JP7172020B2 - Method for producing polyarylene sulfide resin - Google Patents

Description

The present invention relates to a method for producing polyarylene sulfide resin.

Polyarylene sulfide resins (hereinafter abbreviated as "PAS resins") typified by polyphenylene sulfide resins (hereinafter abbreviated as "PPS resins") are excellent in heat resistance, chemical resistance, etc. , electrical and electronic parts, automobile parts, water heater parts, textiles, film applications, etc.

As a representative method for producing PAS resins, a so-called Phillips method, in which an alkali metal sulfide and a dihaloaromatic compound are reacted in an organic amide solvent such as N-methyl-2-pyrrolidone, is generally used. Among them, a method for producing a high-molecular-weight PAS resin with good productivity by using a high-purity alkali metal sulfide of 95% by weight or more as a raw material is known (see Patent Document 1). ). However, in this method, 0.1 to 0.8 mol of water is added per 1 mol of alkali metal sulfide in order to advance the reaction. had its limits.

JP-A-4-145127

Accordingly, the problem to be solved by the present invention is to provide a method for producing a high-molecular-weight polyarylene sulfide resin with good productivity by suppressing side reactions during the polymerization reaction and containing less side components.

The inventors of the present application conducted various investigations and found that a high-molecular-weight polyarylene sulfide resin can be produced by heating an aliphatic cyclic compound, water, and a sulfidating agent in the absence of a polyhaloaromatic compound. The proportion of alkali metal salt (SMAB) in the hydrolyzate of the aliphatic cyclic compound obtained is important, for this reason, in the absence of the polyhaloaromatic compound, the aliphatic cyclic compound, water, the sulfidating agent is heated at a high temperature to liberate the water of crystallization present in the sulfidating agent, and the polyhaloaromatic compound is added after the formation of the alkali metal salt (SMAB) of the hydrolyzate of the aliphatic cyclic compound. The inventors have found that it is important to suppress the side reaction of water by doing so, and have completed the present invention.

That is, the present invention provides a method for producing polyarylene sulfide by reacting a polyhaloaromatic compound with a sulfidating agent in the presence of an aliphatic cyclic compound, comprising:
In the presence of an inert gas, an aliphatic cyclic compound, water and a sulfidating agent are added at a ratio of 1.5 to 4.0 mol of the aliphatic cyclic compound per 1 mol of sulfur atoms in the sulfidating agent. to a range of 200 ° C. or higher, and the alkali metal salt of the hydrolyzate of the aliphatic cyclic compound is contained in the range of 0.05 to 0.6 mol with respect to the total 1 mol of the sulfur atoms. a step (1) of obtaining
Step (2) of cooling the reaction solution obtained in step (1) to a temperature in the range of 150° C. or more and less than 200° C.
A step (3) of adding a polyhaloaromatic compound to the reaction solution obtained through the step (2) and heating it to a temperature in the range of 200° C. or more and 300° C. or less to carry out a polymerization reaction;
It relates to a method for producing a polyarylene sulfide resin, characterized by having

Further, the present invention provides at least one selected from the group consisting of the polyarylene sulfide resin obtained by the production method described above, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer and a curable resin. The present invention relates to a method for producing a polyarylene sulfide resin composition, comprising a step of melt-kneading two.

The present invention also relates to a method for producing a polyarylene sulfide resin molded article, which comprises molding the polyarylene sulfide resin composition obtained by the above-described production method.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for producing a high-molecular-weight polyarylene sulfide resin with good productivity by suppressing side reactions during a polymerization reaction and containing less side components.

The method for producing polyarylene sulfide of the present invention is a method for producing polyarylene sulfide by reacting a polyhaloaromatic compound with a sulfidating agent in the presence of an aliphatic cyclic compound,
In the presence of an inert gas, an aliphatic cyclic compound, water and a sulfidating agent are added at a ratio of 1.5 to 4.0 mol of the aliphatic cyclic compound per 1 mol of sulfur atoms in the sulfidating agent. to a range of 200 ° C. or higher, and the alkali metal salt of the hydrolyzate of the aliphatic cyclic compound is contained in the range of 0.05 to 0.6 mol with respect to the total 1 mol of the sulfur atoms. a step (1) of obtaining
Step (2) of cooling the reaction solution obtained in step (1) to a temperature in the range of 150° C. or more and less than 200° C.
A step (3) of adding a polyhaloaromatic compound to the reaction solution obtained through the step (2) and heating it to a temperature in the range of 200° C. or more and 300° C. or less to carry out a polymerization reaction;
It is characterized by having a method for producing a polyarylene sulfide resin characterized by having

