JPH04159329A - Carboxylated arylene sulfide copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain the title copolymer excellent in heat resistance, moldability, dimensional stability, dyeability, adhesion to another resin and/or an inorganic filler, bondability and compatibility by selecting a carboxylated arylene sulfide copolymer having specified properties. CONSTITUTION:A carboxylated arylene sulfide copolymer having a melting point of 180 deg.C or above and a dynamic viscosity coefficient of 10-10<5>p as measured under the conditions of a temperature 20 deg.C higher than the melting point and a rotational speed of 10rad/sec is selected.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel arylene sulfide copolymer and a method for producing the same. More specifically, the present invention is suitable as a material for various molded products, films, fibers, electric/electronic parts, etc., has excellent heat resistance, moldability, dimensional stability, dyeability, etc., and has other properties. The present invention relates to an arylene sulfide copolymer having good adhesion, adhesion, and compatibility with resins and/or inorganic fillers, and a method for producing the same.

(Prior art) As a method for producing an arylene sulfide copolymer having a carboxyl group, for example, in a polar solvent, (1) a dino-logeno aromatic compound, (2) an alkali metal sulfide, and (3) A method of contacting a dihalogeno aromatic carboxylic acid and/or an alkali metal salt thereof is disclosed in JP-A-63-305131. However, this method has various problems. For example, in the production of arylene sulfide copolymers, which are easily available and industrially advantageous alkali metal sulfides, the hydration water of alkali metal sulfides may inhibit the polymerization reaction or act as a reaction solvent. cause side reactions. To prevent this, it is necessary to remove the hydration water, but this requires special equipment, and in the case of alkali metal sulfides, it is difficult to remove the hydration water. It is also difficult to suppress side reactions such as decomposition of the solvent that occur during this dehydration step. Furthermore,
This method has the problem that side reactions of the carboxyl group of the dihalogeno aromatic carboxylic acid tend to occur, and when an alkali metal salt is used to suppress this side reaction, the salt is easily available industrially. Since it does not enter, new problems such as specialization of reaction equipment and production of salt arise, which is not advantageous from an industrial perspective.

Also, JP-A-58-185625 and JP-A-58
Publication No. 185626 describes the combination of a halothiophenol compound and a hydrogen halide scavenger, in which hydrogen, halogen, nitro group, amino group, alkyl group, carboxyl group, etc. are exemplified as substituents that can be bonded to the benzene nucleus. combination, or the halotiophenol salt with a nickel compound or a divalent or zero-valent, f-radium complex compound (X
Disclosed is a method for producing polyarylene sulfide characterized by the reaction in the presence of a catalyst.
Le.

This method is an excellent method in that it performs the reaction at normal pressure and at a relatively low temperature, but it is difficult to implement industrially because it uses raw materials and catalysts that are expensive and difficult to obtain. is disadvantageous.

(Problems to be Solved by the Invention) The present invention solves the problems that cannot be solved by conventional techniques as described above, and improves heat resistance, moldability, dimensional stability,
To provide a carboxyl group-containing arylene sulfide copolymer that has excellent dyeability, etc., and has good adhesion, adhesion, and eye solubility with other wood grains and/or inorganic fillers; The object of the present invention is to provide an industrially advantageous manufacturing method for this product.

(Means for Solving the Problems) The present inventors have made extensive studies to achieve the above object, and have completed the present invention.

That is, the present invention has the following features: 1. A carboxyl group-containing arylene sulfide copolymer having a melting point of 180° C. or higher) and a dynamic viscosity [η′ measured at 10 rad/sec at 180° C. or higher] of 10 to 101 poise;
and 2. In a polar solvent ζ, (A) dino\rogeno aromatic compound, (B) alkali metal hydrosulfide compound, <
C> Provides a method for producing an arylene sulfide copolymer, which comprises reacting an alkali metal hydroxide and (D) a dihalogeno aromatic carboxylic acid.

The carboxyl group-containing arylene sulfide copolymer of the present invention has a melting point of 180"C or higher, and a dynamic viscosity [η' The arylene sulfide unit containing a carboxyl group preferably ranges from 0.1 to 30+no1%, more preferably from 0.5 to 1511101%, based on the total arylene sulfide unit. It is a certain copolymer.If the uni-cut of arylene sulfide containing a carboxyl group is less than 0.1 mo1%, the adhesion with other resins and/or inorganic fillers, which is the object of the present invention, is improved. The effect of improving adhesion, compatibility, etc. is small, and 30mo
If it exceeds 1%, heat resistance and mechanical strength may decrease.

