JP6836705B2 - Manufacturing method of polyarylene sulfide resin - Google Patents

Description

The present invention relates to a method for producing a polyarylene sulfide resin. More specifically, the present invention relates to a method for producing a polyarylene sulfide resin, in which the polar organic solvent discharged in the process for producing the polyarylene sulfide resin is reused in the process for producing a new polyarylene sulfide resin.

Polyphenylene sulfide resin (PAS resin) represented by polyphenylene sulfide resin is excellent in heat resistance, chemical resistance and the like, and is widely used in electrical and electronic parts, automobile parts, water heater parts, fibers, film applications and the like. In particular, in applications such as packings for lithium ion batteries and gasket members, ultra-high molecular weight polyarylene sulfide resins have been widely used in recent years because of their excellent toughness and moldability.

The polyarylene sulfide resin can be obtained by a method of polymerizing a sulfidizing agent and a polyhalo aromatic compound in a polar organic solvent such as N-methyl-2-pyrrolidone (hereinafter, may be abbreviated as NMP). However, a crude reaction product containing a solvent, a by-product such as sodium chloride, and the polyarylene sulfide resin as the target substance can be obtained.

Polyarylene sulfide resin, which is useful as a product, is produced through various post-treatment processes, but the components discharged in the post-treatment process have been disposed of as industrial waste, and have been effectively utilized. There wasn't.

In particular, the liquid phase components obtained by solid-liquid separation have been disposed of as industrial waste.

Japanese Unexamined Patent Publication No. 2014-005207 Japanese Unexamined Patent Publication No. 2014-005208 Japanese Unexamined Patent Publication No. 2014-005317

Therefore, the present inventors tried to reuse the polar organic solvent discharged in the production process of the polyarylene sulfide resin in the production process of a new polyarylene sulfide resin, but the organic was discharged by solid-liquid separation. Since the polar solvent can be cooled to room temperature, when it is attempted to be subjected to the polymerization reaction again, it takes time and energy to raise the temperature to the polymerization reaction temperature, and there is room for improvement in productivity.

Therefore, the problem to be solved by the present invention is that the polar organic solvent discharged in the production process of the polyarylene sulfide resin is reused in the production process of a new polyarylene sulfide resin with good productivity. The purpose is to provide a manufacturing method.

As a result of various studies conducted by the inventors of the present application, the organic polar solvent obtained by solid-liquid separation of the crude reaction product after the polymerization reaction of the polyarylene sulfide resin has a high temperature immediately after the solid-liquid separation. We have found that if the polyarylene sulfide resin is reused for the polymerization reaction of a new polyarylene sulfide resin while maintaining the high temperature, the temperature raising step of the raw material can be shortened, the time and energy can be reduced, and the productivity can be improved, and the present invention is completed. It came to.

That is, in the present invention, step (1): a step of obtaining an organic polar solvent (a) by removing solid phase components by solid-liquid separation after a polymerization reaction of a polyarylene sulfide resin.
Step (2): A step of supplying the organic polar solvent (a) obtained in the step (1) into the reaction vessel within a range of 80 ° C. from the temperature at the time of solid-liquid separation in the step (1). ,
Step (3): Supply at least a polyhalo aromatic compound, (i) alkali metal sulfide, or (ii) alkali metal hydrosulfide and alkali metal hydroxide, and an organic polar solvent into the reaction vessel. Process,
Step (4): In the reaction vessel obtained through the steps (2) and (3), at least a polyhalo aromatic compound and (i) alkali metal sulfide, or (ii) alkali metal water. The present invention relates to a method for producing a polyarylene sulfide resin, which comprises a step of polymerizing a sulfide and an alkali metal hydroxide as raw materials in an organic polar solvent.

According to the present invention, there is provided a method for producing a polyarylene sulfide resin, in which the polar organic solvent discharged in the production process of the polyarylene sulfide resin is reused in the production process of a new polyarylene sulfide resin with high productivity. be able to.

It is a schematic diagram of an example of a reactor that can be used in carrying out the present invention (schematic diagram of the reactor used in Example 2).

The method for producing a polyarylene sulfide resin of the present invention is a step (1): a step of removing a solid phase component by solid-liquid separation after a polymerization reaction of the polyarylene sulfide resin to obtain an organic polar solvent (a).
Step (2): A step of supplying the organic polar solvent (a) obtained in the step (1) into a reaction vessel within a range of 80 ° C. from the temperature at the time of solid-liquid separation.
Step (3): Supply at least a polyhalo aromatic compound, (i) alkali metal sulfide, or (ii) alkali metal hydrosulfide and alkali metal hydroxide, and an organic polar solvent into the reaction vessel. Process,
Step (4): In the reaction vessel obtained through the steps (2) and (3), at least the polyhalo aromatic compound and (i) alkali metal sulfide, or (ii) alkali metal water. It is characterized by a step of polymerizing a sulfide and an alkali metal hydroxide as raw materials in an organic polar solvent.

