JPH02272024A - Aromatic polyether ketone and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title polymer useful as a material in mechanical field, electric field and electronic field, etc., having excellent heat resistance and moldability by reacting a dihalogenobenzophenone with dihydroxybiphenyl and a hydroxyhalogenobenzophenone in a neutral polar solvent. CONSTITUTION:A 4,4'-dihalogenobenzophenone is reacted with 4,4'- dihydroxybiphenyl and a 4-hydroxy-4'-halogenobenzophenone in a neutral polar solvent (preferably N-methylpyrrolidone) preferably at 220-350 deg.C, preferably 220-350 deg.C for 1-5 hours to give the aimed polymer having a repeating unit shown by formula I, a repeating unit shown by formula II, a molar ratio of the repeating unit shown by formula I based on total amounts of the repeating units shown by formula I and formula II of 0.1-0.5 and 0.3-2.0dl/g reduced viscosity [etasp/c] (in sulfuric acid, 0.5g/dl concentration at 25 deg.C).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an aromatic polyether ketone and a method for producing the same. Concerning ketones and their production methods.

[Conventional technology and issues]

Crystalline aromatic polyethers have excellent heat resistance and solvent resistance, and are therefore widely used in various industrial materials.

Conventional 2 aromatic polyether 5 JP-A-54-SO2
Chemicals having various chemical structures have been proposed in Japanese Patent Application Publication No. EE or Japanese Patent Application Laid-open No. 131-138 El28.

Among these, aromatic polyether with the following structure is a crystalline polymer with a glass transition point (Tg) of 167°C, but its melting point is 420°C, so it is difficult to mold using normal molding methods. be.

Therefore, at present, the aromatic polyether described in the above publication has not been put into practical use.

[Means for solving the above problems] The present invention for solving the above problems has the following features: On the other hand, an aromatic polyether having a repeating unit [I] and the following structure, I
It is commercially available from CI Company.

Its melting point is as high as 365°C, so it is difficult to say that it is a material with good moldability.

Repeat unit [■] ...[I] The present invention aims to solve the above problems.

That is, an object of the present invention is to have a high Tg while
An object of the present invention is to provide an aromatic polyetherketone having a lower m and excellent moldability, and a method for producing the same.

and the molar ratio of the repeating unit [I] to the total of the repeating units [L] and [II] is from 0.1 to
0.5, and the reduced viscosity [ηsp/cl (in sulfuric acid,
(concentration 0.5 g/d, temperature 25°C) is 0.3 to 2. Od
An aromatic polyetherketone characterized by i/g.

Also, 4.4'-dihalogenobenzophenone, 4.
4'-dihydroxybiphenyl and 4-hydroxy-
The method for producing the aromatic polyetherketone is characterized in that 4°-halogenobenzophenone is reacted in a neutral polar solvent.

The present invention will be explained in detail below.

Monoaromatic polyetherketone - The aromatic polyetherketone of the present invention consists of the following repeating units [I] and [II], and the repeating unit [I]
] and [■1], the molar ratio of the repeating unit [I] is 0.1-0.5, and the reduced viscosity [ηsp/
cl (in sulfuric acid, concentration 0.5g/dll, temperature 25℃
) is 0.3 to 2.0 d/g.

... [! ] If the molar ratio is less than 0.1, the melting point will not be lowered sufficiently and moldability will be poor. Moreover, when the molar ratio is larger than 0.5, the melting point becomes too high.

If the reduced viscosity is less than 0.3 dll/g, sufficient heat resistance and mechanical strength for molded products cannot be obtained, and
2. If it exceeds Od/g, the molecular weight will be too large and molding will become difficult.

This aromatic polyetherketone has a glass transition point of 18
It is within the range of 5 to 188°C, and has a melting point of 355°C or less.

Since the aromatic polyetherketone of the present invention has a low melting point while maintaining a high glass transition point, it has excellent heat resistance and moldability.

Production of monoaromatic polyetherketone - The aromatic polyetherketone of the present invention can be produced as follows.

4.4'-dihalogenobenzophenone, 4'-dihydroxybiphenyl and 4-hydroxy-4'-halogenobenzophenone are reacted in a neutral polar solvent, usually in the presence of an alkali metal compound. In this manner, the aromatic polyetherketone of the present invention can be produced.

