JPS62253622A - Production of polyarylene sulfide - Google Patents

Abstract

PURPOSE:To obtain the titled, high-purity, high molecular weight polymer free from discoloration and gelatinization, by reacting a dihalogen aromatic compound with an alkali metallic sulfide in a polar solvent in the presence of a Li compound and in the absence of water under heating, adding water to the reaction system and carrying out reaction under heating. CONSTITUTION:As a first stage, a dihalogen aromatic compound (e.g. dichlorobenzene) is reacted with an alkali metallic sulfide (e.g. sodium sulfide, etc.) in a polar solvent (e.g. N-methylpyrrolidone, etc.) in the presence of a lithium compound (e.g. lithium chloride, etc.) and in the absence of water at 200-270 deg.C and the remaining concentration of the alkali metallic sulfide is made <=5.5g/l calculated as sulfur based on the polar solvent. Then, 0.1-10mol based on 1mol alkali metallic sulfide of water water is added to the reaction system. As a second stage, reaction is carried out at 220-280 deg.C to give the aimed polymer.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing polyarylene sulfide, and more specifically, a method for producing polyarylene sulfide with high purity and high molecular weight. The present invention relates to a method for producing arylene sulfide.

[Prior art and its problems] Polyarylene sulfide such as polyphenylene sulfide is a thermoplastic resin that has thermosetting properties in a part of its molecules, and has excellent chemical resistance and good mechanical properties over a wide temperature range. It has excellent properties as an engineering plastic, such as heat resistance and rigidity.

Polyarylene sulfide such as polyphenylene sulfide is ′! It is known that polyphenylene sulfide is usually obtained by polymerizing a dihalogen aromatic compound and an alkali metal sulfide in a polar solvent; for example, polyphenylene sulfide is produced.

It is usually carried out by polymerizing P-dichlorobenzene and sodium sulfide in a polar solvent (Japanese Patent Publication No. 1V (52-12240U) fJ: i?) -
However, since ordinary polyarylene sulfide has small molecular adhesion, in order to obtain a final product with five polymers, it is necessary to harden the low molecular weight polyarylene sulfide by heat treatment, which is a complicated operation.

Currently, as a method for producing polyphenylene sulfite (cy) for the polymer layer, a method using an alkali metal such as lithium halide as a catalyst (U.S. Pat. No. 40382
No. 83) is known, but this method
Polyphenylene sulfide with a high molecular weight that can be used for applications such as m has not been obtained.

In addition, a method is known in which a compound having three or more halogens in the molecule is present in the reaction system (see Japanese Patent Publication No. 11719/1971 and Japanese Patent Application Laid-open No. 197430/1989), but the resulting polymer It easily gels and has problems in #A construction and quality.

Furthermore, a method of making water exist in the reaction system (Japanese Patent Application Laid-Open No. 5L2
No. 292θ and JP-A No. 11-7332), but the reactor was severely corroded and the quality of the produced polymer was low.
There are problems such as :'.

[Purpose of the invention] This invention was made based on the above article t#.

That is, an object of the present invention is to solve the above-mentioned problems and to provide a stable polyarylene sulfide with a polymer layer that is white, has high purity, and has a small melt flow, without problems such as corrosion of equipment such as a reactor. It is an object of the present invention to provide a new manufacturing method that allows for the production of a variety of materials.

In order to achieve the above object, the inventor conducted intensive studies and found that the reaction was carried out in two stages, the first stage was carried out in the qualitative absence of water, and after the first stage was completed, , a specific amount of water was added to the first reaction system before the second stage reaction, and f5z
The inventors have discovered that the above object can be easily achieved by using a second step reaction method in which a stepwise reaction is carried out, and have thus arrived at the present invention.