The present invention has, as step (1), a step of obtaining an organic polar solvent (a) by removing solid phase components by solid-liquid separation after a polymerization reaction of a polyarylene sulfide resin.

More specifically, the polyhalo aromatic compound is reacted with (i) an alkali metal sulfide, or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide as raw materials in a polar organic solvent. A crude reaction mixture containing a polyarylene sulfide resin, an alkali metal-containing inorganic salt, and the polar organic solvent is obtained (polymerization step), and then the polar organic solvent is separated from the crude reaction mixture by solid-liquid separation to remove solid phase components (step). The solid-liquid separation step) can be exemplified.

In the polymerization step, the polyhalo aromatic compound is reacted with (i) an alkali metal sulfide, or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide as raw materials in a polar organic solvent to form a polyarylene. This is a step of obtaining a crude reaction mixture containing a sulfide resin, an alkali metal-containing inorganic salt, and the polar organic solvent.

Here, the polyhaloaromatic compound used in the polymerization step of the polyarylene sulfide resin is, for example, a halogenated aromatic compound having two or more halogen atoms directly bonded to the aromatic ring. p-dichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, trichlorobenzene, tetrachlorobenzene, dibrombenzene, diiodobenzene, tribrombenzene, dibromnaphthalene, triiodobenzene, dichlorodiphenylbenzene, Dihalo aromatic compounds such as dibrom diphenylbenzene, dichlorobenzophenone, dibrombenzophenone, dichlorodiphenyl ether, dibrom diphenyl ether, dichlorodiphenyl sulfide, dibrom diphenyl sulfide, dichlorobiphenyl, dibrombiphenyl and mixtures thereof. These compounds may be block copolymerized. Among these, benzene dihalogenates are preferable, and those containing 80 mol% or more of p-dichlorobenzene are particularly preferable.

Further, for the purpose of increasing the viscosity of the polyarylene sulfide resin by forming a branched structure, a polyhaloaromatic compound having three or more halogen substituents in one molecule may be used as a branching agent, if desired. Examples of such polyhalo aromatic compounds include 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,4,6-trichloronaphthalene and the like.

Further, polyhaloaromatic compounds having a functional group having an active hydrogen such as an amino group, a thiol group, and a hydroxyl group can be mentioned, and specifically, 2,6-dichloroaniline and 2,5-dichloroaniline. , 2,4-Dichloroaniline, 2,3-dichloroaniline and other dihaloanilines; 2,3,4-trichloroaniline, 2,3,5-trichloroaniline, 2,4,6-trichloroaniline, 3, Trihaloanilines such as 4,5-trichloroaniline; dihaloaminodiphenyl ethers such as 2,2'-diamino-4,4'-dichlorodiphenyl ether, 2,4'-diamino-2', 4-dichlorodiphenyl ether And compounds in which the amino group is replaced with a thiol group or a hydroxyl group in a mixture thereof and the like are exemplified.

Further, the active hydrogen-containing polyhalo in which the hydrogen atom bonded to the carbon atom forming the aromatic ring in these active hydrogen-containing polyhaloaromatic compounds is replaced with another inactive group, for example, a hydrocarbon group such as an alkyl group. Aromatic compounds can also be used.

Among these various active hydrogen-containing polyhaloaromatic compounds, an active hydrogen-containing dihaloaromatic compound is preferable, and dichloroaniline is particularly preferable.

Examples of the polyhaloaromatic compound having a nitro group include mono- or dihalonitrobenzenes such as 2,4-dinitrochlorobenzene and 2,5-dichloronitrobenzene; 2-nitro-4,4'-dichlorodiphenyl ether and the like. Dihalonitrodiphenyl ethers; dihalonitrodiphenylsulfones such as 3,3'-dinitro-4,4'-dichlorodiphenylsulfone; 2,5-dichloro-3-nitropyridine, 2-chlor-3,5 -Mono or dihalonitropyridines such as dinitropyridine; or various dihalonitronaphthalenes and the like.

The alkali metal sulfide used in the polymerization step of the polyarylene sulfide resin includes lithium sulfide, sodium sulfide, rubidium sulfide, cesium sulfide and a mixture thereof. Such alkali metal sulfides can be used as hydrates, aqueous mixtures or anhydrides. Alkali metal sulfides can also be derived by the reaction of alkali metal hydrosulfides with alkali metal hydroxides. It should be noted that a small amount of alkali metal hydroxide may be added in order to react with the alkali metal hydrosulfide and the alkali metal thiosulfate which are usually present in a trace amount in the alkali metal sulfide.

Further, the alkali metal hydrosulfide used in the polymerization step of the polyarylene sulfide resin includes lithium hydrosulfide, sodium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide and a mixture thereof. Such alkali metal hydrosulfides can be used as hydrates, aqueous mixtures or anhydrides.

Examples of the alkali metal hydroxide used in the polymerization step of the polyarylene sulfide resin include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and the like, but these are independent of each other. It may be used, or two or more kinds may be mixed and used. Among these, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferable because they are easily available, and sodium hydroxide is particularly preferable. The amount of the alkali metal hydroxide used is preferably in the range of 0.8 to 1.2 mol per mol of the alkali metal hydrosulfide from the viewpoint of promoting the formation of solid alkali metal sulfide, and in particular, 0. A range of 9 to 1.1 mol is more preferred.

