JPH0473454B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel end-capped aromatic polyetherketone and a method for producing the same. More specifically, the present invention has a chemical structure in which a phenylene group is linked to the p-position via an ether group and a ketone group, and the polymer terminal is capped with an inert aromatic group. There is. The present invention relates to a novel polymer that has excellent heat resistance, chemical resistance, mechanical strength, etc. and can be melt-molded relatively easily, and an industrially advantageous method for producing the same.

Prior Art Until now, aromatic polyetherketones having a structure in which a phenylene group is connected to the p-position via an ether group and a ketone group, for example, have the structural formula A compound having no substituent on the aromatic ring is known, and this compound is attracting attention as a molding material because it has excellent heat resistance, chemical resistance, mechanical strength, etc.

Aromatic polyetherketones represented by this structural formula can be obtained, for example, by heating the potassium salt of 4-(p-chlorobenzoyl)phenol (Japanese Patent Publication No. 1973).
-1020 Publication), or a method in which p-phenoxybenzoyl halide is subjected to a Friedel-Crafts reaction in the presence of a Lewis acid catalyst such as boron trifluoride (Japanese Patent Publication No. 56-33419). Manufactured.

However, the aromatic polyetherketones obtained in this way, which have no substituents on their aromatic rings, have excellent heat resistance, chemical resistance, mechanical strength, etc., but have a melting point of 365 to 367°C. Because of the extremely high temperature, a molding temperature of 400°C or higher is required, which has the drawback of making processing difficult.

Problems to be Solved by the Invention The present invention improves the drawbacks of conventional aromatic polyetherketones, has excellent heat resistance, chemical resistance, and mechanical strength, and can be melted relatively easily. The purpose of this invention was to provide a new moldable polymer and a method for producing the same.

Means for Solving the Problems As a result of various studies conducted by the present inventors to develop a polymer having the above-mentioned preferable characteristics,
First, equation (A) A novel aromatic polyether ketone consisting of a structural unit having a substituent on an aromatic ring, and
The structural unit represented by the above formula (A) and the formula (B) It has been found that a new aromatic polyetherketone having a predetermined proportion of the structural units represented by the following formula is suitable for this purpose (Japanese Patent Application Laid-open No. 148,600/1983, Japanese Patent Application No. 17,557/1983).

As a result of further intensive research, the inventors found that
These novel aromatic polyetherketones are obtained by capping the aryloxy terminals of these novel aromatic polyetherketones or the arylhalogen terminals thereof with an inert aromatic group, but the terminals are not capped. It was discovered that the heat resistance and melt molding processability are even better than those of the conventional method, and based on this knowledge, the present invention was completed.

That is, the present invention provides formula (A) The structural unit represented by and formula (B) It consists of a structural unit represented by 5 to 95 mol%, and has a reduced viscosity of 0.1 or more at a temperature of 30° C. and a concentration of 0.1 g/dl in 98% sulfuric acid. .

This end-capped aromatic polyetherketone is
For example, in the absence of a solvent or in a solvent, 4-(p-halogenobenzoyl)-2,6-dimethylphenol and 4-(p-halogenobenzoyl)phenol are added to the total amount of 4-(p-halogenobenzoyl)-2,6-dimethylphenol. ) -2,6-dimethylphenol is subjected to thermal polycondensation at a ratio of 5 to 95 mol %, and then the resulting polymer is added with an aromatic compound capable of reacting with the aryloxy terminal and, if desired, the aryl. It is produced by reacting an aromatic compound capable of reacting with a halogeno end in any order to seal only the aryloxy end or both this end and the aryl halogeno end.

The raw material monomer used in the present invention has the formula (C) 4-(p-halogenobenzoyl)-2,6-dimethylphenol represented by (X in the formula is a halogen atom) and the formula (D) (X' in the formula is a halogen atom) is 4-(p-halogenobenzoyl)phenol, and each halogen atom may be the same or different. A preferred halogen atom is a fluorine atom or a chlorine atom, and particularly preferred is a case where both compounds are a fluorine atom.

