JPH01207320A - Production of aromatic polyether - Google Patents

Abstract

PURPOSE:To obtain the title polyether having a narrow molecular weight distribution, simple and economical, by reacting a bifunctional phenol with a dihalogenobenzenoid compound using an inert organic high polar amide solvent as a reaction solvent. CONSTITUTION:(A) A bifunctional phenol [preferably hydroquinone and/or one expressed by formula I (Y is -O-, -S-, -SO2-, etc.)] is reacted with (B) a dihalogenobenzenoid compound [preferably expressed by formula II (X is halogen atom; Z is -SO2- or -C-)] of substantially equal molar amount with said bifunctional phenol in the presence of an alkali metal carbonate in an amount of substantially presenting one of more alkali atom to one phenol group, an inert organic high polar amide is used as a reaction solvent and a water arisen by the reaction is distilled off in the absence of azeotropic solvent to afford the aimed polyether.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing an aromatic polyether, and more particularly to a method for producing an aromatic polyether having a narrow molecular weight distribution.

[Conventional technology]

In recent years, engineering plastics, which are high-performance resins, have been actively developed. Thermoplastic aromatic polyetherenes, especially polysulfone, polyethersulfone, and polyetherketone, have excellent heat resistance, mechanical properties, and chemical resistance, so they are widely used in electrical and electronic industries, food industries, medical equipment, automobile parts, precision industries, etc. It is used in various fields.

A method for producing such an aromatic polyether is to polycondense bisphenol and a dihalogenobenzenoid compound in an organic highly polar sulfoxide or sulfone solvent such as dimethyl sulfoxide or sulfolane in the presence of an alkali metal carbonate. Method (Special Public Interest Publication 1977-214)
No. 58), or when polycondensing bisphenol and a dihalobenzenoid compound in an organic highly polar sulfoxide or sulfone solvent in the presence of an alkali metal carbonate, an azeotropic solvent is not used and the solvent is boiled. A method of removing water by distillation (Japanese Patent Publication No. 55-23574) is known.

[Problem to be solved by the invention]

However, the former method had a serious drawback in that the resulting polymer had a wide molecular weight distribution. Furthermore, the former manufacturing method requires the use of an azeotropic solvent to remove the water produced during the polycondensation reaction, which also requires solvent recovery, which complicates the manufacturing process and increases costs. There was also.

Furthermore, since the boiling point of organic highly polar sulfoxide or sulfone solvents is not stable under normal pressure, vacuum distillation is required, complicating the manufacturing process.

Therefore, an object of the present invention is to provide a method for producing an aromatic polyether having a narrow molecular weight distribution without complicating the process.

[Means to solve the problem]

As a result of intensive studies to solve the above problems, the present inventors found that by using an inert organic highly polar amide solvent as a reaction solvent, a predetermined high molecular weight aromatic polyether with a narrow molecular weight distribution can be produced using a complicated process. We were able to successfully manufacture the product without changing it.

That is, the present invention comprises a dihydric phenol and a dihalogenobensenoid compound in a substantially equimolar amount to the dihydric phenol, in an amount having substantially one or more alkali metal atoms per phenol group. A method for producing an aromatic polyether by reacting in the presence of an alkali metal carbonate, the method comprising using an inert organic highly polar amide as a reaction solvent and distilling the water produced by the reaction in the absence of an azeotropic solvent. The present invention provides a method for producing an aromatic polyether, which is characterized in that the aromatic polyether is removed.

The dihydric phenol used in the present invention includes 1
There is no particular restriction as long as it has two phenolic hydroxyl groups in the molecule, but examples include the following.

Dihydroxybenzophenone: Dihydroxydiphenyl sulfone: Dihydroxydiphenyl sulfide: 2.2-bis(hydroxyphenyl)propane: CH3 bis(hydroxyphenyl>methane bis(hydroxyphenyl)ether) Furthermore, the above dihydric phenol substituted with an alkyl group at the ortho position, etc. Examples include.

The dihalogenobenzenoid compound used in the present invention has the general formula (wherein, X represents either F, CI, Br, or I, and Z represents -3[]2- or 100-). , X is Z
However, in order to accelerate the reaction and improve the heat resistance of the resulting polymer, the following dihalogenobenzenoid compounds may be used: is preferred.

4.4'-dichlorodiphenylsulfone 4,4'-difluorodiphenylsulfone 4.4'-dichlorobenzophenone 4.4'-difluorobenzophenone The amount of such dihalogenobenzenoid compound to be used is:
It is usually in the range of 90 to 110 mol% based on dihydric phenol, and in order to obtain a higher molecular weight polymer,
A range of 98 to 103 mol% is preferred.

The inert organic highly polar amide solvent used in the present invention is
This refers to an amide compound that is not reactive with the dihydric phenol and dihalogenobenzenoid compounds used as raw materials, but has a polar group in its molecule and is polar enough to dissolve the produced polymer, and has the general formulas (1) to ( Compounds represented by rV) are preferred, and any compound can be used as long as it can dissolve the polymer produced at the polymerization temperature described below.

