JPH02247221A - Production of polyetherketone - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a method for producing polyetherketone, and more specifically, to a method for producing polyetherketone, which can be suitably used as a material in the mechanical field, electronic/electrical field, etc. The present invention relates to a method for producing polyetherketone, which enables efficient and inexpensive production of etherketone.

[Prior art and problems to be solved by the invention] In recent years,
Engineering resins with various structures have been developed and are used in a wide range of fields such as automobiles, electrical and electronics, precision machinery, OA equipment, and optical communication equipment. However, since the required performance has not yet been fully satisfied, and the required performance has become stricter, it is desired to develop a new material.

By the way, polyetheretherketone, which is one of these engineering resins, is a resin excellent in heat resistance, mechanical strength, etc., and various proposals have been made.

For example, in Japanese Patent Application Laid-Open No. 54-90196,
Production of a crystalline thermoplastic aromatic polyetherketone by polycondensing hydroquinone and difluorobenzophenone under substantially anhydrous conditions, in the presence of an alkali metal carbonate or bicarbonate, and in the presence of a specific solvent. A method is proposed.

However, in this method, difluorobenzophenone, which is difficult and expensive to produce industrially, is used as the 5 raw materials, so the crystalline thermoplastic aromatic polyether ketone obtained by this method has a high production cost. It has the disadvantage of being

Therefore, a method of producing polyetherketone using dichlorobenzophenone, which can be easily produced industrially and is inexpensive, as a raw material instead of difluorobenzophenone has been studied.

However, dichlorobenzophenone reacts with hydroquinone under high temperature conditions, but under low temperature conditions,
It hardly responds to normal methods.

For example, Journal of Bolimar Science A-1 No. 5
Volume (1967) [Journal of PolyI
+erScience, Part A-1, Vol. 5
．． 2386 (1967)], an attempt was made to synthesize polyetherketone from dichlorobenzophenone and hydroquinone.

However, the polyetherketone obtained by this method is only an oligomer, and has sufficient heat resistance and
It has not yet been possible to obtain a practical polyetherketone having mechanical strength and the like.

Furthermore, as mentioned above, the reaction between dichlorobenzophenone and hydroquinone occurs at high temperatures, but since hydroquinone is sublimable, it is necessary to efficiently produce polyetherketone using dichlorobenzophenone and hydroquinone as raw materials. Another problem is that oligomerization must be performed at low temperatures.

The present invention has been made based on the above circumstances.

An object of the present invention is to provide a method for producing polyetherketone that can efficiently and inexpensively obtain a polyetherketone that has a sufficiently high molecular weight and is excellent in heat resistance, mechanical strength, etc.

[Means for Solving the Problems] In order to solve the above-mentioned problems, two inventors of the present invention have made extensive studies and found that a method for producing polyetherketone using dichlorobenzophenone and hydroquinone as raw materials uses a specific solvent. We discovered that dichlorobenzophenone reacts easily even under low temperature conditions when using
We have arrived at the present invention.

The structure of the present invention is to react dichlorobenzophenone and hydroquinone in a mixed solvent consisting of an amide solvent and diphenyl sulfone in the presence of an alkali metal compound at a temperature of 180 to 250°C, and then to react the amide solvent with the hydroquinone. This is a method for producing polyetherketone, which is characterized in that after distillation, polymerization is carried out at a temperature of 300 to 400°C.

The present invention will be explained in detail below.

-Raw materials- In the method of the present invention, dichlorobenzophenone and hydroquinone are used as raw materials.

(A) Dichlorobenzophenone As the dichlorobenzophenone used, 4,4'-dichlorobenzophenone represented by the following formula can be suitably used.

The 4,4'-dichlorobenzophenone is, for example,
It can be easily obtained industrially by reacting chlorobenzene with carbon tetrachloride or phosgene in the presence of a catalyst such as aluminum chloride.

(B) Hydroquinone There are no particular restrictions on the hydroquinone represented by the following formula: For example, it may be obtained by a manufacturing method of oxidizing 2,4-diisopropylbenzene, which is a by-product when synthesizing phenol from benzene and propylene, or aniline. Quinone obtained by oxidizing with sulfuric acid and chromic acid, reduced with sulfite, and purified by a crystallization method can be used.

