JPH0149376B2 - - 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.

[Conventional technology]

Aromatic polyetherketones having no substituents on the aromatic ring are already known. For example, special public service in the 1970s.
In Japanese Patent Publication No. 1020, potassium salt of 4-(parachlorobenzoyl)phenol was heated to 280°C, and in Japanese Patent Publication No. 56-33419, paraphenoxybenzoyl halide was heated with boron trifluoride, etc. By conducting a Friedel-Crafts reaction in the presence of a Lewis acid catalyst of It has been reported that aromatic polyetherketones having the following properties can be obtained. This polymer is 365-367℃
It is a crystalline polymer with a very high melting point, and in order to mold it, it must be heated to a high temperature of 400°C or higher.

[Problem that the invention seeks to solve]

However, the following formula () with two methyl groups at specific positions on the aromatic ring Until now, no aromatic polyetherketone having the repeating unit represented by the following formula has been known.

[Means for solving problems]

The object of the present invention is to provide such a novel polymer, aromatic polyetherketone, and a method for producing the same.

That is, the present invention provides aromas expressed by (1) formula () Group ether ketone structure as repeating unit, 98%
A new polymer with a reduced viscosity of 0.1 or more at 30°C and 0.1 g/dl when sulfuric acid is used as a solvent, and (2) an alkali of 4-(parahalogenobenzoyl)-2,6-dimethylphenol represented by formula () A novel method for producing a polymer consisting of repeating units of the formula (), comprising heating a metal salt. (However, X represents a halogen atom selected from F, Cl, Br, I, and M represents an alkali metal atom) or (3) 4-(parahalogenobenzoyl)-2,6 represented by formula () An object of the present invention is to provide a novel method for producing a polymer comprising repeating units represented by the formula (), which comprises heating dimethylphenol in the presence of an alkali metal carbonate and/or an alkali metal hydrogen carbonate.

(X is as described above) The aromatic polyetherketone, which is the novel polymer of the present invention, may be produced by any method, but one preferred production method is represented by the formula () This is a method of heating an alkali metal salt of 4-(parahalogenobenzoyl)-2,6-dimethylphenol, and the reaction formula is expressed as follows.

Although this polymerization reaction can be carried out without a catalyst, it is of course preferable to use a solvent that does not adversely affect the polymerization reaction. As the solvent, in addition to those that are liquid at room temperature, any solvent that is solid at room temperature but becomes molten 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.

The temperature of the polymerization reaction using this alkali metal salt,
The time and time vary depending on the type of halogen and alkali metal in the alkali metal salt of 4-(parahalogenobenzoyl)-2,6-dimethylphenol that is a monomer, the presence or absence of a solvent, and the type, etc.
Usually at 150-450℃ for 1 minute to 50 hours,
Preferably, the temperature is 200 to 400°C for 5 minutes to 25 hours.

The alkali metal salt of 4-(parahalogenobenzoyl)-2,6-dimethylphenol used in this polymerization reaction may be produced by any method, but for example, an alkali metal hydroxide, After reacting an aqueous solution of carbonate, hydrogen carbonate, etc. or a lower alcohol solution of an alkali metal hydroxide with 4-(parahalogenobenzoyl)-2,6-dimethylphenol, dehydration, drying,
Alternatively, it can be easily obtained by dealcoholization and drying.

Such 4-(parahalogenobenzoyl)-
In the alkali metal salt of 2,6-dimethylphenol, any halogen and alkali metal may be used, but compounds in which the halogen is fluorine or chlorine and the alkali metal is sodium or potassium are particularly preferred.

Another preferred method for producing the aromatic polyetherketone of the present invention is the 4-
This is a method in which (parahalogenobenzoyl)-2,6-dimethylphenol is heated in the presence of an alkali metal carbonate and/or an alkali metal hydrogen carbonate.

Although this polymerization reaction can also be carried out without a solvent, it is also preferable to use the above-mentioned solvent.

In addition, the temperature and time of this polymerization reaction are also determined by the monomer 4-(parahalogenobenzoyl)-2,6
- It varies depending on the type of halogen in dimethylphenol, the type of alkali metal in the alkali metal carbonate and/or alkali metal hydrogen carbonate used at the same time, the presence or absence of a solvent, and the type, but usually 150 to 450.
℃ for 1 minute to 50 hours, preferably
The temperature ranges from 200 to 400°C for 5 minutes to 25 hours.

The monomer 4-(parahalogenobenzoyl)-2,6-dimethylphenol may be produced by any method, but the halogen and hydroxyl group are each in the para position relative to the carbonyl group. There is a need. One of the preferred production methods is a method of subjecting parahalogenated benzoic acid 2,6-dimethylphenol ester to Fries rearrangement. In this case, since the two ortho positions of the hydroxyl group are substituted with methyl, only the desired all-para form is produced.

Also 4-(parahalogenobenzoyl)-2,6
- In dimethylphenol, the halogen may be of any kind, but fluorine or chlorine is particularly preferred.

