JPH05271414A - Production of high-molecular-weight polyarylene sulfide - Google Patents

Abstract

PURPOSE:To obtain a polyarylene sulfide having a low oligomer content, a high molecular weight without thermal cross-linking and excellent impact strength by reacting a polyhaloaromatic compound with a sulfiding agent in an organic polar solvent in two steps. CONSTITUTION:The title process comprises reacting a polyhaloaromatic compound (B) with a sulfiding agent (A) in an organic polar solvent. The reaction is carried out in two steps: step 1 of reacting compound B with agent A in the presence of water in the organic polar solvent to form a polyarylene sulfide prepolymer, and step 2 of adding fresh compound B and fresh water to the system and continuing the reaction to increase the molecular weight of the polyarylene sulfide (prepolymer). The melt viscosity of the prepolymer obtained in step 1 is about 5-1000 P (under conditions of a load of 10kg, a temperature of 316 deg.C and a holding time of 5min).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing high molecular weight polyarylene sulfide (hereinafter abbreviated as PAS). More specifically, a PA which has a substantially linear or branched structure, a small amount of oligomers, and excellent impact strength without using a polymerization aid or thermal crosslinking.
The present invention relates to a method for manufacturing S.

PAS is a thermoplastic resin having excellent properties such as heat resistance, chemical resistance, and dimensional stability of molded products, and is mainly used as electric / electronic device parts, machine parts, automobile parts and the like. In recent years, thermoplastic resins having higher heat resistance and higher mechanical strength have been required for these applications. P obtained by the production method of the present invention
AS can be used for these applications and can be expected to be used for films, sheets, fibers and the like.

[0003]

2. Description of the Related Art A typical manufacturing method of PAS is N
-A method of reacting a dihaloaromatic compound with sodium sulfide in an organic polar solvent such as methylpyrrolidone is disclosed in JP-B-45.
No. 3368. PAS produced by this method has an extremely low molecular weight and melt viscosity,
This PAS was oxidatively cross-linked by heat treatment in air and used as a PAS having a viscosity capable of being injection-molded. However, PAS cross-linked in this way
Was very brittle and lacked in impact strength.

In order to improve such drawbacks, various methods have been proposed for obtaining PAS having a high degree of polymerization without thermal crosslinking. As a representative,
There is a method described in Japanese Patent No. 12240. An alkali metal carboxylate is used as a polymerization aid in the reaction system described above. This method requires not only the raw material cost because the polymerization aid requires an equimolar amount or more with respect to sodium sulfide, but also the purification and separation step after the completion of the polymerization becomes difficult,
This is an economically disadvantageous method.

As a method for greatly improving this cost problem, there is a method described in Japanese Patent Publication No. 63-33775. This is a method in which a large amount of water is used instead of the polymerization aid, and the reaction is carried out by changing the polymerization temperature and the amount of water in two stages. This method can be synthesized at low cost and high molecular weight PAS can be obtained. However, the PA obtained here
Since S has a very large amount of oligomer, it was found that mechanical properties such as impact strength were not sufficiently improved even though it was a linear type.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks in mechanical properties such as impact strength of the non-crosslinked high molecular weight PAS. In other words, it is intended to provide a method for producing PAS in which the amount of the oligomer that causes the decrease is high and the molecular weight is high without oxidative crosslinking treatment, and as a result, mechanical properties such as impact strength are improved. is there.

[0007]

[Means for Solving the Problems] As a result of various studies on a method for producing PAS in which the amount of the oligomer is reduced, which is the reason why the mechanical properties such as impact strength of the linear high molecular weight PAS are not improved, It was found to be effective to add the polyhaloaromatic compound to the reaction system in the two steps. The production method is a method for producing PAS by reacting a sulfidizing agent (A) with a polyhaloaromatic compound (B) in an organic polar solvent, characterized in that this reaction is carried out in at least the following two steps. It is a method for producing a high molecular weight PAS.

