JPH0525275A - Production of polyarylene sulfide - Google Patents

Abstract

PURPOSE:To produce a polyarylene sulfide which has a low oligomer content, a good impact resistance, a high thermal stability, and an excellent moldability. CONSTITUTION:The objective polyarylene sulfide is prepd. by reacting a sulfidizing agent with a dichloroarom. compd. and a dibromoarom. compd. in an amt. of 0.01-20.0mol% based on the dichloroarom. compd. in an org. polar solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for obtaining a polyarylene sulfide having improved thermal stability, moldability and the like, a high melting point and a small amount of an oligomer component.

[0002]

2. Description of the Related Art Polyarylene sulfide resins (PAS resins) represented by polyphenylene sulfide (PPS) are widely used for injection molding, extrusion molding, etc. due to their excellent heat resistance and chemical resistance. ing.

However, general PPS is produced in the manufacturing process,
Residual cyclic compounds, side reaction products, low molecular weight components such as oligomer components (collectively abbreviated as oligomer components below)
Since the amount is large, there is a surface lacking in toughness, and in particular, a molded product containing a large amount of filler has a defect of poor impact resistance. Further, when the fibrous reinforcing material or filler and the polyphenylene sulfide resin are melt-kneaded and molded, they are processed at a high temperature of more than 300 ° C., so that they are melt-kneaded due to the oligomer component, gas generation during molding, die This is a problem because the tar-like substance adheres to the mold and the mold.

Regarding the conventional method for producing PPS, PPS is produced by reacting an alkali metal sulfide represented by sodium sulfide with a dihaloaromatic compound represented by p-dichlorobenzene in an organic amide solvent. The method is described in, for example, Japanese Patent Publication No. 45-3368.

Particularly, a method for obtaining a PAS resin having a small amount of an oligomer component is described in JP-A-61-225217, JP-A-61-255933, and the like.
A method of washing with a solvent that does not dissolve len sulfide is known.

However, in these methods, specific oligomers are used.
Not only the components are reduced, but also the solvent is generally different from the solvent used in the polyarylene sulfide polymerization, so that the recovery of the solvent is complicated and the economy is poor.

Further, JP-A-60-115631 and JP-A-60-62163.
A method of washing with a solvent used at the time of polymerization is disclosed in, for example, the publication of -232437. This method also reduces the amount of oligomer components, but since the melting point is low and the flow characteristics near the molding temperature deteriorate due to gelation etc. when heat-treated, the amount of gas generated during melt-kneading and molding is low, but it is a polymer. The thermal stability and moldability of the composition are extremely poor, and it is not sufficient to improve mechanical strength such as impact resistance.

In order to improve the impact resistance of polyarylene sulfide, reduction of the oligomer component has been studied and various methods have been proposed. In the conventional method, even if the oligomer component is decreased, thermal stability is improved. There was a problem that the moldability and moldability deteriorate.

[0009]

SUMMARY OF THE INVENTION The present invention provides oligomers.
It is an object of the present invention to provide a method for producing a polyarylene sulfide, which has reduced the components and improved the above-mentioned problems such as thermal stability.

[0010]

Means for Solving the Problems The present inventor has made detailed studies on the influence of a dibromoaromatic compound on the initial stage of polymerization and the influence of sodium bromide, etc. produced in the initial stage of polymerization on the polymerization reaction system. As a result, the amount of the oligomer component is reduced, and the dichloroaromatic compound, which is a monomer, is allowed to coexist with a small amount of a dibromoaromatic compound having different reactivity, thereby deteriorating the thermal stability and the fluidity characteristics in a high temperature range as described above. Without increasing the melting point, melting and kneading, reducing the amount of gas generated during molding, and improving moldability, a method for producing a polyarylene sulfide having excellent physical properties has been found.

That is, the present invention uses a sulfidizing agent and a dichloroaromatic compound and a dibromoaromatic compound in a polar solvent in an amount of 0.01 to 20.0 mol% of the dibromoaromatic compound with respect to the dichloroaromatic compound. The method is a method for producing a polyarylene sulfide, which is characterized in that the reaction is carried out.

