JPH0430968B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a novel 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, has excellent heat resistance, chemical resistance, mechanical strength, etc., and is relatively easy to use. The present invention relates to a novel polymer that can be melt-molded and an industrially advantageous method for producing the same. BACKGROUND 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. A method of heating an aromatic polyetherketone represented by this structural formula, for example, the potassium salt of 4-(p-chlorobenzoyl)phenol
1020), or by a method of subjecting p-phenoxybenzoyl halide to a Friedel-Crafts reaction in the presence of a Lewis acid catalyst such as boron trifluoride (Japanese Patent Publication No. 33419/1982). 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 this extremely high temperature, 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 the above-mentioned drawbacks, and to provide a novel polymer which has excellent heat resistance, chemical resistance and mechanical strength, and which can be melt-molded relatively easily. and a manufacturing method thereof. Means for Solving the Problems The present inventors have conducted extensive research and first developed the formula It was found that an aromatic polyetherketone consisting of a structural unit having a substituent on an aromatic ring represented by the formula (2) can be suitable for the above purpose, but as a result of further research, it was found that the structural unit represented by the above formula () and ,
formula A novel aromatic polyetherketone having a predetermined ratio of structural units represented by The inventors have discovered that it can be easily obtained by subjecting benzoyl)-2,6-dimethylphenol and 4-(p-halogenobenzoyl)phenol to a thermal reaction, and have completed the present invention based on this knowledge. That is, the present invention provides formula (A) The structural unit represented by and formula (B) The molar ratio of the (A) units to the (B) units is in the range of 5:95 to 99:1, and the temperature is 30% when 98% sulfuric acid is used as the solvent.
4-(p-halogenobenzoyl)-2,6, which is characterized by having a reduced viscosity of 0.1 or more at a concentration of 0.1 g/dl at a temperature of 4-(p-halogenobenzoyl)-2,6, without a solvent or in a solvent. The present invention provides a method for producing phenol by mixing dimethylphenol and 4-(p-halogenobenzoyl)phenol at a molar ratio of 5:95 to 99:1 and subjecting the mixture to a heating reaction. The raw material monomer used in the present invention has the following general formula: (X in the formula is a halogen atom) 4-(p-halogenobenzoyl)-2,
6-dimethylphenol and the general formula (X' in the formula is a halogen atom) 4-(p-halogenobenzoyl)phenol represented by the following formula, and each halogen atom may be the same or different. Preferred halogen atoms are fluorine atoms and chlorine atoms, and it is particularly preferred that both compounds are fluorine atoms. In the present invention, 4-(p-halogenobenzoyl)-2,6-dimethylphenol represented by the general formula () and 4-(p-halogenobenzoyl)-2,6-dimethylphenol represented by the general formula ()
-(p-halogenobenzoyl)phenol,
By heating and reacting at a molar ratio of 5:95 to 99:1, preferably 80:20 to 99:1,
The desired aromatic polyetherketone is obtained. Although there are no particular limitations on the means for carrying out the condensation, for example, the following two methods are advantageous. 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 with a dehalogenated alkali metal. 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 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. 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 preferably used. In addition, the 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 usually 150~
1 minute to 50 hours at a temperature range of 450℃, preferably
It is about 5 minutes to 25 hours at a temperature range of 200 to 400°C. The above 4-(p-halogenbenzoyl)-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, or dealcoholization and drying. can be easily obtained by The aromatic polyetherketone thus obtained is usually one in which the constituent units represented by the above formula () and the constituent units represented by the formula () are randomly bonded. The second method uses a predetermined ratio of 4-(p-halogenobenzoyl)-2,6-dimethylphenol and 4-(p-halogenobenzoyl)phenol,
This method involves polycondensation by heating in the presence of at least one selected from alkali metal 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, ribidium 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°C to 450°C. de1
The heating time is about 5 minutes to 50 hours, preferably about 5 minutes to 25 hours at a temperature range of 200 to 400°C. 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 each substantially in the p-position relative to the carbonyl group. It is necessary. 4-(p-
One of the preferred methods for producing (halogenobenzoyl)-2,6-dimethylphenol is the Fries rearrangement of p-halogenated benzoic acid 2,6-dimethylphenol ester. 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 polyether ketone obtained in this way has a structural unit (A) represented by the formula () and a structural unit (B) represented by the formula (), similar to that obtained by the above method. are randomly combined. The aromatic polyetherketone of the present invention comprises the structural units (A) represented by the above formulas () and () and
(B), the constituent unit (A) and the constituent unit (B)
The molar ratio is selected in the range of 5:95 to 99:1, but a particularly preferable molar ratio is 20:
The ratio is 80 to 99:1. Constituent unit (A) and constituent unit (B)
When the ratio of . Improved dimensional stability. Moreover, by changing this ratio, it is possible to obtain anything from amorphous to crystalline. Furthermore, the aromatic polyetherketone of the present invention has a temperature of 30% when 98% sulfuric acid is used as a solvent.
The reduced viscosity at ℃ and concentration of 0.1 g/dl is 0.1 or more. The upper limit of this value is not particularly limited as long as it can be molded by melt molding, solution molding, or other methods, but it is generally in the range of 0.1 to 5.0, preferably 0.2 to 3.5. This is desirable. Effects of the Invention The aromatic polyetherketone of the present invention has p-
Heat resistance (in nitrogen flow,
It has extremely excellent chemical resistance (no weight loss up to 430℃), chemical resistance (almost no solvents other than concentrated sulfuric acid), and mechanical strength, and it also contains a structural unit with a substituent on the aromatic ring. Therefore, compared to conventional aromatic polyetherketones that do not have such substituents, molding is relatively easy, for example at temperatures of 300 to 400°C.
It has characteristics such as being able to be melted and molded at a temperature of . 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, 6.48 g of 4-(p-fluorobenzoyl)phenol, and 50 g of diphenyl sulfone were added to a stirrer, a thermometer, a nitrogen introduction tube,
Place in a flask with an air-cooled condenser and heat to 180℃ to make a homogeneous solution. Next, 4.98 g of finely powdered anhydrous sodium carbonate and 0.42 g of anhydrous potassium carbonate.
The mixture was added and reacted with stirring for 1 hour at 200°C, 1 hour at 250°C, and 1.2 hours at 280°C. While still hot, remove the viscous reaction mixture and
After cooling, it was crushed. Diphenylsulfone and inorganic salts were removed by washing and extracting the obtained powder several times with acetone and water, respectively. Then, 21.5 g of a milky white polymer was obtained by drying at 150° C. under reduced pressure. The yield is quantitative and the reduced viscosity of this polymer is 1.8
It was hot. The elemental analysis values of the obtained polymer were as follows: C H Actual value: 80.2% 5.0% Theoretical value: 80.15% 5.01% [as C _14.4 H _10.8 O ₂ )n], and the infrared absorption spectrum was as shown in Figure 1. 2900~2950cm ^-1 : Methyl group, 1640~1670cm ^-1
and 1575 to 1610 cm ^-1 : carbonyl group and benzene ring conjugated thereto; 1100 to 1350 cm ^-1 : ether bond. Based on these results and NMR etc., the polymer is It was identified as an aromatic polyetherketone with a composition of Furthermore, a thermogravimetric analysis chart of this aromatic polyetherketone is shown in FIG. As is clear from Figure 2, this polymer was heated at 440°C in a nitrogen stream.
No weight loss was observed until then. It was also found that this polymer is an amorphous polymer having a glass transition point at about 230°C. Example 2 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.
Polymerization was carried out by reacting at 280°C for 1 hour. As a result of post-treatment in the same manner as in Example 1, a milky white polymer similar to that in Example 1 was obtained.
21.23g was obtained. The yield was quantitative and the reduced viscosity of the polymer was 1.4. The elemental analysis values for this polymer are as follows: C H Actual value: 80.1% 4.9% Theoretical value: 80.08% 4.89% [as C _14.2 H _10.4 O ₂ )n] Based on this result and NMR etc. It was confirmed that the composition was as follows. Examples 3 to 6 Same as Example 1 except that the amounts of 4-(p-fluorobenzoyl)-2,6-dimethylphenol (-a) and 4-(p-fluorobenzoyl)phenol (-a) are changed. By this method, A milky white to slightly pale yellowish aromatic polyetherketone having the structural unit was quantitatively obtained. The physical properties of this material were determined and the results are shown in the table below.

