JP2004352923A - Method for producing polyarylene sulfide resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a new polyarylene sulfide resin that has markedly increased crystallization retardancy. <P>SOLUTION: The method for producing a polyarylene sulfide resin comprises step I where a sulfidizing agent and an aromatic dihalo compound (A) are allowed to react with each other in an organic polar solvent until the consumption rate of the sulfidizing agent attains to ≥ 90 mol.% , followed by step II where an aromatic polyhalo compound (B) bearing a substituent having electron attractive resonance effect is added and allowed to react them to complete the polymerization reaction. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００５１】
【発明の効果】
本発明の製造方法によれば、ＰＡＳの結晶化時間を飛躍的に遅延させることが可能となり、耐熱性、耐薬品性に優れ、特に繊維やフィルム用途等に幅広く利用可能なＰＡＳを提供することが出来る。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a polyarylene sulfide resin which is excellent in heat resistance and chemical resistance, has a delayed crystallization time, and can be widely used for fibers and films.
[0002]
[Prior art]
Polyarylene sulfide resin represented by polyphenylene sulfide resin has excellent heat resistance, chemical resistance, and the like, and has recently been widely used for fiber and film applications. Examples of the method for producing polyarylene sulfide include a method in which an alkali metal sulfide is reacted with a polyhalo aromatic compound in an organic polar solvent.
[0003]
When the polyarylene sulfide resin is used for applications such as fibers and films, it is necessary to control the time from the molten state to the processing into a product (processing time). Since the polyarylene sulfide resin is solidified and crystallized simultaneously with the crystalline resin, the time until solidification means the crystallization time. If the property of delaying the crystallization time (referred to as “crystallization delay property” in the present invention) is large, the processing time can be lengthened, and the workability is improved. Therefore, it is an important property. As a technique for imparting the crystallization retardation property to the polyarylene sulfide resin, a method by introducing a polyhalo aromatic compound such as trichlorobenzene to a molecular terminal can be cited (for example, see Patent Document 1). However, the crystallization retardation of PAS obtained by this production method was insufficient.
[0004]
[Patent Document 1]
JP-A-2002-212292 (pages 2-6)
[0005]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a novel method for producing a polyarylene sulfide resin in which the crystallization retardation of the polyarylene sulfide resin is dramatically improved.
[0006]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, as a result of intensive testing and research, the following findings were obtained.
(1) When a substituent having an electron-withdrawing resonance effect is introduced into the terminal of the polyarylene sulfide resin, the crystallization retardation property is improved.
(2) An effective means for introducing a substituent having an electron-withdrawing resonance effect at the terminal of the polyarylene sulfide resin is to react a sulfidizing agent with a polyhalo aromatic compound to produce a polyarylene sulfide resin. After reacting a sulfidizing agent with a polyhaloaromatic compound until the consumption rate of the sulfidizing agent reaches 90 mol% or more, a polyhaloaromatic having a substituent having an electron-withdrawing resonance effect on the aromatic ring is obtained. The reaction is performed by adding a compound and performing a polymerization reaction in two stages.
(3) When the above-mentioned polymerization reaction is carried out in one step, the resulting polyarylene sulfide resin does not have a high molecular weight, a substituent having an electron-attracting resonance effect cannot be introduced into the molecular terminal, and the crystallization retardation property is low. Has no effect.
[0007]
The present invention is based on such findings. That is, the step I of reacting the sulfidizing agent and the dihalo-aromatic compound (A) in an organic polar solvent until the consumption rate of the sulfidizing agent reaches 90 mol% or more, and then the resonance effect of electron withdrawing property A method for producing a polyarylene sulfide resin comprising a step II of adding a polyhaloaromatic compound (B) having a substituent having an aromatic ring on the aromatic ring to terminate the polymerization reaction.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, polyphenylene sulfide resin is abbreviated as PPS, and polyarylene sulfide resin is abbreviated as PAS.
Examples of the dihalo aromatic compound (A) used in the step I include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2, 5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-di Haloanisole, p, p'-dihalodiphenylether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenylsulfone, 4,4'-dihalodiphenylsulfoxide, 4,4'-dihalodiphenylsulfide And the like.
