JPH01263119A - Production of polyarylene sulfide - Google Patents

Abstract

PURPOSE:To provide the subject polymer having heat resistance, chemical resistance, high strength and low salt content in a short time without using any catalyst, by thermally polymerizing an alkali metal sulfide with a polyhalogenoaromatic compound in the presence of a specific amount of water in a polar solvent, adding water to the polymerization solution and further continue the polymerization reaction. CONSTITUTION:An alkali metal sulfide (e.g., sodium sulfide) and a polyhalogenoaromatic compound (e.g., p-dichlorobenzene) are polymerized in a polar solvent (e.g., N-methylpyrrolidone) by two step polymerization processes to provide the objective polymer. In the first step, the polymerization is performed at 220-300 deg.C in the presence of such an amount of water that the molar ratio of the water to the alkali metal sulfide is <=0.3. In the second step, the polymerization is continued under the same temperature condition as that in the first step, while adding water to the reaction system once or more so that the molar ratio of the water to the metal sulfide in the first step is 5-20.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an improvement in a method for producing polyarylene sulfide. More specifically, the present invention aims to produce high-molecular-weight, white, low-salt polyarylene sulfide, which is useful as engineering plastics with excellent mechanical properties, chemical resistance, heat resistance, etc., without using a catalyst. The present invention relates to a time-consuming and economically advantageous manufacturing method.

[Prior Art] In recent years, polyarylene sulfide, which has a structure in which phenylene groups are connected in a chain through thioether bonds, has been found to have excellent heat resistance and chemical resistance, as well as mechanical properties and
Due to its good flame retardancy, dimensional stability, and workability, it is used in many fields as engineering plastics, such as the automobile field, electric/electronic field, precision machinery field, OA equipment field, and optical communication equipment field. It is widely used in

As a typical method for producing polyarylene sulfide, a method is known in which a dihalogeno aromatic compound and sodium sulfide are reacted in an organic amide solvent such as N-methylpyrrolidone (Japanese Patent Publication No. 45-3368
However, the polyarylene sulfide obtained by this method has a problem that it is difficult to mold into films, sheets, fibers, etc. because the molecular weight is not large enough and the melt viscosity is low.

Therefore, in order to obtain polyarylene sulfide with a high degree of polymerization, various methods have been proposed that are improvements on the above-mentioned methods. For example, a method has been proposed for producing polyarylene sulfide with a high degree of polymerization by adding a trivalent or higher valent polyhalogeno aromatic compound as a splitting agent during polymerization or at the final stage of polymerization (Japanese Patent Publication No. 334/1983).

However, although high molecular weight polyarylene sulfide can be obtained by this method, since this is a crosslinked or branched polymer, it is difficult to mold it into films, fibers, etc. Even if it can be obtained, there are problems such as only those having inferior mechanical properties can be obtained. Further, as a catalyst, a method using an alkali metal carboxylate (Japanese Unexamined Patent Application Publication No. 56-28217, JP-A No. 59-98133) or a method using a lithium compound (Japanese Unexamined Patent Application Publication No. 62-253622)
is proposed.

However, methods using such catalysts inevitably have economic disadvantages, such as the need for catalyst recovery operations and the need to treat wastewater. Moreover, it is difficult to obtain paper salt-containing polyarylene sulfide.
Therefore, in order to obtain polyarylene sulfide for semiconductor encapsulating materials, which particularly requires a low salt content, there are problems such as the need for complicated purification operations.

On the other hand, a method has been disclosed in which water is added to the reaction system in two stages (Japanese Unexamined Patent Publications No. 61-7332, No. 62-1).
However, in this method, the polymerization temperature in the first stage is 180 to 235°C, which is lower than the polymerization temperature in the second stage, 245 to 290"C, so it is difficult to increase the molecular weight. It has the disadvantage of requiring a considerable amount of time.Additionally, there is a step of polymerizing at a relatively low temperature to form an arylene sulfide prepolymer, a step of separating the prepolymer and washing it with an alkaline solution, and a step of washing the washed prepolymer with an organic solvent. A method has been proposed for producing ultra-high molecular weight polyarylene sulfide by sequentially carrying out a step of dispersing the polyarylene sulfide in a polymer and reacting it at high temperature (Japanese Patent Laid-Open No. 6
1-66720), however, this method
Although it is possible to obtain a high molecular weight polyarylene sulfide with a melt viscosity of 10,000 voids or more, it takes a long time to obtain the polyarylene sulfide and the process is complicated, so it cannot be said to be an economically advantageous method. .

