JP6836704B2 - 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, together with the target substance, polyarylene sulfide resin, a solvent, an alkali metal-containing inorganic salt such as sodium chloride, and the following general formula (1)

（式中、ｎは０〜２であり、Ｙ^１はハロゲン原子を、Ｙ^２は水素原子又はハロゲン原子を、Ｒ^１は水素原子又は炭素原子数１〜３のアルキル基又はシクロヘキシル基を表し、Ｒ^２は炭素原子数３〜５のアルキレン基を、Ｘは水素原子又はアルカリ金属原子を表す。）に代表されるカルボキシアルキルアミノ基含有化合物などの副生成物を含有する粗反応生成物が得られる。

(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 represents an alkylene group having 3 to 5 carbon atoms, and X represents a hydrogen atom or an alkali metal atom.) A crude reaction product containing a by-product such as a carboxyalkylamino group-containing compound is obtained. Be done.

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, since the carboxyalkylamino group-containing compound causes a COD load, it is required to reduce it in order to reduce the environmental load, and the carboxyalkylamino contained in the waste water obtained after washing with water or hot water. As the group-containing compound, for example, a polar organic solvent such as NMP (Patent Document 1), a polyhaloaromatic compound such as paradichlorobenzene (Patent Document 2), or a water-insoluble solvent such as xylene (Patent Document 3) is used. A method of separation / extraction or reuse has been proposed.

However, all of the above methods are proposals for separating / extracting or reusing the carboxyalkylamino group-containing compound contained on the solid phase side obtained by solid-liquid separation of the crude reaction product after the polymerization reaction of the polyarylene sulfide resin. In fact, 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 problem to be solved by the present invention is to provide a method for producing a polyarylene sulfide resin, which reuses the polar organic solvent discharged in the production process of the polyarylene sulfide resin in the production process of a new polyarylene sulfide resin. To do.

As a result of various studies conducted by the inventors of the present application, a carboxyalkylamino group-containing compound is also a polar organic solvent on the liquid phase side obtained by solid-liquid separation of the crude reaction product after the polymerization reaction of the polyarylene sulfide resin. The polar organic solvent can be reused for the polymerization reaction of the new polyarylene fide resin. However, when the amount of the carboxyalkylamino group-containing compound increases, the polymerization reaction of the new polyarylene fide resin Since it tends to cause polymerization inhibition when it is attempted to be reused, it has been found that there is a concentration range suitable for reuse, and the present invention has been completed.

That is, the present invention comprises step (1): a step of obtaining an organic polar solvent (a) containing a carboxyalkylamino group-containing compound 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.
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 obtained through the steps (2) and (3), at least the polyhalo aromatic compound and (i) alkali metal sulfide, or (ii) alkali metal water. It has a step of polymerizing a sulfide and an alkali metal hydroxide as raw materials in an organic polar solvent containing a carboxyalkylamino group-containing compound, and in the step (4), the organic polar solvent containing the raw materials. The present invention relates to a method for producing a polyarylene sulfide resin, wherein the ratio of the carboxyalkylamino group-containing compound is in the range of 0.004 mol or less with respect to 1 mol of sulfur atoms in the raw material.

According to the present invention, it is possible to provide a method for producing a polyarylene sulfide resin, which reuses the polar organic solvent discharged in the process for producing the polyarylene sulfide resin in the process for producing a new polyarylene sulfide resin.

The method for producing a polyarylene sulfide resin of the present invention is:
Step (1): A step of obtaining an organic polar solvent (a) containing a carboxyalkylamino group-containing compound 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.
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 obtained through the steps (2) and (3), at least the polyhalo aromatic compound and (i) alkali metal sulfide, or (ii) alkali metal water. It has a step of polymerizing a sulfide and an alkali metal hydroxide as raw materials in an organic polar solvent containing a carboxyalkylamino group-containing compound, and in the step (4), the organic polar solvent containing the raw materials. Among them, the ratio of the carboxyalkylamino group-containing compound is in the range of 0.004 mol or less with respect to 1 mol of sulfur atoms in the raw material.

