JPH02308814A - Production of aromatic polyether ketone - Google Patents

Abstract

PURPOSE:To obtain a high-purity polymer having simple after-treatment by reacting dichlorobenzophenone with a bihydric phenol under a specific condition to form an oligomer, then adding difluorobenzophenone to the reaction system and subjecting the reaction system to high molecular weight formation reaction. CONSTITUTION:4,4'-Dichlorodenzophenone is reacted with a bihydric phenol (e.g. hydroquinone) shown by the formula HO-Ar-OH (Ar is aromatic bifunctional group) in a neutral polar solvent (e.g. DMF) tn the presence of an alkaline metal compound (preferably sodium carbonate, etc.) to form an oligomer. Then 4,4'-difluorobenzophenone is added to the reaction system, which is subjected to high molecular weight formation reaction to give the aimed polymer.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a method for producing aromatic polyetherketone,
More specifically, the present invention relates to a method for producing an aromatic polyetherketone, which allows a simple post-treatment and a highly pure polymer to be obtained at low cost.

[Prior art and problems to be solved by the invention] In recent years, engineered plastics with various chemical structures have been developed and are expected to be used as new materials in a wide range of application fields.

Aromatic polyether kenes can be mentioned as one of the representative examples. This aromatic polyetherketone is a resin with excellent heat resistance, solvent resistance, and mechanical strength.
It is well known as JP-A-54-90296.

However, in the technique described in this publication, the polymer is recovered in the form of lumps, which must be crushed before washing. Because a large amount of potassium fluoride, which is more toxic than the conventional molding, is produced as a by-product, and because the polymer contains a large amount of oligomer, the thermal stability of the molded product is poor, causing surface roughness and white powder precipitation on the surface. There are many problems such as becoming.

Incidentally, there are roughly two methods for producing aromatic polyetherketones, including this publication: one is a method using an electrophilic substitution reaction, and the other is a method using a nucleophilic substitution reaction.

In the former case, the manufacturing cost is relatively low because acid chloride is used, but the heat resistance may be lowered due to the production of products with different substitution positions or residual catalyst. In addition, in the case of the latter nucleophilic substitution reaction,
Due to the low electron-withdrawing properties of carbonyl groups, expensive difluorobenzophenone must be used to obtain polymers of sufficient molecular weight, resulting in high production costs.

An object of the present invention is to solve the above problems.

That is, an object of the present invention is to provide an aromatic polyether ketone that can industrially produce a high molecular weight polymer using a nucleophilic substitution reaction that produces a highly pure polymer with minimal generation of by-products. The purpose of this invention is to provide a method for manufacturing the same.

[Means for Solving the Problems] The first invention of the present application comprises 4,4"-dichlorobenzophenone and a compound represented by the general formula % (wherein Ar represents an aromatic divalent group). A dihydric phenol is reacted in the presence of an alkali metal compound in a neutral polar solvent to generate an oligomer, and then 4,4"-difluorobentzphenone is added to the reaction system to perform a polymerization reaction. Further, the second invention of the present application is characterized in that the 4,4°-dichlorobenzophenone and the dihydric phenol represented by the general formula are mixed with an alkali metal compound in a mixed solvent of an amide solvent and diphenylsulfone. The method is characterized by reacting in the presence of to produce oligomers, then distilling off the amide solvent from the reaction system, and adding 4,4'-difluorobenzophenone to the reaction system to perform a polymerization reaction. .

Hereinafter, the inventions of claims 1 and 2 will be explained in more detail in this order.

In the invention according to claim 1, as raw materials 4,
The following two-step reaction is carried out using 4°-dichlorobenzophenone, the dihydric phenol, and 4,4'-difluorobenzophenone.

(1) Oligomerization (2) High molecular weight Specific examples of the dihydric phenol represented by the above formula 〇〇-Ar-OH include hydroquinone, resorcinol, 4.4°
-biphenol, 4,4°-dihydroxydiphenyl ether, 4,4°-dihydroxydiphenyl sulfone,
4,4'-dihydroxydiphenylsulfi 1-14,
4°-dihydroxydiphenylmethane, 4,4′-dihydroxybenzophenone, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-methyl-4-hydroxyphenyl) ) propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2.2'
-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 3,3-bis(4-hydroxyphenyl)
Pentane, 1,1-diphenyl-1,1-bis(4-hydroxyphenyl)methane, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihy-1-loxinaphthalene, 2,7-dihydroxy Naphthalene, etc. can be mentioned.