Examples of alkali metal carbonates and alkali metal hydrogen carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, and lithium hydrogen carbonate, sodium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and carbonate. Hydrogen, cesium, etc. are used.

The aromatic polyetherketone of the present invention has the formula () having two methyl groups at specific positions on the aromatic ring. It consists of a repeating unit represented by
The polymer has a reduced viscosity of 0.1 or more at 30°C and 0.1 g/dl when 98% sulfuric acid is used as a solvent. Of course, depending on the application, the reduced viscosity may be less than 0.1, but for normal applications, polymers with a reduced viscosity of 0.1 or more are preferred.

The value may be any value as long as it can be formed by melt molding, solution molding, or other methods, but I would say
It ranges from 0.1 to 5.0, preferably from 0.2 to 3.5.

〔Effect of the invention〕

The aromatic polyetherketone of the present invention has heat resistance (in a nitrogen stream,
(There is no weight loss up to 430°C) and chemical resistance (almost no solvents other than concentrated sulfuric acid) are very good.
Furthermore, repeating units without methyl substituents (A) A known aromatic polyetherketone consisting of
Unlike crystalline polymers with a high melting point of 365-367°C, which require special molding equipment that can be used at high temperatures of 400°C or higher, special molding equipment on the aromatic ring The aromatic polyetherketone of the present invention having two methyl substituents at each position is characterized by being an amorphous polymer.

Further, its melt molding can be performed relatively easily at a temperature of about 300 to 360°C.

The aromatic polyetherketone of the present invention has an X-ray diffraction diagram as shown in FIG. 3, and is an amorphous polymer consisting only of a halo without a crystalline peak.

However, as shown in Figure 4, the X-ray diffraction diagram of the known aromatic polyetherketone consisting of the repeating unit (A) has 2θ values of approximately 19°, approximately 20.5°, approximately 23°, and approximately 29°.
There is a peak clearly indicating crystallinity at °.

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.

〔Example〕

The present invention will be further explained below with reference to Examples.
The present invention is not limited to these examples. The reduced viscosity of the polymer is a value measured at 30° C. using 98% sulfuric acid at a concentration of 0.1 g/dl.

Example 1 24.4 g of 4-(parafluorobenzoyl)-2,6-dimethylphenol, 30 g of diphenyl sulfone
g into a flask equipped with a stirrer, thermometer, nitrogen inlet tube, and air-cooled condenser tube, and heat to 180°C to make a homogeneous solution. Next, a mixture of 4.98 g of finely powdered anhydrous sodium carbonate and 0.42 g of anhydrous potassium carbonate was added, and the mixture was heated at 200°C for 1 hour, at 250°C for 15 minutes, and at 280°C.
The reaction was allowed to proceed for 35 minutes with stirring. The viscous reaction mixture was removed while still hot and, after cooling, was triturated. Diphenylsulfone and inorganic salts were removed by washing and extracting the obtained powder several times with acetone and water, respectively. Then under reduced pressure
A milky white polymer was obtained by drying at 150°C. The yield was quantitative. The reduced viscosity of this polymer (solvent: 98% sulfuric acid, 30°C) was 1.4. By infrared absorption spectrum and elemental analysis of a film made from a dope prepared by dissolving this polymer in concentrated sulfuric acid, it was identified as an aromatic polyetherketone consisting of a repeating unit of the following formula.

Γ Elemental analysis value: (C ₁₅ H ₁₂ O ₂ ) as n Calculated value C: 80.4%; H: 5.4% Actual value C: 80.3%; H: 5.2% Γ Infrared absorption spectrum 2900-2950 cm ^-1 : Methyl group; 1650cm ^-1 and 1585
cm ^-1 : carbonyl group and benzene ring conjugated to it; 1100 to 1320 cm ^-1 : ether bond Further, a thermogravimetric analysis chart of this novel aromatic polyetherketone is shown in FIG. As is clear from Figure 2, this polymer is
No weight loss was observed up to 430°C.

This novel aromatic polyetherketone was heated to 350°C.
By pressing under the condition of 100 kg/cm ² , a pale yellow, transparent and strong film was obtained.

Comparative Example 1 Instead of 4-(parafluorobenzoyl)-2,6-dimethylphenol, 21.6 g of 4-(parafluorobenzoyl)phenol and 30 g of diphenyl sulfone were placed in the same flask as in Example 1, and the mixture was heated to 180 g.
It was heated to ℃ to make a homogeneous solution. Next, 4.98 g of finely powdered anhydrous sodium carbonate and anhydrous potassium carbonate.
Add 0.42g of mixture and incubate at 200°C for 1 hour, then at 250°C.
The reaction was carried out under stirring for 15 minutes, at 280°C for 35 minutes, and at 320°C for 1 hour. The viscous reaction mixture was then taken out, cooled and ground. Diphenylsulfone and inorganic salts were removed by washing and extracting the obtained powder several times with acetone and water, respectively.

