C or higher, 140°C, 145°C or higher, 148°C or higher, 149°C or higher, or 150°C or higher, and is 165°C or lower, 160°C or lower, or 155°C or lower. ｇ The glass transition temperature T is preferably 148°C or higher. This has the effect of widening the usable temperature range of products containing PEEK. ｇ is a value measured by the method described in the Examples.

[0021] Melting point T of PEEK ｍ is not particularly limited. In one embodiment, the melting point T ｍ is 300°C or more, 310°C or more, 320°C or more, or 325°C or more, and 350°C or less, 340°C or less, or 335°C or less. ｍ The melting point T of PEEK is preferably 300°C or higher. This has the effect of widening the temperature range in which products containing PEEK can be used. ｍ It is preferable that the melting point T is 340°C or less. This allows the processing temperature of PEEK (heating temperature for injection molding, etc.) to be lowered, thereby improving processability and reducing processing costs. ｍ is a value measured by the method described in the Examples.

[0022] Crystallization temperature T of PEEK ｃ and melting point T ｍ The difference between (T ｍ -T ｃ ) is not particularly limited. In one embodiment, T ｍ -T ｃ is 25°C or higher, 30°C or higher, 35°C or higher, or 40°C or higher, and is 90°C or lower, 85°C or lower, 80°C or lower, 75°C or lower, 73°C or lower, 70°C or lower, 65°C or lower, 60°C or lower, 55°C or lower, 50°C or lower, or 45°C or lower. These upper and lower limits can be combined arbitrarily, and T ｍ -T ｃ may be, for example, 40°C or higher and 73°C or lower, 40°C or higher and 70°C or lower, 40°C or higher and 65°C or lower, 40°C or higher and 60°C or lower, 40°C or higher and 55°C or lower, 40°C or higher and 50°C or lower, or 40°C or higher and 45°C or lower.

[0023] In one embodiment, the exothermic peak width due to crystallization observed in differential scanning calorimetry (DSC) of PEEK is 23.7°C or less, 23.5°C or less, 20.0°C or less, 18.0°C or less, 15.0°C or less, 12.0°C or less, 10.0°C or less, or 9.0°C or less. This increases the crystallization rate of PEEK, further improving processability. The lower limit of the exothermic peak width is not particularly limited and is, for example, 5.0°C or more. These upper and lower limits can be arbitrarily combined, and the exothermic peak width can be, for example, 5.0°C or more and 23.7°C or less, 5.0°C or more and 23.5°C or less, 5.0°C or more and 12.0°C or less, 5.0°C or more and 10.0°C or less, or 5.0°C or more and 9.0°C or less. The exothermic peak width is a value measured by the method described in the examples. The exothermic peak width can be adjusted, for example, by the content of the terminal structure represented by formula (2) in PEEK. Generally, the width of the exothermic peak decreases as the content of the terminal structure represented by formula (2) in PEEK increases.

[0024] Some or all of the ends (usually two) of the molecular chains constituting PEEK (one or both ends when there are two ends) can have the end structure represented by formula (2). Of the ends of the molecular chains constituting PEEK, the ends having the end structure represented by formula (2) are represented, for example, by formula (3) or (4) below.

[0025]

[0026] That is, in PEEK, the terminal structure represented by formula (2) can form a terminal represented by formula (3) or (4). The carbonyl group in formulas (3) and (4) can correspond to the carbonyl group in formula (1). PEEK may have only one of the terminals represented by formulas (3) and (4), or may have both of the terminals represented by formulas (3) and (4). In PEEK, the terminal having the terminal structure represented by formula (2) is not limited to the examples of formulas (3) and (4), as long as it has the terminal structure represented by formula (2).

[0027] Among the terminals of PEEK, the terminal structure of the terminal not having the terminal structure represented by formula (2) is not particularly limited and may be any structure, such as a hydrogen atom, a halogen atom, etc. The terminal structure of the terminal not having the terminal structure represented by formula (2) may be, for example, an arbitrary structure (for example, a hydrogen atom, a halogen atom, etc.) bonded to the right end or left end of the repeating unit represented by formula (1). Note that the PEEK of this embodiment does not necessarily have an ionic group (-A-X; A is an anion and X is a metal cation) as described in Patent Document 1 at the end of the molecular chain, and it is preferable that it does not have such an ionic group.

[0028] In one embodiment, PEEK does not contain any other repeating units other than the repeating unit represented by formula (1), but may have a terminal structure at the end of the molecular chain as described above.

[0029] In one embodiment, the PEEK contains structural units other than the repeating unit represented by formula (1) and the terminal structure represented by formula (2), within a range that does not impair the effects of the present invention. The other structural units are not particularly limited, and examples include those in which the linking position in the terminal structure represented by formula (1) or formula (2) is different (those in which the linking position is not the para position). Another example of the other structural unit is the structural unit represented by the following formula (5) (polyether ether ketone (PEEEK) structural unit).

[0030] The repeating unit represented by formula (1) and the repeating unit represented by formula (5) are different from each other, and in the aromatic polyether copolymer, a partial structure corresponding to the repeating unit represented by formula (5) is considered to be a repeating unit represented by formula (5), but is not considered to be a repeating unit represented by formula (1).

[0031] In one embodiment, the PEEK does not contain a repeating unit represented by the following formula (6), or contains a repeating unit represented by formula (6), and when it contains a repeating unit represented by formula (6), the molar ratio of the repeating unit represented by formula (6) to the total of the repeating unit represented by formula (1) and the repeating unit represented by formula (6) is less than 25 mol%, 20 mol% or less, 15 mol% or less, 10 mol% or less, less than 5 mol%, 4 mol% or less, 3 mol% or less, 1 mol% or less, 0.5 mol% or less, 0.3 mol% or less, or 0.1 mol% or less.

[0032]

[0033] In formula (6), three R １ are each independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium. Three a's are each independently selected from the group consisting of integers of 0 to 4. All three a's may be 0.