It is desirable that the initial stage of polymerization is anhydrous, but water of about 5 mol or less may be present with respect to the sulfur source of alkali metal sulfide or alkali metal hydrosulfide.
Moreover, you may use a catalyst as needed.

There is no particular limitation on the order of addition of the respective raw materials to the polar solvent. Preferably in advance in a polar solvent,
A sulfidizing agent and, if necessary, an alkali metal hydroxide were mixed, and hydration water or crystallization water contained from the beginning or water produced was dehydrated by a dehydration operation such as azeotropic distillation to prepare a mixed solution. After that, it is desirable to react this with a dichloroaromatic compound and a dibromoaromatic compound. It is necessary to always use two or more kinds of this dichloro aromatic compound and dibromo aromatic compound.
This is a major difference from the method for producing len sulfide, and it is not possible to use only one of the compounds.
There is no particular limitation on the addition method or order. For example, a mixture of a dichloroaromatic compound and a dibromoaromatic compound may be added in advance, each may be added separately, or each may be further divided and added. Preferably, it is desirable to add a mixture previously dissolved in a polar solvent.
Also, when using a method such as division, there is no particular limitation, but it is preferable to add the dibromo aromatic compound first and add the dichloro aromatic compound later.

Since the present invention is an improvement of the conventional method for producing PAS, in order to maximize its effect, the product after the reaction is not dissolved in polyarylene sulfide at room temperature, if necessary. You may wash | clean with a solvent, the solvent used at the time of superposition | polymerization, the solution which can control pH as mentioned later, or these mixtures.

The organic polar solvent used in the present invention is preferably an aprotic organic solvent such as an amide compound, a lactam compound, a urea compound and a cyclic organic phosphorus compound.

Specific examples of the amide compound include formamide, acetamide, N-methylformamide,
N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-ethylpropionamide, N, N-dipropylacetamide,
Examples thereof include N, N-dipropylbutyramide, N, N-dimethylbenzoic acid amide, and the like.

Specific examples of the lactam compound include caprolactam, N-methylcaprolactam, N-ethylcaprolactam, N-isopropylcaprolactam and N.
-Isobutyl caprolactam, N-normal propyl caprolactam, N-normal butyl caprolactam, N
-Cyclohexylcaprolactam, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-normalpropyl-2-pyrrolidone, N-normalbutyl- 2-pyrrolidone, N-cyclohexyl-2
-Pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5-trimethyl-2-pyrrolidone, N-
Methyl-2-piperidone, N-isopropyl-2-piperidone, N-ethyl-2-piperidone, N-methyl-6
-Methyl-2-piperidone, N-methyl-3-ethyl-
2-piperidone etc. can be mentioned.

Specific examples of the urea compound include tetramethyl urea, N, N'-dimethylethylene urea, N,
N'-dimethyl propylene urea etc. can be mentioned. Further, specific examples of the cyclic organic phosphorus compound include 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, 1-
Methyl-1-oxophosphorane, 1-normal propyl-1-oxophosphorane, 1-phenyl-1-oxophosphorane and the like can be mentioned.

These solvents may be used alone or as a mixture of two or more kinds. Among the above-mentioned various solvents, N-alkyllactam and N-alkylpyrrolidone are preferable, and N-methylpyrrolidone is particularly preferable. The amount of the polar solvent used is in the range of 1 to 20, preferably in the range of 2 to 10 by molar ratio with respect to the sulfur source such as the alkali metal sulfur compound or the alkali metal hydrosulfide compound. When the amount of the solvent is less than 1, the reaction may be non-uniform, which is not preferable, and when the amount exceeds 20, it is not preferable in that the productivity is lowered.

As the sulfidizing agent of the present invention, for example, both alkali metal sulfides and alkali metal hydrosulfides can be preferably used. Moreover, you may use these mixtures.

Examples of alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide. These may be used alone or in combination of two or more. Alkali metal sulfides are anhydrides, hydrates,
Although any aqueous solution may be used, when a hydrate or an aqueous solution is used, it is preferable to carry out a dehydration operation before the reaction as described later.