(1) (II)11)l (III) (rV) (wherein,
R1-R4 represent a self-C6 hydrocarbon group, and may be the same or different from each other. (n is an integer from 1 to 6) Examples of such solvents include: N, ~-dimethylformamide: N,N-dimethylacetamide: N, N, N', N'-tetramethylurea: N
-Methyl-2-pyrrolidone: N,N"-dimethyl-2-imidazolidinone: and the like.

Such an inert organic highly polar amide solvent is particularly preferable because if its boiling point is approximately the same as the polymerization temperature, the generated water can be easily removed and the reaction can proceed at normal pressure. The reaction may be carried out under reduced pressure using a high boiling point amide solvent at a temperature adjusted to the polymerization temperature.

The amount of the above inert organic highly polar amide solvent used is usually
It is used in an amount of 0.05 to 30 times the weight of the dihydric phenol, more preferably 0.1 to 15 times the weight of the dihydric phenol. If it is less than 0.05 times the weight of the dihydric phenol, it will not act as a solvent for the polymer, and the produced polymer will precipitate in a low molecular weight state, resulting in a polymer with a sufficiently high molecular weight. is not obtained. On the other hand, if the amount of the inert organic highly polar amide solvent is 30 times or more the weight of the dihydric phenol, it is not practical because the monomer concentration decreases and higher temperature and longer reaction conditions are required to increase the molecular weight.

Examples of the alkali metal carbonates used in the present invention include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, and lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, and cesium bicarbonate. Among these, IJ carbonate and potassium carbonate are preferred because they are inexpensive, easy to handle, and have high reactivity.

Further, the alkali metal carbonate described above can be used as a hydrate, but in order to obtain a polymer with a higher molecular weight, it is preferable to use an anhydride.

The amount of the alkali metal carbonate used varies depending on the relationship between the decomposition temperature of the alkali metal bicarbonate produced by the reaction between the dihydric phenol and the alkali metal carbonate and the polymerization reaction temperature. For example, the decomposition temperature of potassium bicarbonate is 100~
200°C, and rubidium bicarbonate and cesium bicarbonate decompose at 175°C. Sodium bicarbonate is somewhat stable, and lithium bicarbonate is extremely stable and does not easily decompose even at high temperatures. When using a metal carbonate that causes little or no decomposition of the metal bicarbonate, it is preferable to use at least 1.8 mol or more, preferably 2.0 mol or more, per 1 mol of dihydric phenol.

Moreover, such alkali metal bicarbonate itself cannot be used. On the other hand, when the polymerization reaction temperature is higher than the decomposition temperature of the alkali metal bicarbonate, the amount of alkali metal carbonate used is at least 0.9 mol or more, preferably 1 mol or more, per 1 mol of dihydric phenol. In the case of alkali metal bicarbonate, the amount is at least 1.8 mol or more, preferably 2 mol or more, per 1 mol of dihydric phenol.

In the method of the present invention, the temperature of the polymerization reaction is appropriately selected depending on the type of reaction raw material components, the type of reaction, etc., but is usually in the range of 80 to 400°C, preferably in the range of 100 to 350°C. If the reaction temperature is less than 80° C., the reaction rate of the desired polymerization reaction is extremely slow and a polymer with a sufficient high molecular weight cannot be obtained, which is not preferable. On the other hand, if the reaction temperature exceeds 400° C., reactions other than the desired polymerization reaction become significant, resulting in coloring of the obtained polymer, which is not preferable. Further, the reaction temperature may be maintained constant, or may be changed gradually or in steps.

Further, the reaction time needs to be appropriately selected depending on the type of reaction raw material components, the type of polymerization reaction, the reaction temperature, etc., but is usually in the range of 10 minutes to 100 hours, preferably 30 minutes.
It ranges from minutes to 24 hours.

In the method of the present invention, the polymerization reaction is preferably carried out in the absence of oxygen, that is, in nitrogen or other inert gas. This is because, in the presence of oxygen, the alkali metal salt of dihydric phenol is easily oxidized by heating, which hinders the desired polymerization reaction, making it difficult to increase the molecular weight, and also causes coloration of the resulting polymer.

In order to stop the above polymerization reaction, it is usually sufficient to cool the reactant. However, in order to stabilize the phenoxide groups that may be present at the ends of the polymer, an aliphatic halide, an aromatic halide, or the like may be added and reacted as necessary. Representative examples of such 10genides include methyl chloride, ethyl chloride, methyl bromide, 4-chlordiphenylsulfone, 4-chlorobenzophenone, 4. Examples include C-dichlorodiphenylsulfone and p-chloronitrobenzene.

After the completion of the above polymerization reaction, the polymer may be separated and purified by a conventional method. For example, the salt precipitated in the reaction solvent (
After filtering off the alkali halide) or excess alkali metal carbonate or bicarbonate, the filtrate, usually the polymer solution, is added dropwise to the polymer non-solvent, or conversely, the polymer non-solvent is added to the polymer solution. By adding it to the solution, the desired polymer can be precipitated. Typical examples of those commonly used as non-solvents for polymers include methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, water, etc.
You may use as a mixture of two or more types.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these in any way.