[0034] The smaller the molar ratio, the more the crystallinity of PEEK can be improved. ｍ and crystallization temperature T ｃ This can improve the usable temperature range of products containing PEEK, and the effect of widening the usable temperature range of products containing PEEK is obtained. When the content is less than 25 mol %, this effect is obtained significantly, and when it is less than 5 mol %, this effect is obtained particularly significantly. From the viewpoint of obtaining this effect, it is most preferable that the PEEK does not contain the repeating unit represented by formula (6) (the above molar ratio is 0 mol %).

[0035] In one embodiment, the proportion (mass %) of the repeating unit represented by formula (1) relative to (i) the portion excluding the terminal structure from the entire PEEK, or (ii) the sum of all repeating units constituting the PEEK, is 50 mass % or more, 60 mass % or more, 70 mass % or more, 80 mass % or more, 90 mass % or more, 95 mass % or more, 97 mass % or more, 99 mass % or more, 99.5 mass % or more, or 100 mass %.

[0036] 2. Method for Producing Polyether Ether Ketone (First Aspect of the Method for Producing Polyether Ether Ketone) A first aspect of the method for producing PEEK according to the present invention is a method for producing PEEK, which produces the PEEK according to the aspect of the present invention described above, and includes reacting hydroquinone with 4,4'-dihalogenobenzophenone, and satisfies the condition b / a<1.00, where a mol is the amount of substance of hydroquinone and b mol is the amount of substance of 4,4'-dihalogenobenzophenone supplied to the reaction.

[0037] Hydroquinone and 4,4'-dihalogenobenzophenone are monomers for producing PEEK by polymerization. By making the amount of hydroquinone used in the reaction greater than the amount of 4,4'-dihalogenobenzophenone (satisfying the condition b / a<1.00), it is possible to suitably produce PEEK containing the repeating unit represented by formula (1) and the terminal structure represented by formula (2). As described for the PEEK according to one embodiment of the present invention, this PEEK has a high crystallization temperature T ｃ It has excellent processability.

[0038] In conventional PEEK production methods, from the viewpoint of production efficiency and the like, synthesis is typically performed under the condition of b / a = 1.00, which theoretically maximizes the molecular weight of the polymer. In contrast, in the present embodiment, PEEK containing repeating units represented by formula (1) and a terminal structure represented by formula (2) is preferably produced by satisfying the condition of b / a < 1.00. Note that in the present embodiment, it is also possible to increase the molecular weight of PEEK containing repeating units represented by formula (1) and a terminal structure represented by formula (2), for example, by increasing the total concentration of hydroquinone and 4,4'-dihalogenobenzophenone used in the reaction (details will be described later).

[0039] In one embodiment of the first aspect, the method for producing PEEK satisfies, for example, the condition b / a≦0.99, b / a≦0.98, or b / a≦0.97. The method for producing PEEK preferably satisfies the condition b / a≦0.98. This reduces the crystallization temperature T ｃ The lower limit of b / a is not particularly limited, and may be, for example, 0.95≦b / a.

[0040] In the first aspect, the 4,4'-dihalogenobenzophenone to be reacted is not particularly limited, and the two halogen atoms may be the same or different. The two halogen atoms may each independently be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. In one embodiment of the first aspect, the 4,4'-dihalogenobenzophenone is one or more selected from the group consisting of 4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone.

[0041] In the first embodiment, the PEEK according to one aspect of the present invention is obtained by reacting (polymerizing) these components in a reaction mixture in which hydroquinone and 4,4'-dihalogenobenzophenone are blended as monomers so as to satisfy the condition b / a<1.00.

[0042] In one embodiment of the first aspect, the reaction mixture contains a solvent. The solvent is not particularly limited, and for example, an aprotic polar solvent can be used. Examples of aprotic polar solvents include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-n-propyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, and N-methyl-3-methyl-2-pyrrolidone. , N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5-trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, N-isopropyl-2-piperidone, N-methyl-6-methyl-2-piperidone, N-methyl-3-ethylpiperidone, dimethyl sulfoxide, diethyl sulfoxide, 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, N,N'-dimethylimidazolidinone, diphenyl sulfone, and the like. Among these, diphenyl sulfone is particularly preferred. The reaction mixture can contain one or more solvents.

[0043] In one embodiment of the first aspect, the reaction mixture contains a base. The base is not particularly limited, and examples thereof include alkali metal salts. Examples of alkali metal salts include alkali metal carbonates and alkali metal bicarbonates. Examples of alkali metal carbonates include potassium carbonate, lithium carbonate, rubidium carbonate, and cesium carbonate. Examples of alkali metal bicarbonates include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, and cesium bicarbonate. Among these, potassium carbonate is particularly preferred. The reaction mixture may contain one or more bases.

[0044] In one embodiment of the first aspect, the amount of the base in the reaction mixture (the total amount when two or more bases are used) is 100 mol parts or more and 300 mol parts or less, 250 mol parts or less, 200 mol parts or less, 180 mol parts or less, 160 mol parts or less, 140 mol parts or less, or 120 mol parts or less, relative to 100 mol parts of the amount of hydroquinone.

[0045] In the first aspect, the total concentration (based on the amount of addition) of hydroquinone and 4,4'-dihalogenobenzophenone in the reaction mixture is not particularly limited. In one embodiment, the total concentration (based on the amount of addition) of hydroquinone and 4,4'-dihalogenobenzophenone in the reaction mixture is 1.0 mol / L or more, 1.2 mol / L or more, 1.3 mol / L or more, 1.4 mol / L or more, or 1.5 mol / L or more, and is 6.0 mol / L or less, 5.0 mol / L or less, or 4.0 mol / L or less.

[0046] In one embodiment of the first aspect, no other monomers than hydroquinone and 4,4'-dihalogenobenzophenone are used as monomers to be subjected to the above-mentioned reaction.

[0047] In one embodiment of the first aspect, the monomers to be subjected to the above-mentioned reaction may contain other monomers in addition to hydroquinone and 4,4'-dihalogenobenzophenone, as long as the effects of the present invention are not impaired.

[0048] In one embodiment of the first aspect, the total amount (mass%) of hydroquinone and 4,4'-dihalogenobenzophenone relative to the amount of all monomers in the reaction mixture is 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, 99 mass% or more, 99.5 mass% or more, or 100 mass%.