・Process (1)
In the production method of the present invention, in the presence of an inert gas, an aliphatic cyclic compound, water and a sulfidating agent are mixed with 1.5 to 4 of the aliphatic cyclic compound per 1 mol of total sulfur atoms in the sulfidating agent. .0 mol of the hydrolyzate of the aliphatic cyclic compound is heated to a temperature of 200° C. or higher, and an alkali metal salt (hereinafter sometimes referred to as SMAB) is added to the total 1 mol of the sulfur atoms. and a step (1) of obtaining a reaction solution containing 0.05 to 0.6 mol.

In step (1), first, an aliphatic cyclic compound, water and a sulfidating agent are charged as essential raw material components into a reactor and mixed. Examples of the sulfidating agent include alkali metal sulfides and alkali metal hydrosulfides. Of these, alkali metal sulfides and alkali metal hydrosulfides are preferably used from the viewpoint of efficient production of SMAB. When an alkali metal sulfide and an alkali metal hydrosulfide are used in combination, the alkali metal sulfide is in the range of 80 to 99.9% by mass, preferably 90%, based on the total of the alkali metal sulfide and the alkali metal hydrosulfide. It is preferable to use it in a proportion of up to 99% by mass and the balance being alkali metal hydrosulfide. In step (1), the inert gas may be introduced at the time of charging the raw material components or at the time of heating, which will be described later.

At that time, the amount of the aliphatic cyclic compound charged is preferably in the range of 1.5 to 4.0 mol per 1 mol of the total sulfur atoms in the sulfidation agent, and furthermore, the productivity is improved. A range of 2.0 to 3.5 mol is more preferable from the viewpoint of further increasing the amount.

The amount of water to be charged is in the range of 0.05 to 0.6 mol, preferably 0.1 to 0.6 mol, per 1 mol of the total sulfur atoms in the reaction solution obtained in step (1). Although it is not particularly limited as long as it can be produced in the range of 0.3 mol, for example, the total amount of water in the reaction system in step (1) is preferably 0.05 per 1 mol of sulfur atoms in the sulfidation agent. The amount of water contained in the raw material (for example, as water of crystallization in the sulfidation agent) (in the present invention, "sulfidation It is preferable to add water at the time of preparation after subtracting the amount of water in the agent).

In the step (1), the mixture containing the aliphatic cyclic compound, water and sulfidation agent as essential raw material components charged in the reactor is then heated in the presence of an inert gas. The heating conditions are not particularly limited, but if the total amount of water in the reaction system at the time of charging exceeds the above range, equip the reaction vessel with equipment such as distillation to keep it within that range, It can be heated and reacted under reduced pressure. However, when the total amount of water in the reaction system at the time of charging is within the above range, it is more preferable to heat and react in a closed system from the viewpoint of improving productivity. As for the temperature condition, heating is performed so as to be in the range of 200° C. or higher. Since step 1 does not involve a polymerization reaction, there is no need to consider the melting point or decomposition temperature of the polyarylene sulfide resin, and there is no need to set the upper limit of the temperature conditions. The temperature is preferably 300° C. or less from the viewpoint of securing the corrosiveness of the part and the design strength. In addition, nitrogen gas, argon gas, helium gas, etc. are mentioned as inert gas.

Here, as the aliphatic cyclic compound used in the present invention, any known compound can be used without particular limitation as long as it can be ring-opened by hydrolysis. Specific examples of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, N-methyl-ε-caprolactam, formamide, acetamide, N-methylformamide, N,N - Aliphatic cyclic amide compounds such as dimethylacetamide, 2-pyrrolidone, ε-caprolactam, hexamethylphosphoramide, tetramethylurea, N-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinoic acid, amidourea , and lactams. Among these, aliphatic cyclic amide compounds, particularly NMP, are preferred because of their good reactivity.