Of these, lithium sulfide and sodium sulfide are preferable, and sodium sulfide is particularly preferable. Examples of the alkali metal hydrosulfide include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, and cesium hydrosulfide. These may be used alone or in combination of two or more. As the alkali metal hydrosulfide, any of an anhydride, a hydrate and an aqueous solution may be used, but when using a hydrate or an aqueous solution, it is better to perform dehydration operation as described later.

Of these, lithium hydrosulfide and sodium hydrosulfide are preferable, and sodium hydrosulfide is particularly preferable. Examples of the dichloroaromatic compound used in the present invention include dichlorobenzenes such as o-dichlorobenzene, m-dichlorobenzene and p-dichlorobenzene; 2,3-dichlorotoluene,
2,5-dichlorotoluene, 2,6-dichlorotoluene, 3,4-dichlorotoluene, 2,5-dichloroxylene, 1-ethyl-2,5-dichlorobenzene, 1,
Alkyl-substituted dichlorobenzenes such as 2,4,5-tetramethyl-3,6-dichlorobenzene, 1-normalhexyl-2,5-dichlorobenzene, 1-cyclohexyl-2,5-dichlorobenzene or Cycloalkyl-substituted dichlorobenzenes; aryl such as 1-phenyl-2,5-dichlorobenzene, 1-benzyl-2,5-dichlorobenzene, 1-p-toluyl-2,5-dichlorobenzene Substituted dichlorobenzenes; Dichlorobiphenyls such as 4,4'-dichlorobiphenyl; 1,4-dichloronaphthalene, 1,6-dichloronaphthalene, 2,6
-Dichloronaphthalene and the like such as dichlornaphthalene.

Among these, dichlorobenzenes are preferable, and p-dichlorobenzene is particularly preferable. Examples of the dibromoaromatic compound used in the present invention include dibromobenzenes such as o-dibromobenzene, m-dibromobenzene and p-dibromobenzene; 2,3-dibromotoluene, 2,5-dibromotoluene and 2,6. -Dibromotoluene, 3,4-dibromotoluene, 2,5-dibromoxylene, 1-ethyl-2,5-dibromobenzene, 1,2,4,5-tetramethyl-3,6-dibromobenzene, 1-normal Alkyl-substituted dibromobenzenes such as ruhexyl-2,5-dibromobenzene, 1-cyclohexyl-2,5-dibromobenzene or cycloalkyl-substituted dibromobenzenes; 1-phenyl-2,5-dibromobenzene, 1-benzyl-2 , 5-dibromobenzene, 1-p-toluyl-2,5-dibromobenzene Ali - Le substituted dibromo benzenes; dibromobiphenyl such as 4,4'-dibromo-biphenyl; 1,4-dibromo-naphthalene, 1,6
-Dibromonaphthalene and dibromonaphthalene such as 2,6-dibromonaphthalene.

Of these, dibromobenzenes are preferable, and p-dibromobenzene is particularly preferable. With respect to the addition ratio of the dibromoaromatic compound used, a sufficient amount of the dibromoaromatic compound is sufficiently effective with respect to the dichloroaromatic compound. Specifically, the addition amount of the dibromoaromatic compound to the dichloroaromatic compound is preferably 0.01 to 20.0 mol%, and particularly preferably 0.1 to 10.0 mol%. If the amount of the dibromoaromatic compound is less than 0.01 mol%, the effect is not sufficient. If it is more than 20.0 mol%, not only will the reaction be hindered by the influence of the solubility of sodium bromide, which is a by-product during the polymerization, in the reaction solvent, but the dibromoaromatic compound will not be as good as the dichloroaromatic compound. It is not preferable to use a large amount because it is costly and economically disadvantageous.

In the present invention, an alkali metal hydroxide is used if necessary. In particular, when using an alkali metal hydrosulfide as a sulfidizing agent, it is necessary to use an alkali metal hydroxide.