One solvent, etc. - In the method of the present invention, the dichlorobenzophenone and hydroquinone are first reacted in a mixed solvent consisting of an amide solvent and diphenyl sulfone in the presence of an alkali metal compound.

(C) Amide solvent In the method of the present invention, the amide solvent used is, 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-isobutyl-2-pyrrolidone,
N-n-propyl-2-pyrrolidone, N-propyl-2-pyrrolidone
2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4
Examples include 5-trimethyl-2-pyrrolidone, III,N''-dimethylimidazolidinone, and tetramethylurea.

These may be used alone or in combination of two or more.

Among these, particularly preferred is N,N'-dimethylimidazolidinone.

(D) Diphenylsulfone In the method of the present invention, diphenylsulfone is used together with the amide solvent.

The diphenyl sulfone to be used is not particularly limited as long as it is represented by the following formula; for example, those obtained as by-products in the production of benzenesulfonic acid and benzenesulfonyl chloride can also be used. .

(E) Mixed solvent The ratio of the amide solvent to the diphenyl sulfone in the mixed solvent is usually 0.5 to 2.0 equivalents, preferably 1 equivalent of the amide solvent to 1 equivalent of the diphenyl sulfone. It is equivalent.

There is no particular restriction on the amount of the mixed solvent used, but
Usually, the amount is selected in the range of 5 to 200 parts by weight per 100 parts by weight of the dichlorobenzophenone and the hydroquinone.

(F) Alkali metal compound In the method of the present invention, the alkali metal compound used may be any compound capable of converting the hydroquinone into an alkali metal salt, and is not particularly limited, but preferred is They are alkali metal carbonates and alkali metal hydrogen carbonates.

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

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

In the method of the present invention, among the various alkali metal compounds described above, sodium carbonate, sodium hydrogen carbonate, and potassium carbonate dipotassium hydrogen carbonate can be particularly preferably used.

In addition, the said alkali metal compound may be used individually by 1 type, and may use 2 or more types together.

- Charge Routine In the method of the present invention, the charge ratio of the dichlorobenzophenone and the hydroquinone is a molar ratio of (dichlorobenzophenone)/(pytroquinone), usually [1
, 99 to 1.02, preferably 1.01. If this molar ratio is less than 0.99, coloring may be significant and only oligomers may be obtained. On the other hand, if it exceeds 1.02, only oligomers may be obtained.

Furthermore, the ratio of the alkali metal compound to the hydroquinone varies depending on the type of the alkali metal compound to be used, and therefore cannot be specifically defined. When using, the molar ratio of (alkali metal carbonate)/(hydroquinone) is usually 1.
．． 005 to 1.02, and sodium bicarbonate.

When using an alkali metal hydrogen carbonate such as potassium hydrogen carbonate, the molar ratio of (alkali metal hydrogen carbonate)/(hydroquinone) is usually 2.01 to 2.04.

1. Reaction temperature and time - In the method of the present invention, the dichlorobenzophenone and the hydroquinone are reacted using a two-step reaction system.

In the first step, a certain amount of the dichlorobenzophenone, the hydroquinone, the mixed solvent, and the alkali metal compound are charged.

At a temperature in the range of 180°C to 250°C, preferably 200°C to 230°C, usually for 30 minutes to 3 hours, preferably 1
If the reaction temperature for producing 2 oligomers by reacting for ~2 hours is less than 180°C, the reaction rate is too slow to be practical, and if it exceeds 250°C, sublimation of the hydroquinone may occur.

Next, in the second step, after distilling off the amide solvent, the temperature is 300°C to 400°C, preferably 300°C to 38°C.
at a temperature in the range of 0°C for 30 minutes to 5 hours, preferably 1
If the reaction temperature for producing a polymer by reacting for ~3 hours is less than 300°C, the reaction temperature in the second reactor is too slow to be practical, and if it exceeds 400°C, it may cause decomposition or crosslinking of the produced polymer. be.

- Distillation of amide solvent - In the method of the present invention, in the second step, the amide solvent is distilled off.