[0049] In the first embodiment, the reaction mixture may or may not contain other components other than hydroquinone, 4,4'-dihalogenobenzophenone, base and solvent.

[0050] In one embodiment of the first aspect, at the start of the reaction, the reaction mixture comprises 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.9% by mass or more, or substantially 100% by mass of the reaction mixture. Note that "substantially 100% by mass" may contain inevitable impurities.

[0051] In the first embodiment, the reaction between hydroquinone and 4,4'-dihalogenobenzophenone can be carried out under an inert gas atmosphere. The inert gas is not particularly limited, and examples thereof include nitrogen gas and argon gas.

[0052] In one embodiment of the first aspect, the reaction mixture is heated during the reaction between hydroquinone and 4,4'-dihalogenobenzophenone. The maximum temperature (maximum temperature reached) of the reaction mixture during the reaction is not particularly limited as long as it is a temperature at which PEEK is produced, and may be, for example, 250 to 350°C. In one embodiment, the maximum temperature reached is greater than 200°C, 210°C or higher, 220°C or higher, 230°C or higher, 240°C or higher, 250°C or higher, 260°C or higher, 270°C or higher, or 280°C or higher. Note that if the maximum temperature reached is 200°C or lower, the terminal structure represented by formula (2) is not usually introduced into the PEEK. Furthermore, when heating the reaction mixture, it is preferable to continue heating at a temperature of 250°C or higher for preferably 3 hours or more (this time includes not only the time during which the temperature is maintained constant, but also the time for heating and cooling; the same applies hereinafter), and more preferably for 3.5 hours or more. Furthermore, during the duration of such heating, the time for which the reaction mixture is heated to 280°C or higher is preferably 1 hour or longer, more preferably 2 hours or longer, which allows the terminal structure represented by formula (2) to be suitably introduced into PEEK.

[0053] (Second Aspect of Method for Producing Polyether Ether Ketone) A second aspect of the method for producing PEEK according to the present invention is a method for producing the PEEK according to the above-described aspect of the present invention, and includes reacting hydroquinone, 4,4'-dihalogenobenzophenone, and one or more selected from the group consisting of 4-phenoxyphenol and 4-halogenodiphenyl ether.

[0054] Hydroquinone and 4,4'-dihalogenobenzophenone are monomers used to produce PEEK by polymerization. 4-Phenoxyphenol and 4-halogenodiphenyl ether are also monomers, and in particular function as end-capping agents while forming the end structure represented by formula (2) (hereinafter, 4-phenoxyphenol and 4-halogenodiphenyl ether may be collectively referred to as "end-capping agent A"). This makes it possible to suitably produce PEEK containing the repeating unit represented by formula (1) and the end structure represented by formula (2). As described for the PEEK according to one embodiment of the present invention, this PEEK has a high crystallization temperature T ｃ It has excellent processability.

[0055] The halogen atoms contained in the 4-halogenodiphenyl ether used as end-capping agent A are not particularly limited. Examples of 4-halogenodiphenyl ethers include 4-fluorodiphenyl ether, 4-chlorodiphenyl ether, 4-bromodiphenyl ether, and 4-iododiphenyl ether. These may be used alone or in combination of two or more. In one embodiment, 4-phenoxyphenol is used as end-capping agent A.

[0056] In the second aspect, when the amount of hydroquinone and the amount of 4,4'-dihalogenobenzophenone used in the reaction are expressed as a mol and b mol, respectively, b / a is not particularly limited, and it is not essential to satisfy the condition b / a<1.00 as in the first aspect. In the second aspect, the condition b / a<1.00 may be satisfied, or the condition 1.00≦b / a may be satisfied. In one embodiment of the second aspect, the method for producing PEEK satisfies, for example, the condition 1.00≦b / a or 1.01≦b / a. The upper limit of b / a is not particularly limited, and can be, for example, b / a≦1.10.

[0057] In the second aspect, the amount (blended amount) of end-capping agent A used in the reaction is not particularly limited. In the second aspect, the content of the end structure represented by formula (2) in the resulting PEEK can be adjusted by adjusting the blended amount of end-capping agent A. Generally, the content of the end structure represented by formula (2) in the resulting PEEK can be increased by increasing the blended amount of end-capping agent A. In one embodiment of the second aspect, when the amount of hydroquinone used in the reaction is expressed in amol and the amount of end-capping agent A is expressed in cmol, the ratio of 0<c / a, 2.50×10 －４ ≦c / a or 1.25×10 －３ ≦c / a, and c / a≦5.00×10 －２ , c / a≦1.00×10 －２ , c / a≦5.00×10 －３ or less or c / a≦2.50×10 －３ Meet the following conditions:

[0058] In the second embodiment, the 4,4'-dihalogenobenzophenone to be subjected to the reaction is not particularly limited, and the explanation given for the first embodiment is applicable.

[0059] In the second embodiment, the PEEK according to one aspect of the present invention is obtained by reacting (polymerizing and end-capping) these components in a reaction mixture containing hydroquinone, 4,4'-dihalogenobenzophenone, and end-capping agent A as monomers.

[0060] In one embodiment of the second aspect, the reaction mixture comprises a solvent. The solvent is not particularly limited, and the explanation given for the first aspect is incorporated herein.

[0061] In one embodiment of the second aspect, the reaction mixture contains a base. The type and amount of the base are not particularly limited, and the explanation for the first aspect is applicable.

[0062] In the second embodiment, the total concentration (based on the blending amount) of hydroquinone and 4,4'-dihalogenobenzophenone in the reaction mixture is not particularly limited, and the explanation given for the first embodiment is applicable.

[0063] In one embodiment of the second aspect, the monomers used in the reaction are hydroquinone, 4,4′-dihalogenobenzophenone, and the end-capping agent A. In the first aspect, the end-capping agent A is not essential, but may or may not be used as another monomer in the reaction.

[0064] In one embodiment of the second aspect, the monomers to be subjected to the above-described reaction may contain other monomers other than hydroquinone, 4,4′-dihalogenobenzophenone, and end-capping agent A, as long as the effects of the present invention are not impaired.