1-4,4°-dihalobenzophenone--as the above-mentioned 4,4°-dihalogenobenzophenone.

For example, 4.4'-difluorobenzophenone, 4.
Examples include 4'-dichlorobenzophenone and 4-chloro-4°-fluorobenzophenone. In addition, 4.
In 4'-dihalogenobenzophenone, the Hensen nucleus may be substituted with a different type of halogen atom.

Among these, 4,4'-difluorobenzophenone and 4'4'-dichlorobenzophenone are preferred.

Incidentally, these 4,4'-dihalogenobenzophenones may be used alone or alternatively.

Two or more types may be used in combination.

-4,4°-dihydroxybiphenyl-4,4
°-Dihydroxybiphenyl can be used as it is as a monomer, but if desired, it can be converted into an alkali metal salt in advance and used as an alkali metal salt of 4'-dihydroxydiphenyl. It can also serve as a component. In addition,
Among the alkali metal salts, sodium salts and potassium salts are preferred.

These various alkali metal salts can be used alone, or two or more can be used together as a mixture, or they can be used in any proportion with 4,4'-dihydroxybiphenyl (dihydroxy form). It can also be used as a mixture.

m-4-Hydroxy-4°-halogenobenzophenone - Examples of the 4-hydroxy-4°-halogenobenzophenone include 4-hydroxy-4°-fluorobenzophenone, turtle-hydroxy-4·°-chlorobenzophenone, and 4-hydroxy-4°-chlorobenzophenone. Examples include hydroxy-4'-bromobenzophenone.

This 4-hydroxy-C-halogenobenzophenone is
It can be used as a monomer as it is, but if desired, it can be converted into an alkali metal salt in advance and used as an alkali metal salt of 4-hydroxy-4-halogenobenzophenone, which serves as both a monomer component and an alkali metal compound component. You can also do that. Note that among the alkali metal salts, sodium salts and potassium salts are preferred.

These alkali metal salts of he-hydroxy-C-halogenobenzophenone can be used alone, or
Two or more types can be used in combination as a mixture, or as a mixture with 4-hydroxy-C-halogenobenzophenone in any proportion.

1 Quantity Ratio - 1 said 4.4°-dihalogenobenzophenone and 4.
The ratio of 4°-dihydroxybiphenyl and the 4-hydroxy-4′-halogenobenzophenone used is as follows.

That is, the molar ratio of 4,4'-dihalogenobenzophenone to 4,4°-dihydroxybiphenyl is 0
．． 98 to 1.02, especially 1.00 to 1.01.

When this molar ratio is smaller than 0.98, coloring may occur during one polymerization, and the molecular weight may not increase sufficiently, and when the molar ratio exceeds 1.02, the molecular weight may not increase sufficiently.

Further, the molar ratio [(A):(B)] of 4.4′-dihalogenobenzophenone (A) and 4-hydroxy-C-halogenobenzophenone CB) is 5 l:9 to 5:5.
It is particularly preferable that the ratio is 2:8 to 3.

If the molar ratio is out of this range, it may be difficult to produce a copolymer.

(1) Alkali metal compound - (1) As the alkali metal compound, those capable of converting the 4,4'-dihydroxybiphenyl or 4-hydroxy-4'-halogenobenzophenone into an alkali metal salt can be used. 1 Usually alkali metal carbonates and/or heavy alkali metal salts are used.

However, when the alkali metal salt of 4,4'-dihydroxydiphenyl or 4-hydroxy-4-herogenobenzophenone is used as a monomer or comonomer, these may be used in combination with the alkali metal compound. What you can do is as described above.

Examples of the alkali metal carbonate include lithium carbonate, sodium FR acid, potassium carbonate, rubidium carbonate, and cesium carbonate, and among these, sodium carbonate and potassium carbonate are preferred.

Examples of the alkali metal bicarbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate,
Examples include rubidium hydrogen carbonate and cesium hydrogen carbonate.

Among these, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, and potassium hydrogen oxide are preferred.

The alkali metal carbonates and alkali metal bicarbonates are usually used in the form of anhydrides, but if desired, they can also be used in the form of water-containing forms such as hydrates and concentrated aqueous solutions.

