JPH07103236B2 - Method for producing aromatic poly (thio) etherketone - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a linear polymerization thermoplastic aromatic poly (thio) etherketone having a high degree of polymerization.

General formula (II) (In the formula [II], R ^{1 to} R ¹² represent a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, X is an oxygen atom or a sulfur atom, and a part of X may be a direct bond. Often,
n represents an integer of 0 to 2), and has an aromatic poly (thio) etherketone structure, particularly structural formula [III] And [IV] The aromatic poly (thio) etherketone having the structure of has a high melting point ([III], T _m = 365 ° C; [IV], T _m = 334 ° C) and a high glass transition point ([III], T _g = 154 ° C). ° C; [IV], T _g = 144
It is known that it is a polymer having a high temperature resistance, mechanical properties, electrical properties and dimensional stability, a low water absorption rate, and a very excellent physical property. In addition, it is a polymer that is insoluble in solvents other than concentrated sulfuric acid and has excellent chemical resistance.

[Conventional technology and its problems]

Conventionally, as a method for producing these polymers, 4,4′-
A method of reacting difluorobenzophenone with an alkali metal salt of 4,4'-dihydroxybenzophenone or dihydroquinone in diphenyl sulfone (JP-A-54-90296).
55-89334, etc.) or a method in which the self-condensation of an alkali metal salt of 4-fluoro-4'-hydroxybenzophenone is carried out in diphenyl sulfone (JP-A-60-1694).
6) is known, but it is necessary to raise the reaction temperature to 300 ° C or higher, and 4,4'-difluorobenzophenone and 4-
Fluoro-4'-hydroxybenzophenone is expensive and there are many drawbacks in its production method.

As a manufacturing method other than the above, a method of reacting 4-phenoxybenzoyl chloride in a hydrogen fluoride solvent in the presence of boron trifluoride (Japanese Patent Publication No. 56-451), or a method of reacting in a trifluoromethanesulfonic acid solvent (JP Sho
57-182321) is known. As a polymerization reaction in the presence of boron trifluoride in a hydrogen fluoride solvent, a reaction between diphenyl ether and S-alkyl-thiochloroformate (Japanese Patent Laid-Open No. 58-17118) is also known. Also in the method, there are many drawbacks in the manufacturing method such as using a solvent having a very strong corrosive property such as hydrogen fluoride or trifluoromethanesulfonic acid.

As another method for producing the aromatic polyether ketone represented by the formula [III], 4-phenoxybenzoyl chloride or 4,4'-diphenyl ether dicarboxylic acid dichloride and diphenyl ether are treated with anhydrous aluminum trichloride in 1,2-dichloroethane. A method of polymerizing in the presence is also known (MILitter and CS Marvell, J. Pol.
ym.Sci; Polym.Chem.Ed, 23 , 2205-2223 (1985)). However, in this method, the precipitation of the polymer occurs as the polymerization proceeds, and the polymer is completely separated from the solution portion in the final stage of the polymerization. The shape of the obtained polymer is a lump that is tightly attached to the stirring rod and a sheet that is tightly attached to the wall of the reaction vessel, and operations such as isolation and recovery of the polymer and washing are very complicated, and It was unsuitable as a statistical process.

As a method of compensating for such drawbacks, a method of carrying out polymerization in the presence of a Lewis base in the polymerization system to enhance the interaction between polymer-Lewis acid-Lewis base-solvent and keeping the system uniform (Tokusho Sho-60- 500961) and a method of adding a suitable dispersant to a polymerization system and polymerizing in a slurry state (Japanese Patent Laid-Open No. 61-83226). However, even with these methods, satisfactory effects have not always been obtained.

That is, in the former method, the activity of the Lewis acid is deactivated by the addition of the Lewis base, so that the Lewis acid must be added in excess and the viscosity of the system significantly increases with the progress of polymerization and stirring. And that it becomes difficult to remove it from the reaction vessel,
Further, in the latter method, a part of the added dispersant remains in the produced polymer to deteriorate the physical properties of the polymer.