[0065] In one embodiment of the second aspect, the total amount (mass%) of hydroquinone, 4,4'-dihalogenobenzophenone, and end-capping agent A relative to the amount of all monomers in the reaction mixture is 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, 99 mass% or more, 99.5 mass% or more, or 100 mass%.

[0066] In the second embodiment, the reaction mixture may or may not contain components other than hydroquinone, 4,4′-dihalogenobenzophenone, endcapping agent A, a base, and a solvent. The explanation for the first embodiment applies to the other components.

[0067] In one embodiment of the second aspect, at the start of the reaction, the reaction mixture comprises 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.9% by mass or more, or substantially 100% by mass of hydroquinone, 4,4'-dihalogenobenzophenone, endcapping agent A, a base, and a solvent. Note that "substantially 100% by mass" may contain inevitable impurities.

[0068] In the second embodiment, the reaction of hydroquinone, 4,4'-dihalogenobenzophenone, and end-capping agent A can also be carried out under an inert gas atmosphere. The inert gas is not particularly limited, and examples thereof include nitrogen and argon gas.

[0069] In one embodiment of the second aspect, the reaction mixture is heated during the reaction of hydroquinone, 4,4′-dihalogenobenzophenone, and endcapping agent A. The explanation for the first aspect applies to the maximum temperature (maximum reached temperature) of the reaction mixture during the reaction.

[0070] In the second embodiment, the endcapping agent A may be added to the reaction mixture either before or after the initiation of the reaction between the hydroquinone and the 4,4'-dihalogenobenzophenone.

[0071] In one embodiment, the PEEK according to one aspect of the present invention and the PEEK produced by the method for producing PEEK according to one aspect of the present invention (particularly the PEEK obtained by the second aspect) are １ The following formula (I) in the H-NMR spectrum Ｘ The integral ratio X expressed by (B / 2) / (A / 4) exceeds 0%. X [%] = {(B / 2) / (A / 4)} × 100 (I Ｘ ) (Formula (I) Ｘ), A is the integral value in the chemical shift range of 7.32 ppm to 7.42 ppm, and B is the integral value in the chemical shift range of 7.89 ppm to 7.93 ppm.) In the integral range corresponding to integral value A (chemical shift range of 7.32 ppm to 7.42 ppm), a peak derived from the repeating unit represented by formula (1) is observed. In the integral range corresponding to integral value B (chemical shift range of 7.89 ppm to 7.93 ppm), a peak derived from the chlorine atoms bonded to the main chain end of PEEK is observed. Integral values ​​A and B are １ It is determined based on the H-NMR spectrum by the following method. The integral value A was determined by connecting the intensities at chemical shifts of 7.15 ppm and 7.42 ppm with a straight line (baseline), and integrating the intensity based on this baseline (the intensity when the baseline intensity is set to 0) over the chemical shift range of 7.32 ppm to 7.42 ppm. If no peak is observed in the chemical shift range of 7.32 ppm to 7.42 ppm, the integral value A is set to 0. The integral value B was determined by connecting the intensities at chemical shifts of 7.89 ppm and 7.93 ppm with a straight line (baseline), and integrating the intensity based on this baseline (the intensity when the baseline intensity is set to 0) over the chemical shift range of 7.89 ppm to 7.93 ppm. If no peak is observed in the chemical shift range of 7.89 ppm to 7.93 ppm, the integral value B is set to 0. An integral ratio X exceeding 0% indicates the presence of PEEK having a chlorine atom bonded to at least one of the main chain ends. One method for obtaining PEEK with an integral ratio X exceeding 0% is to use a monomer containing a chlorine atom (e.g., dichlorobenzophenone) as the monomer used as a raw material for PEEK.

[0072] In one embodiment, the PEEK according to one aspect of the present invention and the PEEK produced by the method for producing PEEK according to one aspect of the present invention may or may not contain fluorine atoms. Also, in one embodiment, the PEEK may or may not contain chlorine atoms. Hereinafter, the fluorine atom content a and the chlorine atom content b of the PEEK are values ​​measured by combustion ion chromatography described in the examples.

[0073] In one embodiment, the fluorine atom content a of the PEEK is less than 2 mg / kg. This allows the effects of the present invention to be exhibited satisfactorily. The lower limit is not particularly limited and may be, for example, 0 mg / kg. Here, the fluorine atom content a is the sum of the content a1 of fluorine atoms contained in the molecular structure of the PEEK and the content a2 of fluorine atoms contained as components (free components) not contained in the molecular structure of the PEEK.

[0074] In one embodiment, the fluorine atom content a of PEEK can be made less than 2 mg / kg by not using a raw material containing fluorine atoms (e.g., 4,4′-difluorobenzophenone) during synthesis of PEEK or by reducing the amount of raw material containing fluorine atoms used during synthesis of PEEK.

[0075] In one embodiment, the free component in the fluorine atom content a2 is one or both of potassium fluoride and 4,4'-difluorobenzophenone.

[0076] In one embodiment, the chlorine atom content b of PEEK is 2 mg / kg or more, 10 mg / kg or more, 100 mg / kg or more, 500 mg / kg or more, 700 mg / kg or more, 1000 mg / kg or more, 2000 mg / kg or more, 33000 mg / kg or more, or 4000 mg / kg or more. This allows the effects of the present invention to be exhibited favorably. The upper limit is not particularly limited, and may be, for example, 10000 mg / kg or less, 9000 mg / kg or less, 8000 mg / kg or less, 7000 mg / kg or less, 6000 mg / kg or less, or 3000 mg / kg or less. The chlorine atom content b of PEEK is, for example, 2 to 10000 mg / kg, preferably 300 to 6000 mg / kg, and more preferably 300 to 3000 mg / kg. Here, the chlorine atom content b is the sum of the chlorine atom content b1 contained in the molecular structure of PEEK and the chlorine atom content b2 contained as components (free components) not contained in the molecular structure of PEEK.