Examples of the polar organic solvent used in the polymerization step of the polyarylene sulfide resin include formamide, acetamide, N-methylformamide, N, N-dimethylacetamide, tetramethylurea, N-methyl-2-pyrrolidone, 2-pyrrolidone, and the like. Amides such as N-methyl-ε-caprolactam, ε-caprolactam, hexamethylphosphoramide, N-dimethylpropylene urea, 1,3-dimethyl-2-imidazolidinone acid, urea and lactams; sulfolane, dimethylsulfolane, etc. Sulfolans; nitriles such as benzonitrile; ketones such as methylphenylketone and mixtures thereof, among which N-methyl-2-pyrrolidone, 2-pyrrolidone, N-methyl-ε-caprolactam , Ε-caprolactam, hexamethylphosphoramide, N-dimethylpropylene urea, and 1,3-dimethyl-2-imidazolidinone acid, which have an aliphatic cyclic structure, are preferable.

In the polymerization reaction of the polyarylene sulfide resin, the alkali metal sulfide is reacted with the polyhalo aromatic compound as a sulfidizing agent in the presence of these polar organic solvents. Alternatively, in the polymerization reaction of the polyarylene sulfide resin, the alkali metal hydrosulfide and the alkali metal hydroxide are reacted with the polyhaloaromatic compound as a sulfidizing agent in the presence of these polar organic solvents. The polymerization conditions should generally be in the temperature range of 200-330 ° C., and the pressure should be in the range of substantially retaining the polyhalo aromatic compound, which is the polymerization solvent and the polymerization monomer, in the liquid phase, generally 0. It is selected from the range of 1 to 20 MPa, preferably 0.1 to 2 MPa. The amount of the polyhalo aromatic compound charged may be in the range of 0.2 mol to 5.0 mol with respect to 1 mol of the sulfur atom of the sulfidizing agent. Further, the amount of the polar organic solvent charged varies depending on the type of the compound used and the water content in the system, and although it cannot be unconditionally specified, the viscosity of the reaction system capable of a uniform polymerization reaction should be maintained. Further, in order to maintain a certain degree of productivity, the amount thereof is preferably in the range of 1.0 to 6.0 mol per mol of the sulfur atom of the sulfide agent, and further, from the viewpoint of further enhancing the productivity. Therefore, the range of 1.2 to 5.0 mol is more preferable, and the range of 1.5 to 4.5 mol is most preferable.

Specific embodiments for polymerizing the sulfidating agent and the polyhaloaromatic compound in the presence of the polar organic solvent described above include, for example.
1) A method using a polymerization aid such as alkali metal carboxylate or lithium halide,
2) Method using a cross-linking agent such as an aromatic polyhalogen compound,
3) A method in which a polymerization reaction is carried out in the presence of a small amount of water, and then water is added to further polymerize.
4) During the reaction between the alkali metal sulfide and the aromatic dihalogen compound, a method of cooling the gas phase portion of the reaction kettle to condense a part of the gas phase in the reaction kettle and reflux it to the liquid phase can be mentioned. ..
5) In the presence of a polyhalo aromatic compound, an alkali metal sulfide or a hydrous alkali metal hydrosulfide and an alkali metal hydroxide are reacted with an amide, urea or lactam having an aliphatic cyclic structure while dehydrating. A step of producing a slurry containing a solid alkali metal sulfide, a step of producing the slurry, a step of further adding a polar organic solvent such as NMP, distilling off water to perform dehydration, and then a dehydration step. In the resulting slurry, a polyhalo aromatic compound, an alkali metal hydrosulfide, and an alkali metal salt of an amide, urea, or lactam hydrolyzate having the aliphatic cyclic structure are mixed in 1 mol of a polar organic solvent such as NMP. On the other hand, there is a method for producing a polyarylene sulfide resin, which comprises a step of reacting with an existing water content of 0.02 mol or less in the reaction system to carry out polymerization as an essential production step.

After the polymerization of the polyarylene sulfide resin is completed, a crude reaction mixture containing the polyarylene sulfide resin, an alkali metal-containing inorganic salt and the polar organic solvent can be obtained. At this time, the crude reaction mixture may contain a carboxyalkylamino group-containing compound.

Next, in the solid-liquid separation step, the polar organic solvent is solid-liquid separated from the obtained crude reaction mixture, and a liquid phase component containing the polar organic solvent as a main component, a polyarylene sulfide resin, and an alkali metal-containing inorganic salt are used. The solid phase component composed of the reaction mixture containing the above is separated, and the solid phase component is removed to obtain a liquid phase component containing a polar organic solvent as a main component. The solid-liquid separation is roughly divided into two types, a flash method and a Quench method, which will be described later. The flash method is a method of evaporating a solvent to recover the solvent and at the same time recovering a solid substance, and is generally carried out by heating to 130 to 200 ° C. under reduced pressure to distill off the solvent. The solvent temperature immediately after the solvent is recovered by the flash method is generally in the range of 130 to 200 ° C. However, since the work is usually performed in a room temperature (for example, 20 ° C., the same applies hereinafter) environment, heat retention measures described later are taken. Also tends to be cooled to the range of 90-190 ° C.