The present invention includes, as step (1), a step of obtaining an organic polar solvent (a) containing a carboxyalkylamino group-containing compound 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, the carboxyalkylamino group-containing compound, 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. A step of removing a solid phase component (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, the carboxyalkylamino group-containing compound, 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.

Of these, when the polyarylene sulfide resin is produced by the polymerization methods 1) to 4), the production of by-products tends to increase, and therefore, the carboxyalkylamino group-containing compound can be reduced by the method of the present invention. preferable.

After completion of the polymerization of the polyarylene sulfide resin, a crude reaction mixture containing the polyarylene sulfide resin, an alkali metal-containing inorganic salt, the carboxyalkylamino group-containing compound, and the polar organic solvent can be obtained.

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 carboxyalkylamino group-containing compound 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., but is usually cooled to the range of 70 to 150 ° C. for work in a room temperature (for example, 20 ° C., the same applies hereinafter) environment. Tends to be. Therefore, in the step (1), in the case of the flash method, the temperature of the obtained organic polar solvent (a) is in the range of 70 to 200 ° 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., and usually tends to be further cooled to the range of 70 to 150 ° C. for work in a room temperature environment. Therefore, in the step (1), even in the case of the quench method, the temperature of the obtained organic polar solvent (a) is in the range of 70 to 200 ° C. 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 at least the above-mentioned carboxyalkylamino group-containing compound with a polar organic solvent as a main component, and also contains water, linear or cyclic PAS oligomers, and the like. Since the concentration of water or oligomer contained in the carboxyalkylamino group-containing compound and others in the polar organic solvent varies greatly depending on the polymerization conditions and solid-liquid separation conditions, the range cannot be unconditionally determined, but the obtained liquid phase It can be easily known by measuring a part of the components by a known analysis method.

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

（式中、ｎは０〜２であり、Ｙ^１はハロゲン原子を、Ｙ^２は水素原子又はハロゲン原子を、Ｒ^１は水素原子又は炭素原子数１〜３のアルキル基又はシクロヘキシル基を表し、Ｒ^２は炭素原子数３〜５のアルキレン基を、Ｘは水素原子又はアルカリ金属原子を表す。）で表されるカルボキシアルキルアミノ基含有化合物が挙げられる。このうち、Ｘのアルカリ金属原子は、重合工程で原料として用いたアルカリ金属硫化物またはアルカリ金属水硫化物のアルカリ金属と同様である。

(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)

（式中、Ｘは水素原子又はアルカリ金属原子を表す。）で表されるものが得られる（この化合物を“ＣＰ−ＭＡＢＡ”と略記し、特にＸが水素原子の場合を“ＣＰ−ＭＡＢＡ（水素型）”、アルカリ金属原子の場合を“ＣＰ−ＭＡＢＡ（アルカリ金属塩型）”、特にＸがナトリウム原子の場合は“ＣＰ−ＭＡＢＡ（Ｎａ塩型）”と略記することがある）。

(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 containing the carboxyalkylamino group-containing compound 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, the ratio of the carboxyalkylamino group-containing compound to the raw material is preferably in the range of 0.004 mol or less with respect to 1 mol of the sulfur atom. Is adjusted to be in the range of 0.003 mol or less. On the other hand, since the carboxyalkylamino group-containing compound is considered to be the cause of the polymerization inhibition of PAS, the lower the ratio of the carboxyalkylamino group-containing compound is, the more preferable. Therefore, the lower limit value may be below the detection limit, but in reality. Specifically, it is preferable to adjust the ratio of the carboxyalkylamino group-containing compound to the raw material so as to be in the range of 0.0001 mol or more with respect to 1 mol of the sulfur atom.

Since the polymerization reaction is carried out in an alkaline environment, the carboxyalkylamino group-containing compound obtained after the polymerization step and the solid-liquid separation step also forms an alkali metal salt unless the acidification treatment is performed. Therefore, it is preferable to prepare the ratio of the carboxyalkylamino group-containing compound to the raw material as the ratio of the alkali metal salt of the carboxyalkylamino group-containing compound to the raw material from the viewpoint of productivity.

The organic polar solvent (a) obtained in the step (1) may be temporarily stored in a container. Once stored in a container, the organic polar solvent immediately after the solid-liquid separation step has a temperature higher than room temperature, so that the organic polar solvent, the carboxyalkylamino group-containing compound, and other by-products Etc. may proceed more than necessary due to the oxygen in the air, and when used (reused) for the subsequent polymerization reaction of the polyarylene sulfide resin, it may cause polymerization inhibition. Since it may be scattered outside the container due to environmental problems, it is preferable to use a container provided with a sealing mechanism to seal the container. Examples of the sealing mechanism include a tension tightening type lock mechanism.

The present invention subsequently has, as step (2), a step of supplying the organic polar solvent (a) obtained in the step (1) into the reaction vessel. The organic polar solvent (a) obtained in the step (1) may be temporarily contained in a container from the solid-liquid separation device in the step (1), taken out from the container, and transferred to a reaction vessel for use. ..

The present invention further comprises, as step (3), at least a polyhalo aromatic compound and (i) alkali metal sulfide, or (ii) alkali metal hydrosulfide and alkali metal hydroxide in a reaction vessel. Has a step of supplying. The step (2) and the step (3) may be performed either of the steps first or at the same time. In the step (3), the organic polar solvent can be supplied into the reaction vessel as needed, and the amount of the organic polar solvent charged in the reaction vessel in the step (2) is relative to the amount required for the polymerization reaction. If there is a shortage, the required amount can be added.

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 containing a carboxyalkylamino group-containing compound. That is, the polar organic solvent containing the carboxyalkylamino group-containing compound is mixed with the raw material to carry out the polymerization reaction of the polyarylene sulfide resin.

Steps (3) and (4) are basic except that the organic polar solvent containing the carboxyalkylamino group-containing compound prepared in step (2) is used as a part of the organic polar solvent used as the reaction solvent. The same is true for 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 then the necessary post-treatment step is carried out from the solid phase component after the solid-liquid separation step to produce a polyarylene sulfide resin. On the other hand, a polar organic solvent containing a carboxyalkylamino group-containing compound can be obtained again from the liquid phase component, and this product is further mixed with a raw material of a novel polyarylene fide resin. It can be used (reused). However, since the concentration of the carboxyalkylamino group-containing compound in the polar organic solvent tends to increase as the reuse is repeated, the ratio of the carboxyalkylamino group-containing compound to the raw material is relative to 1 mol of the sulfur atom. Therefore, it is adjusted and used so as to be within the above range.

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, to 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 was 6 at 300 ° C., 20 kgf / cm 2} , L / D = 10 mm / 1 mm using a high-grade flow tester (“CFT-500D type” flow tester manufactured by Shimadzu Corporation). It is a value measured after holding for a minute.

[Measurement method of composition in filtrate: CP-MABA]
1 ml was sampled from the well-stirred filtrate, 9 ml of the mobile phase of HPLC was added thereto, and the filtrate was used as a measurement sample. The HPLC measurement of the measurement sample was performed, and the concentration in the liquid was determined from the peak area and the calibration curve having the same retention time as the standard sample prepared by the following method. The HPLC measurement conditions are as follows.
Device name: "High Performance Liquid Chromatogram Prominence" manufactured by Shimadzu Corporation
Column: "Phenomenex Luna 5u C18 (2) 100A" manufactured by Shimadzu LLC Co., Ltd.
Detector: DAD (Diode Array Detector)
Data processing: "LC solution" manufactured by Shimadzu Corporation
Measurement conditions: Column temperature 40 ° C
Mobile phase: Water flow rate 1.0 ml / min

(Standard substance: Synthesis of CP-MABA)
83.40 g (1.00 mol) of a 48% NaOH aqueous solution and 297.4 g (3.000 mol) of N-methyl-2-pyrrolidone were placed in a pressure-resistant container equipped with a stirrer and stirred at 230 ° C. for 3 hours. After the stirring was completed, the valve was opened at a temperature of 230 ° C., the pressure was released, the pressure was lowered to 0.1 MPa at 230 ° C., which is about the vapor pressure of N-methyl-2-pyrrolidone, and water was distilled off. Then, it was sealed again and the temperature was lowered to about 200 ° C.