The amide solvent is usually distilled off at 300°C or lower,
It is preferably carried out at a temperature below 250°C; if this temperature exceeds 300°C, coloration may occur in the polyetherketone obtained.

-Others- The polyetherketone obtained by the method of the present invention is a polymer having a melt viscosity of 10.000 voids or more at a temperature of 400°C.

The polyetherketone obtained by the method of the present invention has a sufficiently high molecular weight, excellent heat resistance, mechanical strength, etc.
For example, it can be suitably used as a material in the electrical/electronic equipment field, mechanical field, etc., either as it is or by adding an inorganic filler.

[Example] Next, Examples of the present invention will be shown and the present invention will be explained more specifically.

(Example 1) 25.463 g (0,101 mol) of 4,4'-dichlorobenzophenone,
Hydroquinone 11.011g (0.10 mol), anhydrous potassium carbonate 13.959g (0.101 mol),
60 g of diphenyl sulfone and N as an amide solvent
, N''-dimethyl memidazolidinone was charged. These were heated to 220°C while stirring, and this state was continued for 1 hour. After 1 hour, the transparent liquid became cloudy.
The tone became.

Next, the temperature was raised to 250°C, and the pressure was slightly reduced to completely distill off N,N''-dimethylimidazolidinone over a period of 1 hour. Furthermore, the reaction was carried out at a temperature of 370°C for 2 hours to complete the polymerization.

After the reaction was completed, one polymer solution was poured into a stainless steel vat to form a plate, which was pulverized and washed with acetone and water to remove diphenylsulfone and inorganic salts.

Thereafter, it was dried under reduced pressure at a temperature of 130°C to obtain 28.9 g (yield: 99%) of a polymer.

When the properties of this polymer were measured, the glass transition temperature was 143°C, and the thermal decomposition onset temperature was 562°C (in air, 5%
The melt viscosity (zero shear viscosity) at a temperature of 400° C. was 22,000 voids.

(Example 2) In the above Example 1, anhydrous potassium carbonate 13.959
g (0.1 former mol) in place of anhydrous sodium carbonate 10
．． 6g (0,100 mol) and anhydrous potassium carbonate 0
．． Using 28 g (0,002 mol),
The same procedure as in Example 1 was carried out except that the heating time at a temperature of 220° C. was changed from 1 hour to 3 hours.

The yield of the obtained polymer was 28.3 g (yield 97%).

When the properties of this polymer were measured, the glass transition temperature was 143°C, and the thermal decomposition onset temperature was 550°C (in air, 5%
The melt viscosity (zero shear viscosity) at a temperature of 400° C. was 20,000 voids.

(Example 3) In Example 1, N-methylpyrrolidone was used instead of N,N''-dimethylimidazolidinone, and the reaction temperature was changed from 220°C to 200°C to carry out the reaction.
The test was carried out in the same manner as in Example 1 above, except that the test was carried out for a different time.

The yield of the obtained polymer was 28.6 g (yield: 8%).

When the properties of this polymer were measured, the glass transition temperature was 144°C, and the thermal decomposition onset temperature was 560°C (in air, 5%
The melt viscosity (zero shear viscosity) at a temperature of 400° C. was 18,500 voids.

[Effect of the invention] According to the invention.

(1) Since dichlorobenzophenone and hydroquinone are reacted under specific conditions in a specific solvent, oligomerization is possible at low temperatures without causing sublimation of hydroquinone; (2) dichlorobenzophenone and hydroquinone Using dichlorobenzophenone, which is easy to produce and can be obtained at low cost, as a raw material, it is possible to easily react with
It is possible to provide an industrially useful method for producing polyetherketone, which has the advantage of being able to efficiently obtain polyetherketone with excellent mechanical strength and the like at low cost.

Claims (1)

[Claims] (1) Dichlorobenzophenone and hydroquinone,
In a mixed solvent consisting of an amide solvent and diphenyl sulfone in the presence of an alkali metal compound at a temperature of 180 to 2
A method for producing polyetherketone, which comprises reacting at 50°C, then distilling off the amide solvent, and then polymerizing at a temperature of 300 to 400°C.