It is desirable that the water added to the reaction system and the water generated by the reaction be appropriately removed from the reaction system during or prior to the reaction (condensation reaction).

The alkali metal salts may be used alone or
Any two or more types may be used together in any ratio as a mixture.

The amount of the alkali metal salt used is usually 1.0 G-per total hydroxyl groups of the 4'-dihydroxybiphenyl and 4-hydroxy-4'-halogenobenzophenone.
within the range of 3,00 gram equivalents, preferably 1.0
It is within the range of 5 to 2.00 gram equivalents.

-1 Neutral Polar Solvent -11 As the neutral polar solvent, known ones can be used.

Specific examples include dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, diethylsulfoxide, sulfolane, dimethylimidazolidinone, dimethylimidazolidinone, diphenylsulfone, and the like.

Among these, N-methylpyrrolidone and sulfolane are preferred, and N-methylpyrrolidone is particularly preferred.

In addition, these neutral polar solvents may be used alone, or two or more may be used in combination as a mixed solvent, etc.
Furthermore, it can also be used as a mixed solvent with other inert solvents, especially aromatic solvents such as benzene, toluene, and xylene that can azeotropically remove water from the reaction system.

-1 Reaction Conditions 11 The 4-hydroxy-49-halogenobenzophenone, the 4'-dihalogenobenzophenone, and the 4.4'-dihydroxybiphenyl are combined in the presence of the alkali metal compound. Reaction in a neutral polar solvent (
What is the reaction temperature when producing the aromatic polyether copolymer by the condensation reaction?

Usually in the range of 150 to 380°C, preferably 220°C
~350°C.

Further, the appropriate concentration of heptamer is 0.25 to 4 mol/Jl (total amount of heptamer (mol)/solvent amount (i)).

The reaction time cannot be specified uniformly because it varies depending on the type of sulfuric acid or alkali metal compound used, the proportion used, the reaction temperature, etc., but it is usually in the range of 0.1 to 10 hours, preferably 1 hour. ~5 hours.

There is no particular restriction on the reaction pressure, and the reaction can be carried out under reduced pressure, normal pressure, or increased pressure, but it is usually preferable to carry out the reaction near normal pressure.

The reaction atmosphere is usually preferably under an inert atmosphere such as under an inert gas flow of nitrogen, argon, helium, etc. or under reduced pressure exhaust.

[Example 1] Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

(Example 1) Internal volume 31 equipped with a stirring device and argon gas blowing pipe
4.4゛-difluorobenzophenone 88
．． 11 g (0.3 mol), 4°4°-dihydroxybiphenyl 55.86 g (0.3 mol), 4-hydroxy-4'-fluorobenzophenone 129.73 g
(0.8 mol), potassium carbonate 87.07 g (0
, E13 mol) and 800 g of diphenylsulfone were charged.

While blowing argon gas into the mixture in the reactor, the temperature was raised from room temperature to 180°C over 1 hour.
It was kept at ℃ for 30 minutes. After that, 25 minutes over 30 minutes.
The temperature was raised to 0°C and then held at this temperature for an additional hour. The temperature was further increased to 320°C over 30 minutes. This temperature was then maintained for 30 minutes to complete the reaction.

After the reaction was completed, the contents were poured into two stainless steel bars and cooled.

When cooled, the contents solidified, so they were pulverized in a Warning blender, washed twice with acetone, twice with water, once with methanol, and once with acetone to dissolve diphenyl sulfone and filament salts. was removed and dried to obtain a white powder.

Elemental analysis and infrared analysis of this white powder confirmed that it was an aromatic polyetherketone having the following repeating units.

This aromatic polyether ketone was dissolved in concentrated sulfuric acid at 0.5g/
When dissolved at a concentration of dll and measured at 25°C, the reduced viscosity η sp/c was 1.10 d 41 /g.

Also, the glass transition point (Tg) measured by Seiko Electronics @DSC is IE18.5℃, and the melting point (Tm) is 3
The temperature was 18.2°C. The thermal decomposition onset temperature (T d) as measured by TGA manufactured by Seiko Electronics Co., Ltd. was 585° C. (5% weight loss temperature in air).