Then, the total amount of 4-(p-halogenobenzoyl)-2,6-dimethylphenol represented by the above formula (C) and 4-(p-halogenobenzoyl)phenol represented by the above formula (D) is added. 4-(p-halogenobenzoyl)-2,6-dimethylphenol is 5 mol% or more, preferably 20 to
The desired end-capped aromatic polyetherketone can be obtained by carrying out heating polycondensation at a ratio of 70 mol %, then adding a desired aromatic end-capping agent and causing a capping reaction.

At this time, there are no particular restrictions on the means for carrying out the polycondensation reaction, but the following two methods are advantageously used.

That is, the first method uses 4-(p-halogenobenzoyl)-2,6-dimethylphenol and 4-(p-halogenobenzoyl)phenol in the form of alkali metal salts, and mixes them in the above ratio. This is a method in which polycondensation is carried out by heating and dehalogenating alkali metals. The alkali metal salt is preferably a sodium salt or a potassium salt, and more preferably both compounds are salts of the same alkali metal.

This reaction can be carried out without a solvent or by using a solvent that does not adversely affect the polycondensation reaction. As the solvent, not only those that are liquid at room temperature but also those that are solid at room temperature but melt at the reaction temperature can be used. Examples of such solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoramide, and tetramethylurea; benzonitrile, tolnitrile, etc. nitrile solvents; dialkyl sulfones such as dimethyl sulfone and diethyl sulfone; sulfolanes such as sulfolane and methylsulfolane; diaryl sulfones such as diphenyl sulfone and ditolyl sulfone; diaryl ethers such as diphenyl ether and ditolyl ether; Ketones such as benzophenone, acetophenone, and ditolyl ketone are preferred.

In addition, the polymerization reaction temperature and reaction time vary depending on the types of halogen atoms and alkali metals in the raw material monomers, the presence or absence of solvent, and the type of solvent, but usually
The temperature range is 150 to 450°C for 1 minute to 50 hours, preferably 200 to 400°C for about 5 minutes to 25 hours.

The above 4-(p-halogenobenzoyl)-2,6
-alkali metal salt of dimethylphenol and 4-
The alkali metal salt of (p-halogenobenzoyl)phenol can be produced by any method. For example, aqueous solutions of alkali metal hydroxides, carbonates, hydrogen carbonates, etc., or lower alcohol solutions of alkali metal hydroxides and 4-(p
-Halogenobenzoyl)-2,6-dimethylphenol and 4-(p-halogenobenzoyl)phenol are reacted separately or both compounds are mixed and reacted, followed by dehydration, drying, dealcoholization, and drying. It can be easily obtained by applying

A second preferred method for carrying out the polycondensation reaction is to mix a predetermined ratio of 4-(p-halogenobenzoyl)-2,6-dimethylphenol and 4-(p-halogenobenzoyl)phenol with an alkali metal carbonate. This is a method in which polycondensation is carried out by heating in the presence of at least one selected from salts and hydrogen carbonates. Examples of alkali metal carbonates and hydrogen carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, and lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate. used.

These alkali metal carbonates and hydrogen carbonates are preferably anhydrous, and the amount used is 4
-(p-halogenobenzoyl)-2,6-dimethylphenol and 4-(p-halogenobenzoyl)phenol
It is selected in the range of twice the mole, preferably 0.3 to 2 times the mole.

This polycondensation reaction can also be carried out without a solvent, or can also be carried out using the above-mentioned solvents.

In addition, the reaction temperature and reaction time vary depending on the type of halogen atom in the raw material monomer, the type of alkali metal carbonate or hydrogen carbonate, the presence or absence of a solvent, and the type, but it is usually in the temperature range of 150 to 450°C. The heating time is 1 minute to 50 hours, preferably about 5 minutes to 25 hours at a temperature of 200 to 400°C.