The average degree of polymerization of the copolymer is preferably 10 or more, more preferably 20 or more.

The method for producing this copolymer involves adding (A) a dihalogeno aromatic compound, (B) an alkali metal hydrosulfide compound, (C) an alkali metal hydroxide, and (D) A method of reacting with a dihalogeno aromatic carboxylic acid can be mentioned. Although the polymerization reaction is preferably carried out in an anhydrous system in the initial stage, water may be present in an amount up to about 5 times the mole of the alkali metal hydrosulfide compound. There is also no particular restriction on the order in which the raw materials are added to the polar solvent, but preferably (B) the alkali metal hydrosulfide compound and (C) are added in the polar solvent in advance.
After preparing a mixed solution by reacting the alkali metal hydroxide and dehydrating the generated water and the originally contained hydration water by a dehydration operation such as azeotropic distillation, this and (A) the dihalogeno aromatic compound and ( D) It is desirable to react with a dihalogeno aromatic carboxylic acid.

The polar solvent used is preferably an organic polar solvent that is substantially liquid at that temperature and pressure. Specifically, formamide, acetamide, N-methylformamide, N,N-dimethylacetamide, N, N-
dimethylformamide, N-ethylpropionamide,
N, N-dipropylbutyramide, 2-pyrrolidone, N-methyl-2-pyrrolidone, ε-caprolactam,
Amides, ureas and lactams such as N-methyl-ε-caprolactam, N, N'-ethylenedi-2-pyrrolidone, hexamethylphosphoramide, tetramethylurea, 1,3-dimethyl-2-imidazolidinone: sulfolane , dimethylsulfolane, 1-methyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane and other sulfolanes; benzonitrile and other nitriles; methylphenylketone and other ketones; 1-methyl-1-oxophosphane , 1-n-n-propyl-1-oxophosphane, 1-phenyl-1-oxophosphane, and other cyclic organic phosphorus compounds, and mixtures thereof. Among these solvents, amides and lactams are preferred, and N-methylpyrrolidone is particularly preferred. The amount of the polar solvent used is in the range of 1 to 20, preferably in the range of 2 to 10, as a weight ratio to the total amount of the raw material components (A) to (D).

If the amount of the solvent is less than 1, the reaction may become non-uniform, and if it exceeds 20, productivity may be reduced.

Examples of the dihalogeno aromatic compound (A) used in the present invention include dihalobenzenes such as 0-dihalobenzene, m-dihalobenzene, and p-dihalobenzene: 2
,3-dihalotoluene, 2゜5-dihalotoluene/,2
, 6-cyhalotoluene, 3.4-dihalotoluene, 2,
5-dihaloxylene, 1-ethyl-2,5-dihalobenzene, 1°2, 4. Dihalogenoalkyl- or cycloalkyl-substituted benzenes such as 5-tetramethyl-3,6-dihalobenzene, 1-n-n-hexyl-2,5-dihalobenzene, 1-cyclohexyl-2,5-dihalobenzene; 1-phenyl-2 , 5-dihalobenzene, 1
-benzyl-2+ 5 2 /% lobenzene, 1-p
-Dihalogenoaryl-substituted benzenes such as -tolyl-2,5-dihalobenzene; dihalogenobiphenyls such as 4.4'-dihalobiphenyl; 1,4-dihalonaphthalene, 1,6-di/\lonaphthalene, Examples include dihalogenonaphthalenes such as 2,6-dihalonaphthalene.

The two halogen elements in these dihalogeno aromatic compounds are fluorine, chlorine, bromine, or iodine, and may be the same or different.

Among the dihalogeno aromatic compounds, dichloronzenes are preferred, and p-dichlorobenzene is particularly preferred.

Examples of the alkali metal hydrosulfide compound (B) used in the present invention include lithium bisulfide, sodium bisulfide, potassium bisulfide, rubidium bisulfide, cesium bisulfide, etc., but each of these may be used alone. It is also possible to use a mixture of two or more kinds. Furthermore, the alkali metal hydrosulfide compound may be used in any of anhydrous form, hydrate form, and aqueous solution; however, when using a hydrate or aqueous solution, it is better to perform a dehydration operation before the reaction as described below. .