147.0 g (1.00 mol) of p-dichlorobenzene was heated and dissolved under a temperature condition of 60 ° C. or higher, charged into the reaction mixture, heated to 250 ° C., and stirred for 4 hours. After this stirring was completed, the mixture was cooled to room temperature. The reaction rate of p-dichlorobenzene was 31 mol%. After cooling, the contents were taken out, water was added, and the mixture was stirred. Then, unreacted p-dichlorobenzene was removed as an insoluble matter by filtration.

Next, hydrochloric acid was added to the aqueous solution as a filtrate to adjust the pH of the aqueous solution to 4. At this time, a brown oil-like CP-MABA (hydrogen type) was generated in the aqueous solution. Chloroform was added thereto to extract a brown oily substance. Since the aqueous phase at this time contained N-methyl-2-pyrrolidone and 4-methylaminobutyric acid (hereinafter abbreviated as "MABA") which is a ring-opening product thereof, the aqueous phase was discarded. The chloroform phase was washed twice with water.

Water was added to the chloroform phase to form a slurry, and a 48% NaOH aqueous solution was added to adjust the pH of the slurry to 13. At this time, CP-MABA became a sodium salt and moved to the aqueous phase, and the chloroform phase was discarded because the by-products p-chloro-N-methylaniline and N-methylaniline were dissolved in the chloroform phase. The aqueous phase was washed with chloroform twice.

Dilute hydrochloric acid was added to the aqueous solution to adjust the pH of the aqueous solution to 1 or less. At this time, CP-MABA became a hydrochloride and remained in the aqueous solution, so chloroform was added to the aqueous solution to extract p-chlorophenol as a by-product. The chloroform phase in which p-chlorophenol was dissolved was discarded.

A 48% NaOH aqueous solution was added to the remaining aqueous solution to adjust the pH of the aqueous solution to 4. As a result, the hydrochloride salt of CP-MABA was neutralized, and CP-MABA (hydrogen type) in the form of brown oil was precipitated from the aqueous solution. CP-MABA (hydrogen type) was extracted with chloroform, and chloroform was removed under reduced pressure to obtain CP-MABA (hydrogen type). Further, a 48% NaOH aqueous solution was added to the obtained CP-MABA (hydrogen type) to adjust the pH to 13, and CP-MABA (Na salt type) was obtained.

[Measurement method of composition in filtrate: water]
The water content was measured using a Karl Fischer titer (Karl Fischer titer AQV-300 manufactured by Hiranuma Sangyo Co., Ltd.).

[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)

[Measurement method of composition in filtrate: Oligomer]
After heating the well-stirred filtrate at 200 ° C. for 120 minutes, the non-volatile content was measured and the concentration of the non-volatile content contained in the filtrate was calculated. Next, the CP-MABA concentration was subtracted to obtain the oligomer concentration.

1. 1. Reference Example 1 205.5 parts by mass of flake-shaped sodium sulfide (60.75 wt% Na ₂ S) and 358.7 parts by mass 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 to distill out 49.10 parts by mass of water. Then, the autoclave was sealed and cooled to 180 ° C., and 230.2 parts by mass of paradichlorobenzene (hereinafter, may be abbreviated as p-DCB) and 228.0 parts by mass 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 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 (1).

100.0 parts by mass of the obtained slurry (1) was filtered to remove the solvent, and then 400 parts by mass of warm water at 60 ° C. was used to dissolve the NMP remaining in the filtration residue and sodium chloride as a by-product. After being dispersed and stirred for 10 minutes, the mixture was further filtered, 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 (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 1.440 wt% of oligomer, 0.510 wt% of CP-MABA (Na salt type), 3.050 wt% of water, and 94.71 wt% of NMP. The filtrate (1) was housed in a container with a tension-tightening lock mechanism, left for 30 minutes, cooled to room temperature, and stored.

The autoclave was charged with flaky sodium sulfide _(60.75wt% Na 2 S) 202.4 parts by mass, the NMP196.1 parts by mass and the filtrate was taken out from the container (1) 183.0 parts by mass. The temperature was raised to 212 ° C. with stirring under a nitrogen stream to distill 54.00 parts by mass of water. Then, the autoclave was sealed and cooled to 180 ° C., and p-DCB 227.3 parts by mass (1.546 mol parts) 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).