Specific examples of alkali metal sulfides used in the present invention include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide. Each of these may be used alone, or two or more thereof may be mixed and used. Among these alkali metal sulfides, sodium sulfide and potassium sulfide are preferred, and sodium sulfide is particularly preferred. These alkali metal sulfides may be anhydrides or so-called hydrates containing water of crystallization. Alkali metal sulfides can also be obtained by reacting alkali metal hydrosulfides and alkali metal hydroxides, but those prepared in advance outside the reaction system may also be used. Specific examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Among these, lithium hydroxide, sodium hydroxide and potassium hydroxide are particularly preferred, and sodium hydroxide is particularly preferred. The alkali metal hydroxide is preferably used as an aqueous solution, and its concentration is preferably in the range of 10 to 50% by mass.

Specific examples of the alkali metal hydrosulfide used in the present invention include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide and cesium hydrosulfide. Each of these may be used alone, or two or more thereof may be mixed and used. Among these alkali metal hydrosulfides, sodium hydrosulfide and potassium hydrosulfide are preferred, and sodium hydrosulfide is particularly preferred. Alkali metal hydrosulfides can also be obtained by reacting hydrogen sulfide and alkali metal hydroxides, but those prepared in advance outside the reaction system may also be used.

The sulfidating agent used as a raw material in step (1) has a water content in the range of 0 mol (anhydride) to 0.55 mol per 1 mol of total sulfur atoms. is preferably used, more preferably in the range of 0.01 to 0.29 mol. The use of a sulfidating agent having a water content within the above range is not only preferable from the viewpoint of suppressing side reactions during polymerization and making it possible to increase the molecular weight of the PAS resin, but also the step (1). In , it is possible to adjust the amount of SMAB produced by adjusting the amount of water charged, and as a result of eliminating the need for distillation, it is also preferable from the viewpoint of improving productivity, such as saving the time occupied by the polymerization reaction vessel. When the sulfidating agent used as a raw material in step (1) contains a water content exceeding the above range, the water content within the above range may be obtained in advance outside the reaction vessel used for the polymerization reaction (outside the reaction system). It is preferable to use it after adjusting the water content to . In addition, when a solid alkali metal sulfide is used, the particle size (number average particle size of at least 50 points according to the circle equivalent diameter by microscopy) is in the range of 10 to 800 μm. is more preferable, and it is particularly preferable to use a solid one having a particle size in the range of 50 to 500 μm. However, since the alkali metal sulfide has deliquescent properties, the particles may be partially bonded to each other.

Thus, in the step (1), prior to the polymerization reaction step, in the absence of a polyhaloaromatic compound, a sulfidation agent, particularly an alkali metal sulfide, an aliphatic cyclic compound, water, and an alkali metal hydrosulfide are added in advance. By heat-treating at a temperature range of 200°C or higher, if there is water of crystallization in the sulfidating agent, liberation is promoted, and moisture in the system, which causes side reactions in the polymerization process, is efficiently removed. , It is considered that it is converted to a hydrolyzate of an aliphatic cyclic compound that is believed to exhibit a polymerization promoting effect, and as a result, it is possible to promote the increase in the molecular weight of the PAS resin while suppressing side reactions during polymerization. .

・Process (2)
The reaction solution obtained in step (1) is cooled. At that time, the temperature range of the reaction solution is in the range of 150° C. to less than 200° C., preferably in the range of 180° C. to 199° C., from the viewpoint of efficient production of SMAB and its stable existence. The temperature difference between the temperature after heating the reaction solution in step (1) and the temperature after cooling the reaction solution in step (2) is not particularly limited, but from the viewpoint of productivity, it is 50 to 80°C. is preferably in the range of The cooling conditions may be either an open system or a closed system, and are not particularly limited, but from the viewpoint of improving productivity, the reaction is preferably performed in a closed system.

・Process (3)
Step (3) is a step of adding a polyhaloaromatic compound to the reaction solution obtained through step (2) and heating the mixture to a temperature in the range of 200° C. or higher and 300° C. or lower to carry out a polymerization reaction.