In addition, in Japanese Patent Application Laid-open No. 63-39926, 0 per solvent
．． Add 5 moles to less than 5 moles of water, then further IJ
A technique is disclosed to obtain high molecular weight PPS by adding 6 to 15 moles of water per gram. Although it is possible to obtain a product with a high molecular weight using this method, the molecular weight is not high enough to allow terminal modification or terminal inactivation<<, the yield is low, and there is loss due to side reactions of solvents and monomers. There are also major drawbacks.

[Problems to be Solved by the Invention] The present invention overcomes the drawbacks of such conventional methods for producing high molecular weight polyarylene sulfide, and produces white low salt content polyarylene with high molecular weight and good processability. The purpose of this invention is to provide an economically advantageous method for producing sulfide in a short time using simple steps.

[Means for Solving the Problems] As a result of intensive research to achieve the above object, the present inventors have found that by polymerizing under constant temperature conditions and controlling the water-containing lid of the reaction system, They discovered that a white polyarylene sulfide with high molecular weight and good processability can be obtained in a short time without using a catalyst, and it also has a low salt content. Based on this, the present invention has been completed.

That is, in the present invention, when producing polyarylene sulfide by reacting an alkali metal sulfide and a polyhalogeno aromatic compound in the presence of a polar solvent, the molar ratio of water to alkali metal sulfide is 0.5 or less. a first step of polymerizing at a temperature in the range of 220 to 300°C in the presence of water, and a reaction system such that the molar ratio of water to alkali metal sulfide in the first step is 5 to 20; At least two steps consisting of a second step in which water is added at least once to the polymer and the polymerization is continued under the same temperature conditions as the first step.
The present invention provides a method for producing polyarylene sulfide, which is characterized in that the polymerization reaction is carried out in steps.

The present invention will be explained in detail below.

In the method of the present invention, the polyhalogeno aromatic compound used as a raw material monomer is preferably a dihalogeno aromatic compound, such as dihalogenobenzenes such as m-dihalobenzene or p-dihalobenzene, 2,3-dihalotoluene, 2,5-dihalotoluene, etc. , 2.6-dihalotoluene, 3.4-dihalotoluene, 2,5-dihaloxylene, 1-ethyl-2,5-dihalobenzene, 1,
2,4.5-tetramethyl-3,6-dihalobenzene,
1-Normalhexyl-2,5-dihalobenzene, 1-
Dihalogenoalkyl or cycloalkyl substituted benzenes such as cyclohexyl-2,5-dihalobenzene, 1
-phenyl-2,5-dihalobenzene, 1-benzyl-
2,5-dihalobenzene, 1-p-tolyl-2,5-
Dihalogenoaryl-substituted benzenes such as dihalobenzene, dihalogenobiphenyls such as 4,4'-dihalobiphenyl, 1,4-dihalonaphthalene, 1,6-dihalonaphthalene, 2,6-dihalonaphthalene, etc. Examples include dihalogenonaphthalenes.

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

Among the halogen aromatic compounds, dihalobenzenes are preferred, and p-dichlorobenzene is particularly preferred. In the present invention, these dihalogeno aromatic compounds may be used alone or in combinations of 2N or more. It may also be used in combination with other suitable dihalogeno aromatic compounds, such as dihalogeno aromatic carboxylic acids and their alkali metal salts.

The dihalogeno aromatic carboxylic acid and its alkali metal salt include, for example, the general formula (wherein Xl and X2 are each a halogen atom, and they may be the same or different from each other, R is a hydrogen atom or an alkali metal, Y is a simple bond, -0-1S O2-5-S-5-CH, -1
Examples include compounds represented by C(CH*>2- or -〇 (CF sh-).