[Object of the Invention]

According to the present invention, when a linear aromatic poly (thio) etherketone having a high degree of polymerization is produced, a dielectric constant of a mixed solvent of o-dichlorobenzene (a) and cyclohexane or n-hexane (b) is 5.0. In addition to using a solvent system that is 7.0 or less, it is a very simple method without adding any other component. It is intended to provide a production method which is characterized in that the polymer is obtained in a slurry state without contamination of the polymer by the additive.

The polymer obtained by the invention is concentrated sulfuric acid (specific gravity 1.84).
The polymer has a logarithmic viscosity ηinh measured at 30.0 ° C. of 1.0 g / dl and 0.45 or more, preferably 0.6 or more, and more preferably 0.7 dl / g or more. Moreover, the obtained polymer is linear. Here, the term "straight-chain" refers to the above-mentioned concentrated sulfuric acid.
It means that it does not substantially contain an insoluble gel when dissolved at room temperature at a concentration of 1.0 g / dl.

“Dielectric constant of mixed solvent system” is represented by the following formula (A). ^ε mixed system = ε ₁ X ₁ + ε ₂ X ₂ + ε ₃ X ₃ + ... (A) ^ε mixed system: Dielectric constant of mixed solvent system ε _1,2,3 …: Dielectric constant of each component X _1,2,3 ...: Molar fraction of each component “Lewis acid” means a substance capable of accepting an unshared electron pair from another molecule. The Lewis acid that can be actually used in the present invention is a metal halide that can serve as a catalyst in the Friedel-Crafts acylation reaction, and specific examples will be described later.

[Structure of Invention]

That is, the gist of the present invention is represented by the general formula [I] (In the formula [I], R ^{1 to} R ¹² represent a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, X is an oxygen atom or a sulfur atom, and a part of X may be a direct bond. Often,
Y represents a halogen atom, and n is an integer of 0 to 2), and an aromatic (thio) ethercarboxylic acid halide represented by the general formula [II] is reacted in the presence of a Lewis acid. (In the formula [II], R ^{1 to} R ¹² represent a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, X is an oxygen atom or a sulfur atom, and a part of X may be a direct bond. Often,
n is an integer of 0 to 2), when producing an aromatic poly (thio) etherketone having a repeating unit represented by the following formula, a dielectric constant of a mixed solvent of o-dichlorobenzene and cyclohexane or n-hexane A production method is characterized in that the polymer is obtained in the form of a slurry by using a solvent system of 5.0 or more and 7.0 or less.

The degree of polymerization and the morphology of a polymer obtained by a polymerization reaction using a solvent are closely related to the properties of the polymerization solvent regardless of whether the polymerization reaction is homogeneous or heterogeneous. From a microscopic point of view, it is important to control the catalytic activity by the specific interaction between the catalyst molecule and the solvent molecule and control the growth reaction by solvation to the monomer molecule or polymer growth end. From a macroscopic point of view, when the polarity of the system is controlled to control the solubility of the monomer, the polymer, and the catalyst, and when the produced polymer is deposited, it is greatly involved in the control of the morphology.

The present inventors have arrived at the present invention as a result of earnestly examining the effect of such a microscopic / macroscopic environment of the solvent on the performance of the polymerization reaction.

To explain the present invention in more detail, the aromatic (thio) ethercarboxylic acid halide represented by the general formula [I] used in the present invention includes 4-phenoxybenzoyl chloride and 4-phenoxy-4'-chloro. Formyl diphenyl ether, 3-phenoxybenzoyl chloride, 4-phenylbenzoyl chloride, 4-phenyl-4'-chloroformyl diphenyl ether, 3-methyl-4-phenoxybenzoyl chloride, 3-methoxy-4-phenoxybenzoyl chloride, 4-phenylmercapto Examples thereof include benzoyl chloride and the like, but any of those represented by the general formula [I] can be used, and the present invention is not necessarily limited to these.
In addition, these aromatic (thio) ethercarboxylic acid halides may be used alone or in combination.