Specific examples of the polyhaloaromatic compound used in the present invention include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3, 5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6-trihalonaphthalene, 2,5-dihalotoluene, 1,4-dihalo naphthalene, 1-methoxy-2,5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-di Halonitrobenzene, 2,4-dihaloanisole, p,p'-dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenyl sulfone, 4,4'-dihalodiphenyl sulfoxide, 4 ,4'-dihalodiphenyl sulfide, and compounds having an alkyl group having 1 to 18 carbon atoms as a nuclear substituent on the aromatic ring of each of the above compounds. Further, the halogen atoms contained in each of the above compounds are desirably chlorine atoms and bromine atoms.

Among the above polyhaloaromatic compounds, bifunctional dihaloaromatic compounds are preferred because they are characterized by the ability to efficiently produce a linear high-molecular-weight PAS resin in the present invention. P-dichlorobenzene, m-dichlorobenzene, 4,4'-dichlorobenzophenone and 4,4'-dichlorodiphenylsulfone are preferred, and p-dichlorobenzene is particularly preferred, from the viewpoint of good mechanical strength and moldability. Further, when it is desired to give a branched structure to a part of the polymer structure of the linear PAS resin, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, or 1 , 3,5-trihalobenzene is preferably used in combination.

Alternatively, copolymers containing two or more different reactive units can be obtained by appropriately selecting combinations of polyhaloaromatic compounds, such as p-dichlorobenzene and 4,4′-dichlorobenzophenone or 4,4′-dichlorobenzophenone. It is particularly preferable to use it in combination with 4'-dichlorodiphenyl sulfone, since a polyarylene sulfide having excellent heat resistance can be obtained.
The amount of the polyhaloaromatic compound charged is not particularly limited, but since the amount charged is directly subjected to the polymerization reaction, from the viewpoint of productivity or economy, the total amount of sulfur atoms in the amount charged of the sulfidation agent used in step (1) is It is preferably used in a ratio of 0.8 to 1.2 mol per 1 mol, more preferably in an equimolar ratio. The method of adding the polyhaloaromatic compound to the reaction solution obtained through the step (2) includes a method of adding the amount necessary for charging all at once, a method of adding in two or more portions, and furthermore, , continuous dripping may be used.

In this step (3), a lithium salt compound may be added to the reaction system and the reaction may be carried out in the presence of lithium ions. Specific examples of lithium salt compounds that can be used here include lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium carbonate, lithium hydrogen carbonate, lithium sulfate, lithium hydrogen sulfate, lithium phosphate, and phosphoric acid. Lithium hydrogen, lithium dihydrogen phosphate, lithium nitrite, lithium sulfite, lithium chlorate, lithium chromate, lithium molybdate, lithium formate, lithium acetate, lithium oxalate, lithium malonate, lithium propionate, lithium butyrate, iso Lithium butyrate, lithium maleate, lithium fumarate, lithium butanedioate, lithium valerate, lithium hexanoate, lithium octanoate, lithium tartrate, lithium stearate, lithium oleate, lithium benzoate, lithium phthalate, benzenesulfonic acid Inorganic lithium salt compounds such as lithium, lithium p-toluenesulfonate, lithium sulfide, lithium hydrosulfide, and lithium hydroxide; lithium methoxide, lithium ethoxide, lithium propoxide, lithium isopropoxide, lithium butoxide, lithium phenoxide, etc. and an organic lithium salt compound of Among these, lithium chloride and lithium acetate are preferred, and lithium chloride is particularly preferred. Also, the above lithium salt compound can be used as an anhydride, a hydrous compound, or an aqueous solution. When the lithium salt compound is added to the reaction system in step (3) and the reaction is performed in the presence of lithium ions, the amount used is 1 mol of the total sulfur atoms of the sulfidating agent used in step (1). , preferably in the range of 0.01 mol or more and less than 0.9 mol, because the polyarylene sulfide resin can be made to have a higher molecular weight.

The reaction conditions of step (3) are not particularly limited as long as the temperature range allows polymerization, but the temperature at which the polymerization reaction can easily proceed, that is, the range of 200° C. or higher and 300° C. or lower, preferably 210° C. It is preferable to carry out the reaction in the range of 215°C or higher and 250°C or lower, more preferably in the range of 215°C or higher and 250°C or lower. The timing of heating the reaction solution and adding the polyhaloaromatic compound in step (3) is not particularly limited. Alternatively, the polyhaloaromatic compound may be added while heating.

