JPS61285221A - Aromatic polyether ketone of end group sealing type and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled polyether ketone moldable in a molten state, having improved heat resistance, chemical resistance and mechanical strength, sealing an aryloxy end group of a polymer having a specific constituent unit and a reduced viscosity with an inert aromatic group. CONSTITUTION:(A) 4-(p-Halogenobenzoyl)-2,6-dimethylphenol is made into an alkali metallic salt (e.g., sodium salt, etc.), polymerized in a solvent (e.g., N,N- dimethylformamide, etc.) at 150-450 deg.C and reacted with (B) an aromatic monohalide capable of reacting with an aryloxy end group or an electron attrac tive substituent group-containing aromatic mononitro compound (e.g., nitro benzonitrile, etc.) in an amount corresponding to <=the equivalent amount of the end group, to give the aimed polymer having a constituent unit shown by the formula and >=0.1 reduced viscosity.

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. . This 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. The aromatic polyetherketone having a structure in which a phenylene group is connected to the p-position via a ketone group is represented by, for example, a structural formula. It is known that there are no substituents on the aromatic ring, and this material has attracted attention as a molding material because it has excellent heat resistance, chemical resistance, mechanical strength, etc.

Aromatic polyetherketone td represented by this structural formula
,, Example: Method of heating potassium salt of 4-(p-chlorobenzoyl)phenol (Japanese Patent Publication No. 50-102
0), or p-phenoxybenzoyl halide in the presence of a Lewis acid catalyst such as boron trifluoride,
How to conduct the Friedel-Krach reaction
6-33419).

However, the aromatic polyetherketone that has no substituents on the aromatic ring obtained in this way has excellent heat resistance, chemical resistance, mechanical strength, etc., but has a melting point of 3.
Since the temperature is extremely high at 65 to 367°C, a molding temperature of 400°C or higher is required, making the processing difficult.

Problems to be Solved by the Invention The purpose of the present invention is to improve these drawbacks and to provide a novel polymer that has excellent heat resistance, chemical resistance, and mechanical strength, and can be melt-molded relatively easily. , and a method for producing the same.

Means for Solving the Problems The inventors of the present invention have conducted extensive research, and the results are expressed by the following formula. A novel aromatic polyetherketone consisting of a structural unit having a substituent on an aromatic ring, and the above formula (It
) and a structural unit represented by Formula 1 (IID) in a predetermined ratio, we have discovered that a novel aromatic polyetherketone is suitable for the above purpose (Japanese Patent Application No. 148,600/1983) (Special Application No. 17557/1983)
.

As a result of further intensive research, the present inventors have discovered a novel product in which the aryloxy end of these new aromatic polyetherketones or this and the aryl halogeno end are capped with an inert aromatic group. Aromatic polyetherketone is
It was discovered that the heat resistance and melt molding processability were even better than those without end-sealing, and based on this knowledge, the present invention was completed.

That is, the present invention uses only or together with the structural unit represented by the formula as a repeating unit.

consisting of at least 5 molar units based on the total amount of structural units represented by the formula, having a molecular structure in which at least the aryloxy end of the polymer is capped with an inert aromatic group, and in 98% sulfuric acid, Temperature 30℃, concentration 0.1r/#
The present invention provides an end-capped aromatic polyether ketone characterized by having a reduced viscosity of 0.1 or more. This product can be used, for example, without a solvent or in a solvent.
Can 4-(p-halogenobenzoyl)-2,6-dimethylphenol be polymerized by heating and reacting alone?

Or this product and 4-(p-halogenobenzoyl)phenol in a ratio such that the 4-(p-halogenobenzoyl)-2,6-dimethylphenol is at least 5 molar proportion to the total amount thereof. Polycondensation is carried out under heating, and then the resulting polymer is reacted with an aromatic compound capable of reacting with the aryloxy end thereof and, if desired, an aromatic compound capable of reacting with the aryl halogeno end thereof, in any order. It can be produced by capping only the aryloxy terminus or by capping both the aryloxy terminus and the nuclear halide terminus.

The raw material monomer used in the present invention has the general formula (X in the formula
is a halogen atom) i4 (p-halogenobenzoyl)-2゜6
-dimethylphenol,! :, 4-(p-halogenobenzoyl)phenol represented by the general formula (X' in the formula is a halogen atom), and each halogen atom may be the same or different. Preferred halogen atoms are fluorine atoms and chlorine atoms, and fluorine atoms are particularly preferred in both compounds.

Then, 4-(p-halogenobenzoyl)-2,6-dimethylphenol represented by the above-mentioned general formula (1) is reacted with heat alone, or 4-(p-halogenobenzoyl)-2,6-dimethylphenol represented by the above-mentioned general formula 4 (p-halogenobenzoyl)-2,6-dimethylphenol is heated and polycondensed with 4 (p-halogenobenzoyl)-2,6-dimethylphenol in a ratio of 5 mol or more, preferably 20 mol or more, based on the compound ifa. The desired end-capped aromatic polyetherketone can be obtained by 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-pass method is advantageously used.

That is, the first method uses 4-(p-''logenobenzoyl)-2,6-dimethylphenol alone in the form of an alkali metal salt, or 4-(p-halogenobenzoyl)-2,6- Dimethylphenol and 4-(p-halogenobenzoyl)phenol are each used in the form of an alkali metal salt, and these are mixed in the above proportions and heated to polycondense with the alkali metal de- and halogenated. It's a method.

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 also be carried out without solvent.

It can also be carried out using solvents that do not yet have an adverse effect on the polymerization 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. Such solvents include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoramide,
Amide solvents such as tetramethylurea; Nitrile solvents such as benzonitrile and tolnitrile; Dialkylsulfones such as dimethylsulfone and diethylsulfone; Sulfolanes such as sulfolane and methylsulfolane; Diarylsulfones such as diphenylsulfone and ditrilysulfone. Diaryl ethers such as diphenyl ether and ditolyl ether; Ketones such as benzophenone, acetophenone and ditolyl ketone are preferred.

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

The above 4-(p-halogenobenzoyl) -2,43-
The alkali metal salt of dimethylphenol and the alkali metal salt of 4-(p-halogenobenzoyl)phenol can be produced by any method. For example, an aqueous solution of an alkali metal hydroxide, carbonate, or hydrogen carbonate, or a lower alcohol solution of an alkali metal hydroxide,
4-(p-halogenobenzoyl)-2,6-dimethylphenol and U4-(p-halogenobenzoyl)phenol are reacted separately or both compounds are mixed and reacted, followed by dehydration, drying, or Easily obtained by dealcoholization and drying.

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

These alkali metal carbonates and hydrogen carbonates are preferably anhydrous, and the amount used is determined by the number of moles of 4-Cp-halogenobenzoyl)-2,6-cy)thylphenol or 4-(p- Usually 0.1 to 5 times the mole of 2,6-dimethylphenol (halogenobenzoyl)-2,6-dimethylphenol and 4-(p-halogenobenzoyl)phenol, and 0.3 to 2 times the mole if appropriate. selected within the range.

The polycondensation reaction with 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 of solvent.
1 minute to 50 hours in a temperature range of 50 to 450 °C, preferably fi, 5 minutes to 25 hours in a temperature range of 200 to 400 °C.
It takes about an hour.

Monomer 4-(p-halogenobenzoyl)-2,6-
Dimethylphenol and 4-(p-halogenobenzoyl)phenol can be produced by any method, but it is necessary that the halogen atom and the hydroxyl group are each substantially in the p-position relative to the carbonyl group. One of the preferred methods for producing 4-(p-halogenobenzoyl)-2,6-dimethylphenol is a method of 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 target p-integrated product is generated.