On the other hand, the Quench method is a method in which the polymerization reaction product is cooled to recover the particulate polyarylene sulfide resin. Generally, the reaction slurry is cooled in the reaction vessel while adding a poor solvent as needed. Then, a method of solid-liquid separation after crystallizing the polyarylene sulfide resin can be mentioned. The solid-liquid separation in the Quench method can be obtained by a method of separating by filtration or using a centrifuge such as a screw decanter, then directly adding water to the obtained filtration residue to form a slurry, and then repeating solid-liquid separation. Examples thereof include a method of removing the residual solvent by heating the filtered residue in a non-oxidizing atmosphere. The solvent temperature immediately after the solvent is recovered by the quench method is in the range of 130 to 200 ° C. However, since the work is usually performed in a room temperature environment, the solvent is cooled to the range of 90 to 190 ° C. even if the heat retention measures described later are taken. There is a tendency. The flash method is preferable because the solid matter can be recovered relatively easily, and the Quench method is preferable because the particle size of the polyarylene sulfide resin can be easily controlled, and the polymer particles contain alkali metal-containing inorganic salts and other substances during crystallization. It is preferable in that a high-purity polymer can be obtained because it becomes difficult to take in impurities.

The liquid phase component thus obtained contains a polar organic solvent as a main component, and may contain at least a carboxyalkylamino group-containing compound as other subcomponents, and further includes water, linear or cyclic PAS oligomers, and the like. May be included. The concentration of the carboxyalkylamino group-containing compound that may be contained in the polar organic solvent and the water or oligomer contained in the other compounds varies greatly depending on the polymerization conditions and solid-liquid separation conditions, so the range cannot be unconditionally determined. , A part of the obtained liquid phase component can be easily known by measuring it by a known analysis method.

The carboxyalkylamino group-containing compound has the following general formula (1).

(In the formula, n is 0 to 2, Y ¹ represents a halogen atom, Y ² represents a hydrogen atom or a halogen atom, and R ¹ represents a hydrogen atom or an alkyl group or a cyclohexyl group having 1 to 3 carbon atoms. R ² is an alkylene group having 3 to 5 carbon atoms, X is carboxymethyl alkylamino group-containing compound represented by the representative.) a hydrogen atom or an alkali metal atom. Of these, the alkali metal atom of X is the same as the alkali metal of the alkali metal sulfide or alkali metal hydrosulfide used as a raw material in the polymerization step.

Further, when the polyarylene sulfide resin is produced, for example, when the polar organic solvent is N-methyl-2-pyrrolidone and the polyhaloaromatic compound is p-dichlorobenzene, the carboxyalkyl is used as a raw material for producing the polyarylene sulfide resin. As an amino group-containing compound, the following general formula (2)

(In the formula, X represents a hydrogen atom or an alkali metal atom.) (This compound is abbreviated as "CP-MABA", and particularly when X is a hydrogen atom, "CP-MABA (" Hydrogen type) ”, the case of alkali metal atom may be abbreviated as“ CP-MABA (alkali metal salt type) ”, and in particular, when X is a sodium atom, it may be abbreviated as“ CP-MABA (Na salt type) ”).

The polar organic solvent thus obtained can be mixed with the raw material of the polyarylene fide resin and used (reused) in a new method for producing a polyarylene sulfide resin. When used (reused) in a new method for producing a polyarylene sulfide resin and for the purpose of obtaining a higher molecular weight polyarylene sulfide resin, the carboxyalkylamino group-containing compound with respect to the raw material is used. It is desirable to adjust the ratio of the above to 1 mol of the sulfur atom, preferably in the range of 0.004 mol or less, more preferably in the range of 0.003 mol or less.

In the present invention, as step (2), the organic polar solvent (a) obtained in step (1) is placed in a reaction vessel within 80 ° C., preferably 50 ° C., from the temperature at the time of solid-liquid separation. It has a step of supplying within the range within. The organic polar solvent (a) obtained in the step (1) needs to be moved from the storage tank on the liquid phase side of the solid-liquid separation to the reaction vessel. At that time, it is preferable to supply the polyarylene sulfide resin to a reaction vessel for polymerizing a new polyarylene sulfide resin while maintaining the high temperature state immediately after the solid-liquid separation as much as possible. The temperature of the organic polar solvent on the liquid phase side at the time of solid-liquid separation is not particularly limited because it depends on the temperature setting of the polymerization reaction, but is in the range of 90 to 190 ° C. as a guide. Therefore, in the step (1), the obtained organic polar solvent (a) is supplied and stored in a container equipped with a heat insulating material and, if necessary, a heat insulating mechanism such as a jacket equipped with a heater, and is required. The organic polar solvent (a) is supplied from the storage tank to the reaction vessel in the step (2), or the organic obtained in the step (1) in the step (2). The polar solvent (a) may be supplied to the reaction vessel from the storage tank on the liquid phase side of the solid-liquid separation through a pipe communicating with the reaction vessel. It is preferable to supply the product directly through a pipe because it is easy to maintain a higher temperature state by minimizing the opportunity to come into contact with the outside air. It is preferable that the pipe is also provided with a heat insulating mechanism such as a heat insulating material and a jacket provided with a heater if necessary.
The temperature of the organic polar solvent (a) when supplied into the reaction vessel is not particularly limited because it depends on the temperature of the organic polar solvent on the liquid phase side at the time of solid-liquid separation, but it is a guideline. It is preferably in the range of 80 to 190 ° C.