[0009]
Also, a copolymer containing two or more different reaction units can be obtained by an appropriate combination of dihaloaromatic compounds. The specific combination is not particularly limited, and two or more arbitrarily selected from the dihalo-aromatic compounds can be appropriately combined. Among them, p-dichlorobenzene and 4,4 It is particularly preferable to use a combination of 4'-dichlorobenzophenone or a combination of p-dichlorobenzene and 4,4'-dichlorodiphenylsulfone since polyarylene sulfide having various excellent physical properties can be obtained.
[0010]
The amount of the dihalo aromatic compound used in the step I is preferably in the range of 0.8 to 1.3 mol, more preferably 0.9 to 1.1 mol, per mol of the sulfur source in the sulfidizing agent used. Range. When the amount of the dihaloaromatic compound used is within this range, it is possible to obtain a high molecular weight PAS having excellent physical properties.
[0011]
The polyhalo aromatic compound (B) having a substituent having an electron-withdrawing resonance effect on the aromatic ring used in the step II may be a dihalo compound having a substituent having an electron-withdrawing resonance effect. For example, although not particularly limited, for example, 2,6-dihalobenzonitrile, 4,4′-dihalobenzophenone, 2,4-dihalobenzophenone, 2 ′, 4′-dihaloacetophenone, '-Haloacetophenone, 4-halobenzophenone, 4,4'-dihalodiphenylsulfone, 2,6-dihalobenzamide, methyl 2-halobenzoate, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene , 2,4,5-trihalonitrobenzene, 4-halobenzenesulfonamide and the like.
[0012]
Among these, 2,6-dihalobenzonitrile, 4,4'-dihalobenzophenone, and 4,4'-dihalodiphenylsulfone are preferably used.
[0013]
The halogen atom in the polyhalo aromatic compounds (A) and (B) is preferably a chlorine atom or a bromine atom. Further, as the polyhalo aromatic compounds (A) and (B), those having an alkyl group having 1 to 18 carbon atoms as a substituent on the aromatic ring can also be preferably used.
[0014]
The sulfidizing agent used in step I is not particularly limited, and an anhydride, a hydrate or an aqueous solution of an alkali metal sulfide can be used. Examples of these compounds include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide and cesium sulfide, or hydrates thereof, which may be used alone or in combination of two or more. May be used. Among the alkali metal sulfides, sodium sulfide and potassium sulfide are preferable from the viewpoint of excellent reactivity, and sodium sulfide is particularly preferable.
[0015]
The alkali metal sulfide can be obtained by reacting an alkali metal hydroxide and an alkali metal hydroxide, or hydrogen sulfide and an alkali metal hydroxide, and these materials are previously stored in a reaction vessel. And the metal sulfide can be prepared by reacting before the start of the sulfidation in Step I. Alternatively, these materials can be added together with the organic polar solvent or polyhaloaromatic compound in Step I. In advance, the reaction in Step I can be performed in parallel. Further, metal sulfide may be prepared in advance in another reactor and used.
[0016]
As the alkali metal hydroxide, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and the like, among which lithium hydroxide, sodium hydroxide and potassium hydroxide are preferred And more preferably sodium hydroxide. These may be used alone or in combination of two or more. In addition, both the alkali metal hydrosulfide and the alkali metal hydroxide may be used in the reaction in any form such as a solid state, a liquid state, and a molten state, and there is no particular limitation.
[0017]
Usually, a small amount of alkali metal hydroxide may be added in order to react with a small amount of alkali metal sulfide and alkali metal thiosulfate in the alkali metal sulfide.
[0018]
The alkali metal hydrosulfide is not particularly limited, and can be used as an anhydride, a hydrate or an aqueous solution of the alkali metal hydrosulfide. Examples of the alkali metal hydrosulfide include lithium bisulfide, sodium bisulfide, potassium bisulfide, rubidium bisulfide and cesium bisulfide, and hydrates thereof. These may be used alone or in combination of two or more.