[0077] In one embodiment, the chlorine atom content b of PEEK can be increased to 2 mg / kg or more by including 4,4'-dichlorobenzophenone in the raw materials used in synthesizing PEEK. Also, by using 4,4'-dichlorobenzophenone and hydroquinone as raw materials in synthesizing PEEK and increasing the ratio of the amount of 4,4'-dichlorobenzophenone used to the amount of hydroquinone used, the chlorine atom content b of PEEK can be increased to a range of 2 mg / kg or more.

[0078] In one embodiment, the chlorine atom content b1 is 0 mg / kg or more, 100 mg / kg or more, 200 mg / kg or more, or 400 mg / kg or more. The upper limit is not particularly limited and may be, for example, 10,000 mg / kg or less, 9,000 mg / kg or less, 8,000 mg / kg or less, 7,000 mg / kg or less, 6,000 mg / kg or less, or 3,000 mg / kg or less. In one embodiment, the chlorine atom content b2 is 0 mg / kg or more, 2 mg / kg or more, 5 mg / kg or more, or 10 mg / kg or more. The upper limit is not particularly limited and may be, for example, 500 mg / kg or less, 400 mg / kg or less, or 300 mg / kg or less.

[0079] In one embodiment, the free component in the chlorine atom content b2 is one or both of potassium chloride and 4,4'-dichlorobenzophenone.

[0080] The chlorine atoms contained in PEEK as a free component, potassium chloride, can be quantified using the following method. <Method for Measuring the Chlorine Atoms Contained in PEEK as a Free Component, Potassium Chloride> A solid sample (PEEK) is pulverized in a blender, washed with acetone and then water, and dried in an explosion-proof dryer at 180°C. When using the reaction mixture (product) immediately after the reaction to produce PEEK as the sample, the product is cooled and solidified after the reaction is completed to obtain the solid sample. The blender used is not particularly limited; for example, a Waring 7010HS blender can be used. Approximately 1 g of the dried sample is weighed, 100 ml of ultrapure water is added, and the mixture is stirred at 50°C for 20 minutes. After cooling, the mixture is filtered to separate the solids and the aqueous solution. The aqueous solution is analyzed by ion chromatography, and the chloride ions in the aqueous solution are quantified based on a calibration curve created from a reference of known concentration. The ion chromatography conditions are as follows: <Ion chromatograph> Analytical device: Metrohm 940 IC Vario Column: A guard column (Metrosep A Supp 5 Guard) and a separation column (Metrosep A Supp 4) were used in conjunction (both columns manufactured by Metrohm). Eluent: Na ２ CO ３ (1.8 mmol / l) + NaHCO (1.7 mmol / l) Flow rate: 1.0 ml / min Column temperature: 30°C Measurement mode: Suppressor method Detector: Electrical conductivity detector

[0081] The amount of chlorine atoms contained in PEEK as 4,4'-dichlorobenzophenone, a free component, can be quantified using the following method. <Method for Measuring the Amount of Chlorine Atoms Contained in PEEK as 4,4'-dichlorobenzophenone, a Free Component> A solid sample (PEEK) is pulverized in a blender, washed with acetone and then with water, and dried in an explosion-proof dryer at 180°C. When using the reaction mixture (product) immediately after the reaction to produce PEEK as the sample, the product is cooled and solidified after the reaction is completed to obtain the solid sample. The blender used is not particularly limited; for example, a Waring 7010HS blender can be used. Approximately 1 g of the dried sample is weighed into a recovery flask, to which 10 ml of acetone and boiling stones are added, and the mixture is heated to reflux in a water bath for 5 hours. After cooling to room temperature, the solids are removed by filtration. The resulting acetone solution is evaporated to dryness, and then 10 ml of acetone is added using a volumetric pipette to redissolve the sample. This is measured by gas chromatography to calculate the amount of 4,4'-dichlorobenzophenone (mg / kg) in the sample. The amount of chlorine atoms (mg / kg) contained in the free component 4,4'-dichlorobenzophenone in PEEK is calculated using the following formula: Amount of chlorine atoms (mg / kg) contained in the free component 4,4'-dichlorobenzophenone in PEEK = Amount of 4,4'-dichlorobenzophenone in the sample (mg / kg) ÷ 251.11 (molecular weight of 4,4'-dichlorobenzophenone) × 35.45 (atomic weight of chlorine) × 2 The quantitative value of 4,4'-dichlorobenzophenone is determined based on a calibration curve created from references of known concentrations. The measurement conditions are shown below. <Gas chromatograph> Analytical device: Agilent Technologies 7890B GC column: Agilent Technologies DB-5MS (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm) Injection port temperature: 250°C Oven temperature: 100°C (1 min) → 30°C / min → 250°C (10 min) Flow rate: 1 ml / min Injection volume: 1 μl Split ratio: 40:1 Detector: FID Detector temperature: 250°C

[0082] In one embodiment, the PEEK according to one aspect of the present invention and the PEEK produced by the method for producing PEEK according to one aspect of the present invention are produced using at least hydroquinone and 4,4'-dichlorobenzophenone as monomers.

[0083] 3. Uses The uses of the PEEK according to one aspect of the present invention and the PEEK produced by the method for producing PEEK according to one aspect of the present invention described above (hereinafter, these PEEKs may be collectively referred to simply as "PEEK") are not particularly limited. PEEK has excellent processability and can be preferably applied to various processes.

[0084] As an example of processing, it is preferable to subject PEEK to molding. An example of molding is a method in which PEEK is molded in a molten state and then cooled and solidified. A molded body can be produced by molding PEEK. Known methods such as injection molding, extrusion molding, and blow molding can be used for molding. PEEK can also be press-molded, and known methods such as cold pressing and hot pressing can be used. Furthermore, PEEK can be used in 3D printer ink and molded by a 3D printer.

[0085] As an example of processing, PEEK may be used to form a composite material containing PEEK and fibers. The fibers are not particularly limited, and examples thereof include fibers of inorganic compounds. Examples of inorganic compound fibers include glass fibers and carbon fibers. In the composite material, the fibers may be dispersed in the PEEK, or the fibers (e.g., in the form of a cloth) may be impregnated with PEEK. The cloth is composed of fibers arranged in a plane. The cloth may be, for example, a woven fabric, a nonwoven fabric, or a unidirectional material. The unidirectional material is composed of fibers aligned in one direction. The composite material may be subjected to the above-mentioned molding.