In the present invention, as step (3), at least a polyhalo aromatic compound and (i) alkali metal sulfide, or (ii) alkali metal hydrosulfide and alkali metal hydroxide are contained in a reaction vessel, and organic. It has a step of supplying a polar solvent. The step (2) and the step (3) may be performed either of the steps first or at the same time.

The present invention further comprises, as step (4), at least a polyhalo aromatic compound and (i) alkali metal sulfide, or (ii) alkali metal hydrosulfide and alkali metal hydroxide in the reaction vessel. It has a step of supplying an organic polar solvent. The step (3) and the step (4) may be performed either of the steps first or at the same time.

Next, in the present invention, as step (4), at least the polyhalo aromatic compound and (i) alkali metal sulfide are contained in the reaction vessel obtained through the steps (2) and (3). Alternatively, (ii) has a step of polymerizing the alkali metal hydrosulfide and the alkali metal hydroxide as raw materials in an organic polar solvent. That is, the polar organic solvent obtained in the step (1) is mixed with the raw material to carry out the polymerization reaction of the polyarylene sulfide resin.

The steps (3) and (4) are basically described above, except that the organic polar solvent obtained through the steps (1) and (2) is used as a part of the organic polar solvent used as the reaction solvent. This is the same as the polymerization reaction of the polyarylene sulfide resin described in the step (1). Therefore, after the polymerization reaction is carried out as the step (4), the solid-liquid separation step is carried out, and the solid phase component after the solid-liquid separation step is then subjected to a necessary post-treatment step to produce a polyarylene sulfide resin. On the other hand, the polar organic solvent can be obtained again from the liquid phase component, and this product can be further mixed and used (reused) with the raw material of a new polymer sphid resin. it can.

The post-treatment step required thereafter is not particularly limited, but for example, (a) after completion of the polymerization reaction, the reaction mixture is first used as it is, or an acid or base is added, and then the solvent is used under reduced pressure or normal pressure. Is distilled off, and then the solid after distilling off the solvent is used once or twice with a solvent such as water, a reaction solvent (or an organic solvent having equivalent solubility in a low molecular weight polymer), acetone, methyl ethyl ketone, and alcohols. The method of washing, further neutralizing, washing with water, filtering and drying, or (b) after completion of the polymerization reaction, water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons are added to the reaction mixture. , A solvent such as an aliphatic hydrocarbon (a solvent that is soluble in the polymerization solvent used and is poor at least for polyarylene sulfide) is added as a precipitant to add polyarylene sulfide, an inorganic salt, or the like. A method of precipitating solid products and filtering, washing, and drying them, or (c) a reaction solvent (or an organic solvent having the same solubility as a low molecular weight polymer) in the reaction mixture after completion of the polymerization reaction. After adding and stirring, the low molecular weight polymer is removed by filtration, and then washed once or twice or more with a solvent such as water, acetone, methyl ethyl ketone, alcohols, etc., and then neutralized, washed with water, filtered and dried. (D) After completion of the polymerization reaction, water is added to the reaction mixture for washing with water, filtration, and if necessary, acid is added at the time of washing with water for acid treatment and drying, and (e) completion of the polymerization reaction. After that, a method of filtering the reaction mixture, washing with a reaction solvent once or twice or more, and further washing with water, filtering and drying, and the like can be mentioned.

In the post-treatment methods illustrated in (a) to (e) above, the polyarylene sulfide resin may be dried in vacuum, in air, or in an atmosphere of an inert gas such as nitrogen. You may.

The polyarylene sulfide resin thus obtained can contain a filler in order to further improve the mechanical strength. The filler used in the present invention is not an essential component, but when added, it is more than 0 parts by mass, usually 1 part by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the polyarylene sulfide resin. Moreover, by adding in the range of 600 parts by mass or less, various performances according to the purpose can be improved.

As the filler, a known and commonly used material can be used as long as it does not impair the effect of the present invention, and has various shapes such as a fibrous material and a non-fibrous material such as granular or plate-like. Filling material and the like. Specifically, 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 fiber such as wollastonite. Fillers can be used, as well as glass beads, glass flakes, barium sulfate, calcium sulfate, clay, pyrophyllite, bentonite, sericite, zeolite, mica, mica, talc, attapulsite, ferrite, calcium silicate, calcium carbonate, carbon dioxide. Non-fibrous fillers such as magnesium and glass beads can also be used.

