JPH0423649B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a novel method for producing aromatic polyetherketones. More specifically, the present invention has a chemical structure in which phenylene groups are linked through an ether group and a ketone group, and has physical properties such as heat resistance, flame retardance, solvent resistance, mechanical properties, and thermoplastic moldability. The present invention relates to an efficient and industrially advantageous method for producing highly crystalline aromatic polyetherketones with excellent properties. BACKGROUND ART Conventional polymer compounds having a chemical structure in which phenylene groups are linked via an ether group and a ketone group include, for example, the structural formula or structural formula These are known to have excellent heat resistance, flame retardancy, and mechanical strength, and are attracting attention as molding materials (Japanese Patent Publication No. 57-22938,
(Special Publication No. 56-33419, Publication No. 32642/1982). As a method for producing these high molecular weight polymers, a method of nucleophilic polycondensation of an activated aromatic dihalide and a dihydroxy aromatic compound in the presence of an alkali (Japanese Patent Publication No. 57-22938,
(Japanese Patent Publication No. 60-32642) and a method of electrophilic polycondensation of an aromatic acid halide and an aromatic ether compound by Friedel-Crafts reaction (Japanese Patent Publication No. 1982-32642)
-33419) have been proposed. By the way, the former method and the latter method not only differ in the reaction format and the molecular structure of the produced polymer, but also in the physical properties of the resulting polymer compound.
For example, polymers obtained by the latter Friedel-Crafts reaction

[Formula] () is the polymer obtained by the former nucleophilic reaction.

[However, ηrel is the relative viscosity, c is the concentration (g/100ml), and c → o means that the value of (ηrel−1)/C is extrapolated to the point where the concentration C is 0.]

It was calculated using (2) Crystal melting point (Tm), glass transition temperature (Tg),
Heat of crystal fusion (△H) After heating the polymer powder to 400℃,
The rapidly cooled sample was measured using a DSC (differential scanning calorimeter) at a heating rate of 10°C/min. Reference Example 1 Production of aromatic difluoride (-1) (1) Synthesis of 4,4'-diphenoxyterephthalophenone 20.3 g (0.1 mol) of terephthalic acid dichloride,
51.1 g (0.3 mol) of diphenyl ether and 26.6 g (0.2 mol) of aluminum chloride were dissolved in 350 ml of o-dichlorobenzene cooled to 0°C and reacted for 4.5 hours with stirring. Then,
The reaction mixture was added to a large amount of methanol/hydrochloric acid mixture, and the precipitated solid was filtered off and washed several times with water and methanol. This product had a melting point of 218°C, which was consistent with the standard product of 4,4'-diphenoxyterephthalophenone. (2) Synthesis of aromatic difluoride (-1) 4.7 g (0.01 mol) of 4,4'-diphenoxyterephthalophenone obtained above and 6.00 g (0.045 mol) of aluminum chloride were added to 60 ml of o-dichlorobenzene. 4-fluorobenzoyl chloride at room temperature with stirring.
4.0 g (0.025 mol) was added dropwise. After the dripping is finished,
The temperature was gradually raised and the reaction was carried out at 60°C for 3 hours to complete the reaction. Next, the reaction mixture was added to a methanol/hydrochloric acid mixture, and the precipitated solid was filtered out and purified by washing with water, acetone, N-methylpyrrolidone, and acetone in this order. This substance has a melting point of 308℃, and elemental analysis shows that
formula It was confirmed that the compound is represented by The IR spectrum of this compound is shown in FIG. Reference Example 2 Production of aromatic dichloride (-2) 26.8 g (0.057 mol) of 4,4'-diphenoxyterephthalophenone synthesized in Reference Example 1 and 34.3 g (0.257 mol) of aluminum chloride were o-coated at room temperature. Dissolve in 350 ml of dichlorobenzene and add 25.0 g of 4-chlorobenzoyl chloride while stirring.
(0.143 mol) was added dropwise. Thereafter, the temperature was gradually raised to 60°C for 3 hours to complete the reaction. Next, the reaction mixture was added to a large amount of methanol/hydrochloric acid mixture, and the precipitated solid was filtered off and purified by washing with water, acetone, N-methylpyrrolidone, and acetone in this order. This substance has a melting point of 323℃, and elemental analysis shows that
formula It was confirmed that it is an aromatic dichloride represented by The IR spectrum of this compound is shown in FIG. Example 1 In a 200 ml flask, 21.4 g (0.03 mol) of the aromatic difluoride (-1) obtained in Reference Example 1, 6.21 g (0.045 mol) of potassium carbonate, and 2.0 ml of silica [Aerosil 300, manufactured by Nippon Aerosil Co., Ltd.] After charging g and 45 g of diphenyl sulfone and replacing with nitrogen,
The temperature was raised from room temperature to 310°C over 1 hour, and the reaction was carried out at that temperature for 0.5 hour. Next, the reaction mixture was taken out, pulverized, and washed three times with warm water and hot acetone to obtain 21.5 g of pale yellow solid. The product completely dissolved in concentrated sulfuric acid and became a yellow solution. Further, the intrinsic viscosity at 25°C of 0.1% by weight in concentrated sulfuric acid was 1.15. Furthermore, by pressing this product at 400°C, a pale yellow strong film was obtained. Examples 2 to 5 The procedure was repeated in the same manner as in Example 1, except that the aromatic dihalide as the raw material monomer, the silica-based compound as the catalyst, the alkali metal salt, the type and amount of the copper compound as the co-catalyst, and the reaction time were changed as shown in the attached table. A polymer was obtained. The intrinsic viscosities of these polymers are shown in the table.

【table】 [Brief explanation of drawings]

Figures 1 and 2 are reference examples 1 and 2, respectively.
FIG. 2 is an IR spectrum diagram of an aromatic dihalide obtained in 1 and used as a raw material of the present invention.

Claims (1)

[Claims] 1. In the presence of an alkali metal carbonate or bicarbonate, the general formula (In the formula, X ¹ and X ² are each a halogen atom, and they may be the same or different.) A formula characterized by a heating reaction at a temperature A method for producing an aromatic polyetherketone having a repeating unit represented by: