JPH03122120A - Production of aromatic polyether polymer - Google Patents

Abstract

PURPOSE:To obtain the title high-molecular weight polymer while suppressing side reactions such as gelatinization in reacting a dihalogenobenzene compound with a dihydric phenol in the presence of an alkali under heating by adding a specific organic solvent. CONSTITUTION:100 pts. wt. aromatic sulfone (preferably diphenylsulfone) is blended with 1-20 pts. wt. solvent (preferably benzophenone) having 270-330 deg.C boiling point, the mixed solvent is used as a reaction solvent and a dihalogenobenzenoid compound [preferably bis(4-chlorophenyl)ketone] is reacted with a dihydric phenol (preferably hydroguinone) under heating in the presence of an alkali in the solvent. The reaction is carried out preferably at 250-350 deg.C and the temperature is gradually raised from low temperature in terms of prevention of side reaction, etc.

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, to a method for producing a high molecular weight aromatic polyether from a dihalogenobenzenoid compound and a dihydric phenol. The present invention relates to a method for producing a 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 widely used as molding materials. Applications are expanding in many directions.

Various methods have been known to produce such aromatic polyether polymers, among which a method of heating a dihalogenobenzenoid compound and a dihydric phenol in the presence of an alkali in an organic solvent (particularly a method) is known. Kaisho 59-9372
4) 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. This causes problems such as the molecular weight of the produced polymer not being sufficiently increased or undesirable side reactions such as gelation of the produced polymer occurring.

In addition, in these methods, difluorobenzenoid compounds are generally used as dihalogenobenzenoid compounds, but when economically advantageous dichlorobenzenoid 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]

The purpose of the present invention is to provide a method for producing a high molecular weight aromatic polyether polymer by suppressing undesirable side reactions such as gelation in the reaction of dihalogenobenzenoid compounds, particularly dichlorobenzenoid compounds, and dihydric phenol. It is on offer.

[Means to solve the problem]

The present inventors have demonstrated the production of aromatic polyether polymers based on the economically superior method of reacting a dihalogenobenzenoid compound with a dihydric phenol in the presence of an alkali in organic mB. As a result of intensive research in order to achieve the above purpose, we found that by using a mixed solvent in which 1 to 20 parts by weight of a solvent with a boiling point of 270 to 330 ° C was added to 100 parts by weight of aromatic sulfone as a solvent. The present inventors have discovered that it is possible to obtain a high molecular weight aromatic polyether polymer without causing side reactions such as gelation, while suppressing the deviation from the optimum conditions, and have completed the present invention.

That is, the present invention provides a method for producing an aromatic polyether polymer by thermally reacting a dihalogenobenzenoid compound and a dihydric phenol in the presence of an alkali in an organic solvent, in which aromatic sulfone 100 is used as the organic solvent.
This method of producing an aromatic polyether polymer is characterized by using a mixed solvent in which 1 to 20 parts by weight of a solvent having a boiling point of 2706C to 330C is added to the parts by weight.

The dihalogenobenzenoid compound in the present invention is a compound represented by the following (-Cill CI).