[Measures for solving the above problems] The main points of this invention for solving the above problems and achieving the above objects are as follows:
In a method for producing polyarylene sulfide 1 by contacting a dihalogen aromatic compound and an alkali metal sulfide in a polar solvent, as a first step, in a polar solvent, in the presence of a lithium compound, and substantially are reacted in the absence of water at a temperature range of 200 to 270°C to reduce the residual concentration of alkali metal sulfide to 5.5 g/min of polar solvent or less in terms of sulfur, and then the wood is reacted with the alkali metal This method for producing polyarylene sulfide is characterized in that after adding 1 to 10 moles of sulfide, as a second step, the reaction is carried out at a temperature in the range of 220 to 280°C.

The polar solvents that can be used in the method of this invention include amide compounds, lactam compounds, urea compounds,
There are cyclic organic phosphorus compounds, etc.

Among these, specific examples of suitable solvents are:
For example, N,N-dimenalformamide, N,N-dimethylacetamide, N,N-diethylacetamide,
N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, caprolactam, N-ethylcaprolactam, N-ethylcaprolactam, N-isopropylcaprolactam, N-inbutylcaprolactam, N-propylcaprotictam 2N-petitol Lukabrolacta 1
N-,! / /y 7M A 7,
~, 11, ^ -11, for #b I-%f
J-thyl-2-pyrrolidone, N-ethyl-2-
Pyrrolidone, N-isopropyl-2-pyrrolidone, N-
Inbutyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone.

N-cyclohexyl-2-pyrrolidone, N-methyl-3
-Methyl-2-pyrrolidone, N-cyclohexyl-2-
Pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5,-trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-
piperidone, N-isopropyl-2-piperidone, N-
Methyl-6-methyl-2-piperidone, N-methyl-3
-Ethyl-2piperidone, N-methyl-2-oxo-hexamethyleneimine, N-ethyl-2-oxo-hexamethyleneimine, hexamethylphosphate triamide, hexaethylphosphate triamide, tetramethylurea, 1 ．．
3-dimethylethyleneurea, 1,3-dimethylpropyleneurea, l-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, l-phenyl-1-oxosulfolane, l-methyl-1-oxosulfolane ,! −
Proplu-1-okynphosphane, 1-phenyl-1-
Examples include oxophosphan. These solvents are 1
The species may be used alone or two or more species may be used in combination.

Furthermore, among the various polar solvents mentioned above, N-furkyllactam, N-furkylpyrrolidone, and hexaalkylphosphoric triamide are preferred, and N-methylpyrrolidone is particularly preferred.

As the dihalogen aromatic compound, for example, O-
Dichlorobenzene, m-dichlorobenzene, P-dichlorobenzene, O-dibromobenzene, P-dibromobenzene, m-dibromobenzene, p-shortbenzene,
Dihalogen-substituted benzenes such as 1-chloro-4-bromobenzene and 1-chloro-4-iodobenzene; 2.5-
Dichlorotoluene, 2,5-dichloroxylene, l-ethyl-2,5-dichlorobenzene, 1-ethyl-2,5
-dibromobenzene, 1-ethyl-2-bromo-5-chlorobenzene, 1,2,4.5-tetramethyl-3,
8-dichlorobenzene, l-cyclohexyl-2,5-
Dichlorobenzene, 1-phenyl-2,5-dichlorobenzene, l-benzyl-2,5-dichlorobenzene 51
-phenyl-2,5-dibromobenzene, 1-p-)silyl-2,5-dichlorobenzene, 1-p-tolyl-
2,5-dibromobenzene, l-hexyl-2,5-dichlorobenzene &,? dihalogen-substituted benzenes; dihalogen-substituted biphenyls such as trans-dichlorobiphenyl; dihalogen biphenyl alkanes such as 2,2-di(parachlorophenyl)propane; 1,4-dichloronaphthalene, 1,8-dichloronaphthalene, 2; Examples include dihalogen-substituted naphthalenes such as .8-dichloronaphthalene. Among these, preferred are dihalogen-substituted benzenes, with p-dichlorobenzene being particularly preferred.

Examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, and potassium sulfide.

Examples include rubidium sulfide and cesium sulfide.

What is suitable as this alkali metal sulfide?

These include lithium sulfide and sodium sulfide, with sodium sulfide being particularly preferred. Note that these may be used alone or in combination of 2N or more.