[0086] Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0087] In the following Examples 1 to 5, PEEK is produced by the first embodiment of the PEEK production method, and in Examples 6 and 7, PEEK is produced by the second embodiment of the PEEK production method.

[0088] (Example 1) 0.1617 mol of hydroquinone and 0.1601 mol of 4,4'-dichlorobenzophenone were placed in a 300 ml separable flask as monomers. Potassium carbonate (K ２ CO ３ 0.2425 mol of methyl 2-hydroxybenzoate (special grade, manufactured by Junsei Chemical Co., Ltd.) was added, and 140 g of diphenyl sulfone was added as a solvent.

[0089] A ribbon heater was wrapped around the top of the separable flask, and glass wool was wrapped around it to maintain the temperature. The entire bottom of the separable flask was also wrapped in a mantle heater. Under nitrogen (flow rate: 0.1 L / min), the reaction mixture in the separable flask was heated and stirred using a mechanical stirrer. The ribbon heater was set to 150°C and the mantle heater to 165°C. After heating for 30 minutes while stirring at a stirring speed of 100 rpm, the stirring speed was changed to 210 rpm, and the reaction mixture was heated to 200°C over 30 minutes. After heating, the temperature was maintained at 200°C for 1 hour and then increased again to 250°C over 30 minutes. After maintaining the temperature at 250°C for 1 hour, the stirring speed was changed to 250 rpm, and the temperature was increased to 300°C over 30 minutes. After heating, the temperature was maintained at 300°C for 2 hours, after which the reaction was terminated and the mother liquor was removed. The recovered product was crushed and washed with acetone and water to obtain a polymer.

[0090] <Evaluation Method> (1) Structural Analysis The obtained polymer (sample) was identified and its primary structure was analyzed. １ H-NMR was performed under the following measurement conditions. [Measurement conditions] Magnet: Ascend 500 Spectrometer: AVANCE III HD Probe: 5 mm diameter TCI cryoprobe Number of accumulations: 256 Waiting time: 10 seconds Sample preparation: 0.6 mL of methanesulfonic acid was added to approximately 20 mg of sample and stirred for 1 hour. 0.4 mL of deuterated dichloromethane was added to the sample to prepare the measurement sample.

[0091] The polymer containing the repeating unit represented by formula (1) and the terminal structure represented by formula (2) is １ This was confirmed by observing both a main chain peak and a PhP unit peak in the H-NMR measurement. The PhP unit peak corresponds to two phenyl groups bonded to the 2- and 6-positions of the terminal phenyl groups in the terminal structure represented by formula (2). １ This is observed as a H peak.

[0092] Also, the polymer １ The intensity ratio (peak intensity ratio) of the intensity of the PhP unit peak (chemical shift 7.04 ppm) to the intensity of the main chain peak (chemical shift 7.34 ppm) in the H-NMR measurement was calculated according to the following formula: Peak intensity ratio [%] = (PhP unit peak intensity / main chain peak intensity) × 100

[0093] (2) Combustion Ion Chromatography The fluorine atom content a and chlorine atom content b in PEEK were measured by combustion ion chromatography. Specifically, a sample was introduced into a combustion furnace, thermally decomposed under an argon gas atmosphere, and then combusted in an oxygen-containing gas. The generated gas was collected in an absorption liquid, and the fluoride ions and chloride ions contained in the absorption liquid were measured by ion chromatography. The fluorine and chlorine contents were calculated using a calibration curve. The measurement conditions are shown below. <Sample Combustion> Combustion apparatus: AQF-2100H manufactured by Nitto Seiko Analytech Combustion furnace set temperature: 800°C in front, 1000°C in rear Argon flow rate: 200 ml / min Oxygen flow rate: 400 ml / min Absorbent: Ultrapure water containing hydrogen peroxide <Ion Chromatography> Analytical apparatus: Integration manufactured by Thermo Fisher Scientific Column: AS-12A / AG-12A Eluent: Na2CO3 (2.7 mmol / L) + NaHCO3 (0.3 mmol / L) Flow rate: 1.5 ml / min Column temperature: 30°C Detector: Electrical conductivity detector Note that the lower limit of quantitation for fluorine and chlorine atoms in the above measurement method is 2 mg / kg. When these atoms are below the lower limit of quantitation, they are indicated as "<2" (mg / kg) in Table 1.

[0094] (3) Measurement of thermal properties (differential scanning calorimetry (DSC)) 5 mg of the obtained polymer (sample) was weighed into an aluminum pan and subjected to temperature scanning measurement using a differential scanning calorimeter (PerkinElmer "DSC8500"). The temperature scanning was performed in the following order: nitrogen was circulated at 20 ml / min, the sample temperature was raised from 50°C to 420°C at 20°C / min (first heating), held at 420°C for 1 minute, cooled from 420°C to 50°C at 20°C / min (first cooling), held at 50°C for 1 minute, and heated from 50°C to 420°C at 20°C / min (second heating).

[0095] Crystallization temperature T ｃ was determined by reading the exothermic peak due to crystallization observed during the first cooling. The exothermic peak width was determined as the difference between the "extrapolated onset point" and the "extrapolated end point" of the exothermic peak due to crystallization during the first cooling. Here, in the case of measurements during cooling, the "extrapolated onset point" is the point (temperature) where the tangent to the point of maximum slope on the high-temperature side of the peak intersects with the baseline, and the "extrapolated end point" is the point (temperature) where the tangent to the point of maximum slope on the low-temperature side of the peak intersects with the baseline. Here, the difference between the "extrapolated onset point" and the "extrapolated end point" was determined using thermal analysis software "Pyris" manufactured by PerkinElmer. The glass transition temperature T ｇ The melting point T was calculated by reading the baseline shift due to the glass transition observed during the second heating and determining it as the temperature of the transition midpoint (midpoint of transition). ｍ was determined as the peak top temperature by reading the endothermic peak due to melting observed during the second heating. The DSC curve during the first cooling in the DSC measurement is shown in Figure 1. The vertical axis of the DSC curve, "normalized heat flow [W / g]," refers to the heat flow (amount of heat change per unit time) [W] normalized per 1 g of sample.