(wherein, Represents a hydrocarbon group and may be the same or different from each other. a and b are integers of 0 to 4 and may be the same or different, and n is an integer of 1 to 3.) Specific examples of dihalogenobenzenoid compounds represented by include bis(4-chlorophenyl)sulfone, bis(4-fluorophenyl)sulfone, bis(4-bromophenyl)sulfone, bis(4-iodophenyl)sulfone, Bis(2-chlorophenyl)sulfone, bis(2-fluorophenyl)sulfone, bis(3
, 5-dimethyl-4-chlorophenyl) sulfone, bis(3,5-dimethyl-4-fluorophenyl) sulfone, bis(4-chlorophenyl) ketone, bis(4-fluorophenyl) ketone, bis(4-bromophenyl) Ketone, bis(4-iodophenyl)ketone, bis(2-
chlorophenyl)ketone, bis(2-fluorophenyl)ketone, bis(3,5-dimethyl-4-chlorophenyl)ketone, bis(3,5-dimethyl-4-fluorophenyl)ketone, sup(4-chlorophenyl)sulfoxide , bis(4-fluorophenyl) sulfokide, bis(4-bromophenyl) sulfoxide, bis(4-iodophenyl) sulfoxide, bis(2-chlorophenyl) sulfoxide, bis(2-fluorophenyl) sulfoxide, bis(3,5 -dimethyl-4-chlorophenyl) sulfoxide, bis(3,5-dimethyl-4-fluorophenyl) sulfoxide, bis(4-nitrophenyl) ketone, bis(4-nitrophenyl) sulfone, bis(4-nitrophenyl) sulfoxide , bis-1,4
-(4-chlorobenzoyl)benzene and the like.

Among these, preferred dihalogenobenzenoid compounds are bis(4-chlorophenyl)ketone, bis(3,5dimethyl-4-chlorophenyl)ketone, and bis-1,4-
(4-chlorobenzoyl)benzene, more preferably bis(4-chlorophenyl)ketone. Also,
The above dihalogenobenzenoid compounds may be used alone or in combination of two or more.

In the present invention, the dihydric phenol to be reacted with the dihalogenobenzenoid compound is a compound represented by the following general formula (II).

H〇-A r -OH---[II] to 8 hydrocarbon groups, which may be the same or different from each other (, c
-e is an integer from 0 to 4, f and g are integers from 0 to 3 and may be the same or different, Y is a single bond, -〇--s--5
o--s○.

selected from C--C-, R is hydrogen, carbon 1 Specific examples of the dihydric phenol represented by the above -killing [■] include hydroquinone, Hydroxynaphthalene, 1,7-hydroxynaphthalene, 2゜7-hydroxynaphthalene, 4,4'-diphenol, 22'-diphenol,
Bis(4-hydroxyphenyl)ether, bis(2-
hydroxyphenyl)ether, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(3,5 -dimethyl-4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, 2,2
-bis(4-hydroxyphenyl)hexafluoropropane, 11-bis(4-hydroxyphenyl)ethane, and the like.

Among these, preferred dihydric phenols are hydroquinone, 4,4'-diphenol, and bis(4hydroxyphenyl)ketone, and more preferred is hydroquinone.

Moreover, the above-mentioned dihydric phenols may be used alone or in combination of two or more kinds.

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 aromatic sulfone used in the present invention has the following general formula C
Mention may be made of aromatic sulfones represented by IIN.

Here, Q is a direct bond, an oxygen atom, or two hydrogen atoms, one bonded to each benzene ring, and R and R'
is 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 [I[I] include diphenylsulfone, dibennothiophene dioxide, phenoxathiin dioxide, and 4-phenylsulfonylbiphenyl. A preferred aromatic sulfone is diphenyl sulfone.

As the solvent having a boiling point of 270° C. to 330° C. to be added to the aromatic sulfone, an organic solvent that is thermally stable and does not react with the monomer or alkali at the polymerization temperature is desirable. Examples of such solvents include ■=ethoxynaphthalene, 2-ethoxynaphthalene, 1,2-dimethylnaphthalene, 1-methoxynaphthalene, ■, 4-dimethylnaphthalene, 1,6-
Dimethylnaphthalene, 2,3-dimethylnaphthalene, 2
-methoxynaphthalene, 2,6-dimethylnaphthalene,
Naphthalene compounds such as 2,7-dimethylnaphthalene, long chain saturated aliphatic alkanes such as pentadecane, hexadecane, heptadecane, nonadecane, benzophenone derivatives such as benzophenone, 2-methylbenzophenone, 4-methylbenzophenone; Examples include 1-diphenylethane and 1,2-diphenylethane.

Among these, preferred are 1-ethoxynaphthalene and 2-ethoxynaphthalene.
Ethoxynaphthalene and benzophenone are preferred, and benzophenone is more preferred.