In the present invention, o-dichlorobenzene (a) is used as a solvent.
And a mixed solvent of cyclohexane or n-hexane (b) are used at a mixing ratio such that the mixed solvent has a dielectric constant of 5.0 to 7.0.

There is no limitation on the method for mixing the solvents. That is, a solvent having a predetermined mixing ratio may be prepared in advance and used for the polymerization, or the polymerization may be started in a part of the solvent of the mixed component.
After that, other components may be added to adjust the dielectric constant of the solvent system.

Further, in the present invention, the amount of the mixed solvent used is preferably 10 or more by weight ratio with respect to the aromatic (thio) ethercarboxylic acid halide represented by the general formula [I].

Examples of Lewis acids used in the present invention include aluminum trichloride, aluminum tribromide, boron trifluoride, and secondary chlorides.
Iron, stannic chloride, titanium tetrachloride, boron trichloride, antimony pentachloride, phosphorus trichloride, zinc chloride, gallium trichloride, antimony hexachloride, phosphorus pentachloride, tellurium pentachloride, boron trifluoride diethyl ether complex compound Examples of such anhydrides include, but are not necessarily limited to. Of these, it is most preferable to use anhydrous aluminum trichloride in terms of cost.

The amount of the Lewis acid used in the present invention is 1.0 to 10.0, preferably 1.0 to 5.0, in terms of molar ratio with respect to the aromatic (thio) ethercarboxylic acid halide of the general formula [I].
Is.

In the present invention, the reaction temperature is not particularly limited, but a polymer having a high degree of polymerization can be obtained under mild temperature conditions of -10 ° C or higher (usually 100 ° C or lower). Further, the reaction pressure is not particularly limited, but the reaction may be carried out under normal pressure or under pressure.

〔The invention's effect〕

According to the present invention, a linear poly (thio) etherketone having a high degree of polymerization can be obtained in a slurry form by a very simple method under mild polymerization conditions, and operations such as polymer isolation and washing can be performed. Significantly improved. The aromatic poly (thio) etherketone obtained in the present invention is excellent in mechanical properties such as tensile strength, flexural strength, tensile elastic modulus, flexural elastic modulus, electrical properties and dimensional stability, and has low water absorption. Sex,
It also has excellent chemical resistance.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to Examples.

The logarithmic viscosity ηinh of the polymer is in concentrated sulfuric acid (specific gravity 1.84),
It was measured at 30.0 ° C. at a polymer concentration of 1.0 g / dl.
The melting point T _m of the polymer was measured using a DSC-IB type differential scanning calorimeter manufactured by Perkin-Elmer (in a nitrogen atmosphere, temperature rising rate: 16
C / min). Further, the dielectric constant ε of the mixed solvent was calculated by the above formula A.

Example 1 1.4.7 g (110 mmo) of anhydrous aluminum trichloride purified by sublimation
l) was dissolved in a mixed solvent of o-dichlorobenzene (90 ml) / cyclohexane (90 ml) (ε = 6.1) under ice cooling. 4-phenoxybenzoyl chloride 12.8g (55mmo
l) was gradually added under ice cooling. The dropping vessel is washed with 10 ml of o-dichlorobenzene and added. After the addition was completed, the ice bath was removed and the mixture was stirred at room temperature for 24 hours. After the completion of the polymerization, the polymer was obtained in the form of slurry uniformly dispersed in the solvent system. When the stirring is stopped, the polymer slurry sinks to the bottom of the reaction vessel,
The supernatant was transparent. The polymer slurry could easily be poured from the reaction vessel onto a glass filter.
The obtained polymer was washed once with boiling methanol, twice with a boiling 5% hydrochloric acid aqueous solution and twice with boiling demineralized water, and then dried under reduced pressure at 120 ° C. overnight.