(1) Sulfiding agent (A) and polyhaloaromatic compound (B) in an organic polar solvent in the presence of water (C).
The first step of reacting the polyarylene sulfide prepolymer to produce a polyarylene sulfide prepolymer, (2) and then adding the polyhaloaromatic compound (B) and water (C) into the system to continue the reaction to give a polyarylene sulfide. Second step of increasing the molecular weight of

In the present production method, the polyarylene sulfide prepolymer is produced in the first step. This step is a step in which the monomer is consumed along with the polymerization reaction and the molecular weight increases. However, when the monomer is consumed to some extent and the polymerization reaction proceeds, a decomposition reaction occurs in parallel. This decomposition reaction hinders the increase in the molecular weight and causes the increase in the amount of the oligomer. The decomposition reaction may be due to inorganic sulfur, decomposition of disulfide, decomposition due to chain transfer, etc. Since the end of the oligomer generated by the decomposition reaction is a sulfur end, by adding a dihaloaromatic compound in the second step, the polymerization reaction of the oligomers proceeds to obtain PAS with a small amount of the oligomer. it can.

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 tetramethylurea, N, N'-dimethylethyleneurea, 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 in admixture of two or more.

Of the above various solvents, N is preferable.
-Alkyl lactams and N-alkyl pyrrolidones, particularly preferred is N-methyl pyrrolidone.
The polar solvent is used in a molar ratio of 1 to 20, preferably 2 to 10 with respect to the sulfidizing agent. If the amount of the solvent is less than 1, the reaction may be non-uniform,
On the other hand, if it exceeds 20, the reaction rate will be remarkably slowed and the productivity will be lowered.

In the method of the present invention, for example, an alkali metal sulfide or an alkali metal hydrosulfide can be preferably used as the sulfidizing agent. Moreover, you may use these mixtures.

Examples of the above-mentioned alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and the like. They are,
They may be used alone or in combination of two or more. Further, the alkali metal sulfide is an anhydride,
Either a hydrate or an aqueous solution may be used, but when a hydrate or an aqueous solution is used, it is preferable to carry out a dehydration operation before the reaction as described later. Among 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, cesium hydrosulfide and the like. These may be used alone or in combination of two or more. As the alkali metal hydrosulfide, any of anhydrate, hydrate and aqueous solution may be used. When using a hydrate or aqueous solution, it is better to carry out dehydration operation as described later. Among these,
Preferred are lithium hydrosulfide and sodium hydrosulfide, and particularly preferred is sodium hydrosulfide.

When an alkali metal hydrosulfide is used as the sulfidizing agent, it is used as a mixture with an alkali metal hydroxide. The amount of the alkali metal hydroxide used at this time is in the range of 0.5 to 5, preferably in the range of 0.6 to 3 in molar ratio with respect to the sulfur source of the alkali metal hydrosulfide.

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.

Examples of the polyhaloaromatic compound used in the present invention include dihalobenzenes such as o-dihalobenzene, m-dihalobenzene and p-dihalobenzene; 2,3-dihalotoluene, 2,5-dihalotoluene, 2,6-dihalotoluene, 3,4-dihalotoluene, 2,5-dihaloxylene, 1-ethyl-2,5-dihalobenzene, 1,2,4,5-tetramethyl-3,6
-Dihalogenoalkyl- or cycloalkyl-substituted benzenes such as dihalobenzene, 1-normalhexyl-2,5-dihalobenzene, 1-cyclohexyl-2,5-dihalobenzene; 1-phenyl-2,5-dihalobenzene, 1-benzyl-2 , 5-dihalobenzene, 1-p-
Dihalogenoaryl-substituted benzenes such as toluyl-2,5-dihalobenzene; dihalogenobiphenyls such as 4,4′-dihalobiphenyl; 1,4-dihalonaphthalene,
Dihalogenonaphthalenes such as 1,6-dihalonaphthalene and 2,6-dihalonaphthalene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,4,6-
Examples thereof include trihalonaphthalene.

The plurality of halogen elements in these polyhaloaromatic compounds are each fluorine, chlorine, bromine or iodine, and they may be the same.
They may be different from each other.

These polyhaloaromatic compounds may be used alone or in combination of two or more.

Among the above polyhalo aromatic compounds, polyhalobenzenes are preferable, and p-dichlorobenzene is particularly preferable.

