JPH0460135B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing aromatic polyetherketones. Aromatic polyetherketone is heat resistant,
It is known to be a polymer with excellent mechanical properties, electrical properties, dimensional stability, low water absorption, and very good physical properties. A known method for producing it is to react 4-phenoxybenzoyl chloride in a hydrogen fluoride solvent in the presence of boron trifluoride, but this method requires a very low temperature (for example -78°C). The reaction must be initiated and carried out using a special reactor, and the recovery of the solvent requires very complicated operations. In view of the above points, the present inventors conducted intensive studies and found that aromatic polyetherketones can be easily obtained by using an aprotic organic solvent as a solvent and reacting in the presence of a Lewis acid. I found it. Further, in this method, there is no need to start the reaction at a low temperature of -78°C, and since an aprotic organic solvent is used, recovery of the polymer and solvent can be easily performed. The gist of the present invention is the general formula () (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and
An aromatic aroma produced by reacting diphenyl ethers ( ^R8 represents a hydrogen atom, a halogen atom, an alkoxy group, or a hydrocarbon group) with phosgene in an aprotic organic solvent in the presence of a Lewis acid. The present invention relates to a method for producing a group polyetherketone. To explain the present invention in more detail, the aromatic ethers represented by the general formula () used in the present invention include dipnyl ether, bis(3
-chlorophenyl) ether, bis(3-methylphenyl) ether, bis(3,5 dimethylphenyl) ether, bis(3-methoxyphenyl)
ether, bis(3,5 dichlorophenyl) ether, bis(3-bromophenyl) ether,
Bis(3-fluorophenyl) ether, bis(3,5 difluorophenyl) ether, bis(3-ethylphenyl) ether, etc., but are not necessarily limited thereto.
These may be used alone or as a mixture, with dipnyl ether being the most preferred among these. Examples of the aprotic organic solvent used in the present invention include hydrocarbons, halogenated hydrocarbons, aliphatic ethers, ketones, compounds having a nitro group, and other compounds, specifically, methylene chloride, dichloroethane, 1, 1,2,2-tetrachloroethane, chloroform, carbon tetrachloride, nitrobenzene, nitromethane, carbon disulfide, orthodibromobenzene, orthodichlorobenzene, metadichlorobenzene, diphenyl sulfone, diphenyl ketone, chlorobenzene, benzene, toluene, Acetophenone, tetralin, decalin, hexane, dibutyl ether, heptane, pentane, etc. are used, but are not necessarily limited to these. The amount of the solvent to be used is 1 to 500 times (weight ratio), preferably 5 to 100 times the amount of diphenyl ethers as raw materials. Further, the amount of phosgene used is 1 to 500 times the mole of diphenyl ethers. Lewis acids used in the present invention include aluminum chloride, aluminum bromide, aluminum fluoride, aluminum iodide, ethylaluminum dichloride, diethylaluminium chloride,
Ethylaluminum sesquidichloride, boron trifluoride, ferric chloride, stannic chloride, stannous chloride,
Examples include titanium tetrachloride, boron trichloride, antimony pentachloride, zinc chloride, gallium trichloride, antimony hexachloride, phosphorus trichloride, phosphorus pentachloride, tellurium pentachloride, niobium pentachloride, tungsten hexachloride, etc., but these are not necessarily included. Among these, aluminum chloride, aluminum bromide, and aluminum fluoride are most preferred. The amount of these Lewis acids used is 0.5 to 10.0 times the mole amount of the diphenyl ether, preferably 0.9
~4.0 times the molar amount. Furthermore, in the present invention, a Lewis acid may be added to a solution containing ethers represented by the general formula () and phosgene, or phosgene and ethers represented by the general formula () may be added in the presence of a solvent and a Lewis acid. Alternatively, phosgene gas may be blown in the presence of an ether represented by the general formula (), a solvent, and a Lewis acid. In the present invention, the reaction temperature is not particularly limited, but the reaction can be carried out at -10°C or higher, and there is no need to cool the reaction temperature to -78°C at the start of the reaction. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 Dichloroethane solution of 22.4 g (0.23 mole) of phosgene and 38.6 g (0.23 mole) of diphenyl ether
Add 76.3 g (0.57 mole) of aluminum chloride to 250 ml. At this time, the reaction temperature is maintained at 5° C. or lower by ice cooling. After the addition of aluminum chloride is complete, the reaction is allowed to proceed for 4 hours under stirring and ice-cooling, and then for 16 hours at room temperature.
After the reaction is complete, the reaction mixture is poured into 750 ml of cold methanol to obtain a white powdery polymer. After the polymer was separated from the furnace, it was mixed with 500 ml of methanol and 500 ml of 2% aqueous hydrochloric acid solution.
Wash twice with 500 ml of demineralized water, and vacuum dry at 150°C overnight. The yield was 52%. The infrared absorption spectrum (KBr disc) of the obtained polymer was at 1240 cm ^-1 of aromatic ether,
Absorption of aromatic ketones was observed at 1650 cm ^-1 . ¹ H-NMR spectrum (in heavy concentrated sulfuric acid) is
They were 6.9ppm and 7.6ppm (area intensity 1:1). Also, the viscosity of the obtained polymer (30% in concentrated sulfuric acid)
°C, concentration = 1.0g/dl) is ηinh = 0.31dl/
g, and the result of elemental analysis is the actual value: C, 79.78
%; H, 3.91%, calculated value (C ₁₃ H ₈ O ₂ ): C, 79.58
%; H, 4.01%. Example 2 0.084 mol of dipnyl ether, phosgene
0.84 mol, using 0.22 mol of aluminum chloride,
A polymer was obtained in a yield of approximately 100% in the same manner as in Example 1 except that 150 ml of carbon disulfide was used as a solvent. The melting point of the obtained polymer is 365℃
(DSC), and the viscosity was ηinh=0.59 dl/g. Example 3 Carbon disulfide solution of 7.15 g of diphenyl ether 150
22.25 g of phosgene was introduced into the flask under ice cooling. 14.53 g of anhydrous aluminum chloride was added to this solution while stirring under ice cooling. After the addition of anhydrous aluminum chloride was completed, a polymer was obtained by reacting for 4 hours under ice cooling and then for 15 hours at room temperature. This polymer was mixed with 300 ml of ethanol and 300 ml of 2% aqueous hydrochloric acid solution.
After washing twice with demineralized water, it was vacuum-dried at 120°C overnight. Yield, 6.7g; ηinh, 0.66dl/g; IR, 1650cm
^-1 (aromatic ketone), 1235cm ^-1 (aromatic ether);
Melting point 368℃ (DSC); ¹ NMR, 6.88ppm, d
(