Further, the polyarylene sulfide resin of the present invention is further suitable for polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulphon resin, polyethersulphon resin, poly. Ether ether ketone resin, polyether ketone resin, polyarylene resin, polyethylene resin, polypropylene resin, polytetrafluorinated ethylene resin, polydifluorinated ethylene resin, polystyrene resin, ABS resin, phenol resin, urethane resin, liquid crystal polymer, etc. It may be used as a polyarylene sulfide resin composition containing a synthetic resin or an elastomer such as fluororubber. The amount of these resins used varies depending on the intended purpose and cannot be unconditionally specified, but the present invention is in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. It may be adjusted and used as appropriate according to the purpose and application so as not to impair the effect of.

Further, the polyarylene sulfide resin of the present invention can be used as an additive during molding, as long as it does not impair the effects of the present invention, such as a colorant, a heat-resistant stabilizer, an ultraviolet stabilizer, a foaming agent, and a rust preventive. Various additives such as flame retardants, lubricants, and coupling agents can be contained. The amount of these additives used varies depending on the intended purpose and cannot be unconditionally specified, but is in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin of the present invention. It may be adjusted and used as appropriate according to the purpose and application so as not to impair the effect.

The method for producing the polyarylene sulfide resin composition of the present invention is not particularly limited, and the polyarylene sulfide resin obtained by the production method of the present invention and other additives such as a filler to be added as needed may be added. It is put into a ribbon blender, Henschel mixer, V blender, etc. in various forms such as powder, bellet, and strips, dried and blended, and then melted using a Banbury mixer mixing roll, a single-screw or twin-screw extruder, and a kneer. Examples include a method of kneading. Among them, a method of melt-kneading using a single-screw or twin-screw extruder having sufficient kneading power is typical.

The polyarylene sulfide resin composition thus obtained can be used for various moldings such as injection molding, compression molding, extrusion molding of composites, sheets and pipes, drawing molding, blow molding and transfer molding. , Especially suitable for injection molding because of its excellent releasability. The obtained molded product of the polyarylene sulfide resin composition has excellent adhesiveness to the silicone resin. Therefore, for example, the polyarylene sulfide resin composition is molded by sealing or bonding the plate-shaped or box-shaped molded product made of the polyarylene sulfide resin composition with a silicone resin and then curing the curable resin. A composite molded product obtained by adhering a molded product made of a product and a cured product made of a curable resin can be obtained.

Main applications of composite molded products include box-shaped protection / support members for integrated modules of electrical and electronic components, multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, Condenser, variable condenser case, optical pickup, oscillator, various terminal boards, transformer, plug, printed board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, terminal block, semiconductor, liquid crystal, FDD carriage , FDD chassis, motor brush holder, parabolic antenna, computer-related parts, and other electrical and electronic parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, acoustic parts, audio / laser discs.・ Audio / video equipment parts such as compact discs, DVD discs, and Blu-ray discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, or water supply equipment parts such as water heaters, bath water volume, and temperature sensors. Household and office electrical product parts represented by; office computer related parts, telephone equipment related parts, facsimile related parts, copying machine related parts, cleaning jigs, motor parts, writer, type writer, etc. : Optical equipment such as microscopes, binoculars, cameras, clocks, precision machinery related parts; Alternator terminals, alternator connectors, IC regulators, potentiometer bases for light sensors, relay blocks, inhibitor switches, exhaust gas valves, etc. , Fuel-related / exhaust system / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor , Throttle position sensor, crank shaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, du Stributor, starter switch, ignition coil and its bobbin, motor insulator, motor rotor, motor core, starter reel, sensor Wire harness for lance mission, window washer nozzle, air conditioner panel switch board, coil for fuel-related electromagnetic valve, fuse connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, It can also be applied to automobile / vehicle-related parts such as solenoid bobbins, engine oil filters, and ignition device cases, and various other applications.

Hereinafter, the present invention will be specifically described with reference to examples. These examples are exemplary and not limiting.

[Measurement method of melt viscosity]
The melt viscosity (η) of the obtained polymer is a value measured after holding for 6 minutes at ^{300 ° C., 20 kgf / cm 2, and L / D = 10 using a flow tester manufactured by Shimadzu Corporation.}
[Measurement method of composition in filtrate: NMP]
NMP was diluted 10-fold with acetone and quantified by GC. The GC measurement conditions are as follows.
Device name: "Gas Chromatograph GC-2014" manufactured by Shimadzu Corporation
Column: "G Column G-300" manufactured by Chemical Substances Evaluation and Research Institute
Carrier gas: He (76 kPa)
Analysis temperature: 140 ° C (5 minutes) → 3 ° C / min temperature rise → 200 ° C (20 minutes) Total 45 minutes Injection port temperature: 250 ° C
Detector: FID (250 ° C)