When an alkali metal hydrosulfide is used as the sulfidizing agent, the amount of the alkali metal hydroxide used is 0. 1 in molar ratio to the sulfur source of the alkali metal hydrosulfide.
It is in the range of 5 to 5, preferably in the range of 0.6 to 3.

Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide, which may be used alone or in combination with each other. You may mix and use 1 or more types.

Among the above alkali metal hydroxides, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is particularly preferable. In the method of the present invention, a catalyst may be used, if necessary, within a range not deviating from the object. Examples of the catalyst include lithium halides such as lithium chloride and lithium bromide; lithium carboxylates such as lithium formate and lithium acetate; lithium compounds such as lithium carbonate, lithium oxide and lithium sulfide. Among the above lithium compounds, lithium chloride, lithium acetate and lithium carbonate are preferable. In the present invention, the lithium compounds may be used alone or in combination of two or more.

If necessary, a branching agent such as an active hydrogen-containing halogeno aromatic compound, a polyhalogeno aromatic compound, a halogeno aromatic nitro compound or a molecular weight modifier, a metal salt, etc. may be used without departing from the object of the present invention. Select polymerization additives, reducing agents, inert organic solvents, etc.
The reaction can be carried out by adding it to the reaction system.

The active hydrogen-containing halogenoaromatic compound is a halogenoaromatic compound having a functional group having active hydrogen such as an amino group, a thiol group, a hydroxyl group and a carboxyl group. Is 2,3-dichloroaniline, 2,4-dichloroaniline, 2,5-
Dihaloanilines such as dichloroaniline and 2,6-dichloroaniline; 2,3,4-trichloroaniline and 2,
3,5-trichloroaniline, 2,3,6-trichloroaniline, 2,4,5-trichloroaniline, 2,4
Trihaloanilines such as 6-trichloroaniline and 3,4,5-trichloroaniline; Tetrahaloanilines such as 2,3,4,5-tetrachloroaniline and 2,3,5,6-tetrachloroaniline; 2 , 2'-diamino-
Dihalodiaminodiphenyl ethers such as 4,4′-dichlorodiphenyl ether and 2,4′-diamino-2 ′, 4-dichlorodiphenyl ether; and these compounds, in which the amino group is Examples thereof include compounds substituted with a thiol group, a hydroxyl group and a carboxyl group. Further, an active hydrogen-containing halogeno aromatic compound in which a hydrogen atom bonded to a carbon atom forming an aromatic ring in these active hydrogen-containing halogeno aromatic compounds is substituted with an inactive group such as an alkyl group can also be used. . Among these various active hydrogen-containing halogeno aromatic compounds, active hydrogen-containing dihalogeno aromatic compounds are preferable, and dichloroaniline is particularly preferable.

The polyhalogeno aromatic compound is a compound in which three or more halogen atoms are substituted on the aromatic ring, and specifically, 1,2,4-trichlorobenzene,
1,3,5-trichlorobenzene, 1,4,6-trichloronaphthalene and the like can be mentioned.

The 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-dinitrochlorobenzene and 2,5-dichloro Mono- or dihalonitrobenzenes such as nitrobenzene; 2-nitro-4,4'-
Dihalonitrodiphenyl ethers such as dichlorodiphenyl ether; Dihalonitrodiphenyl sulfones such as 3,3′-dinitro-4,4′-dichlorodiphenyl sulfone; 2,5-Dichloro-3- Nitropyridine, 2-
Examples include mono- or dihalonitropyridines such as chloro-3,5-dinitropyridine; and various dihalonitronaphthalenes.

By using these active hydrogen-containing halogeno aromatic compounds, polyhalogeno aromatic compounds, halogeno aromatic nitro compounds, etc., the degree of branching of the copolymer produced may be increased or the molecular weight may be increased as required. The physical properties of the copolymer can be improved by, for example, reducing the residual salt content.

As the branching agent or the molecular weight adjusting agent, in addition to the above compounds, for example, cyanuric chloride or other 3
A compound having at least one reactive halogen atom can also be used. In the present invention, only one of these branching agents or molecular weight modifiers may be used alone, or 2
You may use it in combination of 2 or more types.