Among the alkali metal hydrosulfide compounds, sodium hydrosulfide and potassium hydrosulfide are preferred, and sodium hydrosulfide is particularly preferred.

Examples of the alkali metal hydroxide (C) used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide.

Each may be used alone, or two or more types may be used in combination.

Among the above alkali metal hydroxide compounds, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferred;
Particularly preferred is sodium hydroxide.

The dihalogeno aromatic carboxylic acid (D) used in the present invention is, for example, in the form (wherein, each of Xl and X is a halogen atom, and they may be the same or different from each other). Good. Y is just a bond, -
0-1-S-5-so, -, -co-1-CH, -1-
C(CH,), -, etc. ) and the like.

Specific examples of the compound represented by the above formula (I) include 2
, 3-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,
5-dihalobenzoic acid, 2,6-dihalobenzoic acid, 3,4
Examples include dihalobenzoic acids such as -dihalobenzoic acid and 3,5-dihalobenzoic acid.

Specific examples of the compound represented by the above formula (Il) include:
4. 4'-dihalobiphenyl-2-carboxylic acid, 4
．． 4'-dihalobiphenyl-3-carboxylic acid, 2,
4''-dihalobiphenyl-(3,4,5 or 6)-carboxylic acid, 3.4'-dihalobiphenyl=(2,4
, 5 or 6)-carboxylic acid, 2.4'-dihalobiphenyl-(2', 3115' or 6')-carboxylic acid, 3. 4'-dihalobiphenyl-(2', 3', 5
' or 6')-carboxylic acid, 2. 3'-dihalobiphenyl-(2'', 4', 5'' or 6'')-carboxylic acid, 2゜3-dihalobiphenyl-(4,5 or 6)-
Carvone L 3,3'-dihalobiphenyl-(2,4
, 5 or 6)-carboxylic acid, 2,2'-dihalobiphenyl-(3,4,5 or 6)-carboxylic acid or the biphenyl group in the above compound is a diphenyl ether group, diphenyl sulfide group, diphenyl sulfone group,
These include compounds substituted with diphenylketone group, diphenylmethane group, and 2,2-diphenylfuropane group.

Specific examples of the compound represented by the above formula (m) include 2
, 5-dihalonaphthalene-1-carboxylic acid, 2. 6-
Cyhalonaphthalene-1-carboxylic acid, 2,7-dihalonaphthalene-1-carboxylic acid, 2゜8-dihalonaphthalene-1-carboxylic acid, 3,5-dihalonaphthalene-1-carboxylic L 3,6 -Cyhalonaphthalene-1-carvone L 3,7-cyhalonaphthalene-1-carvone L
3,8-dihalonaphthalene-1-carboxylic acid, 4. 6
-Cyhalonaphthalene-1-carboxylic acid, 4,7-cyhalonaphthalene-1-carboxylic acid L 4,8-dihalonaphthalene-1-carboxylic acid, 1. 5-dihalonaphthalene-
2-carboxylic acid, 1. 6-cyhalonaphthalene-2-carboxylic acid, 1,7-cyhalonaphthalene-2-carboxylic acid, 3,7-cyhalonaphthalene-2-carboxylic acid, 3.
8-dihalonaphthalene-2=carboxylic L 4,6-cyhalonaphthalene-2-carboxylic acid, 4.7-cyhalonaphthalene-2-carboxylic acid, 4. Examples include s-dihalonaphthalene-2-carboxylic acid.

The two halogen atoms in the dihalogeno aromatic carboxylic acid mentioned above are fluorine, chlorine, bromine or iodine, and these may be the same or different from each other. Furthermore, in the above-mentioned dihalogeno aromatic carboxylic acid, a functional group with low reactivity such as an alkyl group or an alkoxyl group may be introduced into the aromatic ring without departing from the purpose of the present invention.

In each of the above compounds, compounds in which one or more carboxyl groups are further introduced at appropriate positions can also be used.

Further, each of the above dihalogeno aromatic carboxylic acids may be used alone, or two or more types may be used in combination.