[Table] However, ηsp/c is reduced viscosity, Tg is glass transition temperature, IR is infrared absorption spectrum, and TGA is thermogravimetric analysis. The polymers obtained in Examples 3 and 4 are amorphous, the polymer obtained in Example 5 contains some crystalline parts, and the polymer obtained in Example 6 has a melting point around 340°C. It was a crystalline polymer with Example 7 4-(p-chlorobenzoyl)-2,6-dimethylphenol 18.24 g, 4-(p-chlorobenzoyl)phenol 6.98 g, diphenyl sulfone
Put 60g and 6.9g of anhydrous potassium carbonate into a flask,
Polymerization was carried out by reacting at 320°C for 10 hours with stirring. As a result of post-treatment in the same manner as in Example 1, a light brown polymer was obtained. 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 73.2 g of 4-(p-fluorobenzoyl)-2,6-dimethylphenol, 151.2 g of 4-(p-fluorobenzoyl)phenol, 450 g of sulfolane,
Anhydrous sodium carbonate 49.8g, anhydrous potassium carbonate
Put 4.2g into a flask and heat at 200-220℃ for 1 hour.
Polymerization was carried out by reacting at 250°C for 1 hour and at 283°C for 2 hours with stirring. At the reaction temperature, it was an ocher-colored viscous liquid, but it became solid when cooled to room temperature. The solid product was pulverized, washed with water and acetone, and extracted to remove inorganic salts and sulfolane.
Then, by drying at 150°C under reduced pressure, 204 g of an ivory-colored polymer with a slightly yellowish tinge was obtained.
was gotten. The yield is quantitative and the reduced viscosity is
It was 1.4. The infrared spectrum and thermal analysis chart of this polymer were consistent with those obtained in Example 5. Example 9 Polycondensation reaction and post-treatment in the same manner as in Example 1 except that 4.88 g of 4-(p-fluorobenzoyl)-2,6-dimethylphenol and 17.28 g of 4-(p-fluorobenzoyl)phenol were used. As a result, a milky white polymer was obtained in almost 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. It was identified as an aromatic polyetherketone consisting of According to thermogravimetric analysis, this polymer showed no weight loss up to about 470°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.