Polymerization additives such as the metal salts mentioned above include carboxylates of metals such as sodium acetate, potassium acetate and zinc acetate; alkali metal mineral salts such as sodium phosphate; alkaline earth metal mineral salts; benzene. Examples thereof include alkali metal sulfonates such as sodium sulfonate. These metal salts may be used alone or in combination of 2
You may use it in combination of 2 or more types.

Further, examples of the above-mentioned inert solvent include hydrocarbons such as benzene, toluene, xylene, biphenyl and anthracene; ethers such as diphenyl ether and polyethylene glycol. Among them, solvents having a high boiling point are preferable because they are carried out at a relatively high temperature.

Solvents which do not dissolve the above polyarylene sulfide at room temperature include benzene, toluene,
Hydrocarbons such as xylene, biphenyl, o-ta-phenyl, m-ta-phenyl, anthracene; halogenated compounds such as halogenated biphenyl, 1-halogenated naphthalene; methanol, ethanol, propanol, butanol −
Alcohols such as benzyl alcohol, benzyl alcohol, glycerin, ethylene glycol, diethylene glycol;
Ethers such as ter and diphenyl ether; acetone,
Examples thereof include ketones such as methyl ethyl ketone and tetrahydrofuran (THF); sulfones such as sulfolane.

Examples of the above-mentioned pH controllable solution include acidic solutions of phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid and the like;
Examples thereof include alkaline solutions such as sodium hydroxide, potassium hydroxide and aqueous ammonia; salts such as ammonium chloride, ammonium sulfide and ammonium phosphate; and pH buffer solutions prepared from a mixture thereof.

Next, one example of a suitable method in the embodiment of the present invention will be described. First, an alkali metal sulfide or an alkali metal hydrosulfide and an alkali metal hydroxide are mixed in a polar solvent. When a catalyst is used, it is added at the same time and mixed. After heating as necessary, dehydration operation such as azeotropic distillation is performed, and then the dichloroaromatic compound and the dibromoaromatic compound are added simultaneously or separately, and usually 1
The polymerization reaction is carried out by heating to a temperature of 50 to 300 ° C., preferably 180 to 280 ° C. and heating for 0.1 to 40 hours, preferably 0.5 to 20 hours. If the reaction temperature is lower than 150 ° C, the reaction rate is slow and the reaction may be non-uniform, while if it exceeds 300 ° C, the produced polymer is deteriorated. The reaction time depends on the type and amount of the raw materials used, or the reaction temperature, and therefore cannot be specified unconditionally, but if the reaction time is less than 0.1 hours, the polymer produced is likely to have a low molecular weight. Beyond that, productivity falls.

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

The reaction pressure is not particularly limited because it depends on the type and amount of the starting materials and the solvent used, the reaction temperature, etc., and is not particularly limited, but usually the self-pressure of the polymerization reaction system or 40 kg / cm. It is preferable to carry out at ² or less.

The reaction may be a one-step reaction conducted at a constant temperature, a multi-step reaction in which the temperature is raised stepwise, or a reaction in which the temperature is continuously changed.

The produced polymer may be directly separated by a method commonly used after the reaction, such as filtration or centrifugation, or after the reaction is completed, the reaction solution is added to water or an aqueous solution of an acid. You may separate by methods, such as filtration. Further, since the purpose is to remove the oligomer component, in order to enhance the effect, the reaction solution may be added to the polar solvent after completion of the reaction and then separated by a method such as filtration.

Subsequently, the polymer isolated is usually treated with water or warm water in order to remove the raw materials attached to the polymer.
Or methanol, ethanol, acetone, ether,
It is washed with a relatively low boiling point organic solvent such as THF. The use of a relatively dilute aqueous acid solution for cleaning is effective in removing adhering sodium hydroxide, etc. Among them, dilute hydrochloric acid, dilute phosphoric acid, dilute acetic acid are easy to handle and economical. And the like are preferably used. The polymer thus isolated is dried by heating to a temperature at which a solvent such as water evaporates. Drying may be performed under vacuum, or may be performed in air or in an atmosphere of an inert gas such as nitrogen.