[0096] (4) Melt Flow Rate (MFR) The melt flow rate of the obtained polymer (sample) was measured using a melt indexer (L-220) manufactured by Tateyama Kagaku High-Technologies Corporation in accordance with JIS K 7210-1:2014 (ISO 1133-1:2011) under the following measurement conditions. [Measurement Conditions] Measurement temperature: 380°C Measurement load: 2.16 kg Cylinder inner diameter: 9.550 mm Die inner diameter: 2.095 mm Die length: 8.000 mm Piston head length: 6.35 mm Piston head diameter: 9.474 mm Procedure: The sample was dried in advance at 150°C for more than 2 hours. The sample was placed in the cylinder, and the piston was inserted and preheated for 6 minutes. A load was applied, the piston guide was removed, and the molten sample was extruded from the die. A sample was cut out at a predetermined range of piston movement and at a predetermined time (t [s]), and its weight was measured (m [g]). The MFR was calculated using the following formula: MFR [g / 10 min] = 600 / t × m

[0097] (Example 2) In Example 1, the amount of hydroquinone added was changed to 0.1617 mol, the amount of 4,4'-dichlorobenzophenone added was changed to 0.1585 mol, and potassium carbonate (K ２ CO ３ A polymer was obtained in the same manner as in Example 1, except that the amounts of the above-mentioned compounds (a) and (b) were changed to 0.2425 mol. The results of evaluation in the same manner as in Example 1 are shown in Table 1. The DSC curve during the first temperature decrease in the DSC measurement is shown in Figure 1.

[0098] (Example 3) In Example 1, the amount of hydroquinone added was changed to 0.1617 mol, the amount of 4,4'-dichlorobenzophenone added was changed to 0.1568 mol, and potassium carbonate (K ２ CO ３ A polymer was obtained in the same manner as in Example 1, except that the amounts of the above-mentioned compounds were changed to 0.2425 mol. The results of evaluation in the same manner as in Example 1 are shown in Table 1. The DSC curve obtained during the first temperature drop in the DSC measurement is shown in Figure 1. １ The H-NMR spectrum is shown in FIG.

[0099] Example 4 A polymer was obtained in the same manner as in Example 1, except that the heating conditions for the reaction mixture in Example 1 were changed as follows. The results of evaluation performed in the same manner as in Example 1 are shown in Table 1. <Heating Conditions> The ribbon heater was set to 150°C and the mantle heater to 165°C. Heating was performed for 30 minutes while stirring at a stirring speed of 100 rpm, and then the stirring speed was changed to 210 rpm, and the reaction mixture was heated to 200°C over 30 minutes. After heating, the temperature was maintained at 200°C for 1 hour, and then the temperature was again raised to 250°C over 30 minutes. After maintaining the temperature at 250°C for 1 hour, the stirring speed was changed to 250 rpm, and the temperature was raised to 320°C over 30 minutes. After heating, the temperature was maintained at 320°C for 2 hours, and then the reaction was terminated.

[0100] Example 5 A polymer was obtained in the same manner as in Example 1, except that the heating conditions for the reaction mixture in Example 1 were changed as follows. The results of evaluation performed in the same manner as in Example 1 are shown in Table 1. <Heating Conditions> The ribbon heater was set to 150°C and the mantle heater to 165°C. Heating was performed for 30 minutes while stirring at a stirring speed of 100 rpm, and then the stirring speed was changed to 210 rpm, and the reaction mixture was heated to 200°C over 30 minutes. After heating, the temperature was maintained at 200°C for 1 hour, and the temperature was again raised to 250°C over 30 minutes. After maintaining the temperature at 250°C for 1 hour, the stirring speed was changed to 250 rpm, and the temperature was raised to 280°C over 30 minutes. After heating, the temperature was maintained at 280°C for 2 hours, and the reaction was then terminated.

[0101] Comparative Example 1 In Example 1, the amount of hydroquinone added was changed to 0.1617 mol, the amount of 4,4′-dichlorobenzophenone added was changed to 0.1641 mol, and potassium carbonate (K ２ CO ３ A polymer was obtained in the same manner as in Example 1, except that the amounts of the above-mentioned compounds (a) and (b) were changed to 0.2425 mol. The polymer was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0102] (Example 6) 0.1615 mol of hydroquinone and 0.1633 mol of 4,4'-dichlorobenzophenone were charged as monomers into a 300 ml separable flask. 0.0004043 mol of 4-phenoxyphenol was also charged. Potassium carbonate (K ２ CO ３ 0.1860 mol of methyl 2-hydroxybenzoate was added, and 140 g of diphenyl sulfone was added as a solvent.

[0103] A ribbon heater was wrapped around the top of the separable flask, and glass wool was wrapped around it to maintain the temperature. The entire bottom of the separable flask was also wrapped in a mantle heater. Under nitrogen (flow rate: 0.1 L / min), the reaction mixture in the separable flask was heated and stirred using a mechanical stirrer. The ribbon heater was set to 150°C and the mantle heater to 165°C. After heating for 30 minutes while stirring at a stirring speed of 100 rpm, the stirring speed was changed to 210 rpm, and the reaction mixture was heated to 200°C over 30 minutes. After heating, the temperature was maintained at 200°C for 1 hour and then increased again to 250°C over 30 minutes. After maintaining the temperature at 250°C for 1 hour, the stirring speed was changed to 250 rpm, and the temperature was increased to 300°C over 30 minutes. After heating, the temperature was maintained at 300°C for 2 hours, after which the reaction was terminated and the mother liquor was removed. The recovered product was crushed and washed with acetone and water to obtain a polymer. The evaluation was carried out in the same manner as in Example 1, and the results are shown in Table 1.

[0104] A polymer was obtained in the same manner as in Example 6, except that the amount of hydroquinone added was changed to 0.1614 mol and the amount of 4-phenoxyphenol added was changed to 0.0008085 mol. The results were evaluated in the same manner as in Example 1 and are shown in Table 1.