If necessary, a branching agent or a molecular weight modifier such as an active hydrogen-containing haloaromatic compound or a haloaromatic nitro compound, a polymerization additive such as a metal salt, or a reduction agent may be used within the scope of the present invention. The agent, the inert organic solvent, etc. may be appropriately selected and added to the reaction system to carry out the reaction.

The active hydrogen-containing halo aromatic compound is
For example, it is a halogeno aromatic compound having a functional group having active hydrogen such as an amino group, a thiol group, a hydroxyl group and a carboxyl group, and specifically, 2,3-dichloroaniline and 2,4-dichloro Dihaloanilines such as aniline, 2,5-dichloroaniline, 2,6-dichloroaniline; 2,3,4-trichloroaniline, 2,3,3
5-trichloroaniline, 2,3,6-trichloroaniline, 2,4,5-trichloroaniline, 2,4,6-
Trihaloanilines such as trichloroaniline and 3,4,5-trichloroaniline; tetrahaloanilines such as 2,3,4,5-tetrachloroaniline and 2,3,5,6-tetrachloroaniline; '-Diamino-4,
Dihalodiaminodiphenyl ethers such as 4'-dichlorodiphenyl ether and 2,4'-diamino-2 ', 4-dichlorodiphenyl ether; and in these compounds, the amino group is a thiol group. , Compounds substituted with a hydroxyl group or a carboxyl group, and the like. Further, an active hydrogen-containing halo aromatic compound in which a hydrogen atom bonded to a carbon atom forming an aromatic ring in these active hydrogen-containing halo aromatic compounds is substituted with an inactive group such as an alkyl group can also be used. . Among these various active hydrogen-containing haloaromatic compounds, active hydrogen-containing dihaloaromatic compounds are preferable, and dichloroaniline is particularly preferable.

The haloaromatic nitro compound is
A compound in which a halo atom is substituted on an aromatic ring having a nitro group, and specifically, mono- or dihalonitrobenzenes such as 2,4-dinitrochlorobenzene and 2,5-dichloronitrobenzene; 2-nitro-4, Dihalonitrodiphenyl ether such as 4'-dichlorodiphenyl ether
Teres; 3,3'-dinitro-4,4'-dichlorodiphenyl sulfone and other dihalonitrodiphenyl sulfones; 2,5-dichloro-3-nitropyridine, 2-chloro-3,5-dinitropyridine and the like Examples thereof include mono- or dihalonitropyridines; and various dihalonitronaphthalenes.

These active hydrogen-containing haloaromatic compounds,
By using a haloaromatic nitro compound or the like, the degree of branching of the copolymer to be produced may be increased, the molecular weight may be increased, or the residual salt content may be decreased, if necessary. Various physical properties can be improved.

As the branching agent or the molecular weight adjusting agent, in addition to the above compounds, for example, cyanuric chloride or the like
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.

High Oligomeric Low Molecular Weight P of the Invention
The method for producing AS comprises reacting a sulfidizing agent with a polyhaloaromatic compound in an organic polar solvent as described above, and carrying out at least the above two steps.

The first step is a step of forming a polyarylene sulfide prepolymer. There are no particular restrictions on the implementation, but suitable examples will be described below. First, a sulfidizing agent and a polyhaloaromatic compound are added to an organic polar solvent.
When adding the polyhaloaromatic compound, it may be added together with the sulfidizing agent, or may be added to the system in a solid state, a molten state, or an organic polar solvent at a predetermined temperature or in the course of heating. Good. The amount of polyhaloaromatic compound at this time is not particularly limited, but preferably 0.98 mol to 1.02 per mol of the sulfidizing agent.
Mol is good. When an alkali metal hydrosulfide is used as the sulfidizing agent, an alkali metal hydroxide is added, but this addition method is not particularly limited either, and it is a solid at the same time as the alkali metal hydrosulfide or during heating. Alternatively, it can be added as an aqueous solution. However, the addition of the alkali metal hydroxide is preferably performed before the addition of the polyhaloaromatic compound. The alkali metal hydroxide is preferably 0.93 to 1.20 with respect to 1 mol of the sulfidizing agent. In such a range, the reaction proceeds smoothly and the molecular weight is easily increased. The temperature rising process is preferably performed in a nitrogen atmosphere, and if necessary, water in the system can be distilled out of the system in an unnecessary amount.
However, if the amount of water in the system is small, water will be added. The amount of water at this time is not particularly limited, but preferably 0.5 mol to 2.4 mol per 1 mol of the sulfidizing agent. After the above operation, the reaction is performed at a predetermined temperature for a predetermined time. The reaction temperature at this time is preferably 180 ° C to 2 ° C.
It is better to carry out at 60 ° C.

