JPH0352924A - Preparation of aromatic polyether polymer - Google Patents

Abstract

PURPOSE:To improve the quality of an aromatic polyether polymer by adding an organic phosphorus compound to a section mixture when a dihalogenobenzenoid compound is heated and reacted with hydroquinone is the pressure of an alkali is an organic solvent to provide the aromatic polyether polymer. CONSTITUTION:A dihalogeno benzenoid compound (preferably 4,4'- dichlorobenzophenone) is heated and reacted with hydroquinone in the presence of an alkali (preferably potassium carbonate) and an organic phosphorus compound [preferably a compound of formula I, II or III (Ar is monovalent aromatic residual group)] in an organic solvent (preferably diphenyl sulfone) (preferably at 250-350 deg.C) while inhibiting the gelation of the product during the reaction, thereby preferably providing an aromatic polyether polymer having a high quality.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing an aromatic polyether polymer, and more specifically, relates to a method for producing an aromatic polyether polymer, and more specifically, a method for producing an aromatic polyether polymer using a dihalogenobenzenoid compound and a dihydric phenol. The present invention relates to a method for producing an aromatic polyether polymer.

[Conventional technology]

Aromatic polyether polymers, especially aromatic polyether polymers with ketone groups in the main chain, are known to have excellent mechanical, thermal, and electrical properties, and have recently been used as a material for molding. Applications are expanding in many fields.

Various methods have been known to produce such aromatic polyether polymers, among which is a method in which a dihalogenobenzenoid compound and a dihydric phenol are subjected to a thermal reaction in the presence of an alkali in an organic solvent ( Japanese Patent Publication No. 59-937
No. 24) is a good method with excellent economical efficiency. However, in these conventionally proposed methods, the range of optimal reaction conditions for obtaining high-quality aromatic polyether polymers is narrow, and the range of optimal reaction conditions for obtaining high-quality aromatic polyether polymers is narrow, and even when the conditions are slightly changed due to scale-up, etc. There is a problem in that deviations from the temperature range occur and undesirable side reactions such as gelation of the resulting polymer occur. In addition, in these methods, difluorobenzenoid compounds are generally used as dihalogenobenzenoid compounds, but when economically advantageous dichloropenzenoid compounds are used, the above-mentioned problems become even more serious. The reality is that a substantially linear, high molecular weight aromatic polyether polymer cannot be obtained.

[Problem to be solved by the invention]

An object of the present invention is to provide a method for producing an aromatic polyether polymer of excellent quality by suppressing undesirable side reactions such as gelation in the reaction between a dihalogenobenzenoid compound, particularly a dichlorobenzenoid compound, and hydroquinone. There is something to do.

[Means to solve the problem]

The present inventors have developed an aromatic polyether polymer based on an economically superior method of reacting a dihalogenobenzenoid compound with a dihydric phenol in the presence of an alkali in an organic solvent. As a result of intensive research to achieve the above-mentioned purpose in the manufacturing method, it was discovered that gelation during the reaction is dramatically suppressed when the reaction is carried out in the presence of an organic phosphorus compound. It has been completed.

That is, the present invention provides a method for producing an aromatic polyether polymer by heating a dihalogenobenzenoid compound and hydroquinone in the presence of an alkali in an organic solvent, in which the reaction is carried out in the presence of an organic phosphorus compound. This is a method for producing an aromatic polyether polymer.

The dihalogenobenzenoid compound in the present invention is a compound represented by the following general formula CI).

X-Ar-X...1 (
a divalent aromatic residue selected from the group I); X represents a halogen atom or a nitro group; In preferred divalent aromatic residues, X is a chlorine atom.

Specific examples of the dihalogenobenzenoid compound represented by the general formula CI) include 4,4''-dichloropenzophenone, 4,4'-difluoropenzophenone, 4,4
゛-dibromobenzophenone, 4.4゛-dinitrobenzophenone, 2,6-dichloroanthraquinone, 2,
6-difluoroanthraquinone, 2,6-dinitroanthraquinone, 4,4'-dichlorobibenzoyl, 4,4
'-difluorobibenzoyl, bis-1,4-(4-chlorobenzoyl)benzene, bis-1,4-(4-chlorobenzoyl)biphenyl, and the like.