Raw material monomer 4-(p-halogenobenzoyl)
-2,6-dimethylphenol and 4-(p-halogenobenzoyl)phenol can be produced by any method, but the halogen atom and the hydroxyl group are located at substantially p-position relative to the carbonyl group, respectively. It is necessary that there be. 4-(p
-Halogenobenzoyl)-2,6-dimethylphenol is preferably produced by subjecting p-halogenated benzoic acid 2,6-dimethylphenol ester to Fries rearrangement. In this case, since the 2nd and 6th positions of the hydroxyl group are substituted with methyl groups, only the desired p-form is produced.

The aromatic polyetherketone obtained by such a polycondensation method can be obtained by using 4-(p-halogenobenzoyl)-2,6-dimethylphenol and 4-(p-halogenobenzoyl)phenol as raw materials. , the structural unit represented by the formula (A) and the structural unit represented by the formula (B) are usually randomly combined.

This aromatic polyetherketone has an aryloxy group and an arylhalogeno group at its terminal ends, but in the present invention, at least the aryloxy terminal is blocked by performing an end-capping reaction with an aromatic compound. The aryl halide terminals are also capped if necessary. Although there are no particular restrictions on the method for carrying out this sealing reaction, the following method is usually preferably used.

That is, after a polymer having a predetermined degree of polymerization is produced by a polymerization reaction, (1) an aromatic compound capable of reacting with the aryloxy end is added thereto, and the aryloxy end is sealed by the reaction. (2) After performing the above operation, add an aromatic compound capable of reacting with the aryl halogeno end and sealing the aryl halogeno end by reacting; (3) An aromatic compound capable of reacting with the aryl halogeno end. After adding a compound and reacting to seal the aryl halogeno terminal, add an aromatic compound that can react with the aryloxy terminal and react to seal the aryloxy terminal. Then, only the aryloxy terminus or both the aryloxy terminus and the aryl halogeno terminus are sealed.

As the aromatic compound capable of reacting with the aryloxy terminal, for example, aromatic monohalides and aromatic mononitro compounds having an electron-withdrawing substituent are preferably used. Examples of aromatic monohalides include monohalogenated benzenes such as fluorobenzene, chlorobenzene, bromobenzene, and iodobenzene, monohalogenated naphthalenes such as fluoronaphthalene, chloronaphthalene, bromonaphthalene, and iodonaphthalene, and general formula (X'' in the formula is a halogen atom, Q is a simple chemical bond, -O-, -S-, -CO-, -SO-, -SO ₂ -,
^A divalent group such as _-CH2- , -C( ^R1R2 )-,
R ¹ and R ² are lower alkyl groups).

Furthermore, in these aromatic monohalides, one or more hydrogen atoms in the aromatic ring may be further substituted with a lower alkyl group, a lower alkoxy group, a phenyl group, a cyano group, an ester group, or the like.

Among these aromatic monohalides, the general formula (In the formula, X is a halogen atom, Y is -CO- or _-SO2- ) Compounds represented by the following are preferred, and among them, 4-benzoyl-chlorobenzene, 4-benzoyl-fluorobenzene, 4-benzene Sulfonyl-chlorobenzene, 4-benzenesulfonyl-
Fluorobenzene is preferred.

In addition, examples of aromatic mononitro compounds having an electron-withdrawing substituent include nitrobenzonitrile (each isomer), cyanonitronaphthalene (each isomer), general formula (In the formula, Q has the same meaning as above), N-phenyl-4-nitrophthalimide, and the like are preferably used.

Furthermore, in these aromatic mononitro compounds, one or more hydrogen atoms in the aromatic ring may be further substituted with a lower alkyl group, a lower alkoxy group, a phenyl group, a cyano group, an ester group, or the like.

On the other hand, as the aromatic compound that can react with the aryl halogen terminal, aromatic monohydroxyl compounds are suitable, such as phenol, naphthol, general formula (In the formula, Q has the same meaning as above.) Compounds represented by the following are used.