[0046]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 1300 g of N-methylpyrrolidone (NMP) and NaSH.xH ₂ were added to 4 liter autoclave.
O 309.3 g (4.0 mol), sodium hydroxide 17
Charge 6.0 g (4.4 mol), under nitrogen atmosphere, 200 ℃
Water-NMP mixture is distilled off by heating to
I dehydrated. Then, the system was sealed and a solution of 586.5 g (3.99 mol) of p-dichlorobenzene and 2.4 g (0.01 mol) of p-dibromobenzene in 300 g of NMP was added under pressure, and the mixture was further added at 220 ° C. for 5 hours. 2 at 240 ° C
The reaction was performed under pressure in a nitrogen atmosphere for an hour. After cooling the reaction vessel, the contents were taken out, washed with 4 Kg of NMP, washed once with 30 Kg of water, and then washed twice with hot water at 80 ° C. The polymer was separated by filtration, purified, and dried under reduced pressure at 80 ° C. to obtain a white powdery arylene sulfide polymer. The melting point of this polymer is 285 ° C., and THF
The extraction rate was 0.39%. Furthermore, this polymer is 2
When heat-treated at 50 ° C. for 1 hour, the melting point is 284 ° C., the melt viscosity is 300 ° C., the load is 10 kg, and the temperature is 550 pois in a hold for 5 minutes.
It was e. When this sample was held at 300 ° C. for 15 minutes, it was 600 poise (10 kg load), and the melt stability was 0.92.

The THF extraction rate was determined as follows.
To 70 ml of THF, 5 g of powdered PPS was added and stirred at room temperature for 1 hour. A condenser is attached, the mixture is refluxed for 1 hour in a hot bath at 75 ° C., the vessel is capped and left for about 15 hours, and then filtered. The filtrate was concentrated using an evaporator and then at 80 ° C.
After vacuum drying for about 15 hours, the THF extraction rate was obtained from the weight of the extract.

The melting point was measured by a differential scanning calorimeter (DSC) manufactured by Seiko Denshi. The melt viscosity was measured under various described conditions using a flow tester manufactured by Shimadzu Corporation. The melt stability was calculated by the following equation.

[0050] Example 2 In the same manner as in Example 1, except that 582.1 g (3.96 mol) of p-dichlorobenzene and 9.4 g (0.04 mol) of p-dibromobenzene were dissolved in 300 g of NMP. Was carried out in the same manner as in Example 1 above. The melting point of this polymer is 285 ° C.,
The THF extraction rate was 0.30%. Further, when this polymer was heat-treated at 250 ° C. for 1 hour, the melting point was 283 ° C. and the melt viscosity was 510 poise (300 ° C., 10 kg load, 5 minutes hold). And after holding for 15 minutes, 5
It was 50 poise and the melt stability was 0.93. [Example 3] In the same manner as in Example 1, except that 558.6 g (3.80 mol) of p-dichlorobenzene and 47.2 g (0.20 mol) of p-dibromobenzene were added to 300 g of NMP. Was carried out in the same manner as in Example 1 above. The melting point of this polymer was 286 ° C., and the THF extraction rate was 0.22%. Further, when this polymer is heat-treated at 250 ° C. for 1 hour, the melting point is 284.
℃, melt viscosity 515 poise (300 ℃, 10kg load,
5 minutes hold). When it was held for 15 minutes, it was 530 poise and the melt stability was 0.94.