Specific examples of the compound represented by the above formula (1) include:
2,3-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2
, 5-dihalobenzoic acid, 2,6-dihalobenzoic acid, 3.
Examples include 4-dihalobenzoic acid, 3,5-dihalobenzoic acid, and alkali metal salts thereof. Further, specific examples of the compound represented by the general formula (II) include 4,
4′-dihalobiphenyl-2-carboxylic acid, 4.4°-
Dihalobiphenyl-3-carboxylic acid, 3,4°~dihalobiphenyl=(2,4,5 or 6)-carboxylic acid, 2
．． 4′-dihalobiphenyl-(3,4,5 or 6)-
Carboxylic acid, 3,4'-dihalobiphenyl-(2',
3′, 5′ or 6°)-carboxylic acid, 2.4′-dihalobiphenyl-(2′, 3°, 5° or 6′)-carboxylic acid, 2.3-dihalobiphenyl-(4, 5 or 6)-carboxylic acid, 2,3゛-dihalobiphenyl-(2
", 4°, 5" or 6")-carboxylic acid, 3,3-dihalobiphenyl (2,4,5 or 6)-carboxylic acid,
2,2'-dihalobiphenyl (3,4,5 or 6)-
Carboxylic acids and their alkali metal salts, or biphenyl groups in the above compounds are diphenyl ether groups, diphenylsulfone groups, diphenylthioether groups, diphenylmethane groups, 2,2'-diphenylpropane groups, 1,1,1,3,3. 3-hexafluoro-2
, a compound substituted with a 2-diphenylpropane group, and the like.

Specific examples of the compound represented by the above-mentioned -torido (I[[) include 2.5-dihalonaphthalene-1-carboxylic acid, 2.6
-Cyhalonaphthalene-1-carboxylic acid, 2.7-dihalonaphthalene-1-carboxylic acid, 2.8-dihalonaphthalene-2-carboxylic acid, 3.5-dihalonaphthalene-1-carboxylic acid, 3. 6-Cyhalonaphthalene-1-carboxylic acid, 3.7-cyhalonaphthalene-1-carboxylic acid, 3.8
-dihalonaphthalene-1-carboxylic acid, 4,6-cyhalonaphthalene-1-carboxylic acid, 4,7-cyhalonaphthalene-1-carboxylic acid, 4,8-dihalonaphthalene-1-
Carboxylic acid, 1.5-dihalonaphthalene-2-carboxylic acid, 1.6-cyhalonaphthalene-2-carboxylic acid, 1.
7-cyhalonaphthalene-2-carboxylic acid, 3.5-dihalonaphthalene-2-levonic acid, 3.6-cyhalonaphthalene-2-carboxylic acid, 3.7-cyhalonaphthalene-2-carboxylic acid acid, 3,8-dihalonaphthalene-2-carboxylic acid, 4,6-cyhalonaphthalene-2-carboxylic acid,
4,7-cyhalonaphthalene-2-carboxylic acid, 4.8-
Examples include dihalonaphthalene-2-carboxylic acid and alkali metal salts thereof.

The two halogen atoms in these halogen aromatic carboxylic acids and their alkali metal salts are fluorine, chlorine, bromine, or iodine, and these may be the same or different, or Preferred examples of alkali metal salts include sodium salts and potassium salts.

'Furthermore, as the halogeno aromatic carboxylic acid or its alkali metal salt, compounds in which one or more carboxyl groups or alkali metal salt-type carboxyl groups are further introduced at appropriate positions in each of the above compounds may also be used. be able to.

In the method of the present invention, the halogeno aromatic carboxylic acid or the alkali metal salt thereof may be used alone or in combination of two or more, and those containing free carboxyl groups, Although it is also possible to use an alkali metal salt type, the preferred one is 2.
．． 4-dichlorobenzoic acid and sodium 2,4-dichlorobenzoate.

Further, in the present invention, a trivalent or higher valent polyhalogeno aromatic compound can also be used in combination with the dihalogeno aromatic compound. Examples of the trivalent or higher polyhalogeno aromatic compounds include 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, and 1,2,3,5-tetrahalobenzene. Benzene, hexahalobenzene, 1,3.5-trihalo2,4.6
-) Limethylbenzene, 2.2', 4.4'-tetrahalobiphenyl, 2,2°, 5.5'-tetrahalobiphenyl, 2.2', 6.6'-tetrahalo 3.3'
, 5,5'-tetramethylbiphenyl, 1,2,3.
4-tetrahalonaphthalene, 1,2.4-) rimlow 6
-Methylnaphthalene, etc., which may be used alone or in combination of two or more.Each halogen atom in this polyhalogeno aromatic compound is fluorine, chlorine, bromine or iodine, and these may be the same or different.