The aromatic polyetherketone obtained by such a polycondensation method has a structure represented by the above formula (II) when 4-(p-halogenobenzoyl)-2,6-dimethylphenol is used alone as a raw material. In addition, when using 4-(p-halogenobenzoyl)-2,6-dimethylphenol and 4-(p-halogenobenzoyl)phenol as raw materials, the above formula (n) The structural unit represented by the above formula (■) is usually randomly combined with the structural unit represented by the formula (■).

These aromatic polyetherketones have an aryloxy group and an arylhalogeno group at their terminals, but
In the present invention, at least the aryloxy end is blocked by an end-capping reaction with an aromatic compound.
, and the aryl halide terminals are also capped if necessary.

There are no particular restrictions on the method of carrying out this sealing reaction, but
Usually, the following method is preferably used.

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

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, frombenzene, and iodobenzenato; monohalogenated naphthalenes such as fluoronaphthalene, chlornaphthalene, fromnaphthalene, and iodonaphthalene; In the formula, X' is a halogen atom, and Q is a simple chemical bond.

-〇-%-8-. -C-, -8o-%-802-.

Examples include compounds represented by a divalent group such as -CH2-1-C(R'R2)-, where R1 and R2 are lower alkyl groups. In addition, in these aromatic monohalides, one or more hydrogen atoms in the aromatic ring are
It may be substituted with an inert group such as a lower alkyl group, lower alkoxy group, phenyl group, cyano group, or ester group.

Among these aromatic monohalides, the general formula (in the formula, X"' is a halogen atom, Y is -C- or -5o
2- ) Compounds represented by 0 are preferred, especially 4-benzoyl-chlorobenzene, 4-benzoyl-fluorobenzene% 4-
Benzenesulfonyl-chlorobenzene and 4-benzenesulfonyl-fluorobenzene are preferred.

Examples of aromatic mononitro compounds having an electron-withdrawing substituent include 1, for example, nitrobenzonitrile.

(each isomer), cyanonitronaphthalene (each isomer)
, a compound represented by the general formula (in which Y 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 phenyl group, a cyan group, an ester group, or the like.

On the other hand, as the aromatic compound that can react with the aryl halogeno terminal, aromatic monohydroxyl compounds are suitable, such as phenol, naphthol, and compounds represented by the general formula (Q in the formula has the same meaning as above). etc. are used. Furthermore, in these aromatic monohydroxyl compounds, one or more hydrogen atoms of the aromatic ring is a lower alkyl group.

It may be substituted with an inert group such as a lower alkoxy group, phenyl group, cyano group, or ester group.

Furthermore, these aromatic monohydroxyl compounds can also be used in the form of their alkali metal salts.

The sealing reaction temperature and reaction time 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 150 to 45
1 minute to 50 hours at a temperature range of 0°C, preferably 200
It is about 5 minutes to 20 hours at a temperature range of -400°C.

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 the structural unit represented by the formula (n), or a structural unit represented by the formula (II) (A1). , (B) has a skeleton consisting of constitutional units represented by the formula (I and has a structure in which at least the aryloxy end of the polymer is capped with an inert aromatic group, and in 98 sulfuric acid,
The reduced viscosity at a temperature of 30°C and @ degree OAf/dl is 0.
1 or more. The value of this reduced viscosity is 0
．． If it is 1 or more, it can be molded by melt molding, solution molding, or other molding methods, and there is no particular restriction,
It is usually within the range of 0.1 to 5.01, preferably 0.2 to 3.5.

In addition, in the terminal-capped aromatic polyether keto/ of the present invention having a skeleton of (A) units and (B) units, (A
) The molar fraction of the (4) units to the sum of the (B) units is 5% or more, particularly preferably 20% or more.

(Products with a content ratio of N units in this range have a glass transition temperature about 10°C higher than that of known aromatic polyetherketones consisting only of (B) units, so they cannot be used at much higher temperatures. The dimensional stability is improved.Also, by changing this ratio, it is possible to obtain any type from amorphous to crystalline.
Aromatic polyetherketones end-capped with inert aromatic groups are among the most preferred non-polymer polymers having a glass transition temperature of about 230°C.