In addition, in the method of the present invention, the alkali metal sulfide may be an anhydride, a hydrate, or an aqueous mixture, and a hydrate is preferred.

When using aqueous mixtures! ! As stated.

It is necessary to perform a dehydration operation before the reaction. Therefore, it is possible to use one that is anhydrous.

This is preferable in that no dehydration operation is required.

Examples of the lithium compounds used in the method of the present invention include lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium carbonate, lithium hydrogen carbonate, lithium sulfate, lithium hydrogen sulfate, lithium phosphate dihydrogen phosphate Lithium mineral salts such as lithium, lithium dihydrogen phosphate, lithium sulfate, lithium chloride, lithium sulfite, etc. Lithium oxygen salts such as lithium oxide, lithium chromate, lithium molybdate; Lithium acid, lithium malonate, lithium propionate, lithium acetate, lithium inoacetate, lithium maleate 5 Lithium fumarate, lithium butane diate, lithium valerate, lithium hexanoate, lithium octoate, lithium tartrate, lithium stearate , lithium carboxylates such as lithium oleate, lithium tartrate, lithium benzoate, lithium phthalate; lithium sulfonates such as lithium benzenesulfonate, lithium P-toluenesulfonate, lithium methoxy F, lithium ethoxide, lithium iso Lithium alkoxylates such as propoxide, lithium-n-propoxide, lithium butoxide, and lithium futoxy; various lithium compounds such as lithium acetate or organolithium compounds such as lithium acetylacetonate, lithium sulfide, lithium oxide, and lithium hydroxide; can be mentioned. Among these, lithium halides such as lithium chloride, lithium carboxylates such as lithium acetate,
Lithium carbonate and the like are preferred, and lithium chloride is particularly preferred. Even if these lithium compounds are used alone,
You may use two or more types in combination.

In addition, in the method of this invention, the lithium compound can be an anhydride, a hydrate, or an aqueous mixture. However, when a hydrate or an aqueous mixture is used, as described below, 2. It may be necessary to perform a dehydration operation before the reaction.

In the method of the present invention, in the first stage reaction and/or the second stage reaction, an active hydrogen-containing halogen aromatic compound, a polyhalogen aromatic compound, a polyhalogen aromatic compound is added to the reaction system as necessary. Branching agents or molecular framework regulators such as nitro compounds, and/or liquid regulators such as alkali hydroxides, and/or polymerization additives such as metal salts, and/or reducing agents, and/or inert organic The reaction can be carried out in the presence of a solvent. Each of these components can be used in an aqueous state or in a water-containing state such as a hydrate, a water-containing product, or an aqueous mixture.
Said 1st r! When using a water-containing product for the lt-floor reaction, it should be thoroughly dehydrated before the reaction.
It is necessary to subject it to the reaction in a qualitatively anhydrous state.

The active hydrogen-containing halogen aromatic compound has at least one aromatic ring, and a group having active hydrogen is bonded to at least one (111) of the carbon atoms forming the aromatic ring. , carbon which simultaneously forms an aromatic ring; aromatic compounds in which halogen atoms are bonded to at least two carbon atoms among the I atoms can be used.

Said son-in-law 11t/II/nee 1-47! Examples of active hydrogen-containing halogen aromatic compounds include active hydrogen-containing dihalogen benzene compounds such as dihalogeno-2, dihalogenothiophenols, dihalogenothiophenols, and dihalogen(phenyl)7minobenzenes;
Active hydrogen-containing compounds such as trihalogenoanilines, 2,4.5-trihalogenothiophenols, trihalogenophenols, and trihalogeno(phenylami/)benzenes 1
Examples include polyhalogenbenyne compounds.

Other examples include diaminodihalogenodiphenyl ethers.

In this invention, the active hydrogen atom in which the hydrogen atom bonded to the elementary atom in l forming the aromatic ring in the active hydrogen-containing halogen aromatic compound is substituted with another inert group, for example, a hydrocarbon group such as an alkyl group. Halogen-containing aromatic compounds can also be used.