Among these, preferred dihalogenobenzenoid compounds are 4,4'-dichlorobenzophenone, 2,6-dichloroanthraquinone, and bis-1,4-(4-chlorobenzoyl)benzene, and more preferred are 4,4'-dichlorobenzophenone, and bis-1,4-(4-chlorobenzoyl)benzene. 4
゜-Dichloropenzophenone.

As the organic solvent in the present invention, various organic solvents that are stable under the reaction conditions can be used, and preferred organic solvents include aromatic sulfones represented by the following general formula [■].

Here, Q is a direct bond, an oxygen atom, or two hydrogen atoms, one bonded to each benzene ring, and R and R° are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. .

Specific examples of the aromatic sulfone represented by the general formula [III] include diphenyl sulfone, dibenzothiophene dioxide, phenoxathiin dioxide, and 4-phenylsulfonylbiphenyl. A preferred aromatic sulfone is diphenyl sulfone.

The alkali in the present invention refers to an alkali that can form a salt with the above-mentioned dihydric phenols, and specific examples of such alkalis include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; Examples include alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate. Among these, preferred alkalis are alkali metal carbonates, and more preferred is potassium carbonate.

The purpose of the present invention, which is to obtain a high-quality aromatic polyether polymer by suppressing gelation during the reaction, can only be achieved by the presence of an organic phosphorus compound in the reaction system during the reaction. Examples of organic phosphorus compounds include phosphines such as triphenylphosphine and tributylphosphine, phosphites such as triphenylphosphine and tributylphosphite, phosphoric acid esters such as triphenylphosphate and tributylphosphate, and tetrakis ( 2,4-di-t-butylphenyl)4,4'-biphenylene diphosphonite, 9
．． Examples include organic phosphorus compounds such as 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

Among these, preferred are organic phosphorus compounds of the following general formula [I
V], [V] or [VI].

P (A r )s P (O A r )s [IV] [V1 0= P (OA r )s
[VI] (In the formula, Ar represents a l-valent aromatic residue.)
Among these, the use of P(Ar)s is more preferable because gelation during the reaction is particularly suppressed and the resulting polymer molded product has particularly excellent mechanical strength.

In carrying out the method of the present invention, the dihalogenobenzenoid compound and the hydroquinone are used in a ratio of approximately equimolar, but from the viewpoint of quality or molecular weight control of the resulting polymer, the dihalogenobenzenoid compound and the hydroquinone are It may be preferable to use an excess of 5 mol%.

The alkali is used in an equivalent amount or in an excess of up to 20 equivalent percent relative to the hydroquinone used.

The amount of the organic phosphorus compound to be used is not particularly limited, but is 0.001 to 0.1 mol, preferably 0.001 to 0.1 mol per mol of the dihalogenobenzenoid compound commonly used. 0
It is used in a proportion of 0.02 to 0.02 mole.

The organic solvent is used in such a proportion that the concentration of the polymer to be produced is 10 to 40% by weight, preferably 20 to 35% by weight.

The reaction is carried out at a temperature of 250-350°C.

Generally, in order to avoid undesirable side reactions, etc., it is preferable to start the reaction at a low temperature and increase the temperature stepwise or continuously.

The reaction time cannot be unconditionally determined because the suitable range varies depending on the type of raw materials used, the selected temperature conditions, etc., but a time in the range of 1 to 24 hours is generally selected.

This reaction yields a fluid reaction mixture in the form of a solution in which the produced polymer is dissolved in an organic solvent or in the form of a slurry in which the produced polymer is dispersed in an aromatic sulfone.

This reaction mixture is either directly poured into water under stirring conditions to form a slurry, or it is cooled and then pulverized. By subsequent solid-liquid separation in the case of slurrying or directly in the case of grinding, a solid containing the product polymer and the organic solvent is obtained. The solid is then washed to remove the organic solvent with an organic non-solvent that dissolves the organic solvent but not the resulting polymer. ．． Examples of such organic non-solvents include ketones such as methyl ethyl ketone and acetone, alcohols such as methanol, ethanol and propanol, and ethers such as ethyl ether, tetrahydrofuran and dioxane. Among these, preferred organic nonsolvents are acetone and methanol. Washing is preferably carried out under heating conditions, usually under reflux conditions.