[0019]
Examples of the organic polar solvent used in Step I and Step II of the present invention include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexylpyrrolidone, N-methyl-ε-caprolactam, and formamide. , Acetamide, N-methylformamide, N, N-dimethylacetamide, 2-pyrrolidone, ε-caprolactam, hexamethylphosphoramide, tetramethylurea, N-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone Examples include acid amide ureas and lactams; sulfolane such as sulfolane and dimethyl sulfolane; nitriles such as benzonitrile; ketones such as methylphenyl ketone; and mixtures thereof. Among these organic polar solvents, N-methyl-2-pyrrolidone is particularly preferred from the viewpoint of improving the reactivity of the sulfidizing agent.
[0020]
The amount of the organic polar solvent used in the present invention depends on the type of the solvent to be used and the amount of water with respect to the solvent in the system, and is not particularly limited, but in order to maintain the reaction system in a stirrable state. The amount of the organic polar solvent used in the polymerization is preferably in the range of 1.0 to 6.0 mol per mol of the sulfur source in the sulfidizing agent, and is preferably in the range of 1.0 to 6.0 mol per mol of the sulfur source in the sulfidizing agent. A range of 5 to 4.5 mol is more preferred.
[0021]
The polymerization conditions in Step I and Step II of the present invention are not particularly limited, but are preferably in the range of 200 to 300 ° C, more preferably in the range of 220 to 260 ° C.
[0022]
In the step II of the present invention, the addition time of the polyhalo aromatic compound (B) is preferably after the reaction is substantially completed, for the purpose of introducing the polyhalo aromatic compound (B) into the molecular terminal of the polymer. It is necessary to add at the stage where the consumption rate of the agent is 90 mol% or more, and particularly preferably at the stage where the consumption rate of the sulfidizing agent is 93 mol% or more. The upper limit of the consumption rate of the sulfidizing agent is preferably as high as possible. However, if the upper limit is usually in the range of 93 to 99.1 mol%, a PAS having excellent crystallization retardation can be obtained. Here, the “consumption rate of the sulfidizing agent” is derived from the ratio between the remaining amount of the sulfidizing agent and the charged amount.
[0023]
The amount of the polyhaloaromatic compound (B) that can be used in the step II is preferably in the range of 0.01 to 10 mol%, particularly preferably, the sulfur source in the sulfidizing agent charged in the step I. Ranges from 0.1 to 5 mol%. If the amount of the polyhaloaromatic compound used in the step II is within such a range, it is possible to obtain a PAS having a retarded crystallization which is the object of the present invention.
[0024]
Further, the reaction vessel used in the reaction of Step I and Step II is not particularly limited, but a reaction vessel having excellent corrosion resistance made of titanium, chromium, zirconium, or the like in the liquid contact portion, In addition, it is preferable that any of the reactions is performed in an inert gas atmosphere. Examples of the inert gas to be used include nitrogen, helium, neon, and argon. Of these, nitrogen is preferable from the viewpoints of economy and easy handling.
[0025]
The reaction mixture containing PAS obtained in the polymerization reaction is separated into a liquid and a solid by filtration under normal pressure or reduced pressure, the solvent is recovered from the liquid part, and a double product such as salt is recovered from the solid part. In order to remove unreacted raw materials and the like, it is common practice to repeat washing with water and solvent, and finally dry and take out the PAS.
[0026]
Specific post-treatment methods for the reaction mixture containing PAS after the polymerization reaction include, for example, the following post-treatment methods (1) to (3).
{Circle around (1)} After completion of the polymerization reaction, first, the reaction mixture is left as it is, or after adding an acid or a base, the solvent is distilled off under reduced pressure or normal pressure, and then the solid after distilling off the solvent is treated with water, acetone, methyl ethyl ketone, A method of washing once or twice or more with a solvent such as alcohols, and further neutralizing, washing, filtering and drying to separate and extract PAS;
[0027]
(2) After the completion of the polymerization reaction, the reaction mixture is mixed with a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons (for the organic polar solvent used in Step I). A solvent that is soluble and is at least a poor solvent for PAS) is added as a precipitant to precipitate solid products such as PAS and inorganic salts. Is separated, washed and dried to separate and obtain PAS;
[0028]
{Circle around (3)} After completion of the polymerization reaction, the same organic polar solvent (or an organic solvent having the same solubility in a low molecular weight polymer) as that initially added to the reaction mixture is added, stirred, filtered, and filtered to obtain a low molecular weight. After the coalescence, the organic polar solvent and its dissolved substance are removed, the solid containing PAS is washed once or twice with a solvent such as water, acetone, methyl ethyl ketone, or alcohols, and then neutralized, washed with water, filtered and A method of drying and taking out the PAS.