The various dihydric phenols mentioned above can be used alone or in combination of two or more.

In the present invention, among the various dihydric phenols, bisphenols and biphenols are preferable,
Particularly preferred are 2,2-bis(4-hydroxyphenyl)propane and 4.4°-biphenol.

In the present invention, the above dihydric phenol and 4,4'-dichloropentuphenone are reacted in the presence of an alkali metal compound in a neutral polar solvent to produce an oligomer.

The above-mentioned neutral polar solvent is not particularly limited as long as it is neutral to the extent that it does not affect the reaction in the present invention and has polarity. For example, for example, N
, N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, N- Methyl-2
-pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-inbutyl-2-pyrrolidone, N-n-propyl-2-pyrrolidone, N-n-
Butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone,
N-ethyl-3-methyl-2-pyrrolidone, tomethyl-
3,4,5-)methyl-2-pyrroli-1ζone, N-methyl-2-piperidone, N-ethyl-2-piperidone, N
-isopropyl-2-piperidone, N-methyl-6-methyl-2-piperidone, N-methyl-3-ethylpiperidone, dimethyl sulfoxide, diethyl sulfoxide,
1-methyl-1-oxosulfolane, 1-ethyl-1-
Examples include oxosulfolane, -phenyl-1-oxosulfolane, N,N'-dimethylimidazolidinone, and diphenylsulfone.

The above-mentioned various neutral polar solvents can be used singly, or two or more of them can be used in combination.

In any case, the proportion of the neutral polar solvent to be used is such that the concentration of the raw materials (dihydric phenol and 4.4'-dichlorobenzophenone) is 0.1 to 1.5 mol/solvent. Is it appropriate to adjust it to

The alkali metal compound is not particularly limited as long as it can convert the dihydric phenol into an alkali metal salt, and preferred are alkali metal carbonates and alkali metal hydrogen carbonates, such as sodium carbonate, potassium carbonate, and carbonate. Examples include rubidium, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate.

Among these, particularly preferred are sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, and the like.

In addition, two or more types of the alkali metal compounds can also be used in an appropriate combination.

The proportion of the alkali metal compound to be used is appropriately 1.05 equivalent or more per hydroxyl group of the dihydric phenol.

Furthermore, the reaction temperature for oligomerization is usually 150 to 250
℃, preferably 200 to 230℃.

Moreover, the reaction time is usually 0.5 to 3 hours.

In addition, in the oligomerization reaction, it is also possible to accelerate the reaction by adding potassium fluoride to the reaction system.

In the present invention, once the oligomer is produced as described above, as a second step, 4,4'-cyfluoropennephenone is added to the reaction system to carry out a reaction to increase the molecular weight of the oligomer.

In this case, the reaction temperature is generally in the range from 180 to 400°C, preferably from 200 to 350°C.

Moreover, the reaction time is usually in the range of 1 to 3 hours.

Regarding the purchasing ratio of the raw material monomers in the oligomerization reaction and polymerization reaction in the present invention,
, 4'-dichlorobenzophenone is A mole, the dihydric phenol is B mole, and 4.4'-difluorobenzophenone is C mole, (A+C)/B (molar ratio) is 1.00 to 1.01, C /(A0G) (molar ratio) is preferably 0.02 to 0.2.

If the ratio of C is less than 0.02, the effect of increasing the molecular weight of the oligomer will not be obtained, and even if it exceeds 0.2, the effect of improving the high molecular weight ratio will be commensurate with the increased amount, which is economically disadvantageous. be.

After the completion of the polymerization reaction, the reaction product liquid is washed with a usual washing solvent such as water, alcohol, acetone, etc., and the solid content separated by a usual method such as filtration is dried to remove the aroma. It is possible to isolate family polyetherketones.