Ηinh of the obtained polymer was 1.01 dl / g. Also, T _m
Was 373 ° C. The bulk density of the polymer was 0.26 g / cm ² .

Comparative Example 1 o-Dichlorobenzene was added to 1,2-dichloroethane (130 ml)
The reaction was performed in the same manner as in Example 1 except that the above was changed. (Ε =
7.6) The obtained polymer was in the form of a lump or a sheet that was in close contact with the walls of the stirring rod and the reaction vessel, and the siphoning from the vessel was complicated. After the recovery and washing, the polymer was dissolved in concentrated sulfuric acid at a concentration of 1 g / dl, and a large amount of insoluble gel was generated.

Example 2 A reaction was performed in the same manner as in Example 1 except that n-hexane (90 ml) was used instead of cyclohexane. (Ε = 6.
3) The polymer obtained was in the form of a slurry, and ηinh was 0.81 dl / g.

Comparative Example 2 The ratio of o-dichlorobenzene / cyclohexane was 140 ml / 50.
The reaction was performed in the same manner as in Example 1 except that the amount was changed to ml. (Ε =
7.8) ηinh of the obtained polymer was 1.06 dl / g, but the polymer shape was lumpy.

Comparative Example 3 The ratio of o-dichlorobenzene / cyclohexane was 60 ml / 130.
The reaction was performed in the same manner as in Example 1 except that the amount was changed to ml. (Ε =
4.5) ηinh of the obtained polymer was 0.88 dl / g, but the polymer shape was lumpy.

Comparative Example 4 13.3 g (100 mmol) of anhydrous aluminum trichloride purified by sublimation
Was added to 250 ml of cyclohexane (ε = 2.02) under ice cooling. 11.6 g (50 mmol) of 4-phenoxybenzoyl chloride was gradually added to this mixture. After removing the ice bath, the reaction mixture was reacted at 80 ° C. for 3 hours.

The product was a slurry, but ηinh was 0.4 dl / g.

Examples 3 and 4 The amount of anhydrous aluminum trichloride used was 18.3 g (138 mmo
l) and 22.0 g (165 mmol) except that the reaction was carried out in the same manner as in Example 1.

The obtained polymer was in a slurry state, and ηinh was 0.94 dl / g and 1.04 dl / g, respectively.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-60-58435 (JP, A) JP-A-47-13347 (JP, A) JP-A-60-104126 (JP, A) JP-A-60- 101119 (JP, A) JP 60-72923 (JP, A) JP 57-182321 (JP, A) Special table Sho 60-500961 (JP, A) JP 41-990 (JP, B1)

Claims (3)

[Claims] 1. A general formula [I] (In the formula [I], R ^{1 to} R ¹² represent a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, X is an oxygen atom or a sulfur atom, and a part of X may be a direct bond. Often,
Y represents a halogen atom, and n is an integer of 0 to 2), and an aromatic (thio) ethercarboxylic acid halide represented by the general formula [II] is reacted in the presence of a Lewis acid. (In the formula [II], R ^{1 to} R ¹² represent a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, X is an oxygen atom or a sulfur atom, and a part of X may be a direct bond. Often,
n is an integer of 0 to 2), when producing an aromatic poly (thio) etherketone having a repeating unit represented by the following formula, the dielectric constant of a mixed solvent of o-dichlorobenzene and cyclohexane or n-hexane is A method for producing an aromatic poly (thio) etherketone, which comprises obtaining the polymer in a slurry form using a solvent having a ratio of 5.0 or more and 7.0 or less. 2. The method according to claim 1, wherein the amount of the solvent used is 10 or more in weight ratio with respect to the aromatic (thio) ethercarboxylic acid halide represented by the general formula [I]. Method. 3. The logarithmic viscosity (ηinh) of the obtained aromatic poly (thio) etherketone is 0.45 dl / g or more at a polymer concentration of 1.0 g / dl and 30.0 ° C. in concentrated sulfuric acid (specific gravity 1.84). The manufacturing method according to claim 1.