In the production method of the present invention, the water content at the start of polymerization in step (3) is preferably as small as possible, and for example, it is preferably in the range of the detection limit to 0.08 mol per 1 mol of the total sulfur atoms. More preferably, the range is from the detection limit to 0.05 mol. Since water is produced as the polymerization reaction progresses, it is preferable that 0.1 to 0.3 mol of water is produced per 1 mol of the total sulfur atoms at the end of the polymerization reaction in step (3). The above range is preferably satisfied after the conversion rate of the group compound exceeds 80 mol %, more preferably after 60 mol %, more preferably immediately after the initiation of polymerization.

Here, the conversion rate of the polyhaloaromatic compound is represented by the following formula.
Conversion rate (%) = (charged amount - residual amount) / charged amount x 100
However, the "amount charged" represents the mass of the polyhaloaromatic compound charged into the reaction system, and the "remaining amount" represents the mass of the polyhaloaromatic compound remaining in the reaction system.

- Post-treatment step The reaction mixture containing the polyarylene sulfide resin obtained by the polymerization reaction can be subjected to a post-treatment step. The post-treatment step may be any known method and is not particularly limited. For example, after the completion of the polymerization reaction, the reaction mixture is first treated as it is, or after adding an acid or base, it is treated under reduced pressure or normal pressure. and then wash the solid after solvent distillation with a solvent such as water, acetone, methyl ethyl ketone, alcohols once or twice, and then neutralize, wash with water, filter and dry, or After completion of the polymerization reaction, water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons, and other solvents (soluble in the polymerization solvent used and A solvent which is a poor solvent for at least polyarylene sulfide resins) is added as a precipitant to precipitate solid products such as polyarylene sulfide resins and inorganic salts, which are separated by filtration, washed and dried. Alternatively, after the completion of the polymerization reaction, the reaction mixture is added with a reaction solvent (or an organic solvent having a solubility equivalent to that of the low-molecular-weight polymer), stirred, filtered to remove the low-molecular-weight polymer, and then water, A method of washing once or twice or more with a solvent such as acetone, methyl ethyl ketone, alcohols, etc., followed by neutralization, washing with water, filtration and drying, and the like.
In the above post-treatment method, the polyarylene sulfide resin may be dried in a vacuum, in the air, or in an atmosphere of an inert gas such as nitrogen.

The polyarylene sulfide resin thus obtained can be used as it is for various molding materials, etc. However, it may be subjected to heat treatment in air, oxygen-enriched air, or under reduced pressure conditions for oxidative cross-linking. The temperature of this heat treatment is preferably in the range of 180.degree. C. to 270.degree. In addition, the heat treatment may be performed using an extruder or the like at a temperature higher than the melting point of the polyarylene sulfide resin and in a state in which the polyarylene sulfide resin is molten. It is preferable to carry out at +100° C. or lower.

・Production apparatus In the reaction apparatus used in each of the above steps in the method for producing a polyarylene sulfide resin of the present invention, the contact portion with the raw material, the reaction solution, or the product obtained after the reaction is composed of titanium, zirconium, and nickel alloys. It is preferable to use the

Examples of the reaction apparatus include a batch-type reaction vessel (reaction vessel) equipped with a stirring blade inside, and a reaction vessel (polymerization line) such as a continuous reaction vessel (polymerization line), stirring blades, baffle plates, and the like.

For example, a batch-type reaction vessel may be any vessel that can hold a reaction liquid or a crude reaction mixture inside the reaction vessel, and is composed of, for example, an upper lid, a body, and a bottom, and optionally Examples include those having a structure that can be sealed, and those having a structure having a stirring blade, a shaft for transmitting power to the stirring blade, a baffle, and a coiled tube for temperature control are preferable from the viewpoint of excellent stirring efficiency. Here, examples of the stirring blades include anchor-type stirring blades, turbine-type stirring blades, screw-type stirring blades, double-helical stirring blades, and the like. From the viewpoint of facilitating heat conduction and heat control, it is preferable that the lower end of the baffle plate (baffle) is installed to the vicinity of the bottom surface of the reaction vessel, while the upper end is installed to the position above the liquid surface.