Added to 100 parts by weight of aromatic sulfone, with a boiling point of 2
As for the amount of solvent at 70 to 330°C, if it is less than 1 part by weight, the effect will not be sufficient, and if it exceeds 25 parts by weight, the polymer will precipitate midway through and the polymerization will not proceed any further (so, it will not be effective for aromatic sulfones. It is preferable to add 1 to 25 parts by weight. Particularly preferably, 1 to 20 parts by weight is added to the aromatic sulfone.
It is best to add parts by weight.

In carrying out the method of the present invention, the dihalogenobenzenoid compound and the dihydric phenol are used in a ratio of approximately equimolar. It may be preferable to use an excess of 1 to 5 mol%.

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

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 generally a time in the range of 1 to 24 hours is 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 solvent that dissolves the organic solvent but not the resulting polymer. Examples of such organic solvents include ketones such as methyl ethyl ketone and acetone, alcohols such as methanol, ethanol, and propatool;
Examples include ethers such as ethyl ether, tetrahydrofuran, and dioxane. Among these, preferred organic solvents are acetone and methanol. The washing is preferably carried out under heating conditions, usually under reflux conditions.

In addition to washing with these organic 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 stably obtain a high molecular weight aromatic polyether polymer very economically, and the obtained aromatic polyether polymer takes advantage of its high quality. It can be processed into high-performance films, fibers, various resin molded products, etc., and 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.

The reduced viscosity (η, /C) in the examples is a value measured at 25° C. for a sulfuric acid solution with a concentration of 03 g/dl.

Example 1 62.78 g of bis(4-chlorophenyl)ketone was placed in a four-piece separable flask with an internal volume of 5001 rLl equipped with a stirrer, a nitrogen inlet tube, a thermometer and a near condenser.
(0.25 mol), hydroquinone 27.53 g
(0°25 mol), 176 g of diphenylsulfone and 8.9 g of benzophenone were charged. These raw materials were heated to 210°C while stirring under a nitrogen stream to form a solution, and 137.57 g of anhydrous potassium carbonate (0,
27 mol) was added. 1 hour at that temperature, then increase the temperature to 230°C, 1 hour at that temperature, then reduce the temperature to 230°C.
Increase the temperature to 50°C for 1 hour, then increase the temperature to 27°C.
Increase the temperature to 0°C for 1 hour, and finally increase the temperature to 290°C.
℃ and kept at that temperature for 1 hour to obtain the reaction mixture in solution.

The reaction mixture was poured into vigorously stirred water 31 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 to obtain powdered aromatic polyether polymer 70. .5 g was obtained (98% yield). The obtained polymer was completely dissolved in concentrated sulfuric acid at a concentration of 0.5 g/dl, and the reduced viscosity was 0.88 d//g.

Examples 2 to 4 Aromatic polyether polymers were obtained by carrying out the reaction and post-treatment in the same manner as in Example I, except that 8.9 g of benzophenone in Example 1 was changed to the amount shown in Table 1. The reduced viscosity of this polymer was measured. The results are shown in Table ■.

Comparative Example 1 Same as Example 1 except that benzophenone was not added.
The reaction was carried out in the same manner as in Example 1. Although a large amount of sublimate adhered to the upper part of the flask from 2300C, the reaction continued. Post-treatment was performed in the same manner as in Example 1 to obtain an aromatic polyether polymer. The reduced viscosity of this polymer was measured. The results are shown in Table 1.

Claims (1)

[Claims] In a method for producing an aromatic polyether polymer by thermally reacting a dihalogenobenzenoid compound and a dihydric phenol in the presence of an alkali in an organic solvent, based on 100 parts by weight of aromatic sulfone as the organic solvent, A method for producing an aromatic polyether polymer, comprising using a mixed solvent containing 1 to 20 parts by weight of a solvent having a boiling point of 270 to 330°C.