1 Claim 2- On the other hand, in accordance with the invention of Claim 2, a mixed solvent of an amide solvent and diphenyl sulfone is used as a solvent during the production of the oligomer, and 4
, 4'-difluorobenzophenone, the amide solvent is distilled off from the reaction system, and the other conditions are the same as those stated in claim 1.

According to the invention of claim 2, there is an effect that the reaction for increasing the molecular weight of the oligomer can be carried out more smoothly, and in order to enhance this effect, the reaction temperature for increasing the molecular weight of the oligomer is raised higher than the reaction temperature for oligomerization. That's preferable.

Specifically, it is preferable to raise the reaction temperature in polymerization by 50 to 200°C than the reaction temperature in oligomerization reaction.

In this way, by increasing the reaction temperature, the molecular weight of the aromatic polyetherketone can be further increased.

Regarding the mixed solvent, the amide solvent and diphenyl sulfone described in claim 1 can be appropriately used as the amide solvent.

The diphenylsulfone is not particularly limited, and for example, those obtained as by-products from the production of benzenesulfonic acid or benzenesulfonyl chloride can be used.

Among the various solvents mentioned above, particularly preferred is N
, is a mixed solvent of N'-dimethylimidazolidinone and diphenyl sulfone.

The ratio of the amide solvent to the diphenyl sulfone in the mixed solvent is usually 0.5 to 2.0 to 1 equivalent of the diphenyl sulfone.
equivalent, preferably 1 equivalent.

The amount of the mixed solvent to be used is not particularly limited and is the same as the amount of the solvent explained in the invention of claim 1 above.

Also in the invention according to claim 2, after the completion of the polymerization reaction, the aromatic polyetherketone can be isolated by a simple operation as explained in the invention according to claim 1.

In addition, in both claims 1 and 2, it is possible to partially replace 4,4'-dichloropentuphenone, which is one of the raw materials, with another specific compound. , 4'-dichlorobenzophenone can be replaced with dichlorodiphenyl sulfone in an amount of 2 to 60 mol %.

[Examples] Next, the present invention will be explained in more detail based on Examples and Comparative Examples.

(Example 1) In a 300 mM separable flask equipped with an argon gas inlet tube, a Dean-Starck trap, a thermocouple, and a stirring device, 20.16 g of 4,4"-dichlorobenzophenone was added.
9g (0,08 mol), 2,2-bis(4-hydroxyphenyl)propane 22.57g (0,099
mol), potassium carbonate 16.58 g (0.12 mol)
and N,N'-dimethylimidazolidinone 180 mJ
1 was charged, and the temperature was raised from room temperature to 220°C over 50 minutes.

After that, toluene was added and water was distilled off by reflux. After continuing this state for 120 minutes and carrying out the reaction, 4.35 g of 4.4゛-difluorobenzophenone was added.
A solution of (0.02 mol) dissolved in 20 mM of N,N'-dimethylimidazolidinone was added, and a polymerization reaction was further carried out at this temperature for 60 minutes.

The obtained reaction solution was poured into methanol to precipitate a solid, which was pulverized using a Warninta blender, washed with water and methanol, and dried.

The yield of the aromatic polyether obtained was 39.
3 g (yield 97%). The glass transition temperature of this product was 1489C, and the reduced viscosity at 30'C of a solution with a concentration of 0.2 g/d in N-methylpyrrolidone as a solvent was 0.81 dl/g. Furthermore, the oligomer content obtained by extracting this aromatic polyetherketone with acetone was 2.21% by weight.

(Example 2) 4,4
“-Dichlorobenzophenone 22.851g (0,0!
]1 mol), Bis7:r-/-le A 22.8g
(0,1 mol), potassium carbonate 16.59 g (0,12
mol), 2.9 g (0.05 mol) of potassium fluoride, and 1.10 ml of dimethyl imida solidinone, and heated to 220°C for 1 hour and 30 minutes while stirring while blowing argon gas. Well, the temperature rose. At this time, a small amount of toluene was added to remove water azeotropically.

Next, in this state, a solution of 2.182 g (0.01 mol) of 4.4"-difluorobenzophenone dissolved in dimethylimida solidinone 1 (1° C.) was added, and then
A polymerization reaction was carried out at °C for 1 hour with stirring.