[0051] Example 4 4l o - Tokure - Bed in N- methylpyrrolidone _{(NMP) 1300g, Na 2 S} · 9H 2
Charge O 312.2 (4.0 mol), and under nitrogen atmosphere, 2
The water-NMP mixture was distilled by raising the temperature to 00 ° C. for dehydration. Then, the system was sealed and a solution of 586.5 g (3.99 mol) of p-dichlorobenzene and 2.4 g (0.01 mol) of p-dibromobenzene in 300 g of NMP was added under pressure, and the mixture was further added at 220 ° C. for 5 hours. 240
The reaction was performed under pressure in a nitrogen atmosphere at 2 ° C. for 2 hours. The treatment after the completion of the reaction was performed in the same manner as in Example 1 to obtain a white powdery arylene sulfide polymer. This polymer
Had a melting point of 285 ° C. and a THF extraction rate of 0.37%. Furthermore, when this polymer is heat-treated at 250 ° C. for 1 hour, the melting point is 284 ° C., the melt viscosity is 300 ° C., 10 Kg.
The load was 580 poise at the hold for 5 minutes. And when this sample was held at 300 ° C for 15 minutes, 6
It is 20 poise (10 kg load) and the melt stability is 0.
It was 92.

[0052] Comparative Example 1 4l o - Tokure - Bed in N- methylpyrrolidone (NMP) 1300g, NaSH · xH 2
O 309.3 g (4.0 mol), sodium hydroxide 17
Charge 6.0 g (4.4 mol), under nitrogen atmosphere, 200 ℃
Water-NMP mixture is distilled off by heating to
Dehydrated. Then, the system was closed and a solution of 588.0 g (4.00 mol) of p-dichlorobenzene dissolved in 300 g of NMP was added under pressure, and the mixture was further added at 220 ° C. for 5 hours and further at 240 ° C.
The reaction was performed for 2 hours under pressure in a nitrogen atmosphere. The treatment after the completion of the reaction was performed in the same manner as in Example 1 to obtain a white powdery arylene sulfide polymer. The melting point of this polymer was 282 ° C., and the THF extraction rate was 0.66%. Furthermore, when this polymer was heat-treated at 250 ° C. for 1 hour, the melting point was 281 ° C. and the melt viscosity was 1500 poise.
(300 ° C., 10 kg load, 5 minutes hold). When this was held for 15 minutes, gelation occurred and solidified during the measurement.

[0053] Comparative Example 2 4l o - Tokure - Bed in N- methylpyrrolidone _{(NMP) 1300g, Na 2 S} · 9H 2
Charge O 312.2 (4.0 mol), and under nitrogen atmosphere, 2
The water-NMP mixture was distilled by raising the temperature to 00 ° C and dehydrated. Then, the system was sealed and a solution of 588.0 g (4.00 mol) of p-dichlorobenzene dissolved in 300 g of NMP was added under pressure, and the mixture was further added at 220 ° C. for 5 hours for 2 hours.
The reaction was carried out at 40 ° C. for 2 hours under pressure in a nitrogen atmosphere. The treatment after the completion of the reaction was performed in the same manner as in Example 1 to obtain a white powdery arylene sulfide polymer. The melting point of this polymer is 280 ° C, and the THF extraction rate is 0.69%.
Met. Further, when this polymer is heat-treated at 250 ° C. for 1 hour, the melting point is 280 ° C. and the melt viscosity is 1520 po.
It was ise (300 ° C., load of 10 kg, hold for 5 minutes). When this was held for 15 minutes, gelation occurred and solidified during the measurement.

[Comparative Example 3] In the above-mentioned Example 1, dichlorobenzene 587.971 g (3.9998 mol), p
The same procedure as in Example 1 was repeated except that 0.047 g (0.0002 mol) of dibromobenzene was dissolved in 300 g of NMP. The melting point of this polymer was 282 ° C., and the THF extraction rate was 0.64%. Furthermore, when this polymer is heat-treated at 250 ° C. for 1 hour, the melting point is 282 ° C. and the melt viscosity is 970 poise (300
C., 10 kg load, hold for 5 minutes). And 15
When held for minutes, it was 8000 poise, and the melt stability was 0.12.

[0055]

The polyarylene sulfide of the present invention has a small amount of oligomer components, and therefore has good impact resistance.
Excellent thermal stability and moldability.

Claims (1)

Claim: What is claimed is: 1. A sulfidizing agent, a dichloroaromatic compound and a dibromoaromatic compound in an organic polar solvent.
A method for producing a polyarylene sulfide, which comprises reacting 1 to 20.0 mol%.