Effects of the Invention The aromatic polyetherketone of the present invention has heat resistance (in a nitrogen stream,
No weight loss up to 40°C).

It has excellent chemical resistance (there are almost no solvents other than llI arsenic acid) and mechanical strength, and since it has a structural unit with l=-cy and a substituent on the aromatic ring, it has Molding is relatively easy compared to conventional aromatic polyetherketones that do not have
It has characteristics such as being able to be melted and molded at a temperature of .

Furthermore, the aromatic polyetherketones of the present invention are more advantageous than corresponding aromatic polyetherketones that are not end-capped because at least the aryloxy ends of the polymer are capped with inert aromatic groups. In addition, the thermal decomposition initiation temperature is improved by 10° C. or more, and gelation during hot molding is also prevented, resulting in even more excellent molding processability.

The polymer of the present invention can be used alone in structural materials, films, fibers,
It can be used for fibrils, coatings, etc., or as a blend with other polymers, or glass fiber, carbon fiber, aramid fiber.

It can also be used as a composite material containing reinforcing materials or fillers such as calcium carbonate and calcium silicate. It is not limited in any way.

The reduced viscosity of the polymer is a value measured using 98 thiosulfuric acid as a solvent at a concentration of 0.1 fl/di and a temperature of 30°C.

Example 1 4-(p-fluorobenzoyl)-2,6-dimethylphenol 25I and diphenylsulfone 801 were placed in a flask equipped with a stirrer, thermometer, nitrogen inlet, and air-cooled condenser tube, and heated to 170°C. Heat to make a homogeneous solution.

Next, fine powder anhydrous sodium carbonate 6.199 and anhydrous potassium carbonate 0.43! ! and add 200' (:! to 1
The polycondensation reaction was carried out by stirring at 250° C. for 15 minutes and at 270° C. for 4 hours under a nitrogen atmosphere.

Next, a solution of 1.25.9 p-fluorobenzophenone dissolved in 10 liters of sulfolane was added, and the mixture was heated at 270°C.
The end-capping reaction was performed by stirring for 1 hour. During the polymerization reaction, the solution was yellowish and viscous, but by adding p-fluorobenzophenone and stirring, the yellow color disappeared and the solution turned into a whitish viscous solution. This indicates that the alkali metal phenoxyto group at the end of the polymer disappeared and the end was capped with a stable aromatic group.

Next, the viscous reaction mixture was taken out while hot, and after cooling, it was ground. The obtained powder was washed and extracted several times with acetone and water, respectively, to remove diphenylsulfone, surumedi, and inorganic salts. A milky white polymer 22.2, lit was then obtained by drying at 150° C. under reduced pressure. The yield was quantitative and the reduced viscosity of this polymer was 1.7.

The infrared absorption spectrum of this polymer is shown in FIG.

As can be seen, there is a methyl group at 2900-2980m-1, 1640-167o♂ and 1580-161゜α
-1 is a carbonyl group and a benzene ring conjugated to it,
It has characteristic absorption due to ether bonds at 11oo to 1350CM-1.

Based on the disappearance of the yellow color due to the alkali metal phenoxyto group due to the capping reaction and the results of the infrared absorption spectrum, this polymer was identified as an end-capped aromatic polyetherketone with the following structure, in which the phenoxy end was capped. It was done.

Furthermore, the thermogravimetric analysis chart of this polymer is shown in Figure 2 (
A thermogravimetric analysis chart of the polymer without capping the phenoxy end is shown in FIG. 2 ('').

From these figures, it can be seen that by sealing the phenoxy terminal, the thermal decomposition onset temperature is increased by about 25°C from about 430°C to about 455°C.

Further, this polymer was an amorphous polymer having a glass transition temperature of about 260°c1.