Furthermore, in these aromatic monohydroxyl compounds, one or more hydrogen atoms in the aromatic ring may be further substituted with a lower alkyl group, a lower alkoxy group, a phenyl group, a cyano group, an ester group, or the like. Furthermore, these aromatic monohydroxyl compounds can also be used in the form of their alkali metal salts.

The temperature and reaction time of the sealing reaction using these terminal capping agents vary depending on the type and amount of the polymer terminal, the type and amount of the sealing agent, the presence or absence of solvent, and the type, but usually a temperature of 150 to 450°C. 1 minute to 50 hours at a temperature range of 200 to 400℃, preferably 5 minutes to 50 hours at a temperature range of 200 to 400℃
It takes about 20 hours.

Further, the amount of the terminal capping agent used may be equal to or less than the amount of the polymer terminal to be sealed, but it is preferably used in an equal amount or more.

The novel end-capped aromatic polyetherketone of the present invention thus obtained has a skeleton consisting of a structural unit represented by the above formula (A) and a structural unit represented by the above formula (B). , the molar fraction of (A) units to the sum of (A) units and (B) units is 5 to 95%, and at least the aryloxy end of the polymer is capped with an inert aromatic group. structure, and 98%
The reduced viscosity in sulfuric acid at a temperature of 30°C and a concentration of 0.1 g/dl is 0.1 or more. Regarding the value of this reduced viscosity, if it is 0.1 or more, it can be molded by melt molding, solution molding, or other molding methods, and there is no particular restriction, but it is usually in the range of 0.1 to 5.0, preferably 0.2 to 3.5. .

In addition, in the end-capped aromatic polyether ketone of the present invention having a skeleton of (A) units and (B) units, the molar amount of the (A) units relative to the sum of the (A) units and (B) units is The fraction is between 5 and 95%, particularly preferably between 20 and 70%. (A) If the content ratio of units is within this range,
Compared to known aromatic polyetherketones consisting only of (B) units, the glass transition temperature is approximately 10°C higher, resulting in improved dimensional stability at higher temperatures. Moreover, by changing this ratio, it is possible to arbitrarily obtain anything from a non-crystalline product to a crystalline product.

Effects of the Invention The aromatic polyetherketone of the present invention has heat resistance (weight loss up to 440°C in a nitrogen stream) because the aromatic rings as a polymer skeleton are bonded at the p-position by carbonyl bonds and ether bonds. do not have),
It has excellent chemical resistance (almost no solvents other than concentrated sulfuric acid) and mechanical strength, and because it has a structural unit with a substituent on the aromatic ring, it is superior to conventional aromatic polyamides that do not have such substituents. Compared to ether ketone, it is relatively easy to mold and process, such as
It has characteristics such as being able to be melt-molded at temperatures of 300 to 400°C.

Furthermore, in the aromatic polyetherketone of the present invention, at least the aryloxy terminal of the polymer is capped with an inert aromatic group.
Compared to the corresponding aromatic polyetherketone, which is not end-blocked, not only does the thermal decomposition onset temperature improve by more than 10℃, but it also prevents gelation during hot molding, resulting in improved moldability. It will be further improved.

The polymer of the present invention can be used alone for structural materials, films, fibers, fibrils, coating materials, etc., and can also be used as a blend with other polymers, such as glass fiber, carbon fiber, aramid fiber, calcium carbonate, etc. It is also used as a composite material mixed with reinforcement or filler such as calcium silicate.

Examples Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

The reduced viscosity of the polymer is a value measured using 98% sulfuric acid as a solvent at a concentration of 0.1 g/dl and a temperature of 30°C.