Among the various active blister-containing halogen aromatic compounds exemplified above, those represented by the above formula (1) are preferred, and active hydrogen-containing halogen aromatic compounds are also preferred, with dichloroaniline being particularly preferred.

The polyhalogen aromatic compound is an aromatic compound in which three halogen atoms are substituted. Specifically, for example, 1-111'Xf/74,2.4-trichlorobenzene, 1,3.
Examples include 5-trichlorobenzene and 1,4.8-trichloronaphthalene.

As the polyhalogen aromatic nitro compound.

Examples include dihalogenonitrobenzenes, dihalogen/nitronaphthalene, and the like.

By using these active hydrogen-containing aromatic compounds and/or polyhalogen aromatic compounds and/or polyhalogen aromatic nitro compounds, the degree of branching of the produced polyarylene sulfide can be increased or
It is possible to further increase the molecular weight, and it is also possible to improve various physical properties of the produced primer, such as reducing melt flow and reducing the amount of residual coalescence.

In addition to the various compounds mentioned above, organic compounds having three or more reactive halogen atoms, such as cyanuric chloride, can be used as the branching agent or molecular weight regulator.

In addition, these various compounds that are branching agents or molecular weight regulators are l:! 4 may be used alone or in combination of two or more.

The gold-11 salt used as the polymerization additive is a carboxylate of a metal belonging to Groups 1 to 2 of the periodic table, such as sodium acetate, potassium acetate, zinc acetate, etc.;
Examples include alkali metal mineral salts such as sodium phosphate, alkaline earth metal mineral salts, and alkali metal sulfone salts such as sodium benzenesulfonate.

These metal salts may be used alone or in combination of two or more as a polymerization additive.

Examples of the reducing agent include hydrazine, metal hydride, alkali formate, etc., and preferred ones include:
Mention may be made of metal hydrides, in particular sodium borohydride, calcium hydride and the like.

Examples of the inert solvent include hydrocarbons such as benzene, toluene, xylene, biphenyl, terphenylnaphthalene, and anthracene, and ethers such as diphenyl ether, p-diphenoxybenzene, and polyethylene glycol. Among these, high boiling point inactivated organic solvents are preferred.

In the method of the present invention, the reaction in the first step involves combining the dihalogen aromatic compound (component (A)) and the alkali metal sulfide (CB) (4 minutes) and the lithium compound as the catalyst (component [C]). ) and the polar solvent (component [D)], or (A) and (B).
), (C), and CD) components, and in addition to these, the active hydrogen-containing halogen aromatic compound, the polyhalogen aromatic compound, the polyhalogen nitro compound, the branching agent such as cyanuric chloride, or the molecular weight 3I The method can be carried out by blending one or more components selected from a conditioning agent, the liquid Iil conditioning agent, the Kamaki polymerization additive, the reducing agent, and the inert solvent as necessary. . However, in the method of this invention, one of the important points is that
The point is that the first stage reaction needs to be carried out in the substantial absence of water.

When each component such as (A), (B), (C), and CD) is substantially anhydrous or does not contain water, the order of blending of each component in the first stage reaction There are no particular restrictions.

On the other hand, if at least one of the above-mentioned components contains wood, one reaction may be carried out by performing a dehydration operation to make the reaction system qualitatively anhydrous before the reaction. Then, the order and method of blending each component and dehydration operation are adjusted.

This first stage reaction substantially occurs by the reaction between the component (A) and the component CB). therefore,
At least the IM component of the components used is
If it is in a hydrated state or in a hydrated state,
Before combining component (A) and component (B), or
[Before blending 83 minutes and component (A), it is desirable to dehydrate the water-containing component or the water-containing mixture, etc., and use it in a substantially anhydrous state. .

Specifically, for example, the reaction at the ffg1 stage is performed using Makki (A) component, CB) component, [C] component, and CD).
If carried out by contacting the components; CB used) I&min;
[C] Component 2 [D] When at least one component of the components is in a hydrated state or in a hydrated state (for example, using a hydrated salt such as sodium sulfide nonahydrate as (Xi) lj 5 min) In this case, the CB) component, the (C) rIt component, and the CD) component are blended to prepare a mixed solution for preparing the reaction system.