In addition to washing with these organic non-solvents, washing with water is also performed for the purpose of removing inorganic components such as alkali salts.

The wet polymer that has been washed is subjected to ordinary drying treatments such as vacuum drying and fluidized fluid drying, and finally becomes a powdered aromatic polyether polymer.

〔Effect of the invention〕

According to the method of the present invention described in detail above, it is possible to obtain a high quality aromatic polyether polymer very economically, and the obtained aromatic polyether polymer takes advantage of its high quality and has a high quality. It can be processed into high-performance films, fibers, and various resin molded products, and can be put to practical use in various fields. Therefore, the industrial value of the present invention is extremely large.

〔Example〕

The method of the present invention will be explained in more detail with reference to Examples below, but the scope of the present invention is not limited by these Examples.

Note that the reduced viscosity (η., /C) in the examples is a value measured at 25° C. for a sulfuric acid solution with a concentration of 0.5 g/dl. Additionally, measurements of tensile properties and notched Izod impact strength (N1) were conducted using ASTM D63, respectively.
8 and ASTM D256.

Example 1 A four-neck separable flask with an internal volume of 2 liters was equipped with a stirrer, a nitrogen inlet tube, a thermometer, and an air condenser.
゜ -Dichlorobenzophenone 256oOg (1.02
mole), hydroquinone 110. 1 g (1.0
0 mol), triphenylphosphine 2. 62 g (
0. 01 mol) and 680 g of diphenylsulfone were charged.

Stir these raw materials under a nitrogen stream and heat them to 180°C to form a solution, and add 145% of anhydrous potassium carbonate.
．． 5 g (1.05 mol) was added. temperature 2
00°C and at that temperature for 1 hour, then increase the temperature to 250°C.
℃, and at that temperature for 4.5 hours, and finally the temperature was increased to 290℃.
The temperature was raised to 0.degree. C., and the sublimate adhering to the upper part of the flask was scraped off with a spatula, and the temperature was maintained for 1.2 hours to obtain a reaction mixture in a solution state.

The reaction mixture was poured into 10 liters of vigorously stirred water in a large mixer without losing fluidity. The resulting slurry was centrifuged to isolate the wet solids. After sequentially washing the wet solid twice with boiling acetone, three times with water, and twice with acetone/methanol, the obtained solid was vacuum dried at 140° C. for one day and night until the reduced viscosity was x. 43
Powdered aromatic polyether polymer with dl/g 279
I got g. The obtained aromatic polyether polymer was
It was extruded at 0°C and pelletized. The beret 3
Injection molding was performed at 90°C to create various test pieces for physical measurements.

Table 1 shows the physical property values obtained for the test piece.

Examples 2 to 5 Reaction, post-treatment, pelletization, and injection were carried out in the same manner as in Example 1, except that 0.01 mol of triphenylphosphine in Example 1 was changed to the type and amount of the organic phosphorus compound shown in Table 1. A test piece was prepared by molding.

Table 1 shows the physical property values obtained for these test pieces.

Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that triphenylphosphine was not used. The viscosity of the reaction system increased rapidly during the reaction at 290°C, and the viscosity reached the specified level in 10 minutes after reaching this temperature. It has reached . Thereupon, the reaction was stopped, and post-treatment, pelletization, and injection molding were performed in the same manner as in Example 1 to prepare test pieces. A test piece was prepared by pelletizing and injection molding.

Table 1 shows the physical property values obtained for these test pieces.

Comparative Example 2 The reaction was carried out in the same manner as Comparative Example 1, except that the reaction continued even when the predetermined viscosity was reached.
At 0 minutes, the reaction mixture became lumpy and could no longer be stirred due to gelation.

Claims (2)

[Claims] (1) In a method for producing an aromatic polyether polymer by heating a dihalogenobenzenoid compound and hydroquinone in the presence of an alkali in an organic solvent, the reaction is carried out in the presence of an organic phosphorus compound. A method for producing an aromatic polyether polymer characterized by: (2) The method for producing an aromatic polyether polymer according to claim 1, wherein the organic phosphorus compound is a compound represented by the following general formula [I], [II] or [III]. P(Ar)_3…………[I] P(OAr)_3…………[II] O=P(OAr)_3…………[III] (In the formula, Ar is a monovalent aromatic residue (represents the group)