Among the dihalogeno aromatic carboxylic acids, dihalobenzoic acids are preferred, and 2,4-dichlorobenzoic acid is particularly preferred.

In the method of the present invention, a catalyst may be used as necessary within a range that does not depart from the purpose thereof. Examples of the catalyst include lithium halides such as lithium chloride and lithium bromide; lithium carboxylates such as lithium formate and lithium acetate; and lithium compounds such as lithium carbonate, lithium oxide, and lithium sulfide. Among the above lithium compounds, lithium chloride, lithium acetate, and lithium carbonate are preferred. In the present invention, each of the above lithium compounds may be used alone, or two or more types may be used in combination.

The usage ratio of the various raw material components mentioned above in the method of the present invention is (
A) dihalogeno aromatic compound (amol), (B) alkali metal hydrosulfide compound (bmol), (C) alkali metal hydroxide (cmol) and (D) dihalogenoaromatic carboxylic acid (d mol) -(A ) component and (D)
The ratio of the components is usually 0.001≦d/(a+cl)≦
0.5, preferably 0°01≦d/(a+cl)
≦0.4, more preferably 0.02≦d/(a+d)
≦0.3. If the proportion of component (D) used is too small and deviates from the above range, the adhesion between the copolymer and other resins and/or inorganic fillers, which is the object of the present invention, may deteriorate.
If the effect of improving adhesion, compatibility, etc. is not sufficiently exhibited, and if the proportion of component (D) used is too large, heat resistance will decrease.

The ratio of (A) component + (D) component and (B) component is usually:
0.75≦(a+d)/b≦2.0, preferably 0.75≦(a+d)/b≦2.0.
90≦(a+6)/b≦1.2.

The ratio of component (B), component (C) and component (D) is (c-
It is preferable that b)≧d, and carrying out the reaction at this ratio has the effect of preventing side reactions of the carboxyl group of the dihalogeno aromatic carboxylic acid.

Furthermore, when a lithium compound or the like is used as a catalyst, the catalyst (emol) is (B) an alkali metal hydrosulfide compound (
bmol), usually e/b≦2.0, preferably e/b≦1.6. If the amount of this catalyst exceeds the above range, the catalytic effect will not be sufficiently exerted in proportion to the amount, and the catalyst may remain at a high concentration in the produced copolymer, making the cleaning process more complicated. invite

In the production method according to the present invention, the polar solvent of the raw material component, (
A) dihalogeno aromatic compound, (B) alkali metal hydrosulfide compound, (C) alkali metal hydroxide, and (D) dihalogeno aromatic carboxylic acid, all of which are inexpensive and easily available as an industrial vegetable, are used. Moreover, in this production method, dehydration of hydration water and the like is easy, and side reactions such as decomposition of the solvent and side reactions of carboxyl groups can be suppressed.

In addition, within the scope of the purpose of the present invention, polymerization of active hydrogen-containing halogeno aromatic compounds, polyhalogen aromatic compounds, halogeno aromatic nitro compounds, branching agents or molecule 1 regulators, metal salts, etc. The reaction can also be carried out by appropriately selecting additives, reducing agents, inert organic solvents, etc. and adding them to the reaction system.

The above-mentioned active hydrogen-containing halogen aromatic compound refers to a halogen aromatic compound having a functional group having active hydrogen, such as an amine group, a thiol group, or a hydroxyl group,
Specifically, dihaloanilines such as 2,3-dichloroaniline, 2,4-dichloroaniline, 2°5-dichloroaniline, and 2,6-cycloaniline; 2. 3. 4
- trichloroaniline, 2. 3. 5-trichloroaniline, 2, 3. 6-trichloroaniline, 2.
4. 5-trichloroaniline, 2. 4. 6-trichloroaniline, 3. 4. Trihaloanilines such as 5-trichloroaniline; 2. 3. 4. 5-tetrachloroaniline, 2. 3. 5. Tetrahaloaniline U such as 6-tetrachloroaniline; 2,2'-diamino-4,4''-dichlorodiphenyl ether, 2
．． Examples include dihalodiamino diphenyl ethers such as 4'-diamino-2' and 4-dichlorodiphenyl ether; and compounds in which the amine group is substituted with a thiol group or a hydroxyl group. It is also possible to use active hydrogen-containing halogen aromatic compounds in which the hydrogen atom bonded to the carbon atom forming the aromatic ring in these active hydrogen-containing halogen aromatic compounds is substituted with an inert group such as an alkyl group. . Among these various active hydrogen-containing halogenoaromatic compounds, active hydrogen-containing dihalogenoaromatic compounds are particularly useful, and dichloroaniline is particularly preferred.