Example 2 25 g of 4-(p-fluorobenzoyl)-2,S-dimethylphenol and 751 diphenylsulfone were added to Example 1.
After stirring in a nitrogen atmosphere and heating to 160°C to form a solution, add 5.01 J of anhydrous sodium carbonate and 0.7 J of anhydrous potassium carbonate as fine powders.
2 J was added, and the polycondensation reaction was carried out at 200°C for 1 hour, at 250°C for 30 minutes, and at 270-280°C for 4.5 hours.

Next, 2.52 y of p-chlordiphenylsulfone dissolved in 5 txl of sulfolane was added, and an end-capping reaction was carried out with stirring at 275 to 280°C for 1 hour.
The yellow viscous solution turned into an eyelid-colored viscous solution. By the same treatment as in Example 1, 25.4 g/l of a milky white polymer with a phenoxy end-capped structure having the following structure was obtained. The reduced viscosity of this polymer was 1.6. ``The infrared absorption spectrum of this polymer is shown in FIG. 3, and the thermogravimetric analysis chart is shown in FIG. 4.

Example 3 17.08 g of 4-(p-fluorobenzoyl)-2,6-dimethylphenol and 6.48 g of 4-(p-fluorobenzoylphenol) were placed in the same flask as in Example 1, and under a nitrogen atmosphere, 160℃ while stirring
After heating to a homogeneous solution, add 5.01 g of finely powdered anhydrous sodium carbonate and 0.72 g of anhydrous potassium carbonate.
and incubate at 200°C for 1 hour, 250°C for 30 minutes, 2
Polycondensation reaction was carried out at 70 to 280°C for 4 hours. Next, p-chlordiphenylsulfone 2,52 lI dissolved in 5 ml of sulfolane was processed and end-blocked at 275°C for 1 hour while stirring. It turned into a simple solution. Next, by carrying out the same treatment as in Example 1, a milky white polymer 21.817 was obtained in a fairly quantitative yield.

The reduced viscosity of this polymer was 1.5. The infrared absorption spectrum of this product is shown in FIG. According to this infrared absorption spectrum and NMR analysis, this polymer is an aromatic polyether ketone whose skeleton consists of was identified.

Furthermore, a thermogravimetric analysis chart of this product is shown in FIG. As is clear from the graph, no weight loss was observed in this polymer up to a nitrogen flow width of about 450°C. It was also found that this polymer is an amorphous polymer having a glass transition point at about 230°C.

Example 4 4-(p-fluorobenzoyl)-2,6-dimethylphenol 12,2,9,4-(p-fluorobenzoyl)phenol 10.81! and as an end capping agent, p
-Fluorobenzophenone2. OI! By carrying out the polycondensation reaction, end-capping reaction, and post-treatment in the same manner as in Example 3, except for using the same method as in Example 3, a milky white polymer of 21.1% was obtained with a very quantitative yield. I got i. The reduced viscosity of this polymer was 1.6.

The infrared absorption spectrum of this product is shown in FIG. According to this infrared absorption spectrum and NMR analysis, this polymer is an aromatic polyetherketone whose skeleton consists of was identified.

Furthermore, a thermogravimetric analysis chart of this product is shown in FIG. As is clear from the graph, no weight loss was observed in this polymer up to about 455°C in a nitrogen stream. Further, this polymer was found to be an amorphous polymer having a glass transition point at about 210°C.

Example 5 After reacting 4-(p-fluorobenzoyl)-2,6-dimethylphenol with an aqueous solution of potassium hydroxide, the resulting yellow powder 4 was dehydrated and vacuum dried (150°C). -(p-fluorobenzoyl)-
Potassium salt of 2,+5-dimethylphenol 16.92
g, and the potassium salt of 4-(p-fluorobenzoyl)phenol prepared in a similar manner 10,16,9. Polycondensation was carried out by putting 45 g of diphenylsulfone into a flask and reacting at 240°C for 1 hour and at 280°C for 3 hours while stirring. Next, sulfolane 5s
p-fluorobenzophenone 2.0I dissolved in tl
When the end-capping reaction was carried out at 280°C for 1 hour with stirring, the yellow viscous solution changed to an eyelid-colored viscous solution. Next, by carrying out the same treatment as in Example 1, a milky white polymer 21.59 was obtained in a fairly quantitative yield. The reduced viscosity of this polymer was 1.4.