A milky white polymer was then obtained by drying at 150° C. under reduced pressure. The reduced viscosity of this polymer was 1.2. (In addition, the product obtained under the same reaction conditions as in the example without the reaction at 320°C had a reduced viscosity of 0.5.) The obtained polymer was composed of the repeating unit (A) described above. It was a crystalline aromatic polyetherketone consisting of a crystalline aromatic polyetherketone with a melting point of 365-367°C. The X-ray diffraction pattern of this polymer is shown in FIG.

This polymer was heated at 350℃ and 100℃ in the same manner as in Example 1.
Although it was pressed under conditions of Kg/cm ² , no film-like molded product was obtained at all. 450 press molding machines
Instead of the high temperature type that can be heated up to 410℃, 100Kg/
A film-like molded product was obtained only by pressing at cm ² .

As shown in this comparative example, in order to produce the known crystalline polyetherketone consisting of the repeating unit (A), an apparatus capable of carrying out the reaction at a high temperature of over 300°C is required, and In order to mold it, a molding machine that can be used at extremely high temperatures of 400°C or higher is required.

Example 2 After reacting 4-(parafluorobenzoyl)-2,6-dimethylphenol with an aqueous solution of potassium hydroxide, the resulting yellow powder was dehydrated and vacuum dried (150°C). 8.46 g of potassium salt of 4-(parafluorobenzoyl)-2,6-dimethylphenol and 9 g of diphenylsulfone were placed in a flask and heated at 240°C for 1 hour at 280°C while stirring.
Polymerization was carried out by reacting for 30 minutes. 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. The reduced viscosity of this polymer was 1.2, and the yield was quantitative.

Example 3 4-(parachlorobenzoyl)-2,6-dimethylphenol 3.2g, diphenylsulfone 10g,
Polymerization was carried out by putting 0.86 g of anhydrous potassium carbonate into a flask and 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 0.5 and the yield was 90%.

Example 4 4-(parafluorobenzoyl)-2,6-dimethylphenol 7.32g, sulfolane 15g, anhydrous sodium carbonate 1.55g, anhydrous potassium carbonate 0.11g
into a flask and incubate at 200-220℃ for 1 hour at 250℃.
Polymerization was carried out by stirring at 283°C for 15 minutes and 1.5 hours at 283°C. At the reaction temperature, it was an ocher-colored viscous liquid, but it became solid when cooled to room temperature. By crushing this solid product, washing and extracting with water and acetone,
Inorganic salts and sulfolane were removed. Then, by drying at 150° C. under reduced pressure, an ivory-colored polymer with a slightly yellowish tinge was obtained. The yield was quantitative and the reduced viscosity was 1.2.

Example 5 30g to 40g of diphenyl sulfone of Example 1
reaction time at 280°C from 35 min to 70 min.
Polymerization and post-treatment were carried out in the same manner as in Example 1, except that the polymerization was extended to 1.5 minutes, and as a result, a milky white polymer with a reduced viscosity of 1.5 was quantitatively obtained.

Example 6 4-(parafluorobenzoyl)-2,6-dimethylphenol 6.1g, anhydrous potassium carbonate 3.6
A mixture of 40 g of diphenyl sulfone was heated at 240° C. for 1 hour at 280° C. with stirring under a nitrogen atmosphere.
After reacting for 1 hour at 300°C and 1 hour at 300°C, the reaction mixture was taken out in a molten state, cooled, and the solidified mixture was ground and washed several times with acetone and water, respectively. By heating and drying the obtained solid object under reduced pressure, 5.2 g of brown powdery polymer was obtained.
was gotten. (Yield 93%) The reduced viscosity of this polymer was 0.90, but it contained a small amount of gel.

[Brief explanation of drawings]

FIG. 1, FIG. 2, and FIG. 3 are respectively Example 1.
4 is an infrared absorption spectrum chart, a thermogravimetric analysis chart, and an X-ray diffraction diagram of the aromatic polyetherketone of the present invention obtained by Comparative Example 1. FIG. It is an X-ray diffraction diagram of polyetherketone.

Claims (1)

[Claims] 1. Fragrance represented by formula () A new polymer with a repeating unit having a group ether ketone structure and a reduced viscosity of 0.1 or more at 30°C and 0.1 g/dl when using 98% sulfuric acid as a solvent. 2. A method for producing a novel polymer comprising repeating units represented by the formula (), which comprises heating an alkali metal salt of 4-(parahalogenobenzoyl)-2,6-dimethylphenol represented by the formula (). (However, X represents a halogen atom selected from F, Cl, Br, and I, and M represents an alkali metal atom.) 3 In formula (), X is F or Cl according to claim 2 the method of. 4 A process represented by the formula () consisting of heating 4-(parahalogenobenzoyl)-2,6-dimethylphenol represented by the formula () in the presence of an alkali metal carbonate and/or an alkali metal hydrogen carbonate A method for producing a novel polymer consisting of repeating units. (X is as described above) 5. The method according to claim 4, wherein in formula (), X is F or Cl.