This mixed solution is subjected to a dehydration operation such as azeotropic distillation to prepare a substantially anhydrous reaction system preparation j11 polymerization solution i, and this mixed solution is combined with the substantially anhydrous component (A). A method is preferably used in which a reaction system is constructed by blending the following.

In addition, regarding the reaction on the 111th floor of the appetizer record, the above (A) and (B
), (C), and CD), and if necessary, the above-mentioned components may be used, for example, [
At least ls of component B), (C) tlik component, and [D] acid component is in a hydrated state, or if it is in a hydrated state, the (B) component, (C) component, and ( D) Components, etc. are mixed to prepare a mixed solution for producing the reaction system rA, and wood is removed from this mixture by a dehydration operation such as azeotropic M distillation.
A substantially anhydrous mixed solution for reaction 7A is prepared, and this mixed solution is mixed with substantially anhydrous (A) l&, at the same time or in stages to form a reaction, etc. The method can be suitably used.

In addition, each of the above-mentioned components used to configure the reaction etc.
When the composition is in a substantially anhydrous state, the same blending order, method, etc. as mentioned above can be suitably used without performing a dehydration operation.

In any case, as long as the first reaction is carried out in the substantial absence of water, there are no particular by-products in the order or method of blending the components.

Here, the above-mentioned "substantially absence of water" cannot be uniformly defined because its definition range differs depending on various other conditions such as the types of components used, compounding ratio, reaction conditions, etc. It is important that the amount of wood contained is usually 0.1 mol or less, preferably 0.05 mol or less per 1 mol of component (B) used.

If the amount of water is more than 0.1 mole per mole of component (B) used, the two reactors may be corroded, the obtained polyarylene sulfide may become young, its purity may decrease, or it may have a high molecular weight. Polymer may not be obtained.

In the first stage reaction. It is desirable that the blending ratio or blending ratio of each of the components is as follows.

That is, the molar ratio of (A) 1 min/(B) component is 0.75 to 2.0, preferably 0.111) -1,2
There is -11'. Since the reaction between the conodihalogen aromatic compound (A) and the alkali metal sulfide CB) is an equimolar reaction, it is usually set in the range +iii.

The molar ratio of component (C)/component (B) is normal.

0.001-2.0 Te, preferably 0.01-1
．． There is 5-1'. If this molar ratio is less than 0.001, the molecule ψ of the polyarylene sulfide produced may be low, or the content of salts such as common salt, that is, contaminant salts remaining in the polymer may not be sufficiently low.
On the other hand, if it is larger than 2.0, the salt used as a catalyst may remain in the produced polymer at a high concentration.

However, when lithium sulfide is used as the component (B), the lithium sulfide can be considered to be both the component (B) and the component [C).

(D) l&min/[B] Acid component 7) Molar ratio is 1 to 1
5, preferably 2 to IO. If this molar ratio is smaller than 1, the reaction may become non-uniform, and if the molar ratio is larger than 15, productivity may decrease.

The reaction in the first step in the method of this invention usually includes:
If the temperature range is 200-270°C, preferably 210-285°C, one reactor degree will not be sufficient if the zero reactor degree is lower than 200'O, while if it is higher than 270'C, the 5. The reaction time is 0, in which polyarylene sulfide may not be obtained.
It is set to be within the range of 5 g/cross, preferably 2.7 g/7 sentence or less. Therefore, this reaction time varies depending on various other conditions such as the type and amount of each component used, reaction temperature, etc., and cannot be uniformly specified, but it is usually 20.2
It can be in the range of ~2 hours.

In the method of this invention, after the reaction in step 5f,
Water is added to the reaction system and the second stage reaction (f
[Condensation reaction] is carried out.

The mixing ratio of the water is usually 1.0% per 811 moles of the alkali metal sulfide used. IN is 10 mol, preferably 0.5 to 2.5 mol. If the blending ratio of water is less than 0.1 mole per mole of the alkali metal sulfide CB), a high molecular weight polyarylene sulfide may not be obtained.