According to NMR analysis and infrared absorption spectroscopy, this polymer is identified as an aromatic polyether ketone whose skeleton consists of Ta.

Example 6 4-(p-fluorobenzoyl)-2,6-dimethylphenol L22,9,4-(p-fluorobenzoyl)
Example 4 except using phenol 20.52.9'
As a result of performing the υ polycondensation reaction, end-capping reaction, and post-treatment in the same manner as above, a milky white polymer was obtained in a fairly quantitative yield. The reduced viscosity of this polymer was 1.3. The infrared absorption spectrum of this product is shown in FIG. According to this infrared absorption spectrum and NMR analysis, this polymer is an aromatic polyetherketone whose skeleton is composed of , and whose phenoxy end is capped with an aromatic group represented by the following formula. Identified.

Further, a thermogravimetric analysis chart of this product is shown in FIG. As is clear from this, C: This polymer showed no weight loss up to about 510° C. in a nitrogen stream. It was also found that this polymer is a crystalline polymer that exhibits a melting point around 350°C.

Example 7 4-(p-fluorobenzoyl)-2,6-dimethylphenol4. ss,p,4-(p-fluorobenzoyl)phenol 17.28. Example 4 except that F is used.
As a result of polycondensation reaction, end-capping reaction, and post-treatment in the same manner as above, a milky white polymer was obtained in a fairly quantitative yield. The reduced viscosity of this polymer was 1.5. Furthermore, based on NMR analysis and infrared absorption vector analysis, it was determined that this polymer has a skeleton structure like this, and that it is an aromatic polyetherketone whose phenoxy end is capped with an aromatic group represented by the following formula. Ta.

A thermogravimetric analysis chart of this product is shown in FIG. As is clear from this, this polymer has approximately 4
No weight loss was observed up to 80°C. In addition, this polymer has a glass transition point around 200°C, and
Since it has a melting point around ℃, it was found that it is a partially crystalline polymer.

Example 8 25 g of 4-(p-fluorobenzoyl)-2,6-dimethylphenol and 100 I of sulfolane were placed in the same flask as in Example 1, heated to 180°C to make a homogeneous solution, and then finely powdered carbonic acid anhydride was added. Sodium 6.21! , add 0.6 g of anhydrous potassium carbonate, under nitrogen atmosphere, 2006
The polycondensation reaction was carried out by stirring at Q for 1 hour, at 250°C for 1 hour, and at 280°C for 5 hours. Then p
- Fluorobenzophenone 1.29 to sulfolane 108
A phenoxy terminal blocking reaction was performed by adding a solution dissolved in / and stirring at 280° C. for 1 hour.

Furthermore, a solution in which p-hydroxydiphenyl 1,111 was dissolved in 10 g/sulfolane was added, and the mixture was stirred at 280° C. for 1 hour to perform a fluorine terminal blocking reaction.

Next, by carrying out the same treatment as in Example 1, a milky white polymer 21.9fi was obtained in a fairly quantitative yield. The reduced viscosity of this polymer was 1.4.

Furthermore, no weight loss was observed in this polymer up to about 455° C. in a nitrogen stream.