Example 1 17.08 g of 4-(p-fluorobenzoyl)-2,6-dimethylphenol and 6.48 g of 4-(p-fluorobenzoyl)phenol were added to a stirrer, a thermometer, a nitrogen inlet, and an air-cooled cooling tube. Place in a flask and heat to 160℃ under nitrogen atmosphere while stirring.
After heating to a uniform solution, 5.01 g of anhydrous sodium carbonate and 0.72 g of anhydrous potassium carbonate were added.
g, and heated at 200℃ for 1 hour and 250℃ for 30 minutes at 270℃.
The polycondensation reaction was carried out at ~280°C for 4 hours. Then,
When 2.52 g of p-chlorodiphenylsulfone dissolved in 5 ml of sulfolane was added and stirred at 275°C for 1 hour to carry out an end-capping reaction, a yellowish and viscous solution turned into an ariboly-colored sticky substance. It changed into a solution. This indicates that the alkali metal phenoxide group at the polymer end disappeared and the end was capped with a stable aromatic group.

The hot, viscous reaction mixture was then removed and, after cooling, ground. The obtained powder was washed and extracted several times with acetone and water to remove diphenyl sulfone, sulfolane and inorganic salts, and then dried at 150°C under reduced pressure to obtain a milky white product. 21.8 g of polymer was obtained. The yield was quantitative and the reduced viscosity of the polymer was 1.5.

The infrared absorption spectrum of this polymer is shown in FIG. As can be seen, a methyl group at 2900 to 2980 cm ^-1 , a carbonyl group at 1640 to 1670 cm ^-1 and 1580 to 1610 cm ^-1 , and a benzene ring conjugated thereto,
It has characteristic absorption due to ether bonds at 1100 to 1350 cm ^-1 . This infrared absorption spectrum and
NMR analysis has shown that this polymer has a skeleton. The phenoxy end is expressed by the following formula: It was identified as an aromatic polyetherketone capped with an aromatic group represented by

Furthermore, the thermogravimetric analysis chart of this material is shown in Figure 2.
Shown below. As is clear from this, no weight loss was observed in this polymer up to about 450°C in a nitrogen stream. It was also found that this polymer is an amorphous polymer with a glass transition point at about 230°C.

Example 2 Except for using 12.2 g of 4-(p-fluorobenzoyl)-2,6-dimethylphenol, 10.8 g of 4-(p-fluorobenzoyl)phenol, and 2.0 g of p-fluorobenzophenone as the terminal capping agent. By performing a polycondensation reaction, an end-capping reaction, and a post-treatment in the same manner as in Example 1, 21.1 g of a milky white polymer was obtained in an almost quantitative yield.
I got it. The reduced viscosity of this polymer was 1.6.

The infrared absorption spectrum of this product is shown in FIG. This infrared absorption spectrum and NMR analysis revealed that the skeleton of this polymer is The phenoxy end is expressed by the following formula: It was identified as an aromatic polyetherketone capped with an aromatic group represented by

Furthermore, the thermogravimetric analysis chart of this material is shown in Figure 4.
Shown below. As is clear from this, no weight loss was observed in this polymer up to about 450°C in a nitrogen stream. It was also found that this polymer is an amorphous polymer with a glass transition point at about 210°C.

Example 3 Yellow powder obtained by reacting 4-(p-fluorobenzoyl)-2,6-dimethylphenol with an aqueous solution of potassium hydroxide, followed by dehydration and vacuum drying (150°C). 16.92 g of the potassium salt of 4-(p-fluorobenzoyl)-2,6-dimethylphenol, 10.16 g of the potassium salt of 4-(p-fluorobenzoyl)phenol prepared in the same manner, and 45 g of diphenylsulfone were placed in a flask. and stir at 240℃ for 1 hour.
Polycondensation was carried out by reacting at 280°C for 3 hours. Then, p dissolved in 5 ml of sulfolane
- When 2.0 g of fluorobenzophenone was added and an end-capping reaction was carried out while stirring at 280°C for 1 hour, the yellow sticky solution changed to an ivory sticky solution. Next, by carrying out the same treatment as in Example 1, 21.3 g of a milky white polymer was obtained in an almost quantitative yield. The reduced viscosity of this polymer was 1.4.

NMR analysis and infrared absorption spectra revealed that this polymer has a skeleton. The phenoxy end is expressed by the following formula: It was identified as an aromatic polyetherketone capped with an aromatic group represented by

Example 4 Polycondensation reaction, terminal As a result of the sealing reaction and post-treatment, a milky white polymer was obtained in a nearly quantitative yield. The reduced viscosity of this polymer was 1.3.