The above-mentioned polyhalogeno aromatic compound is a compound in which an aromatic ring is substituted with three or more halogen atoms, and specifically, 1,2,4-trichlorobenzene, 1. 3. 5-
Examples include trichlorobenzene and 1,4°6-trichloronaphthalene.

Further, the above-mentioned halogeno aromatic nitro compound is a compound in which a halogen atom is substituted on an aromatic ring having a nitro group, and specifically, 2,4-dinitocochlorobenzene, 2
．． Mono- or dihalonitrobenzenes such as 5-dichloronitrobenzene; dihalonitrodiphenyl ethers such as 2-nitro-4,4'-dichlorodiphenyl ether; Dihalonitrodiphenyl sulfones: 2
, 5-dichloro-3-nitropyridine, 2-chloro-3
, 5-dinitropyridine and other mono- or dihalonitropyridines; and various dihalonitronaphthalenes.

By using these active hydrogen-containing halogen aromatic compounds, polyhalogeno aromatic compounds, halogeno aromatic nitro compounds, etc., it is possible to increase the degree of branching and molecular weight of the copolymer produced as necessary. Alternatively, various physical properties of the copolymer can be improved, such as by reducing the residual salt content.

In addition to the above-mentioned compounds, compounds having three or more reactive halogen atoms, such as cyanuric chloride, can also be used as branching agents or molecular TG regulators. In the present invention, one type of these branching agents or molecular ffi regulators may be used alone, or two or more types may be used in combination.

Polymerization additives such as the metal salts mentioned above include metal carboxylates such as sodium acetate, potassium acetate, and zinc acetate; potassium metal mineral salts and alkaline earth metal mineral salts such as sodium phosphate; benzenesulfonic acid; Examples include alkali metal sulfonates such as sodium. These metal salts may be used alone or in combination of two or more.

Examples of the reducing agent include hydrazine and metal hydrides. Among these, metal hydrides are preferred, and among these, sodium borohydride, calcium hydride, etc. are particularly preferred.

Furthermore, as the above-mentioned inert solvent, benzene, toluene,
Examples include hydrocarbons such as xylene, biphenyl, anthrace, and ethers such as diphenyl ether and polyethylene glycol. Among these, solvents with a high boiling point are preferred since the reaction is carried out at a relatively high temperature.

Next, to explain an example of a preferred method in the embodiment of the present invention, first, (B) an alkali metal hydrosulfide compound and (C) an alkali metal hydroxide are mixed in a polar solvent,
After heating as necessary and performing dehydration operations such as azeotropic distillation, (A) dihalogeno aromatic compound and (D) dinologeno aromatic carboxylic acid are added simultaneously or separately,
Usually heated to a temperature of 150-300°C, preferably 180-280°C for 0.1-40 hours, preferably 0.5-40 hours.
The polymerization reaction is carried out by heating for 20 hours. This reaction temperature is 1
If it is less than 50°C, the reaction rate is slow and the reaction may become non-uniform, while if it exceeds 300°C, side reactions such as decomposition of carboxyl groups or deterioration of the produced polymer will occur. In addition, the reaction time cannot be determined unconditionally because it depends on the type and amount of raw materials used and the reaction temperature.
If the heating time is less than 0.1 hour, there is a high possibility that the produced polymer will have a low molecular weight, and if the heating time exceeds 40 hours, the productivity will decrease.

This polymerization reaction is usually preferably carried out under an inert gas atmosphere such as nitrogen, helium, or argon, and nitrogen is particularly preferred from the viewpoint of economy and ease of handling.

There is no particular limit to the reaction pressure as it depends on the types and amounts of the raw materials and solvents used, the reaction temperature, etc., so there is no particular limit, but it is usually under the autogenous pressure of the polymerization reaction system or 40 kg/am'' or less. It is preferable to do so.

Further, the reaction may be a one-stage reaction carried out at a constant temperature, a multi-stage reaction in which the temperature is raised stepwise, or a reaction in which the temperature is continuously changed.