There is no particular restriction on the polyarylene sulfide prepolymer obtained in the first step, but it is preferable that the prepolymer is obtained by reacting 98 mol% or more at the conversion of the polyhaloaromatic compound defined below. When the viscosity of the obtained poly (arylene sulfide prepolymer) is 5 to 1000 poise (316 ° C., load 10 Kg, hold for 5 minutes), and more preferably in the range of 350 to 800 poise, a higher molecular weight, and It is possible to produce PAS with lower amounts of oligomers.

Here, the conversion rate of the polyhaloaromatic compound is obtained by the following formula. (B1): Charge amount of polyhalo aromatic compound (mol) (B2): Remaining amount of polyhalo aromatic compound (mol) (B3): Charge amount of sulfidizing agent (mol)

[0035]

The second step is basically a step of increasing the molecular weight by reacting the polyarylene sulfide prepolymers obtained in the first step. Particularly, in this step, by adding both the polyhaloaromatic compound and water, a polymerization reaction of the oligomers produced by the decomposition reaction is caused, and as a result, a high molecular weight PAS having a small amount of the oligomer is obtained.

In adding the polyhaloaromatic compound,
The addition form of the compound may be solid, molten, or dissolved in an organic polar solvent. The system at that time may be an open system or a closed system. The addition timing is not particularly limited and can be suitably performed at any time. For example, immediately after the reaction in the first step, the temperature is once lowered after the reaction in the first step, and then the reaction temperature in the second step is increased. It can be added after the temperature is raised or at any stage such as during each temperature rise.

The amount of the polyhaloaromatic compound added in the second step is 0.01 to 0.
20 mol is preferred. Further, the total amount of the polyhaloaromatic compound added in the first step and the second step is preferably 1.00 to 1.15 mol per 1 mol of the sulfidizing agent.

The same applies to the addition of water, and the addition method and the addition timing can all be suitably performed. Incidentally, supplementing the time of addition of water, it can be carried out at the same time as the addition of the polyhaloaromatic compound, before the addition, after the addition, or the like. The amount of water added in the second step is preferably 0.10 to 6.00 with respect to 1 mol of the sulfidizing agent. In addition, the total amount of water added in the first and second steps is 1.4 to 1 mol of the sulfiding agent.
It is preferably 6.5 mol.

The reaction temperature in the second step is 235 to 290.
It is better to perform at ℃.

[0041]

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] 1. First step 4 l autoclave with N-methylpyrrolidone (NMP)
1260g, NaSH · xH₂O 309.3g (4.00m
ol), equipped with an alkali trap, and under a nitrogen atmosphere
In the open system, the temperature starts to rise, and at 100 ℃
164.8 g (4.12 mol) of sodium iodide was added to water 178.
Add an aqueous solution dissolved in 5 g and continue heating.
It was The water-NMP mixture started to distill around 145 ° C.
It was distilled up to 00 ° C. The water distilled at this time was 221.
6g, NMP is 184.9g, S ^2-Is 68.73 mmol
It was. Then, the system is sealed and p-dichlorobenzene 5 is added.
77.9 g (3.93 mol) (monomer ratio 1.00) of N
The solution dissolved in MP311.2g was added by press-fitting,
172.5 g of NMP was added. And 220 ° C for 5 hours
Further, the reaction is performed under pressure in a nitrogen atmosphere at 240 ° C. for 2 hours.
It was After the reaction is complete, the reaction mixture is cooled and half of the slurry is taken as a liquid component.
After separating the solid components by filtration, 30 minutes using 15 kg of warm water at 80 ° C
After stirring, the mixture was separated and this was repeated twice. And depressurize at 80 ℃
Dry, white powdery polyarylene sulfide pres
A polymer was obtained. The melt viscosity of this polymer was measured by Shimadzu
Hold at 316 ° C for 5 minutes using a rotor tester, 10 kg load
It was 450 poise when measured by weight. Got again
The conversion rate obtained from the slurry was 99.2%.
It was