When such a polyhalogeno aromatic compound having a valence of 3 or more is used in combination with a dihalogeno aromatic compound, it acts as a branching agent and a branched polyarylene sulfide can be obtained.

Furthermore, in the method of the present invention, in addition to the polyhalogeno aromatic compound, a polyhalogeno aromatic nitro compound or an active hydrogen-containing halogen aromatic compound may be added as necessary to adjust the molecular weight of the resulting polymer, improve the physical properties, etc. They can also be used together for this purpose. Examples of the polyhalogeno aromatic nitro compounds include dihalogenonitrobenzenes and dihalogennitronaphthalenes. Further, the active hydrogen-containing halogen aromatic compound has at least one aromatic ring,
A group having active hydrogen is bonded to at least one of the carbon atoms forming this aromatic ring, and at the same time, a halogen atom is bonded to at least two of the carbon atoms forming the aromatic ring. aromatic compounds can be used. Specific examples of such active hydrogen-containing halogen aromatic compounds include active hydrogen-containing dihalogenobenzenes such as dihalogenoanilines, dihalogenophenols, dihalogenothiophenols, dihalogenophenyl)aminebenzenes, and trihalogenobenzenes. Anilines,
Examples include active hydrogen-containing trihalogen benzenes such as 2,4.5-)-dihalogenothiophenols, trihalogenophenols, trihalogen(phenyl)aminebenzenes, and other diamino dihalogenophenyl ethers. . Furthermore, in the active hydrogen-containing halogeno aromatic compound, the hydrogen atom bonded to the carbon atom forming the aromatic ring is substituted with another inert group, for example, a hydrocarbon group such as an alkyl group. can also be used. Among these active hydrogen-containing halogenoaromatic compounds, dichloroaniline is preferred.

The polyhalogeno aromatic nitro compounds and active hydrogen-containing halogen aromatic compounds may be used alone or in combination of two or more, and each halogen atom in the compound may be fluorine, chlorine, bromine, or iodine. and they may be the same or different from each other.6 In the present invention, in addition to the above-mentioned compounds, three or more branching agents or molecular weight regulators such as siatal chloride may be used. An organic compound having a reactive halogen atom can also be used in combination if necessary.

Examples of the alkali metal sulfide used in the method of the present invention include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, etc. Each of these may be used alone or in combination of two or more. May be used.

Preferred among the alkali gold lff1 compounds are lithium sulfide and sodium sulfide, with sodium sulfide being particularly preferred. Furthermore, the alkali metal sulfide can be used in any form, such as an anhydride, a hydrate, or an aqueous mixture. However, when a hydrate or an aqueous mixture is used, the water content is 0 relative to the alkali metal sulfide. If the amount is more than .5 times the mole, it is necessary to perform a dehydration operation before the reaction so that the amount is 0.5 times the mole or less.

In the method of the present invention, the reaction between the polyhalogeno aromatic compound and the alkali metal sulfide is carried out in a polar solvent in a molar ratio of usually 0.75:1 to 1.30:1, preferably 0.85:1 to 1. .6 If the ratio of both used exceeds the above range, it may not be possible to obtain a high molecular weight polyarylene sulfide.
This is undesirable because side reactions occur and thiophenols are produced.

Examples of the polar solvent include amide compounds, lactam compounds, urea compounds, and cyclic organic phosphorus compounds.
Specifically, N,N-dimethylformamide, N,N-
Dimethylacetamide, N,N-diethylacetamide-N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, caprolactam, tomethylcaprolactam, N-ethylcaprolactam, toisobrovir prolactam, N-isobutylcaprolactam, N- Normal propyl caprolactam, normal butyl prolactam, trichlorhexyl caprolactam, tomethyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-
Isopropyl-2-pyrrolidone, N-isobutyl-Z-
Pyrrolidone, ton-normal broby-2-pyrrolidone, ton-normal butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, tocyclohexyl-Z-pyrrolidone, N-ethyl -3-methyl-2-pyrrolidone, N-methyl-3,4
, 5-1-dimethyl-2-pyrrolidone, N-methyl-2
-piperidone, toethyl-2-piperidone, toisoprobyl-2-piperidone, tomethyl-6-methyl-2-piperidone, tomethyl-3-ethyl-2-piperidone, tetramethylurea, N,N'-diothylethyleneurea, N
, N'-dimethylpropylene urea, 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane,
1-phenyl-1-oxosulfolane, 1-methyl-1
-oxophosphane, 1-normalpropyl-1-oxophosphane, 1-phenyl-1-oxophosphane, and the like. These solvents may be used alone or in combination of two or more. Among the various polar solvents mentioned above, N-alkyl lactams and N-alkylpyrrolidone are preferred, and N-methyl pyrrolidone is particularly preferred. -2-pyrrolidone is preferred.