On the other hand, if the amount exceeds 10 moles, problems such as corrosion of the reactor may occur.

The reaction temperature of the second stage reaction is usually 220 to 28
0°C, preferably 240-270°C. If this reaction temperature is lower than 220°C, the reaction rate of the polycondensation reaction may not be sufficient and a high molecular weight polyarylene sulfide may not be obtained. On the other hand, if it is higher than 280°C, side reactions may be induced. The productivity of high molecular weight polyarylene sulfide may decrease. The reaction time for this reaction is usually within 20 hours, particularly about 0.1 to 8 hours.

The reaction pressures of the first stage reaction and rjS2 stage reaction are not particularly limited, but are usually from the autogenous pressure of the reaction system such as the solvent to about 10 kg/(absolute pressure). These reactions may be carried out in an atmosphere of an inert gas such as nitrogen or 1&m dioxide.

In the method of the present invention, when carrying out the second-stage reaction, each of the above-mentioned components can be added to the reaction system and carried out once, if necessary. There are no particular restrictions on the order or method of blending these components, but usually, for example, after the addition of the water, each of the components is added to the reaction system as necessary, and then the second stage reaction is carried out. A method of performing this can be suitably used.

The amount of each component added during the second stage reaction is the amount of each component added during the first stage reaction and the amount of each component newly added and blended during the second stage reaction. It can be set so that the sum total falls within the blending ratio range of each component listed in #.

In addition, if each of the above components added as necessary during the second stage reaction contains water, the total amount of water in each component added and the amount added before the second stage reaction It is desirable that the total amount including the amount of water falls within the range of the mixing ratio of water.

After completion of said second stage reaction, the polyarylene sulfide can be separated directly from the reaction solution by standard methods, e.g. by filtration or centrifugation, or after addition of e.g. water and/or diluted acid. 1. It can be obtained by fractionating from the reaction solution.

The filtration step is generally followed by a water wash to remove any inorganic components that may adhere to the polymer, such as alkali metal sulfides. It is also possible to wash or extract with other washes such as methanol in addition to or after this washing step. You can also collect combinations.

In this way, white, highly pure polymeric polyarylene sulfide such as l-polyphenylene sulfite can be easily produced.
And it can be obtained stably.

In addition, the recovered polyarylene sulfide can be further subjected to various desalting treatments as necessary to reduce the concentration of salt such as common salt in the polymer, and can be suitably used in the electrical and electronic fields. .

When polyarylene sulfide such as polyphenylene sulfide obtained by the method of this invention is molded into various products, other polymers, pigments and fillers such as graphite, metal powder, glass powder, quartz powder or glass fiber, carbon It can be mixed with fibers or with additives customary for polyarylene sulfides, such as customary stabilizers or mold release agents.

The polyarylene sulfide such as polyphenylene sulfide obtained by the method of the present invention is white, has high purity, has low melt flow, and can be produced as a resin with high affinity in grade 1, so it can be used for various molded products and An excellent engineering plastic that can be used as a matrix resin for composite materials, and can also be made into various molded products, films, mixes, etc., and can be suitably used not only for mechanical parts but also for electrical and electronic parts.

It is.

[Effects of the Invention] According to the present invention, polyarylene sulfide of white color, high purity, high molecular weight polyphenylene sulfide rod with small melt flow can be easily produced.

There is no vertical erosion of equipment such as reactive groups, and the resulting polymer can be produced stably and in good yield without causing gelation or the like. Furthermore, the degree of branching and molecular weight of the polyarylene sulfide can be adjusted over a wide range, if necessary.

That is, according to the method of the present invention, in the production of polyarylene sulfide such as polyphenylene sulfide, it is possible to achieve significantly superior effects in terms of processing E, quality, etc., compared to conventional methods.