[0105] Comparative Example 2 In Example 6, the addition of 4-phenoxyphenol was omitted, the amount of hydroquinone added was 0.1617 mol, the amount of 4,4′-dichlorobenzophenone added was 0.1641 mol, and potassium carbonate (K ２ CO ３A polymer was obtained in the same manner as in Example 6, except that the amounts of the above-mentioned compounds (a) and (b) were changed to 0.1860 mol. The results of evaluation in the same manner as in Example 1 are shown in Table 1. The DSC curve obtained during the first temperature decrease in the DSC measurement is shown in Figure 1.

[0106] Comparative Example 3: 0.5775 mol of hydroquinone and 0.5717 mol of 4,4'-dichlorobenzophenone were placed in a 2 L (liter) separable flask as monomers. Potassium carbonate (K ２ CO ３ 0.8663 mol of methyl methyl acrylate (Junsei Chemical Co., Ltd., special grade) was added, and 408 g of diphenyl sulfone was added as a solvent. A ribbon heater was wrapped around the top of the separable flask, and glass wool was wrapped around that to maintain the temperature. The entire bottom of the separable flask was also wrapped in a mantle heater. Under nitrogen (flow rate: 0.06 L / min), the reaction mixture in the separable flask was heated and stirred using a mechanical stirrer. The ribbon heater was set to 150°C and the mantle heater to 165°C, and the temperatures were maintained until the raw materials were dissolved. After dissolution, the stirring speed was changed to 250 rpm, and the reaction mixture was heated to 200°C over 30 minutes. After heating, the temperature was maintained at 200°C for 1 hour and then increased again to 250°C over 70 minutes. After maintaining the temperature at 250°C for 1 hour, the temperature was increased to 300°C over 110 minutes. After the temperature increase was complete, a portion of the mother liquor was withdrawn. The recovered product was crushed and washed with acetone and water to obtain a polymer. １ The H-NMR spectrum is shown in Figure 3. １ From the H-NMR spectrum, it was found that the polymer of Comparative Example 3 did not exhibit a peak attributable to the terminal structure represented by formula (2), and did not have this terminal structure.

[0107]

[0108] <Evaluation> From Table 1, in Examples 1 to 5, 6 and 7, １Since the intensity ratio (peak intensity ratio) of the PhP unit peak to the main chain peak in the H-NMR measurement is greater than 0, it can be seen that PEEK containing the repeating unit represented by formula (1) and the terminal structure represented by formula (2) was obtained. By containing the repeating unit represented by formula (1) and the terminal structure represented by formula (2), the crystallization temperature T ｃ On the other hand, the melting point T ｍ It can be seen that the change in the crystallization rate is suppressed even when the terminal structure represented by formula (2) is introduced. Furthermore, Table 1 and Figure 1 show that the crystallization rate is improved (the exothermic peak width is narrowed) when PEEK contains a repeating unit represented by formula (1) and a terminal structure represented by formula (2). From these facts, it can be seen that PEEK with excellent processability can be obtained according to the present invention.

[0109] Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will readily be able to make numerous modifications to these exemplary embodiments and / or examples without substantially departing from the novel teachings and advantages of the present invention. Accordingly, these numerous modifications are within the scope of the present invention. The contents of all documents cited in this specification and of the applications from which this application claims priority under the Paris Convention are incorporated by reference in their entirety.

Claims

1. A polyether ether ketone comprising a repeating unit represented by the following formula (1) and a terminal structure represented by the following formula (2). 【Chemistry 7】

2. １ 2. The polyether ether ketone according to claim 1, wherein the ratio of the phenoxyphenol unit peak intensity to the main chain peak intensity in H-NMR measurement is 0.0150% or more.

3. The polyether ether ketone according to claim 1 or 2, having a melt flow rate of 200 g / 10 min or less.

4. Crystallization temperature T ｃ The polyether ether ketone according to claim 1 or 2, wherein the melting point is 260° C. or higher.

5. Melting point T ｍ The polyether ether ketone according to claim 1 or 2, wherein the melting point is 300° C. or higher.

6. 3. The polyether ether ketone according to claim 1 or 2, wherein the width of an exothermic peak due to crystallization observed in differential scanning calorimetry is 23.7° C. or less.

7. The repeating unit represented by the following formula (6) is not included, or the repeating unit represented by the formula (6) is included, 3. The polyether ether ketone according to claim 1 or 2, wherein when the polyether ether ketone contains a repeating unit represented by formula (6), a molar ratio of the repeating unit represented by formula (6) to a total of the repeating unit represented by formula (1) and the repeating unit represented by formula (6) is less than 25 mol%. 【Chemistry 8】 (In formula (6), three R １ are each independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium. The three a's are each independently selected from the group consisting of integers from 0 to 4.

8. 3. The polyether ether ketone according to claim 1 or 2, having a chlorine atom content of 2 mg / kg or more.

9. The polyether ether ketone according to claim 1 or 2, produced using at least hydroquinone and 4,4'-dichlorobenzophenone as monomers.

10. A method for producing a polyether ether ketone, comprising the steps of: producing the polyether ether ketone according to claim 1 or 2, The method includes reacting hydroquinone with 4,4'-dihalogenobenzophenone, A method for producing polyether ether ketone, wherein the condition b / a<1.00 is satisfied, where the amount of the hydroquinone used in the reaction is amol and the amount of the 4,4'-dihalogenobenzophenone is bmol.

11. The method for producing polyether ether ketone according to claim 10, wherein the condition b / a≦0.99 is satisfied.

12. A method for producing a polyether ether ketone, comprising the steps of: producing the polyether ether ketone according to claim 1 or 2, A method for producing polyether ether ketone, comprising reacting hydroquinone, 4,4'-dihalogenobenzophenone, and one or more members selected from the group consisting of 4-phenoxyphenol and 4-halogenodiphenyl ether.

13. The method for producing polyether ether ketone according to claim 10, wherein the 4,4'-dihalogenobenzophenone is at least one selected from the group consisting of 4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone.

14. 11. A method for producing polyether ether ketone according to claim 10, comprising heating the reaction mixture at a temperature of 250°C or greater for 3 hours or more.

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