Regarding the amount of the polar solvent used in the method of the present invention,
There is no particular restriction, as long as the amount is 1.7 mm, which is sufficient for the reaction to proceed uniformly, but it is usually 0.1 mm based on the total weight of the raw material components.
Carried in a range of 1 to 10 times the weight. If this amount is less than 0.1 times the weight, the reaction may become non-uniform;
If the weight exceeds twice the weight, the volume effect will be poor and productivity will be lowered, which is not preferable.

In the method of the present invention, it is necessary to carry out the polymerization reaction in at least two steps.

First, in the first step, the required amount of alkali metal sulfide is added to the desired polar solvent, and if necessary, dehydration is performed by azeotropic distillation, etc., and then the required amount of polyhalogeno aromatic compound is added. Further, the water content of the reaction system is adjusted to be 0.5 times the mole or less, preferably 0.3 times the mole or less, of the alkali gold ffl sulfide.
The polymerization reaction is carried out by heating to a temperature in the range of 0°C. If the water content of the reaction system exceeds 0.5 times the mole of the alkali metal sulfide, many side reactions will occur, making it difficult to obtain high molecular weight polyarylene sulfide, and the quality will deteriorate due to by-products. There is a risk of causing

Next, in the second step, when the residual amount of the raw material polyhalogeno aromatic compound in the first step becomes preferably 15 mol% or less of the initial amount, the water content of the reaction system is reduced to the alkali. Water is added in an amount of 5 to 20 times the amount of metal sulfide, preferably 7 to 15 times in mole,
Continue the polymerization reaction at the same temperature as in the first step. Water may be added at once, or may be added in two or more times. If the water content of the reaction system exceeds the above range, it will be difficult to obtain a high molecular weight polyarylene sulfide. When water is added in this second step, an alkali metal hydroxide may be used in combination, if desired, in order to obtain a polymer with a higher molecular weight.

Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and mixtures thereof.

The polymerization temperature in the second step is the same as the polymerization temperature in the first step. That is, in the method of the present invention, the polymerization temperature is maintained constant in the range of 220 to 300°C throughout the entire polymerization reaction.

If this temperature is less than 220'C, the reaction rate is too slow and polymerization takes a long time, while if it exceeds 300'C, polymer decomposition may occur, side reactions may occur, or solvent may deteriorate. . Furthermore, since the polymerization temperature is the same in both the first step and the second step, the time required to vary the temperature can be saved, and the total polymerization time can be shortened. Furthermore, in the conventional two-step method, the polymerization temperature in the first step is much lower than the second step, in the range of 180 to 235°C, whereas in the method of the present invention, the polymerization temperature in the first step is Since the temperature is as high as 220-300°C, the polymerization time is much shorter than in conventional two-step processes, and the total polymerization time is usually within 20 hours.

In the method of the present invention, high molecular weight polyarylene sulfide can be obtained in a short period of time without using a catalyst, but if desired, a known catalyst may be added as long as it does not impair the purpose of the present invention. . This catalyst may be added in the first step or in the second step. Examples of the catalyst include sodium acetate, sodium propionate, sodium 2-methylpropionate, sodium acetate, sodium valerate, sodium hexanoate,
Sodium heptanoate, sodium 2-methyloctoate, sodium dodecanoate, sodium 4-ethyltetradecanoate, sodium octadecanoate, sodium heneaicosanoate, sodium cyclohexanecarboxylate, sodium cyclododecanecarboxylate,
Sodium 3-methylcyclopentanecarboxylate, sodium cyclohexyl acetate, sodium benzoate, m-
) Sodium ruylate, sodium phenylacetate, 4-
Sodium phenylcyclohexanecarboxylate, sodium p-toluyl acetate, sodium 4-ethylcyclohexyl acetate, alkali metal carboxylates such as potassium salt, lithium salt, rubidium salt, cesium salt, lithium fluoride, lithium chloride, Examples include lithium compounds such as lithium halides such as lithium bromide and lithium iodide, and lithium mineral salts such as lithium carbonate, lithium phosphate, and lithium sulfate. These catalysts may be used alone or in combination of two or more.