The infrared absorption spectrum of this product is shown in FIG. This infrared absorption spectrum and NMR analysis revealed that this polymer has a skeleton structure. The phenoxy end is expressed by the following formula: It was identified as an aromatic polyetherketone capped with an aromatic group represented by

Furthermore, the thermogravimetric analysis chart of this material is shown in Figure 6.
Shown below. As is clear from this, no weight loss was observed in this polymer up to about 510°C in a nitrogen stream. It was also found that this polymer is a crystalline polymer with a melting point around 350°C.

Example 5 Polycondensation reaction, terminal As a result of the sealing reaction and post-treatment, a milky white polymer was obtained in a nearly quantitative yield. The reduced viscosity of this polymer was 1.5.

In addition, NMR analysis and infrared absorption spectra revealed that this polymer has a skeleton. The phenoxy end is expressed by the following formula: It was identified as an aromatic polyetherketone capped with an aromatic group represented by

A thermogravimetric analysis chart of this product is shown in FIG.
As is clear from this, no weight loss was observed in this polymer up to about 480°C in a nitrogen stream.
Furthermore, since this polymer has a glass transition point around 200°C and a melting point around 350°C, it was found that it is a partially crystalline polymer.

Example 6 14.64 g of 4-(p-fluorobenzoyl)-2,6-dimethylphenol, 8.64 g of 4-(p-fluorobenzoyl)phenol, diphenylsulfone
Put 90g into a flask similar to Example 1 and heat at 180℃.
After heating to a uniform solution, 5.8 g of finely powdered anhydrous sodium carbonate and 1.2 g of anhydrous potassium carbonate were added, and the mixture was stirred under a nitrogen atmosphere at 200°C for 1 hour, 250°C for 1 hour, and 280°C for 4 hours. Therefore, a polycondensation reaction was carried out. Next, a solution of 1.9 g of p-hydroxybenzophenone dissolved in 5 ml of sulfolane was added and stirred at 280 DEG C. for 1 hour to carry out a reaction for blocking the phenylfluorine terminals. Furthermore, a solution of 2.4 g of p-chlorodiphenyl sulfone dissolved in 5 ml of sulfolane was added, and the mixture was heated at 280°C for 1 hour.
The phenoxy end-capping reaction was carried out by stirring for a period of time. Next, by carrying out the same post-treatment as in Example 1, a milky white polymer was obtained in an almost quantitative yield.

This polymer has an infrared absorption spectrum,
The skeleton was determined by NMR analysis etc. The phenoxy end is expressed by the following formula: It was identified as an aromatic polyetherketone which was capped with an aromatic group represented by , and the other terminal was capped with a benzoylphenyl group. The reduced viscosity of this polymer is 1.3 and is approximately 460°C in a nitrogen stream.
No weight loss was observed until then.

Example 7 4-(p-chlorobenzoyl)-2,6-dimethylphenol 18.24 g, 4-(p-chlorobenzoyl)phenol 6.98 g, diphenylsulfone 60
g, put 6.9 g of anhydrous potassium carbonate into the flask,
Polycondensation was carried out by reacting at 320°C for 10 hours while stirring. Next, 2.52 g of p-chlorodiphenyl sulfone was added and reacted at 300° C. for 1 hour to carry out a reaction for blocking the phenoxy end. Next, post-treatment was performed in the same manner as in Example 1 to obtain a light brown polymer. The infrared absorption spectrum and thermal analysis chart of this polymer were consistent with those obtained in Example 1. The reduced viscosity of this polymer was 0.6 and the yield was 90%.