1. 1. Reference Example 1 205.5 kg of flaky sodium sulfide (60.75 wt% Na ₂ S) and 358.7 kg of NMP were charged into an autoclave for producing a polyarylene sulphod resin. The temperature was raised to 212 ° C. with stirring under a nitrogen stream, and 49.10 kg of water was distilled off. Then, the autoclave was sealed and cooled to 180 ° C., and 230.2 kg of paradichlorobenzene (hereinafter, may be abbreviated as p-DCB) and 228.0 kg of NMP were charged. The temperature was increased to 108,000 Pa using nitrogen gas at a liquid temperature of 165 ° C. to start the temperature rise. The temperature was raised to 240 ° C. over 135 minutes and maintained for 30 minutes. After that, the temperature was raised to 250 ° C. over 40 minutes and held for 73 minutes to complete the reaction, and then cooled to obtain a slurry (1).

100.0 kg of the obtained slurry (1) was filtered to remove the solvent, and then dispersed in 400 kg of warm water at 60 ° C. for 10 minutes to dissolve the NMP remaining in the filtration residue and sodium chloride as a by-product. After stirring, the mixture was further filtered, and 400 kg of warm water at 60 ° C. was passed through the filtered cake. After repeating this operation three times, the hydrous filtered cake was dried in a hot air circulation dryer at 120 ° C. for 3 hours to obtain a white powdery polymer (1). The melt viscosity was measured and found to be 40 Pa · s.

2. 2. Example 1
A slurry (1) was obtained in the same manner as in Reference Example 1. The obtained slurry (1) was filtered to obtain a filtrate (1) containing a solvent. The main composition of this filtrate (1) was NMP 94.71 wt%. The temperature of the filtrate (1) at the time of solid-liquid separation was 150 ° C. The filtrate (1) was housed in a container with a tension-tightening lock mechanism having a heat insulating jacket attached to the outside of the container, sealed, and left for 10 minutes.

The autoclave was charged with 202.4 kg of flaky sodium sulfide (60.75 wt% Na ₂ S), 196.1 kg of NMP, and 183.0 kg of the filtrate (1) taken out from the container. The temperature of the filtrate (1) when supplied to the autoclave was 130 ° C. The temperature was raised to 212 ° C. with stirring under a nitrogen stream, and 54.00 kg of water was distilled off. Then, the autoclave was sealed and cooled to 180 ° C., and p-DCB 227.3 kg and NMP 238.0 parts by mass were charged. The temperature was increased to 108,000 Pa using nitrogen gas at a liquid temperature of 165 ° C. to start the temperature rise. The temperature was raised to 240 ° C. over 135 minutes and maintained for 30 minutes. After that, the liquid temperature was raised to 250 ° C. over 40 minutes and held for 73 minutes to complete the reaction, and then cooled to 120 ° C. over 3 hours to obtain a slurry (2).

Next, 100.0 kg of the obtained slurry (2) was filtered (a cellulose filter paper having 1 μm of reserved particles was drawn on the Kiriyama funnel, a beaker containing the slurry was placed in a water bath, and after the slurry temperature reached 50 ° C., the funnel was used. (Put in, filter under reduced pressure with a water flow pump) to remove the solvent, disperse in 400 parts by mass of warm water at 60 ° C. to dissolve the NMP remaining in the filtration residue and sodium chloride as a by-product, and stir for 10 minutes. Further filtration was performed, and 400 parts by mass of warm water at 60 ° C. was passed through the filtered cake. After repeating this operation three times, the hydrous filtered cake was dried in a hot air circulation dryer at 120 ° C. for 3 hours to obtain a white powdery polymer (2). The melt viscosity was measured and found to be 46 Pa · s.

3. 3. Example 2
Experiments were also performed using the device shown in FIG.
205.5 kg of flaky sodium sulfide (60.75 wt% Na ₂ S) and 358.7 kg of NMP were charged in the autoclave 1. The temperature was raised to 212 ° C. with stirring under a nitrogen stream, and 49.10 kg of water was distilled off. Then, the autoclave 1 was sealed and cooled to 180 ° C., and 230.2 kg of paradichlorobenzene (hereinafter, may be abbreviated as p-DCB) and 228.0 kg of NMP were charged. The temperature was increased to 108,000 Pa using nitrogen gas at a liquid temperature of 165 ° C. to start the temperature rise. The temperature was raised to 240 ° C. over 135 minutes and maintained for 30 minutes. After that, the temperature was raised to 250 ° C. over 40 minutes and held for 73 minutes to complete the reaction, and then cooled to obtain a slurry (1).

The obtained slurry (1) was filtered through a solid-liquid separator 19 to obtain a filtrate (1) containing a solvent. The main composition of this filtrate (1) was NMP 94.71 wt%. The temperature of the filtrate (1) at the time of solid-liquid separation was 150 ° C. The filtrate (1) was stored in the storage tank 25 which communicates directly with the autoclave 1 through the pipe 22. As the storage tank 24 and the pipe 22, those with a heat insulating jacket attached to the outside of the storage tank and the pipe were used.