The produced copolymer may be separated directly after the completion of the reaction by a commonly used method, such as filtration or centrifugation, or alternatively, after the completion of the reaction, the reaction solution may be added to water or an aqueous solution of an acid, followed by filtration, etc. It may be separated by the following method.

The isolated copolymer is then washed, usually with water or warm water, or with a relatively low boiling point organic solvent such as methanol, ethanol, acetone, ether, or THF, to remove the raw materials adhering to the copolymer. be done. The use of a relatively dilute aqueous acid solution during cleaning is effective in removing adhering sodium hydroxide, etc. Among them, it is preferable to use dilute hydrochloric acid for ease of handling and economic efficiency.

The thus isolated copolymer is dried by heating to a temperature at which the solvent such as water substantially evaporates. Drying may be carried out under vacuum, in air or under an inert gas atmosphere such as nitrogen.

The copolymers obtained in this way can be used as they are for various molding materials, etc., but they can also be thickened by heat treatment in air or oxygen-enriched air, and such copolymers can be used as necessary. It may be used for various molding materials etc. after performing a viscosity-increasing operation. Moreover, this heat treatment temperature is 20
It is preferably 0°C or higher and lower than the melting point of the copolymer. If the heat treatment temperature is less than 200° C., the rate of viscosity increase is very slow and productivity is poor, and if the heat treatment temperature is above the melting point of the copolymer, the operation is virtually impossible.

The copolymer obtained by the present invention can be directly injection molded,
By various melt processing methods such as extrusion molding, compression molding, and blow molding, molded products with excellent heat resistance, moldability, dimensional stability, etc. can be obtained.

However, in order to further improve performance such as strength, heat resistance, and dimensional stability, it is also possible to use it in combination with various fillers as long as the purpose of the present invention is not impaired.

Examples of the filler include fibrous fillers and inorganic fillers. Examples of fibrous fillers include glass fiber, carbon fiber,
Silane glass fibers, ceramic fibers, aramid fibers, metal fibers, fibers such as potassium titanate, silicon carbide, calcium sulfate, calcium silicate, natural fibers such as wollastonite, etc. can be used. Inorganic fillers include barium sulfate, calcium sulfate, clay, pyroferrite,
Bentonite, sericite, zeolite, mica, mica, talc, attalbulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass peas, etc. can be used.

In addition, small amounts of mold release agents, colorants, heat stabilizers, ultraviolet stabilizers, foaming agents, rust preventives, flame retardants, lubricants, and cups may be used as additives during molding without departing from the purpose of the present invention. A ring agent can be included. Furthermore, the following synthetic resins and elastomers can be mixed and used in the same manner. These synthetic resins include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, polyarylene, polytetrafluoroethylene, and polydifluoride. Examples of the elastomer include ethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, and urethane resin. Examples of the elastomer include polyolefin rubber, fluorine rubber, and silicone rubber.

(Examples) The present invention will be specifically explained below using Examples, but the present invention is not limited only to these Examples.

Example 1 21 N-Methylpyrrolidone (NMP) in an autoclave
600g, Na5H-xHzO154°7g (2,
0 mol), sodium hydroxide 88.0 g (2.2 m
ol) was charged, and the water-NMP mixture was distilled off by raising the temperature to 200° C. under a nitrogen atmosphere. Next, 2646 g (1.8 mol) of p-dichlorobenzene was added to this system.
, a solution of 38.2 g of 2,4-dichlorobenzoic acid (0,20 city 01) dissolved in 230 g of NMP was added, and 22
The reaction was carried out at 0°C for 5 hours and then at 240°C for 2 hours under a nitrogen atmosphere. After cooling the reaction vessel, the contents were taken out and washed several times with hot water, diluted hydrochloric acid and methanol, and the polymer cake was filtered off. This cake was dried under reduced pressure at 80°C to obtain a white powdery arylene sulfide copolymer.

The melting point of this polymer is 268°C, 290°C, 10
The dynamic viscosity [η'] measured in rad/sec is 2
It was 5 to 60 voices. Furthermore, 250% of this polymer
When heat treated at ℃ for 1 hour, 290℃, 10rad/sec
The dynamic viscosity [η'] measured was 400 to 700 poise.