Next, this aromatic polyetherketone was extruded using an extruder equipped with a 300 mesh stainless steel filter and cut into pellets. Next, this beret,
It was fed into a 22 l plasticizing extrusion apparatus equipped with a tube-on coating die having a total diameter of 1.5 mm and coated onto 1 layer 1 diameter silver plated copper wire at an extrusion temperature of 300-350°C. That is, the copper wire was passed through a die at a speed of about 7 minutes, and the extrusion device was operated at a discharge rate of about 1.0 kg/hour to form a coating film with an average thickness of 0 to 25 mm on the steel wire. .

This coating film was smooth, had no defects, and had sufficient electrical insulation properties.

(Examples 2 to 5) The same procedure as in Example 1 was carried out except that the raw material and top additives were charged at a ratio corresponding to the composition shown in Table PIIJ1.

Table 1 shows the physical properties of the aromatic polyetherketone obtained.

(Comparative Example 1) In the same apparatus as in Example 1, 218.21 g (1 mol) of 4-fluoro-4'-hydroxybenzophenone was added.

82.93 g (0.8 mol) of potassium carbonate and 800 g of diphenylsulfone were charged.

Next, the temperature was raised to 180°C under an argon stream, and then kept at that temperature for 30 minutes, and then heated for 2 hours over 30 minutes.
The temperature was raised to 50°C, maintained at that temperature for 1 hour, and further raised to 330°C over 30 minutes, and maintained at that temperature for 3 hours.
The reaction was carried out by holding for 0 minutes.

After the reaction is completed, the same treatment as in Example 1 is carried out to obtain white powder 1.
90.3 g (yield 87%) was obtained.

Elemental analysis and infrared analysis of this white powder confirmed that it was an aromatic polyetherketone having the following repeating units.

Table 1 shows the physical properties of this aromatic polyetherketone.

(Comparative Example 2) In the same apparatus as in Example 1, 218.20 g (1 mol) of 4,4°-difluorobenzophenone and 4,4°-difluorobenzophenone were added.
dihydroxybiphenyl 188.21 (1 mol),
145.12 g (1.05 mol) of potassium carbonate and 800 g of diphenylsulfone were charged.

Next, under an argon stream, the temperature was raised to IH"c, and then kept at that temperature for 30 minutes, then the temperature was raised to 280 ° C. over 1 hour and 30 minutes, and maintained at that temperature for 1 hour. The temperature was further increased to 380''C over 30 minutes, and the reaction was carried out by maintaining this temperature for 1 hour.

After the reaction is completed, the same treatment as in Example 1 is performed to obtain white powder 3.
57.1 g (yield 98%) was obtained.

Single element analysis and infrared analysis of this white powder confirmed that it was an aromatic polyetherketone having 2 or less repeating units.

Table 1 shows the physical properties of this aromatic polyetherketone.

Discussion〉 As is clear from the results in Table 1, aromatic polyetherketones that satisfy the conditions of the present invention have a higher glass transition point and a reliably lower melting point than comparative examples that do not meet the conditions of the present invention. It can be seen that the moldability is low and the moldability is excellent.

[Effects of the Invention] The aromatic polyetherketone of the present invention has a high glass transition point, so it has excellent heat resistance, and has a low melting point, so
Excellent moldability. Moreover, according to the manufacturing method of the present invention,
The above copolymer can be easily prepared from 4,4'-dihalogenobenzophenone, 4,4'biphenol, and sho-hydroxy-4°-halobenzophenone.

Due to these features, the aromatic polyetherketone of the present invention will make a significant industrial contribution as a material in various fields such as mechanical, electronic, and electrical fields that require mechanical strength, heat resistance, electrical insulation, etc. .

Claims (2)

[Claims] (1) It has a repeating unit [I] and ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] Repeating unit [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] The molar ratio of the repeating unit [I] to the total of the repeating units [I] and [II] is 0.1
~0.5, and the reduced viscosity [ηsp/c] (in sulfuric acid, concentration 0.5 g/dl, temperature 25°C) is 0.3 to 2.0.
An aromatic polyetherketone characterized in that dl/g. (2) 4,4'-dihalogenobenzophenone, 4,4'
-dihydroxybiphenyl and 4-hydroxy-4'
- The method for producing an aromatic polyetherketone according to claim 1, characterized in that the halogenobenzophenone is reacted in a neutral polar solvent.