[Example] (Example 1) p-Schif* Rohe7in 8t, 5g (0.55aol
) t3 anhydrous lithium sulfide 25.0g (0.54aa
Autoclave l) for 2 sentences (Material: SUS 3/BL)
2-in, N-/l chill-2-pyro IJ door 308
Add (NMP) *fL(0,23aal),
After flowing nitrogen for 10 minutes at room temperature, the temperature was increased to 120°C while stirring.
The temperature rose to . Seal the autoclave and heat at 5230°C.
．． The lithium sulfide in the reaction system, which was held for 5 hours and carried out the first stage reaction, was measured by ion chromatography and was 2.1 g/NMP based on the sulfur content.
Next, after adding 9.7 g (0.54 aal) of distilled water to the reaction system, the temperature was gradually raised to 285°C and a polymerization reaction (second stage reaction) was carried out over 2 hours. After the completion of the reaction, the mixture was stirred. The reaction mixture, which was cooled to 175° C. and then allowed to reach room temperature, was poured into water of Ii, filtered, washed with water, and washed with meta/-At. The resulting white bonyphenylene sulfide melt flow flll (measurement conditions: 300
"Q, load 50 Kg/cnn", nozzle length 10j+m) is 4.2 tau/sec, DS
The melting point measured at C was 290''0 and the yield was 85% by weight.

(Example 2) Sodium sulfide 9 Kimasu 130 in a 2-liter autoclave,
4 g (0,541lol), JlIJ lithium
2G-Og(0,54101) and N-methyl-2-
Add 370 m of pyrrolidone and remove 8 ml of ice by azeotropic distillation.
8 ml was removed. Then p-dichlorobenzene 81
．． 5g (0,!J+mol), and N-methyl-2-
Pyrrolidone 110@n was added and the first stage reaction was carried out at 255°C for 1 hour in a nitrogen atmosphere.The lithium sulfide in the reaction system was measured by ion chromatography, and the sulfur content was 1.8 g/fL- It was NMP.

After adding 9.7 g (0.4 sub-o1) of A clear water to the reaction system.

The temperature was gradually raised to 280°C and the polymerization reaction (second
A stepwise reaction) was performed. After the reaction was completed, the mixture was cooled, filtered, washed with water, and washed with methanol. The melt flow value of the obtained white polyphenylene sulfate was 2. il ml2. /
gsc, the melting point was 290°C, and the yield was 94%.

(Comparative Example 1) In Example 1, 9.7 g of distilled water was added before the first punching reaction.
The same operation was carried out except that (0.54 aal) was added and distilled water was not added in the first stage reaction.

The residual concentration of lithium sulfide before adding distilled water is 5
It was 7.8 g/day-1'iMP. The melt flow value of the obtained polyphenylene sulfide was 13.8 steps/sec.
, the melting point was 288°C, and the yield was 90% by weight.

In addition, the inner wall of the autoclave had a black wedge (Comparative Example 2). The same operation as in Example 1 was performed except that distilled water was not added. The resulting light yellow polyphenylene sulfide had a melt flow value of 5.8 an/see, a melting point of 28!9''0, and a yield of 83 tm%.

(Comparative Example 3) In Example 2, 8.7 g of distilled water was added before the first stage reaction.
The same operation was performed except that (Q, 54@01) was added and distilled water was not added during the second stage reaction. The residual concentration of lithium sulfide before adding distilled water is 5.
6.9g/! It was L-NMP. The melt flow value of the obtained pale yellow polyphenylene sulfide was 1G, 2 si/
sea, melting point is 283℃, yield is 9゜ffi%
Met.

(Comparative Example 4) The same operation as in Example 2 was performed except that distilled water was not added. The resulting pale yellow polyphenylene sulfide had a melt flow value of 3.4 fL/sea, a melting point of 282°C, and a yield of 94% by weight.

Procedural amendment (self-effect 1. Indication of the case, 1986 Japanese Patent Application No. 98947. 2. Title of the invention: Process for producing polyarylene sulfide 3. Person making the amendment. Relationship with the case. Patent applicant address: 2-1 Marunouchi, Chiyoda-ku, Tokyo. No. 1 4 Agent address: 3rd floor, Central Nishi-Shinjuku, 8-9-5, Nishi-Shinjuku, Shinjuku-ku, Tokyo Telephone: 03-361-2738 Name: Patent attorney (8759) Naoki Fukumura, 5
Date of amendment order None (Self-effect 6 Number of inventions increased by amendment None Part 7 Subject of amendment ``Detailed details of the invention'' column of the specification.