Example 2 The amount of sodium hydroxide was 84.0 g (2.1 mol)
, the amount of p-dichlorobenzene was 279.3 g (1,
9 mol), the amount of 2,4-dichlorobenzoic acid was 19.1
The same procedure as in Example 1 was carried out except that g (0.10 mol) was used. The melting point of this polymer is 276°C and 300°C
The dynamic viscosity [η'] measured at 110 rad/see was 60 to 100 voids. Furthermore, add this polymer to 2
When heat treated at 50℃ for 2 hours, 300℃, 10 rad
The dynamic viscosity [η'] measured at /sec is 500 to 80
It was 0 poise.

Example 3 The amount of sodium hydroxide was 100.0 g (2.5 m0
1), the amount of p-dichlorobenzene was 222.5 g (1
, 5 mol), and the amount of 2,4-dichlorobenzoic acid was 95.
The same procedure as in Example 1 was carried out except that 5 g (0.50 mol) was used. The melting point of this polymer is 236°C;
Dynamic viscosity measured at 0°C and 10 rad/sec [
η゛] was 20 to 40 voids. Furthermore, when this polymer was heat-treated at 220°C for 2 hours, it was heated to 260°C and 10
The dynamic viscosity [η゛] measured in rad/sec is 350
It was ~650 boise.

Comparative Example 1 P without using 2,4-dichlorobenzoic acid in Example 1
-dichlorobenzene294. Og (2,,0snol
) was carried out in the same manner as in Example 1. Obtained PPS
The melting point of is 280℃, 300℃510rad/se
The dynamic viscosity [η'] measured at c was 200 to 400 voids. Further, when this polymer was heat-treated at 250°C for 10 hours, the dynamic viscosity [η'] measured at 300°C and 10 rad/sec was 600 to 900 voids.

When the infrared absorption spectra of the polymers obtained in Example 1.2.3 and Comparative Example 1 were measured, it was found that Example 1.2.
Absorption was observed near 1700 cm' and 3000 cm'' in Example 3, but not in Comparative Example 1. This is due to the presence of carboxyl groups in the polymer of Example 1.2.3, and shows that it does not exist.

(Effects of the Invention) The present invention has excellent heat resistance, moldability, dimensional stability, dyeability, etc., and also good adhesion, adhesion, and compatibility with other resins and/or inorganic fillers. A carboxyl group-containing arylene sulfide copolymer can be provided, and during the production of this copolymer, dehydration of hydration water is easy, and side reactions such as decomposition of solvents and side reactions of carboxyl groups can be suppressed. Therefore, it can be produced very easily and efficiently (stablely).

Claims (1)

[Claims] 1. The melting point is 180°C or higher and the melting point plus 20°C, 10
Dynamic viscosity [η'] measured in rad/sec is 10~
A carboxyl group-containing arylene sulfide copolymer characterized by having a poise of 10^5. 2. Carboxyl characterized by reacting (A) a dihalogeno aromatic compound, (B) an alkali metal hydrosulfide compound, (C) an alkali metal hydroxide, and (D) a dihalogeno aromatic carboxylic acid in a polar solvent. A method for producing a group-containing arylene sulfide copolymer. 3. In claim 2, (B) an alkali metal hydrosulfide compound, (bmol) and (C) an alkali metal hydroxide (c
mol) and (D) dihalogeno aromatic carboxylic acid (dmo
1) A method for producing a carboxyl group-containing arylene sulfide copolymer in which the ratio of (c-b) to d is within the range of (c-b)≧d. 4. In claim 2, the usage ratio of (A) dihalogeno aromatic compound (amol) and (D) dihalogeno aromatic carboxylic acid (dmol) is 0.001≦(d/(a
+d)) A method for producing a carboxyl group-containing arylene sulfide copolymer in the range of 0.5. 5. The method for producing a carboxyl group-containing arylene sulfide copolymer according to claim 2, wherein the dihalogeno aromatic carboxylic acid (D) is 2,4-dichlorobenzoic acid. 6. A method for producing a carboxyl group-containing arylene sulfide copolymer, which comprises treating the obtained copolymer with an acid after the reaction. 7. A method for producing a carboxyl group-containing arylene sulfide copolymer, which comprises heat-treating the obtained copolymer after the reaction.