Example 1 2.2-bis-(4
-Hydroxyphenyl)furopane 45.66g (0,
2 mol), 4.4”-dichlorodiphenylsulfone 57
．． 42g (0.2 mol), anhydrous potassium carbonate 55.2
8 g (0.4 mol) and 300 g of N,N-dimethylacetamide were charged, and nitrogen gas was introduced for 30 minutes to purge the inside of the system with nitrogen. Raise the temperature to the boiling point of the reaction solution,
Approximately 60 g of N,N-dimethylacetamide was distilled out over a period of 2 hours. At this time, about 3.6 g of 820 was distilled out at the same time. After that, after reacting for 4 hours under reflux, 10
The temperature was lowered to 0°C, and N,N-dimethylacetamide 120
g was added to lower the viscosity of the reaction crude liquid, and methyl chloride gas was blown in at 300 ml/ml for 30 minutes. The temperature was returned to room temperature, the precipitated salt and excess potassium carbonate were filtered off, and the filtrate was poured into a large amount of methanol to precipitate the produced polymer. The resulting polymer was isolated, washed several times with methanol, and then dried under reduced pressure at 150° C. for 3 hours.

The yield of the obtained polymer was 97%, with 0.5% Wt
The reduced viscosity of /VOI in a chloroform solution at 25°C was 1.34 J/g. Furthermore, the degree of dispersion of the molecular weight distribution measured by GPC (gel permeation chromatography) was also /Hn=2.01.

Example 2 4. Amount of 4'-dichlorodiphenylsulfone 58,5
A polymer was obtained by carrying out an experiment in the same manner as in Example 1, except that the amount was changed to 7 g (0,204 mol). The yield of the obtained polymer was 98%, and the reduced viscosity was 0 under the same conditions as Example 1.
．． It was 412/g. The degree of dispersion of the molecular weight distribution measured by GPC was -/Hn = 1.98.

Example 3 Amount of 4.4-dichlorodiphenylsulfone 57.2
A polymer was obtained by carrying out an experiment in the same manner as in Example 1, except that the amount was changed to 7 g (0,196 mol). The yield of the obtained polymer was 96%, and the reduced viscosity was 0.5% under the same conditions as in Example 1.
4M! /g. The degree of dispersion of the molecular weight distribution by GPC measurement was 1.99.

Example 4 The recipe of Example 2 was scaled up using a 40 g reactor, and a polymer with a reduced viscosity of 0.47 J/g was obtained under the same conditions as in Example. Dispersity of molecular weight distribution by GPC measurement h/! Jn = 1.97.

Comparative Example 1 The same raw materials as in Example 1 were prepared except that 300 g of dimethyl sulfoxide was used as the solvent, and about 60 g of dimethyl sulfoxide was distilled off over 2 hours under a reduced pressure of 230 mmHg, and then refluxed at 160°C under reduced pressure. The reaction was continued for an additional 4 hours. After the reaction was completed, 120 g of dimethyl sulfoxide was added to lower the viscosity of the reaction crude liquid, and 300 m of methyl chloride gas was added.
The air was blown at 1/min for 30 minutes. Thereafter, the same operation as in Example 1 was performed to isolate the produced polymer. The yield of the obtained polymer was 95%, and the reduced viscosity at 25°C in a 0.5% ivt/vol chloroform solution was 0.79.
a/g, the dispersion degree of molecular weight distribution by GPC measurement was -7 -2.13.

〔Effect of the invention〕

As explained above, the aromatic polyether obtained by the present invention has a narrow molecular weight distribution, making it possible to provide high-quality products.

Furthermore, the manufacturing method of the present invention does not require complicated steps,
This is a simple and economical method.

Applicant's agent Kaoru Furutani

Claims (1)

[Claims] 1. A dihydric phenol and a dihalogenobenzenoid compound in a substantially equimolar amount to the dihydric phenol, which has substantially one or more alkali metal atoms per phenol group. A method for producing an aromatic polyether by reacting in the presence of a certain amount of alkali metal carbonate, the method comprising: using an inert organic highly polar amide as a reaction solvent, and reacting water produced by the reaction in the absence of an azeotropic solvent. A method for producing aromatic polyether, which comprises removing it by distillation. 2 The above dihydric phenol is hydroquinone and/or the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Y is a direct bond, -O-, -S-, -SO_2
The method for producing an aromatic polyether according to claim 1, wherein the aromatic polyether is a dihydric phenol represented by -, -CO-, or a divalent hydrocarbon group. 3 The above dihalogenobenzenoid compound has the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X is a halogeno atom, Z is -SO_2- or -
The aromatic polyester according to claim 1 or 2, which is at least one kind of halogenobenzenoid compound represented by CO-, and X is at the ortho or para position with respect to Z. How to make ether. 4 The above solvent has the following formulas (I) to (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I), ▲ Mathematical formulas
There are chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III), ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ (IV) (In the formula, R_1 to R_4 represent C_1 to C_6 hydrocarbon groups, and may be the same or different. n is an integer from 1 to 6) The method for producing an aromatic polyether according to any one of claims 1 to 3, wherein the aromatic polyether is at least one selected from organic highly polar amides.