Example 9 4-(p-fluorobenzoyl)-2,6-dimethylphenol 14.64 g, 4-(p-fluorobenzoyl)phenol 8,64,9. Diphenylsulfone 9
011 was placed in a flask similar to that in Example 1, and 180' (
! After heating to make a homogeneous solution, finely powdered anhydrous sodium carbonate 5, 8, 9. A polycondensation reaction was carried out by adding 1.2 g of anhydrous potassium carbonate and stirring under a nitrogen atmosphere at 200°C for 1 hour, at 25[]'C for 1 hour, and at 28d'Cj for 4 hours. Next, a solution of 1,911 p-hydroxybenzophenone dissolved in 5 yzl of sulfolane was added, and the mixture was stirred at 280°C for 1 hour to carry out a reaction for blocking the phenylfluorine terminals. Furthermore, a solution in which 2.4 I of p-chlordiphenylsulfone was dissolved in 5 yxl of sulfolane was added, and the mixture was stirred at 280° C. for 1 hour to carry out a reaction for blocking the phenoxy end. Next, by carrying out the same post-treatment as in Example 1, a milky white polymer was obtained in a fairly quantitative yield. This polymer is
Infrared absorption spectroscopy, NMR analysis, etc. revealed that the skeleton consisted of O, the phenoxy end was capped with an aromatic group represented by the following formula, and the other end was capped with a benzy/L4 phenyl group. It was identified as an aromatic polyetherketone. The reduced viscosity of this polymer was 1.3, and no weight loss was observed up to about 460°C in a nitrogen stream.

Example 10 4-(p-chlorobenzoyl)-2,6-dimethylphenol 18.24.9. 60 g of 4-(p-chlorobenzoyl)phenol 6.98!11 diphenyl sulfone and 6.9 fi of anhydrous potassium carbonate were placed in a flask and reacted at 620° C. for 10 hours with stirring to perform polycondensation. Then, 2,52 g of p-chlordiphenylsulfone was completely processed, phenoxy-terminated by reacting at 300 °C for 1 h.

I sealed it. 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 6.

The reduced viscosity of this polymer was 0.6 and the yield was 90%.

Example 11 4-(p-fluorobenzoyl)-2,6-dimethylphenol 20.74.9.4-(p-fluorobenzoyl)phenol 3.24y was used in the same manner as in Example 3. A condensation reaction was performed. Then sulfolane 5ttt
2.29 g of p-nitrobenzophenone dissolved in 1 liter of water was added thereto, and an end-capping reaction was carried out at 260° C. for 1 hour while stirring. Next, by carrying out the same treatment as in Example 1, a milky white polymer was obtained in a fairly quantitative yield. This polymer is an amorphous polymer with a glass transition point of about 230°C, and its skeleton consists of C, and its phenoxy end is capped with an aromatic group represented by the following formula. there were.

Further, the reduced viscosity of this polymer was 1.4.

Example 12 23.18 g of 4-(p-fluorobenzoyl)-2,6-dimethylphenol, 1.08,9 g of 4-(p-fluorobenzoyl)phenol and 2 p-fluorobenzophenone as an end capping agent. A milky-white polymer was obtained in a fairly quantitative yield by performing a polycondensation reaction, an end-capping reaction, and a post-treatment in the same manner as in Example 3 except that .0 g was used. This polymer is approximately 250℃
The polymer was an amorphous polymer having a glass transition point of 200 mm, the skeleton of which was composed of ◯, and its phenoxy terminal end capped with an aromatic group represented by the following formula.

○ Note that the reduced viscosity of this polymer was 1.7.

[Brief explanation of the drawing]

Figures 1, 3, 5, 7 and 9 are infrared absorption spectra charts by diffuse reflection FT-IH of examples of end-capped aromatic polyetherketones of the present invention. Figure 2(a), Figure 4, Figure 6, Figure 8, and Figure 10 are thermogravimetric analysis charts under a nitrogen stream for the examples corresponding to the above, and Figure 11 is the end of Example 7. It is a thermogravimetric analysis chart of a sealed aromatic polyether ketone. Further, FIG. 2 (1)) is a thermogravimetric analysis chart of an aromatic polyether ketone whose ends are not capped, which corresponds to the end-capped aromatic polyether ketone of FIG. 2 (al).