[0029]
In the post-treatment methods exemplified in the above (1) to (3), drying of the PAS may be performed in a vacuum, in air or in an inert gas atmosphere such as nitrogen. There is no particular limitation.
[0030]
The PAS obtained in this way can be used as it is for various molding materials, but it is possible to increase the viscosity during melting by heat treatment in air or oxygen-enriched air or under reduced pressure. If necessary, such a thickening operation (usually, such an operation is referred to as “crosslinking”) may be performed and then used for various molding materials.
[0031]
The temperature at which the cross-linking is performed, that is, the cross-linking temperature, cannot be unconditionally specified because it differs depending on the heat treatment time for performing the target cross-linking and the atmosphere in which the heat treatment is performed.
[0032]
When the crosslinking is performed by an extruder or the like, the crosslinking may be performed in a molten state higher than the melting point of the PAS, but may be performed at a temperature lower than the melting point by 100 ° C. or more in order to avoid thermal deterioration of the PAS.
[0033]
The PAS obtained by the above-mentioned production method can be processed into a molded product excellent in heat resistance, workability, dimensional stability, and the like by a molding method such as injection molding, extrusion molding, compression molding, and blow molding. Furthermore, the composition added with the silane coupling agent can also dramatically improve the toughness of the molded product.
[0034]
The silane coupling agent is not particularly limited, for example, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, epoxycyclohexyltrimethoxysilane, glycidoxypropylmethylethoxysilane, aminopropyltrimethoxy Silane and the like.
[0035]
The amount of the silane coupling agent to be used is not particularly limited, but is preferably 0.01 to 2 parts by weight based on 100 parts by weight of PAS from the viewpoint that the effect of improving the toughness of the molded product is remarkable. preferable.
[0036]
In addition, the composition can be used in combination with various fillers as far as the object of the present invention is not impaired in order to further improve the performance such as strength, heat resistance, and dimensional stability. The filler used in the present invention is not particularly limited, and examples thereof include a fibrous filler and an inorganic filler. Examples of the fibrous filler include glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate fiber, silicon carbide fiber, calcium sulfate fiber, calcium silicate fiber, and wollastonite fiber. Fiber can be used. Examples of the inorganic filler include barium sulfate, calcium sulfate, clay, viroferrite, bentonite, sericite, zeolite, mica, mica, talc, atalpargite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, and glass beads. Can be used.
[0037]
In addition, various additives such as a release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust inhibitor, a flame retardant, and a lubricant are used as additives during the molding process without departing from the object of the present invention. Can be contained.
[0038]
Further, similarly, the following synthetic resins and elastomers can be mixed and used. The synthetic resin used in the present invention is not particularly limited, but includes polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, Examples thereof include polyarylene, polyethylene, polypropylene, polytetrafluoroethylene, polydifluoroethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, and liquid crystal polymer. Further, the elastomer is not particularly limited, and examples thereof include polyolefin rubber, fluorine rubber, and silicone rubber.
[0039]
The composition containing PAS obtained by the production method of the present invention and a silane coupling agent, various fillers, synthetic resins, and / or elastomers also has various properties such as heat resistance and dimensional stability inherent to PAS. Therefore, for example, electrical and electronic components such as connectors, printed circuit boards and molded products, automotive parts such as lamp reflectors and various electrical components, various building materials, interior materials such as aircraft and automobiles, or OA Injection molding or compression molding of precision parts such as equipment parts, camera parts and watch parts, or extrusion molding of composites, sheets, pipes, etc., or as a material for various molding processes such as pultrusion molding, or for fibers or films It is widely useful as a material.