Further, for example, the reaction vessel can be further equipped with various measuring devices such as a thermometer, a pressure gauge, and a safety valve. In addition, when the total amount of water in the reaction system at the time of charging in step (1) exceeds the above range, the reaction vessel is equipped with a steam distillation line, a condenser, a decanter, a distillation It is preferably provided with a column, a distillate return line, an exhaust line, a hydrogen sulfide capture device, etc. (referred to as distillation equipment in the present invention).

On the other hand, the continuous reaction vessel includes, for example, a tubular reactor in which a plurality of mixing elements having no moving parts are fixed, a polymerization line in which the tubular reactors are connected in series, or a plurality of tubular reactors. Examples thereof include those forming a continuous cyclic polymerization line that connects reactors and has a structure in which a part of the reaction solution is circulated to the raw material inlet of the tubular reactor. These continuous reactors can feed raw materials and transfer reaction liquids by means of plunger pumps or the like.

In the reaction apparatus used in the present invention, the "portion in contact with the raw material, the reaction solution, or the product obtained after the reaction" refers to the raw material, that is, the organic polar solvent, the polyhaloaromatic compound, and the sulfide, inside the reaction apparatus. It is part or all of the inner wall surface of the reaction apparatus with which the reaction agent, alkali catalyst, etc., mixture thereof, and the product obtained after the polymerization reaction thereof come into contact. The raw material, the reaction solution, or the product obtained after the reaction may be in the form of a slurry. Inorganic salts containing alkali metals such as substances are also included.

The reaction device used in the present invention may have at least a portion, preferably all, of its contact portions made of the nickel alloy. The nickel alloy used here is an alloy composed of 43 to 47% by mass or more of chromium, 0.1 to 2% by mass of molybdenum, and the balance of nickel and unavoidable impurities from the viewpoint of corrosion resistance. be. Contents of tungsten, iron, cobalt and copper are preferably below the detection limit.

In the present invention, the term "inevitable impurities" means minute amounts of impurities that are technically difficult to remove. In the present invention, for example, carbon atoms contained in the alloy in a proportion of 1% by mass or less, preferably a detection limit or less, can be mentioned.

・Molding processing, etc. The polyarylene sulfide resin obtained by the production method of the present invention detailed above is subjected to various melt processing methods such as injection molding, extrusion molding, compression molding, and blow molding to improve heat resistance, moldability, and dimensional properties. It can be processed into moldings with excellent stability.

In addition, the polyarylene sulfide resin obtained by the present invention can be used as a polyarylene sulfide resin composition in combination with various fillers in order to further improve performance such as strength, heat resistance and dimensional stability. I can. Examples of fillers include, but are not limited to, fibrous fillers and inorganic fillers. Fibrous fillers include fibers such as glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium sulfate, calcium silicate, and natural fibers such as wollastonite. can be used. Inorganic fillers include barium sulfate, calcium sulfate, clay, viroferrite, bentonite, sericite, zeolite, mica, mica, talc, attalpalgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, and glass beads. can be used. In addition, various additives such as release agents, colorants, heat stabilizers, UV stabilizers, foaming agents, rust preventives, flame retardants and lubricants can be added during molding.

Furthermore, the polyarylene sulfide resin obtained by the present invention can be suitably used for polyesters, polyamides, polyimides, polyetherimides, polycarbonates, polyphenylene ethers, polysulfones, polyethersulfones, polyetheretherketones, polyethers, etc. Ketone, polyarylene, polyethylene, polypropylene, polytetrafluoroethylene, polydifluoroethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, synthetic resin such as liquid crystal polymer, or polyolefin rubber It may be used as a polyarylene sulfide resin composition containing an elastomer such as fluororubber, silicone rubber or the like.

Since the polyarylene sulfide resin obtained by the production method of the present invention has various properties inherent in polyarylene sulfide resin such as heat resistance and dimensional stability, it can be used, for example, in connectors, printed circuit boards and sealed moldings. Injection molding or It is widely useful as a material for various molding processes such as compression molding, extrusion molding of composites, sheets, pipes, etc., pultrusion molding, or as a material for fibers or films.

EXAMPLES The present invention will be specifically described below with reference to examples. These examples are illustrative and not limiting.

(Measurement of melt viscosity (V6) of PPS resin)
The produced PPS resin is held for 6 minutes at 300° C., load: 1.96×10 ⁶ Pa, L/D=10 (mm)/1 (mm) using a flow tester “CFT-500D” manufactured by Shimadzu Corporation. measured after.