[Formula]), 7.58ppm, d (

【formula】). Example 4 Carbon disulfide solution of 7.15 g of diphenyl ether
Add 14.53 g of anhydrous aluminum chloride to 150 ml under ice cooling.
was added. This solution was stirred at room temperature for 1 hour, then cooled on ice again, and 22.25 g of phosgene was introduced. After stirring for 1 hour under ice cooling, the mixture was returned to room temperature and reacted for 17 hours to obtain a polymer. The subsequent treatment method followed the method of Example 3. Yield, 5.9g; ηinh, 0.73dl/g; IR, 1650cm
^-1 (aromatic ketone), 1235cm ^-1 (aromatic ether);
Melting point 366℃ (DSC); ¹ NMR, 6.90ppm, d
(

[Formula]), 7.60ppm, d (

【formula】). Example 5 The reaction was started in the same manner as in Example 3, and after reacting for 1 hour under ice cooling and 1 hour at room temperature, a reflux tube cooled with ice water was attached to the reaction vessel, and the mixture was gently refluxed at a bath temperature of 45°C. A polymer was obtained by reacting for 9 hours while distilling the mixture. The subsequent operations followed the method of Example 3. Yield, 6.8g; ηinh, 0.67dl/g; IR, 1650cm
^-1 (aromatic ketone), 1240cm ^-1 (aromatic ether). Example 6 Polymerization was carried out in the same manner as in Example 3 except that n-hexane was used instead of carbon disulfide. The obtained polymer was in powder form. Yield, 4.8g; ηinh, 0.12dl/g; IR, 1650cm
^-1 (aromatic ketone), 1235cm ^-1 (aromatic ether). Example 7 Polymerization was carried out in the same manner as in Example 3 except that chlorobenzene was used instead of carbon disulfide. Yield, 8.1g; ηinh, 0.05dl/g; IR, 1660cm
^-1 (aromatic ketone), 1250cm ^-1 (aromatic ether). Example 8 Polymerization was carried out in the same manner as in Example 3, except that o-dichlorobenzene was used instead of carbon disulfide. Yield, 7.4g; ηinh, 0.14dl/g; IR, 1650cm
^-1 (aromatic ketone), 1240cm ^-1 (aromatic ether). Example 9 Polymerization was carried out in the same manner as in Example 3, except that 20.0 g of anhydrous gallium chloride was used instead of anhydrous aluminum chloride. Yield, 3.5g; ηinh, 0.12dl/g; IR, 1650cm
^-1 (aromatic ketone), 1240cm ^-1 (aromatic ether).

Claims (1)

[Claims] 1 General formula () (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and
An aromatic aroma produced by reacting diphenyl ethers ( ^R8 represents a hydrogen atom, a halogen atom, an alkoxy group, or a hydrocarbon group) with phosgene in an aprotic organic solvent in the presence of a Lewis acid. A method for producing group polyetherketones.