Claims (1)

[Scope of Claims] 1 Consists of a structural unit represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and has a molecular structure in which at least the aryloxy end of the polymer is capped with an inert aromatic group, and in 98% sulfuric acid, temperature 30°C, concentration 0
．． An end-capped aromatic polyether ketone having a reduced viscosity of 0.1 or more at 1 g/dl. 2. The aromatic polyetherketone according to claim 1, wherein the inert aromatic group is a benzoylphenyl group or a benzenesulfonylphenyl group. 3 Consists of a structural unit represented by the formula (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and a structural unit represented by the formula (B) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ At least the aryloxy terminal of the polymer has a molecular structure sealed with an inert aromatic group, and (A) for the sum of (A) and (B)
is at least 5 mol%, and the reduced viscosity in 98% sulfuric acid at a temperature of 30°C and a concentration of 0.1 g/dl is 0.
1 or more. 4. The aromatic polyetherketone according to claim 3, wherein the inert aromatic group is a benzoylphenyl group or a benzenesulfonylphenyl group. 5. The aromatic polyetherketone according to claim 3 or 4, wherein the molar fraction of the (A) units is 20% or more. 6 Heat polycondensation of 4-(p-halogenobenzoyl)-2,6-dimethylphenol in the absence of a solvent or in a solvent, and then add an aromatic compound capable of reacting with the aryloxy end of the obtained polymer and the desired Formula ▲ mathematical formula, chemical formula, characterized in that the aryloxy end or this end and the aryl halogeno end are sealed by reacting an aromatic compound that can react with the aryl halogeno end in any order according to the formula. There are tables, etc. ▼ It is composed of the structural unit represented by ▼, has a molecular structure in which at least the aryloxy end of the polymer is capped with an inert aromatic group, and is prepared in 98% sulfuric acid at 30°C and at a concentration of 0.
．． A method for producing an end-capped aromatic polyetherketone having a reduced viscosity of 0.1 or more at 1 g/dl. 7 The aromatic compound that can react with the aryloxy terminal is
The production according to claim 6, which is a compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Z in the formula is a halogen atom or a nitro group, and Y is a carbonyl group or a sulfonyl group) Method. 8. The manufacturing method according to claim 6 or 7, wherein 4-(p-halogenobenzoyl)-2,6-dimethylphenol is used in the form of an alkali metal salt. 9. The method according to any one of claims 6 to 8, wherein 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. 10. The manufacturing method according to any one of claims 6 to 9, wherein the halogen atom of the 4-(p-halogenobenzoyl)-2,6-dimethylphenol is a fluorine atom or a chlorine atom. 11 4-(p-halogenobenzoyl)-2,6-dimethylphenol and at least 5 mol % of 4-(p-halogenobenzoyl)-2,6-dimethylphenol based on the total amount, without solvent or in a solvent. is subjected to heating polycondensation, and then the obtained polymer is reacted with an aromatic compound capable of reacting with the aryloxy terminal and, if desired, an aromatic compound capable of reacting with the aryl halogeno terminal in any order to form the aryl. (A
) formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and (B) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. It has a molecular structure sealed with an active aromatic group, and (
A method for producing an end-capped aromatic polyetherketone in which the proportion of A) is at least 5 mol % and the reduced viscosity at a temperature of 30° C. and a concentration of 0.1 g/dl in 98% sulfuric acid is 0.1 or more. 12 An aromatic compound that can react with an aryloxy end is represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Z is a halogen atom or a nitro group, and Y is a carbonyl group or a sulfonyl group) The manufacturing method according to claim 11, which is a compound. 13. The manufacturing method according to claim 11 or 12, wherein the molar fraction of the (A) units is 20% or more. 14 4-(p-halogenobenzoyl)-2,6-dimethylphenol and 4-(p-halogenobenzoyl)phenol are each used in the form of an alkali metal salt according to any one of claims 11 to 13. Manufacturing method described. 15. The method according to any one of claims 11 to 14, wherein 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. 16 The halogen atom of 4-(p-halogenobenzoyl)-2,6-dimethylphenol and the halogen atom of 4-(p-halogenobenzoyl)phenol are fluorine atoms or chlorine atoms, respectively. The manufacturing method according to any one of Item 15.