[0040]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples. All parts and percentages are by weight unless otherwise specified.
[0041]
(Measurement method of melt viscosity)
The melt viscosity η of the polyphenylene sulfide obtained by the production methods of Examples and Comparative Examples described below was 300 ° C., a shear rate of 100 sec ⁻¹ , a nozzle hole diameter of 0.5 mm, and a length of 1. using a Koka flow tester. It was measured at 0 mm.
[0042]
The crystallization retardation was evaluated by measuring the crystallization temperature by the following method, and judging the degree of crystallization rate.
The crystallization temperature is determined by using a differential scanning calorimeter in a nitrogen atmosphere at 350 ° C. for 3 minutes and then cooling to 120 ° C. at a speed of 20 ° C./min. The peak temperature of the exothermic peak during crystallization was determined as the crystallization temperature. (The difference in the crystallization speed comes out as the difference in the crystallization temperature, and the lower the crystallization temperature, the slower the crystallization speed and the higher the crystallization retardation.)
[0043]
Example 1
(Step I) 804.2 g of sodium sulfide hydrate (hereinafter abbreviated as Na ₂ S.H ₂ O) in a titanium-lined stainless steel 4-liter autoclave with stirring blades connected to a temperature sensor, a cooling tower, a dropping tank, and a dropping pump. (5.0 mol) and 1586 g (16 mol) of NMP were charged at room temperature, and the temperature was raised to 205 ° C. under a nitrogen atmosphere with stirring to distill 315.0 g of water. Thereafter, the reaction system was sealed, the temperature was further raised to 220 ° C., and a mixed solution of 735.0 g (5.0 mol) of p-dichlorobenzene (hereinafter abbreviated as p-DCB) and 396 g (4 mol) of NMP was added dropwise. After stirring at 220 ° C. for 3 hours, the mixture was heated to 250 ° C. and stirred for 1 hour. At this point, the remaining amount of the sulfidizing agent was measured, and it was confirmed that the consumption rate of the sulfidizing agent was 95 mol%. (Step II) Then, a mixed solution of 4.30 g of 2,6-dichlorobenzonitrile (0.025 mol; 0.5 mol% based on the sulfur source in the sulfidizing agent charged in step I) and 30.0 g of NMP Was added to the system and stirred at 250 ° C. for 1 hour.
[0044]
After cooling, the resulting slurry was filtered, and the cake (filtered product) was again stirred with 5 L of NMP for 1 hour, washed, and filtered. Next, the cake was poured into 20 liters of water, stirred at 80 ° C. for 1 hour, and filtered. The cake was again stirred in 5 liters of hot water for 1 hour, washed and filtered. This operation was repeated four times, followed by filtration and drying in a hot air dryer at 120 ° C. overnight to obtain 508 g (94% yield) of white powdery PPS. The melt viscosity of the obtained PPS was 47 Pa · s. Next, Table 1 shows the evaluation results of the crystallization retardation obtained by the above-described method of evaluating the crystallization retardation.
[0045]
Example 2
In Step II, instead of 4.30 g (0.025 mol) of 2,6-dichlorobenzonitrile, 6.28 g of 4,4′-dichlorobenzophenone (0.025 mol; in the sulfidizing agent charged in Step I) The same operation as in Example 1 was performed except that the amount was changed to 0.5 mol% based on the sulfur source. The melt viscosity of the obtained PPS was 42 Pa · s. Next, Table 1 shows the evaluation results of the crystallization retardation obtained by the above-described method of evaluating the crystallization retardation.
[0046]
Example 3
In Step II, instead of 4.30 g (0.025 mol) of 2,6-dichlorobenzonitrile, 7.18 g (0.025 mol) of 4,4′-dichlorodiphenyl sulfone in the sulfidizing agent charged in Step I was used. The same operation as in Example 1 was performed except that the amount was 0.5 mol% based on the sulfur source. The melt viscosity of the obtained PPS was 40 Pa · s. Next, Table 1 shows the evaluation results of the crystallization retardation obtained by the above-described method of evaluating the crystallization retardation.