(Production rate of alkali metal salt (SMAB) of hydrolyzate of aliphatic cyclic compound)
A 1 L autoclave was charged with Na ₂ S, NMP and water, and heated to a constant temperature. After that, it was cooled to 200° C. and charged with DCB. At 200° C., the valve was slightly opened to drain residual water from the interior of the autoclave. The extracted water was diluted with acetone and the water content was measured. Since the amount of water consumed and the SMAB production rate are equal, the SMAB production rate was calculated from the following formula.
SMAB production rate (%) = (moisture content (g) - removed moisture content (g)) / moisture content (g) x 100

(Quantification of phenol (by-product) amount)
10 g of the obtained PPS slurry and 0.2 g of the internal standard substance (chlorobenzene) are weighed out and diluted with 15 g of acetone. The resulting diluted solution was treated with ultrasonic waves for 5 minutes and subjected to solid-liquid separation with a centrifuge. After that, 1 μL of the supernatant was sampled and measured with a gas chromatograph.

The gas chromatograph was measured using Shimadzu Gas Chromatography "GC2014" (column: column "G300" manufactured by Foundation for Chemical Evaluation and Research, carrier gas: helium, measurement column conditions: held at 140°C for 5 minutes → 3°C The temperature was raised to 200° C. at a rate of 1/min→holding at 200° C. for 20 minutes). In order to determine the phenol concentration, first, a calibration curve was created using standard samples. Next, from the chromatogram obtained by measuring the supernatant prepared above, the peak area with the same retention time as the standard sample was obtained. The concentration in the measured solution was obtained from the peak area and the calibration curve, and the number of moles of phenol per 1 mol of the sulfidation agent (1 mol of the total sulfur atoms charged) was calculated as a percentage (hereinafter, "mol%/S" ).

(Quantification of moisture content)
The water content was measured by the Karl Fischer volumetric titration method using a Karl Fischer moisture analyzer (AQV-300, manufactured by Hiranuma Sangyo Co., Ltd.).

[Example 1]
The inner wall (wetted part) connecting the pressure gauge, thermometer, and raw material transportation pipe is made of titanium, and 128.42 g of Na ₂ S with a moisture content of 1.1% is placed in a 1 L titanium autoclave with a stirring blade (Na ₂ S: 1.64 mol, solid with an average particle size of 300 μm), 7.47 g of 45% NaSH (NaSH: 0.06 mol), 0.55 g of water (total amount of water: 0.20 mol), NMP 301.55 g was charged and nitrogen substitution was performed. After charging, the autoclave was sealed and the temperature was raised to 250° C. over 3 hours while stirring. Next, after cooling to 195° C. or less, p-dichlorobenzene (hereinafter abbreviated as p-DCB) 249.90 g (DCB: 1.70 mol) was melted at 80° C. from the outside into the autoclave through the raw material transportation pipe. was added all at once and held for 1 hour. When the water content in the system was measured, it was 0.02 mol. Next, the temperature was raised to 220° C. and held at 220° C. for 3 hours. Further, the temperature was raised to 250° C., the mixture was reacted at 250° C. for 1 hour, and then cooled to room temperature.

After adding 400 g of ion-exchanged water at 70° C. to 100 g of the obtained polymerization slurry and stirring for 10 minutes, the mixture was filtered, and 600 g of ion-exchanged water at 70° C. was added to the filtered cake to wash the cake. After adding 400 g of ion-exchanged water at 70°C to the resulting water-containing cake and stirring for 10 minutes, the mixture was filtered, and 600 g of ion-exchanged water at 70°C was added to the filtered cake to wash the cake. This operation was repeated twice. The resulting water-containing cake was dried at 120° C. for 4 hours using a hot air dryer to obtain a white powdery polymer.

The melt viscosity of the obtained polymer was 155 Pa·s. The SMAB yield was 90%. The amount of phenol as a by-product (number of moles per 1 mole of total sulfur charged, hereinafter “mol/S”) was 0.05 mol %/S.

[Example 2]
"After charging, the autoclave was closed and the temperature was raised to 250 ° C. over 3 hours while stirring." Example 1 was followed, except for the "heated" point. After the addition of DCB, the water content in the system was measured and found to be 0.05 mol.
The melt viscosity of the obtained polymer was 103 Pa·s. The SMAB yield was 74%. The amount of phenol as a by-product was 0.11 mol %/S.