Next, the inside of the autoclave 1 was cleaned and emptied. Furthermore, the reservoir bath 11 to 38.41 wt% Na ₂ S aqueous solution of NMP to the reservoir bath 14, was charged with p-DCB in the reservoir bath 17.

The autoclave 1, the reservoir bath 11 from 38.41 wt% Na ₂ S aqueous solution 320.2kg through a pipe 9 and _(Na 2 S1576 mol), reservoir bath 25 Kararo through NMP196.1kg and pipe 23 from the reservoir bath 14 via a pipe 12 Liquid (1) 183.0 kg was charged. The temperature of the filtrate (1) when supplied to the autoclave was 135 ° C. The temperature was raised to 212 ° C. with stirring under a nitrogen stream, and 54.00 kg of water was distilled off. Then, the autoclave was sealed and cooled to 180 ° C., and 227.3 kg of p-DCB from the storage tank 17 through the pipe 15 and 238.0 parts by mass of NMP from the storage tank 14 through the pipe 12 were charged into the autoclave 1. The temperature was increased to 108,000 Pa using nitrogen gas at a liquid temperature of 165 ° C. to start the temperature rise. The temperature was raised to 240 ° C. over 135 minutes and maintained for 30 minutes. After that, the liquid temperature was raised to 250 ° C. over 40 minutes and held for 73 minutes to complete the reaction, and then cooled to 120 ° C. over 3 hours to obtain a slurry (2).

Next, 100.0 kg of the obtained slurry (2) was filtered (a cellulose filter paper having 1 μm of reserved particles was drawn on the Kiriyama funnel, a beaker containing the slurry was placed in a water bath, and after the slurry temperature reached 50 ° C., the funnel was used. (Put in, filter under reduced pressure with a water flow pump) to remove the solvent, disperse in 400 kg of warm water at 60 ° C to dissolve the NMP remaining in the filtration residue and sodium chloride as a by-product, stir for 10 minutes, and then further filter. Then, 400 kg of hot water at 60 ° C. was passed through the filtered cake. After repeating this operation three times, the hydrous filtered cake was dried in a hot air circulation dryer at 120 ° C. for 3 hours to obtain a white powdery polymer (2). The melt viscosity was measured and found to be 48 Pa · s.

1 Reaction vessel 2 Stirring blade 3 Smelting tower 4 Capacitor (condenser)
5 Decanter for statically separating the liquid component from the condenser 6 Recirculation pump that returns the liquid in the lower layer of the decanter to the rectification tower 7 Valve (pressure control valve that adjusts the pressure of the gas component inside the rectification tower and condenser)
8 reaction pipe 13 NMP for supplying the reservoir bath 12 NMP pump 11 Na ₂ S for supplying the pipe 10 Na ₂ S for supplying valve 9 Na ₂ S to the reaction vessel to the reaction vessel to the reaction vessel Pump for supplying to the vessel 14 NMP storage tank 15 Piping for supplying p-DCB to the reaction vessel 16 Pump for supplying p-DCB to the reaction vessel 17 Storage tank for p-DCB 18 Reaction vessel contents 19 Solid-liquid separator 20 Piping for transferring solid-phase components 21, 24 Pumps 22 and 23 for transferring liquid-phase components Piping for transferring liquid-phase components 25 Liquid phase component storage tank

Claims (4)

Step (1): A step of obtaining an organic polar solvent (a) by removing solid phase components by solid-liquid separation after the polymerization reaction of the polyarylene sulfide resin.
Step (2): A step of supplying the organic polar solvent (a) obtained in the step (1) into the reaction vessel within a range of 80 ° C. from the temperature at the time of solid-liquid separation in the step (1). ,
Step (3): A step of supplying at least a polyhalo aromatic compound and (i) alkali metal sulfide, or (ii) alkali metal hydrosulfide and alkali metal hydroxide into the reaction vessel.
Step (4): In the reaction vessel, at least the polyhalo aromatic compound obtained through the steps (2) and (3) and (i) alkali metal sulfide, or (ii) alkali metal. Having a step of polymerizing hydrosulfide and alkali metal hydroxide as raw materials in an organic polar solvent (a).
A method for producing a polyarylene sulfide resin, wherein the temperature of the organic polar solvent (a) when supplied into the reaction vessel in the step (2) is in the range of 90 to 190 ° C. The step wherein the organic polar solvent obtained through the (1) (a), method according to claim 1 Symbol placement is intended to include polyarylene sulfide resin oligomer. In the step (2), the organic polar solvent (a) obtained in the step (1) is transferred to the reaction vessel through a pipe communicating the organic polar solvent (a) from the storage tank on the liquid phase side of the solid-liquid separation to the reaction vessel. The method for producing a polyarylene sulfide resin according to claim 1 or 2 to be supplied. In the step (1), the obtained organic polar solvent (a) is supplied to a storage tank provided with a heat retention mechanism, and in the step (2), the organic polar solvent (a) is supplied from the storage tank to the reaction vessel. The method for producing a polyarylene sulfide resin according to any one of claims 1 to 3, which is supplied.