2. Second step 2l autoclave with slurry 128 obtained in the first step
Taking 3.9 g, 8.67 g of p-dichlorobenzene (0.
059mol) (monomer ratio 1.03), water 127.2g
_{(H 2 O / S = 5.00} ), was added NMP194.79G. After making the system a nitrogen atmosphere, the system is closed and the temperature is set to 250 ° C. for 5 minutes.
The reaction was carried out over time. The obtained product was separated by filtration to separate solid components, and then the mixture was stirred with 15 kg of warm water at 80 ° C. for 30 minutes and then separated, and this was repeated twice. And it dried under reduced pressure at 80 degreeC and the white granular polyarylene sulfide polymer was obtained. When the melt viscosity of this polymer was measured, it was 17
It was 00 poise (316 ° C., 10 kg load). See also T
HF extraction rate is 3.09%, Izod impact test 13.0
It was Kgf · cm / cm ² (no notch).

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.

In the Izod impact test, a sample piece was prepared using an injection molding machine and the measurement was performed without a notch. The sample piece used had a cross-sectional area of (3.2 × 3.2) mm ² .

[Example 2] 1. First Step In the first step of Example 1, after adding p-dichlorobenzene, the temperature was raised to 240 ° C. for 5 hours at 220 ° C., and then increased to 4 ° C.
The same procedure as in the first step of Example 1 was carried out except that the reaction was carried out for a time. The melt viscosity of the obtained poly (arylene sulfide) prepolymer was 650 poise. Further, the conversion rate obtained from the obtained slurry was 99.8%.

2. Second step The same process as the second step of Example 1 was performed. The polymer obtained as a result had a melt viscosity of 1750 poise and a THF extraction rate of 3.05%. The Izod impact test is 13.
It was 1 Kgf · cm / cm ² .

Example 3 1. First Step In the first step of Example 1, after adding p-dichlorobenzene, the temperature was raised to 240 ° C. for 4 hours at 220 ° C. and further increased to 1
The same procedure as in the first step of Example 1 was carried out except that the reaction was carried out for a time. The melt viscosity of the obtained polyarylene sulfide prepolymer was 100 poise. Further, the conversion rate obtained from the obtained slurry was 98.7%.

2. Second Step The second step of Example 1 was repeated, except that the reaction temperature was 260 ° C. The resulting polymer had a melt viscosity of 1600 poise,
The THF extraction rate was 3.30%. The Izod impact test was 12.5 Kgf · cm / cm ² .

[Embodiments 4 to 5] In the first embodiment, the second
The same procedure as in Example 1 was carried out except that the monomer ratio in the step was 1.01 to 1.10. The polymerization conditions and results are summarized in Tables 1 and 2.

Example 6 The procedure of Example 2 was repeated, except that the monomer ratio in the first step was 1.01 and the monomer ratio in the second step was 1.05. The polymerization conditions and results are summarized in Tables 1 and 2.

Comparative Example 1 First step 4 l autoclave with N-methylpyrrolidone (NMP)
1260g, NaSH · xH₂O 309.3g (4.00m
ol), equipped with an alkali trap, and under a nitrogen atmosphere
In the open system, the temperature starts to rise, and at 100 ℃
164.8 g (4.12 mol) of sodium iodide was added to water 178.
Add an aqueous solution dissolved in 5 g and continue heating.
It was The water-NMP mixture started to distill around 145 ° C.
It was distilled up to 00 ° C. The water distilled at this time was 221.
6g, NMP is 184.9g, S ^2-Is 68.73 mmol
It was. Then, the system is sealed and p-dichlorobenzene 5 is added.
77.9 g (3.93 mol) (monomer ratio 1.00) of N
The solution dissolved in MP311.2g was added by press-fitting,
172.5 g of NMP was added. And nitrogen atmosphere, pressurization
The reaction was allowed to proceed at 220 ° C for 3 hours. Cooling after the reaction
Then, take half of the slurry and separate the liquid and solid components by filtration.
After stirring for 30 minutes with 15 kg of warm water at 80 ° C, separate after
Was performed twice. And dried under reduced pressure at 80 ℃, white powder
A polyarylene sulfide prepolymer was obtained. This
The polymer had a melt viscosity of 70 poise. Got again
The conversion rate obtained from the slurry obtained was 95.2%.
It was.