[Brief explanation of drawings]

Figures 1, 3, 5, 7 and 9 are infrared absorption spectrum charts by diffuse reflection FT-IR of the aromatic polyetherketone of the present invention; FIG. 4, FIG. 6, FIG. 8, and FIG. 10 are thermogravimetric analysis charts under a nitrogen stream for the examples corresponding to the above.

Claims (1)

[Claims] 1 Formula (A) The structural unit represented by and formula (B) The molar ratio of the (A) units to the (B) units is in the range of 5:95 to 99:1, and the temperature is 30% when 98% sulfuric acid is used as the solvent.
An aromatic polyetherketone having a reduced viscosity of 0.1 or more at a temperature of 0.1 g/dl at a concentration of 0.1 g/dl. 2. The aromatic polyetherketone according to claim 1, wherein the molar ratio of (A) units to (B) units is 20:80 to 99:1. 3 In the absence of a solvent or in a solvent, the alkali metal salt of 4-(p-halogenobenzoyl)-2,6-dimethylphenol and the alkali metal salt of 4-(p-halogenobenzoyl)phenol were mixed in a molar ratio of 5:
Formula (A), characterized by heating the reaction at a ratio of 95 to 99:1 The structural unit represented by and formula (B) The molar ratio of the (A) units to the (B) units is in the range of 5:95 to 99:1, and the temperature is 30% when 98% sulfuric acid is used as the solvent.
A method for producing an aromatic polyetherketone having a reduced viscosity of 0.1 or more at a temperature of 0.1 g/dl at a concentration of 0.1 g/dl. 4. The production method according to claim 3, wherein the molar ratio of the (A) units to the (B) units is 20:80 to 99:1. 5 Halogen atom of 4-(p-halogenobenzoyl)-2,6-dimethylphenol and 4-(p-
5. The production method according to claim 3 or 4, wherein the halogen atom of the (halogenobenzoyl)phenol is a fluorine atom or a chlorine atom, respectively. 6 In the absence of a solvent or in a solvent, 4-(p-halogenobenzoyl)-2,6-dimethylphenol and 4-( p-halogenobenzoyl)phenol in a molar ratio of 5:95.
Formula (A) characterized by heating the reaction at a ratio of 99:1 to 99:1. The structural unit represented by and formula (B) The molar ratio of the (A) units to the (B) units is in the range of 5:95 to 99:1, and the temperature is 30% when 98% sulfuric acid is used as the solvent.
A method for producing an aromatic polyetherketone having a reduced viscosity of 0.1 or more at a temperature of 0.1 g/dl at a concentration of 0.1 g/dl. 7. The production method according to claim 6, wherein the molar ratio of the (A) units to the (B) units is 20:80 to 99:1. 8 Halogen atom of 4-(p-halogenobenzoyl)-2,6-dimethylphenol and 4-(p-
8. The production method according to claim 6 or 7, wherein the halogen atom of the (halogenobenzoyl)phenol is a fluorine atom or a chlorine atom, respectively.