[Comparative Example 1]
128.42 g of Na ₂ S with a moisture content of 1.1% (Na ₂ S: 1.64 mol) was placed in a 1 L autoclave with a stirring blade and an inner wall (liquid contact part) connecting a pressure gauge and a thermometer made of titanium. , 7.47 g of 45% NaSH (NaSH: 0.06 mol), 0.55 g of water (total amount of water: 0.20 mol), 249.90 g of p-dichlorobenzene (hereinafter abbreviated as p-DCB) (DCB: 1.70 mol) and 301.55 g of NMP were charged, and nitrogen substitution was performed. After charging, the autoclave was sealed and heated to 200° C. over 3 hours while stirring. Incidentally, when the water content in the system was measured, it was 0.10 mol. After that, the temperature was raised to 220° C. and held at 220° C. for 3 hours. After that, the temperature was raised to 250° C. and held at 250° C. for 1 hour.

After adding 400 g of ion-exchanged water at 70° C. to 100 g of the obtained polymerization slurry and stirring for 10 minutes, the mixture was filtered, and 600 g of ion-exchanged water at 70° C. was added to the filtered cake to wash the cake. After adding 400 g of ion-exchanged water at 70°C to the resulting water-containing cake and stirring for 10 minutes, the mixture was filtered, and 600 g of ion-exchanged water at 70°C was added to the filtered cake to wash the cake. This operation was repeated twice. The resulting water-containing cake was dried at 120° C. for 4 hours using a hot air dryer to obtain a white powdery polymer.

The melt viscosity of the obtained polymer was 41 Pa·s. The SMAB reaction rate was 51%. The amount of phenol as a by-product was 0.38 mol %/S.

Claims (5)

A method for producing polyarylene sulfide, comprising reacting a polyhaloaromatic compound with a sulfidating agent in the presence of an aliphatic cyclic compound,
In the presence of an inert gas, an aliphatic cyclic compound, water and a sulfidating agent are added in an amount ranging from 1.5 to 4.0 mol of the aliphatic cyclic compound per 1 mol of sulfur atoms in the sulfidating agent. A reaction containing 0.05 to 0.6 mol of the alkali metal salt of the hydrolyzate of the aliphatic cyclic compound in the range of 0.05 to 0.6 mol with respect to 1 mol of the total of the sulfur atoms by heating to a ratio of 200 ° C. or higher the step of obtaining a liquid (1),
Step (2) of cooling the reaction solution obtained in step (1) to a temperature in the range of 150° C. or more and less than 200° C.
a step (3) of adding a polyhaloaromatic compound to the reaction solution obtained through the step (2) and heating the mixture to a temperature in the range of 200° C. or more and 300° C. or less to carry out a polymerization reaction;
the amount of water in the sulfidating agent in step (1) is in the range of 0 to 0.55 mol per 1 mol of sulfur atoms;
Heating and reacting in a closed system in step (1);
The step (2) is reacting in a closed system;
A method for producing a polyarylene sulfide resin , wherein the aliphatic cyclic compound is an aliphatic cyclic amide compound. The temperature difference between the temperature after heating the reaction solution in step (1) and the temperature after cooling the reaction solution in step (2) is in the range of 50 to 80 ° C., and the reaction solution in step (2) 2. The production method according to claim 1, wherein the temperature after cooling is in the range of 180° C. or higher and 199° C. or lower. 2. The method for producing a polyarylene sulfide resin according to claim 1, wherein steps (1) to (3) are all carried out in a closed reaction vessel and in the same reaction vessel. A step of obtaining a polyarylene sulfide resin by the production method according to any one of claims 1 to 3, the polyarylene sulfide resin obtained in this step, an inorganic filler, and a thermoplastic other than the polyarylene sulfide resin A method for producing a polyarylene sulfide resin composition, comprising the step of melt-kneading at least one other component selected from the group consisting of resins, elastomers and curable resins. A method for producing a polyarylene sulfide resin molded product, comprising the steps of obtaining a polyarylene sulfide resin composition by the method of claim 4 and molding the polyarylene sulfide resin composition obtained in this step.