2. Second step 2l autoclave with slurry 128 obtained in the first step
Taking 3.9 g, 127.2 g of water (H ₂ O / S = 5.0
0) and NMP194.79g were added. After making the system a nitrogen atmosphere, the system was closed and the reaction was carried out at 260 ° C. for 5 hours.
The obtained product was separated by filtration to separate solid components, and then the mixture was stirred with 15 kg of warm water at 80 ° C. for 30 minutes and then separated, and this was repeated twice. And it dried under reduced pressure at 80 degreeC and the white granular polyarylene sulfide polymer was obtained. When the melt viscosity of this polymer was measured, it was 1400 poise (316
C., 10 kg load). The THF extraction rate is 4.3.
It was 0% and the Izod impact was 10.7 Kgf · cm / cm ² .

Comparative Example 2 1. First Step In the first step of Comparative Example 1, after the addition of p-dichlorobenzene, the temperature was raised to 240 ° C. for 4 hours at 220 ° C. and then increased to 1
The same procedure as in the first step of Comparative Example 1 was performed except that the reaction was performed for a time. The melt viscosity of the obtained polyarylene sulfide prepolymer was 100 poise. Further, the conversion rate obtained from the obtained slurry was 98.8%.

2. Second Step The second step was performed in the same manner as the second step of Comparative Example 1. The polymer obtained as a result had a melt viscosity of 1200 poise and a THF extraction rate of 4.50%. The Izod impact test was 10.
It was ² Kgf · cm / cm ² .

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

According to the method of the present invention, a high molecular weight PAS having a small amount of oligomer and excellent impact strength can be obtained.

Claims (7)

[Claims] 1. A sulfidizing agent (A) in an organic polar solvent.
And polyhaloaromatic compound (B) are reacted to give polyary
A method for producing a high-molecular-weight poly (arylene sulfide), characterized in that the reaction is carried out in at least the following two steps. (1) First step of reacting a sulfidizing agent (A) with a polyhaloaromatic compound (B) in an organic polar solvent in the presence of water (C) to produce a polyarylene sulfide prepolymer, (2) ) Then, the second step of adding the polyhaloaromatic compound (B) and water (C) to the system and continuing the reaction to increase the molecular weight of the polyarylene sulfide. 2. In the second step, the polyhaloaromatic compound (B) is added in an amount of 0.01 to 0.20 mol based on 1.00 mol of the sulfidizing agent (A), and water (C).
The method according to claim 1, wherein the addition amount of 0.10 to 6.00 mol relative to 1.00 mol of the sulfidizing agent (A). 3. The sulfidizing agent (A) in the first step
Molar ratio of polyhaloaromatic compound (B) to [[B]
/ (A)] ₁ is 0.98 to 1.02, the molar ratio of water (C) to sulfidizing agent (A) [(C) / (A)] ₁
Is 0.5 to 2.4, and the sulfidizing agent (A)
Of the total amount of the polyhaloaromatic compound (B) added in the first step and the second step with respect to [(B) / (A)] ₂ is 1.00 to 1.15, The molar ratio [(C) / (A)] ₂ of the total amount of water (C) added in the first step and the second step is 1.4 to 6.5.
The manufacturing method described. 4. The method according to claim 1, 2 or 3, wherein the reaction is carried out in the first step until the conversion of the polyhaloaromatic compound becomes higher than 98 mol%. 5. The melt viscosity of the polyarylene sulfide prepolymer obtained in the first step is 5 to 1000 poise (316 ° C., load 10 kg, hold for 5 minutes, the same applies hereinafter). Production method. 6. The production method according to claim 2, 3 or 4, wherein the melt viscosity of the polyarylene sulfide prepolymer obtained in the first step is 350 to 800 poise. 7. The reaction temperature in the first step is 180 to 2
60 ° C. and the reaction temperature in the second step is 235
The manufacturing method according to claim 2, 3, 4 or 5, which is 290 ° C.