In the present invention, if desired, a reducing agent may be added to perform the polymerization reaction. Examples of the reducing agent include metal hydrides such as sodium borohydride and calcium hydride, hydrazine, and alkali formate. Among these, metal hydrides such as sodium borohydride and calcium hydride are preferred.

Furthermore, in the present invention, an inert solvent can be used in combination with the polar solvent if necessary.

Examples of this inert solvent include benzene, toluene, xylene, biphenyl, terphenyl, naphthalene,
Hydrocarbons such as anthracene, diphenyl ether,
Examples include ethers such as p-diphenoxybenzene and polyethylene glycol.

The polymerization reaction in the method of the present invention can be carried out in an atmosphere of an inert gas such as nitrogen, argon, carbon dioxide, or water vapor, and there is no particular restriction on the reaction pressure, but it is usually carried out under the autogenous pressure of the polymerization reaction system such as a solvent. The reaction is carried out at pressures up to 50 kg/cm'' (absolute pressure).

The polyarylene sulfide produced in this way is
It can be made into a product by post-processing according to conventional methods.

That is, the product slurry obtained by cooling the polymerization reaction completed liquid is either used as it is or is diluted with water or acid, and then filtered or centrifuged to separate the solids. Polyarylene sulfide can be obtained by washing with water, methanol, etc. and drying.

The polyarylene sulfide obtained in this way is
If necessary, the polymer can be subjected to a known salt treatment to reduce the concentration of electrolytes such as alkali metal halides contained in the polymer, and can be suitably used in the electronic field.

When molding the polyarylene sulfide, carbon black, calcium carbonate powder, silica powder, titanium oxide powder, graphite, metal powder,
Powdered fillers such as glass powder, fibrous fillers such as carbon fiber, glass fiber, asbestos, polyaramid fiber, etc.
Polycarbonate, polyphenylene ether, polysulfone, polyarylene, polyacetal, polyimide,
Synthetic resins such as polyamide, polyester, polystyrene, and ABS, or additives such as stabilizers and flame retardants can be blended.

[Effects of the Invention] According to the method of the present invention, a white, low salt content polyarylene sulfide with high molecular weight and good processability can be produced economically and advantageously in a simple process in a short time without using a catalyst. be able to.

The polyarylene sulfide obtained by the method of the present invention can be easily molded into films, sheets, Aa fibers, etc., and can also be processed into various molded products by injection molding, extrusion molding, rotary molding, etc. I can do it. These molded products have excellent heat resistance and chemical resistance, as well as good mechanical properties, flame retardance, and dimensional stability.

Therefore, the polyarylene sulfide obtained by the method of the present invention can be used as engineering plastics, for example, in the automobile field, electric/electronic field, precision machinery field,
It is suitably used in many fields such as A equipment field and optical communication equipment field.

[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

(Example 1) 1e - In an autoclave, sodium sulfide 0.2 hydrate equivalent (purity N a 2 S equivalent: 89.3%), 47
．． 461F<0.543 moi, 79.8 g (0,543 moZ) of p-dichloride benzene, and 304 xl of N-methylpyrrolidone were added and heated at 260°C for 3 hours, at which time the amount of water per IAg of N-methylpyrrolidone was 0.35 mol. After the specified time, water 46.8
After the completion of the reaction, the reaction mixture was poured into water in Step 11, washed twice with water and once with acetone in this order, and the polyphenylene sulfide in the form of granules was prepared. 48.5 g <yield 83%) was obtained.

The solution viscosity ηinh of this product was measured as a 1-chloronaphthalene solution (concentration 0.49/11') at 206°C, and was found to be 0.268.

(Example 2) In Example 1, instead of adding 46.8 g of water, 2.17 g (0,0543 mol) of sodium hydroxide was dissolved in 46.8 g (2,60 moffi) of water and added. When carried out in exactly the same manner as in Example 1,
40.2 g of granular polyphenylene sulfide (yield: 6
9%). The ηinh of this product was 0.357.