[0047]
Comparative Example 1
(Step I) Sodium sulfide hydrate (hereinafter abbreviated as Na ₂ S · H ₂ O) 804 in a titanium-lined stainless steel 4-liter autoclave with stirring blades connected to a temperature sensor, a cooling tower, a dropping tank, and a dropping pump. Then, 0.2 g (5.0 mol) and 1983 g (20 mol) of NMP were charged at room temperature, and the temperature was raised to 205 ° C. under a nitrogen atmosphere while stirring to distill 315.0 g of water. Thereafter, the reaction system was sealed, the temperature was further raised to 220 ° C, p-DCB 735.0 g (5.0 mol) was added dropwise, and the mixture was stirred at 220 ° C for 3 hours, then heated to 250 ° C and stirred for 1 hour. did. (Step 2) Next, 4.54 g (0.025 mol; 1,2,4-trichlorobenzene (hereinafter abbreviated as 1,2,4-TCB); with respect to the sulfur source in the sulfidizing agent charged in Step I) (0.5 mol%) and 5.0 g of NMP were added into the system, and the mixture was stirred at 250 ° C. for 1 hour.
[0048]
After cooling, the resulting slurry was filtered, and the cake (filtered product) was again stirred with 5 L of NMP for 1 hour, washed, and filtered. Next, the cake was poured into 20 liters of water, stirred at 80 ° C. for 1 hour, and filtered. The cake was again stirred in 5 liters of hot water for 1 hour, washed and filtered. This operation was repeated four times, followed by filtration and drying in a hot air dryer at 120 ° C. overnight to obtain 508 g (yield: 94%) of white powdery polyphenylene sulfide. The melt viscosity of the obtained polymer was 45 Pa · s (the operation described in Example 3 of JP-A-2002-212292). Next, Table 1 shows the evaluation results of the crystallization retardation obtained by the above-described method of evaluating the crystallization retardation.
[0049]
Comparative Example 2
Except that in Step I, 4.30 g (0.025 mol; 0.5 mol% based on the sulfur source in the sulfidizing agent) of 2,6-dichlorobenzonitrile was added dropwise simultaneously with p-DCB. The reaction was carried out under the same conditions as in step I of step 1, and after cooling, the obtained slurry was filtered, and the cake (filtered product) was again stirred with 5 liters of NMP for 1 hour, washed, and filtered. . Next, the cake was poured into 20 liters of water, stirred at 80 ° C. for 1 hour, and filtered. The cake was again stirred in 5 liters of hot water for 1 hour, washed and filtered. This operation was repeated four times. After filtration, the powder was dried in a hot air dryer at 120 ° C. overnight to obtain a white powdery PPS. The melt viscosity of the obtained polymer was 23 Pa · s, and the molecular weight was lower than that of PPS obtained by the two-step reaction of the present invention. Next, Table 1 shows the evaluation results of the crystallization retardation obtained by the above-described method of evaluating the crystallization retardation.
[0050]
[Table 1]

[0051]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to the manufacturing method of this invention, it becomes possible to drastically delay the crystallization time of PAS, and to provide PAS which is excellent in heat resistance and chemical resistance, and which can be widely used especially for fibers and films. Can be done.

Claims (3)

Step I of reacting the sulfidizing agent with the dihalo-aromatic compound (A) in an organic polar solvent until the consumption rate of the sulfidizing agent reaches 90 mol% or more, and then has an electron-withdrawing resonance effect. A method for producing a polyarylene sulfide resin, comprising a step II of adding a polyhaloaromatic compound (B) having a substituent on an aromatic ring and reacting to terminate the polymerization reaction. 2. The method for producing a polyarylene sulfide resin according to claim 1, wherein the amount of the polyhalo aromatic compound (B) added is in the range of 0.01 to 10 mol% based on the charged amount of the sulfidizing agent in Step I. 3. . The polyhalo aromatic compound (B) is at least one compound selected from the group consisting of 2,6-dihalobenzonitrile, 4,4′-dihalobenzophenone and 4,4′-dihalodiphenylsulfone. Item 3. The method for producing a polyarylene sulfide resin according to item 1 or 2.