After cooling the reaction product, it was placed in one volume of methanol to precipitate the polymer, acidified with an aqueous oxalic acid solution, and washed twice with one volume of water and once with one volume of methanol,
Then it was dried.

The yield of the aromatic polyether ketone obtained was 39 g (
Yield: 96%), reduced viscosity: 1.1.3 db/g (3[1
°C, N-methylpyrrolidone solvent, 0.2 g/dJl concentration). Further, the amount of oligomer in this aromatic polyether kene was 1.6% by weight.

(Comparative Example 1) The amount of 4.4"-dichlorobenzophenone charged was 25.3
The same procedure as in Example 1 was carried out except that the amount was 62 g (0.101 mol) and 4,4'-difluorobenzophenone was not added.

The yield of the obtained polymer was 38.7 g (yield 95%),
The reduced viscosity was 0.35 dung (30°C, N-methylpyrrolidone solvent, 0.2 g/di concentration). Also, the amount of oligomer in this polymer was 6.8% by weight.

(Example 3) The amount of 4.4-dichlorobenzophenone used was 22.6
9 g (0,119 mol), and the amount of 4,4°-difluorobenzophenone used was 2. ], 82 g (
The procedure was carried out in the same manner as in Example 1, except that the amount was 0.01 mole) and 1 mole.The yield of the aromatic polyetherketone obtained was 39.
．． 7g (yield 98%). In addition, the glass transition temperature of this material is 148°C, and the reduced viscosity is 0.86 db/g.
(30°C, N-methylpyrrolone solvent, 0.2g/d
sentence concentration).

The amount of oligomer obtained by extracting this aromatic polyetherketone with acetone was 3.1% by weight.

(Example 4) 22.69 g (0.09 mol) of 4,4'-dichloropentsuphenone was placed in a 300 mM Sebaraturu flask equipped with an argon gas inlet tube, a distillation device, and a stirring device.
Hydroquinone 10.90g (0,099mol), potassium carbonate 14.097g (0,102mol), N
, N.-dimethylimidazolidinone [10 mM and 6f1 g of diphenyl sulfone were charged, and the reaction was carried out at 220° C. for 90 minutes with stirring.

Then, 2.18 4,4'-difluorobenzophenone
After adding 2 g (0.01 mol) of N,N-dimethylimidazolidinone solution, reduce the pressure inside the flask and add N.
, N.-dimethylimida solidinone was distilled off. Next, the temperature was raised to 220°C, and a polymerization reaction was carried out at this temperature for 60 minutes with stirring. After the reaction was completed, the product was cooled, pulverized, washed with acetone, water, and acetone in this order, and dried.

The yield of the aromatic polyether ketone obtained was 28.
6g (yield 99%). Further, the glass transition temperature of this product was 146°C, and the solvent viscosity at 400°C was 2[i,000 voids]. Further, the amount of oligomer obtained by extracting this aromatic polyetherketone with acetone was 0.1% by weight.

When this aromatic polyetherketone was press-molded at 400°C, an extremely bullet-like film was obtained. [Effects of the Invention] According to the present invention, post-treatment is simple and there are no by-products. , it is possible to provide a method for producing an aromatic polyetherketone, which can industrially produce a high-purity and high-molecular-weight polymer.

Claims (2)

[Claims] (1) 4,4'-dichlorobenzophenone and general formula H
A dihydric phenol represented by O-Ar-OH (in the formula, Ar represents an aromatic divalent group) is reacted in the presence of an alkali metal compound in a neutral polar solvent to generate an oligomer. A method for producing an aromatic polyetherketone, which comprises: then adding 4,4'-difluorobenzophenone to the reaction system to carry out a polymerization reaction. (2) 4,4'-dichlorobenzophenone and general formula H
A dihydric phenol represented by O-Ar-OH (in the formula, Ar represents an aromatic divalent group) is reacted in the presence of an alkali metal compound in a mixed solvent of an amide solvent and diphenyl sulfone. of aromatic polyetherketone, which is characterized in that the amide solvent is distilled off from the reaction system and 4,4'-difluorobenzophenone is added to the reaction system to perform a polymerization reaction. Production method.