(Example 3) In Example 1, instead of the sodium sulfide 0.2 hydrate equivalent, a sodium sulfide anhydrous salt equivalent (purity Na2S
97.5%) 43.5 g (N a 2 SO,
543mo6, moisture content in this 43.5y is 0.1
3y (The number of moles of water per 1 moN of Na2S is 0.
The procedure was carried out in exactly the same manner as in Example 1, except that a product containing 01mon)) was used to obtain granular polyphenylene sulfide 51.2y (yield: 88%). The y7inh of this product was 0.321.

(Comparative Example 1) In Example 1, N azs 0.2 hydrate was used and 5.5 ml of water was added during preparation. ．． 9g (0,33m offi)
added. At this time, the amount of water per 1 kg of solvent is 1.4
It was 4 moles. Also, this is 0 per mole of sodium sulfide.
, 8o water salt. The reaction was continued at 260° C. for 6 hours, and after the reaction was completed, the same operation as in Example 1 was performed.

As a result, 55.9 g (yield 72%) of polyphenylene sulfide was obtained. The ηinh of this product was 0.253.

As a result, compared to Example 1.3, the molecular weight was lower and the yield was also lower.

Comparative Example 2) Example 2 except that 60% sodium sulfide was used in place of the sodium sulfide 0.2 hydrate equivalent product in Example 2.
I did it in exactly the same way. All of the obtained polymers were in powder form, yield M 56 , 1 g (95% yield), ηi
nh O, 195.

(Comparative Example 3) Completely the same as Example 2 except that in Example 2, the amount of water in the second stage was replaced with 46.8 g and 19.5 g of water (the number of moles of water per 1 moZ of NazS was 2 mof) was added. All the obtained polymers were in powder form and 56
．． 6 g (yield 96%), η1nhO, 159.

(Example 4) Example 1 was carried out in exactly the same manner except that the reaction temperature was changed to 245°C. The polymer yield was 46.9y (yield 80%), ηinh O,24.

(Comparative Example 4) In Example 1, the initial reaction was carried out at 240°C, and after adding 46.8g (2.60mol) of water, the reaction was carried out at 275°C.
The subsequent treatment was carried out in the same manner as in Example 1. The obtained polymer was 47.2y (yield 80.5%)
), y7inh O, 251, but had a brownish tinge compared to the polymers obtained in other Examples, and N-methylpyrrolidone also had a brownish color, indicating deterioration of the solvent.

Patent applicant: Idemitsu Petrochemical Co., Ltd. “Continued amendment,!T 2 Name of the invention: Process for producing polyarylene sulfide 3 Relationship with beach water properties to be amended Patent applicant address: 1-1 Shiratama-chome, Maruno, Chiyoda-ku, Tokyo Name Idemitsu Petrochemical Co., Ltd. Representative Mutsumi Mizugo 4 Address of agent 6, Central Nishi-Shinjuku 3rd floor, 8-9-5 Nishi-Shinjuku, Shinjuku-ku, Tokyo Number of claims increased by amendment 07 Subject of amendment "Details of the invention" in the description Column 8 “Explanation” Contents of the amendment (1) ro stated in the third line of page 7 of the specification,
Correct 5J to ro, 3J.

(2) ro stated on page 17, line 2 of the specification
, 5J is corrected to rO,3J.

(3) ro stated on page 17, line 3 of the specification
, 5J is corrected to rO,3J.

(4) The phrase "0.5 times the mole or less, preferably" written in the second line of page 20 of the specification is deleted.

(5) rO, 5J described on page 20, line 5 of the specification
is corrected to ro, 3J.

−1 above

Claims (2)

[Claims] (1) When producing polyarylene sulfide by reacting an alkali metal sulfide and a polyhalogeno aromatic compound in the presence of a polar solvent, the molar ratio of water to alkali metal sulfide is 0.3 or less. water present, 2
A first step of polymerizing at a temperature in the range of 20 to 300°C, and adding water to the reaction system at least once so that the molar ratio of water to alkali metal sulfide in the first step is 5 to 20; A method for producing polyarylene sulfide, characterized in that the polymerization reaction is carried out in at least two steps, each consisting of a second step in which polymerization is continued under the same temperature conditions as in the first step. (2) A method for producing polyarylene sulfide according to claim 1, characterized in that an alkali metal hydroxide is used in combination when adding water in the second step.