Example 8 A polycondensation reaction was carried out in the same manner as in Example 1 using 20.7 g of 4-(p-fluorobenzoyl)-2,6-dimethylphenol and 3.24 g of 4-(p-fluorobenzoyl)phenol. Next, 2.2 g of p-nitrobenzophenone dissolved in 5 ml of sulfolane was added, and an end-capping reaction was carried out with stirring at 260° C. for 1 hour. Next, by carrying out the same treatment as in Example 1, a milky white polymer was obtained in an almost quantitative yield. This polymer is an amorphous polymer with a glass transition point of approximately 230°C, and its skeleton is The phenoxy end is expressed by the following formula: It was capped with an aromatic group represented by: Further, the reduced viscosity of this polymer was 1.4.

Example 9 Except for using 23.18 g of 4-(p-fluorobenzoyl)-2,6-dimethylphenol, 1.08 g of 4-(p-fluorobenzoyl)phenol, and 2.0 g of p-fluorobenzophenone as the terminal capping agent. By performing a polycondensation reaction, an end-capping reaction, and a post-treatment in the same manner as in Example 1, a milky white polymer was obtained in an almost quantitative yield. This polymer is an amorphous polymer with a glass transition point at approximately 230℃, and its skeleton is The phenoxy end is expressed by the following formula: It was capped with an aromatic group represented by: Further, the reduced viscosity of this polymer was 1.7.

[Brief explanation of drawings]

Figures 1, 3 and 5 are infrared absorption spectrum charts by diffuse reflection FT-IR of examples of the end-capped aromatic polyetherketone of the present invention; FIG. 6 is a thermogravimetric analysis chart under a nitrogen stream for the example corresponding to the above, and FIG. 7 is a thermogravimetric analysis chart of the end-capped aromatic polyether ketone of Example 5.

Claims (1)

[Claims] 1 Formula (A) The structural unit represented by and formula (B) It consists of a structural unit represented by An end-capped aromatic polyether ketone having a reduced viscosity of 0.1 or more at a concentration of 0.1 g/dl in 98% sulfuric acid at a temperature of 30°C. 2. The aromatic polyetherketone according to claim 1, wherein the inert aromatic group is a benzoylphenyl group or a benzenesulfonylphenyl group. 3. The aromatic polyetherketone according to claim 1 or 2, wherein the molar fraction of (A) units is 20 to 70%. 4 In the absence of a solvent or in a solvent, 4-(p-halogenobenzoyl)phenol and 5 to 95 mol% of 4-(p-halogenobenzoyl)- based on the total amount.
2,6-dimethylphenol is subjected to thermal polycondensation, and then an aromatic compound capable of reacting with the aryloxy end of the polymer and, if desired, an aromatic compound capable of reacting with the aryl halogeno end, is added to the resulting polymer. Formula (A), characterized in that the aryloxy end or this end and the aryl halogeno end are blocked by reacting in this order: The structural unit represented by and formula (B) It consists of a structural unit represented by 5 to 95 mol%, and has a reduced viscosity of 0.1 or more at a temperature of 30° C. and a concentration of 0.1 g/dl in 98% sulfuric acid. 5 The aromatic compound that can react with the aryloxy terminal has the general formula 5. The manufacturing method according to claim 4, which is a compound represented by the formula (in the formula, Z is a halogen atom or a nitro group, and Y is a carbonyl group or a sulfonyl group). 6. The manufacturing method according to claim 4 or 5, wherein the molar fraction of (A) units is 20 to 70%. 7 Claims 4, 5 or 6 in which 4-(p-halogenobenzoyl)-2,6-dimethylphenol and 4-(p-halogenobenzoyl)phenol are each used in the form of an alkali metal salt
Manufacturing method described in section. 8. The method according to any one of claims 4 to 7, in which the polycondensation reaction and the end-capping reaction are carried out in the presence of at least one selected from alkali metal carbonates and hydrogen carbonates. Production method. 9 Halogen atom of 4-(p-halogenobenzoyl)-2,6-dimethylphenol and 4-(p-
9. The production method according to any one of claims 4 to 8, wherein the halogen atom of the (halogenobenzoyl)phenol is a fluorine atom or a chlorine atom, respectively.