8. Contents of the amendment (1> “Dekoru” written on page 5, line 3 of the specification 1
Correct it to "possible".

(2) "Rople" written on page 8, line 2 of the specification is amended to "robil".

(3) “Ziclo” described on page 8, line 17 of the specification
"Roxylene" is corrected to "dichloro p-xylene".

(4) "Lithium sulfate" written on page 10, line 18 of the specification is amended to "lithium nitrate."

(5) "Lithium tartrate" stated on page 11, line 8 of the specification is deleted.

(6) From page 14, line 12 to line 14 of the specification, “the formula (1) is preferably . Preferably correct it.

(7) "ter7enylnaphthalene" described on page 16, lines 16 to 17 of the specification is amended to "terphenyl, naphthalene."

(8) “Inactivation” stated on page 16, line 20 of the specification
Correct to "inactive".

(8) The phrase "the above-mentioned catalyst" written in lines 4 and 5 of page 17 of the specification is deleted.

(10) The phrase “of item F” written in page 22, line 16 of the specification is corrected to “high molecular weight.”

(11) No rlOkg/described on page 24, line 7 of the specification.
Correct to J'ir 1Bkg/cm2 J.

(12) “Dilution C” described on page 25, line 13 of the specification
is corrected to "diluted".

(13) r3/8L described on page 28, line 10 of the specification
Correct to "Hat r31/8L".

(“306:N stated on page 28, line 11 of the specification
MP) J is corrected to r (NIIIP) 308J.

(15) "Poniphenylene" written on page 29, line 3 of Specification S is corrected to "polyphenylene".

(1B) "4.2 ■ 目" written on page 29, line 5 of the specification is amended to "r 4.2 x 10-26 sentences."

(17) "Litiram" written on page 29, line 16 of the specification is corrected to "sodium."

(18) “2,
8.2” to r2.8 XIO? mJIJ 2 correction.

(19) Written on page 30, lines 12 and 13 of the IN1 specification77, ty) r 13. [l ml J r
13. [lX 10-2* l J d correction.

(20) Written on page 30, lines 19 and 20 of Ming #I Ancient 1tf) r 5.8m, i'' to ``5.L+JL
10-' sJI J k: Correct.

(21) “Lithium” described in page 31, line 6 of the specification
Correct to "sodium".

(22') r stated on page 31, line 9 of the IJI specifications
10.2 Proverbs' r l(1,2X 1(12s l
J Correction.

(23) r3.4sl J described in line 14 to line 15 in item 31 of the IJJ specifications to r3.4 x 10-2
al l d correction.

−1 above

Claims (5)

[Claims] (1) In a method for producing polyarylene sulfide by contacting a dihalogen aromatic compound and an alkali metal sulfide in a polar solvent, as a first step, in a polar solvent, in the presence of a lithium compound, and substantially The dihalogen aromatic compound and the alkali metal sulfide are reacted in the temperature range of 200 to 270°C in the absence of water, and the residual concentration of the alkali metal sulfide is 5.5 g/l in terms of sulfur. of polyarylene sulfide, which is characterized by adding 0.1 to 10 moles of water per mole of the alkali metal sulfide, and then reacting at a temperature in the range of 220 to 280°C as a second step. Production method. (2) The method for producing polyarylene sulfide according to claim 1, wherein the dihalogen aromatic compound is p-dichlorobenzene. (3) The method for producing polyarylene sulfide according to claim 1 or 2, wherein the alkali metal sulfide is sodium sulfide and/or lithium sulfide. (4) The method for producing polyarylene sulfide according to any one of claims 1 to 3, wherein the lithium compound is lithium chloride and/or lithium sulfide. (5) The method for producing polyarylene sulfide according to any one of claims 1 to 4, wherein the polar solvent is N-methylpyrrolidone.