In addition, a sulfur atom (1.575 mol part) derived from flaky sodium sulfide (60.75 wt% Na ₂ S) and a sulfur atom (0.02438 mol) derived from an oligomer in the filtrate (1) in the raw material. However, when the weight of the oligomer is calculated by dividing the weight of the oligomer by the molecular weight (108.1) of the repeating unit of PPS, the same shall apply hereinafter), the sulfur atom is 1.599 mol parts. .. Since 0.940 parts by mass (0.003756 mol) of CP-MABA (Na salt type) derived from the filtrate (1) is added to the raw material, CP-MABA (Na salt type) added to the raw material The ratio of was 0.0023175 mol to 1 mol of sulfur atom contained in the raw material.

Next, 100.0 parts by mass of the obtained slurry (2) was filtered (a cellulose filter paper having 1 μm of reserved particles was drawn on a Kiriyama funnel, a beaker containing the slurry was placed in a water bath, and after the slurry temperature reached 50 ° C., It was put into a funnel and filtered under reduced pressure with a water flow pump) to remove the solvent, and in order to dissolve the NMP remaining in the filtration residue and sodium chloride as a by-product, it was dispersed in 400 parts by mass of warm water at 60 ° C. and stirred for 10 minutes. After that, it was further filtered, 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
A filtrate (1) was obtained in the same manner as in Example 1. The main composition of this filtrate (1) was 1.440 wt% of oligomer, 0.510 wt% of CP-MABA (Na salt type), 3.050 wt% of water, and 94.71 wt% of NMP. The filtrate (1) was housed in a container with a tension-tightening lock mechanism, left for 30 minutes, cooled to room temperature, and stored.

The autoclave was charged with flaky sodium sulfide _(60.75wt% Na 2 S) 205.5 parts by mass, the NMP198.3 parts by mass and the filtrate was taken out from the container (1) 183.0 parts by mass. The temperature was raised to 212 ° C. with stirring under a nitrogen stream to distill out 55.20 parts by mass of water. Then, the autoclave was sealed and cooled to 180 ° C., and 229.5 parts by mass (1.560 mol parts) of p-DCB and 231.4 parts by mass 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 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 (3).

In addition, a sulfur atom (1.60 mol part) derived from flaky sodium sulfide (60.75 wt% Na ₂ S) and a sulfur atom (0.02438 mol part) derived from an oligomer in the above filtrate in the raw material. In total, the sulfur atom was 1.624 mol parts. Since 0.940 parts by mass (0.003783 mol) of CP-MABA (Na salt type) derived from the filtrate (1) is added to the raw material, CP-MABA (Na salt type) added to the raw material The ratio of was 0.002330 mol to 1 mol of sulfur atom contained in the raw material.

From the obtained slurry (3), a white powdery polymer (3) was obtained in the same manner as in Example 1. The melt viscosity was measured and found to be 43 Pa · s.

4. Example 3
A filtrate (1) was obtained in the same manner as in Example 1. The main composition of this filtrate (1) was 1.440 wt% of oligomer, 0.510 wt% of CP-MABA (Na salt type), 3.050 wt% of water, and 94.71 wt% of NMP. The filtrate (1) was housed in a container with a tension-tightening lock mechanism, left for 30 minutes, cooled to room temperature, and stored.

The autoclave was charged with flaky sodium sulfide _(60.75wt% Na 2 S) 205.5 parts by mass, the NMP138.0 parts by mass and the filtrate was taken out from the container (1) 244.5 parts by mass. The temperature was raised to 212 ° C. with stirring under a nitrogen stream to distill out 55.20 parts by mass of water. Then, the autoclave was sealed and cooled to 180 ° C., and 225.6 parts by mass (1.534 mol parts) of p-DCB and 235.3 parts by mass 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 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 (4).

The sulfur atom (1.60 mol parts) derived from flaky sodium sulfide (60.75 wt% Na ₂ S) and the sulfur atom (0.03257 mol) derived from the oligomer in the filtrate (1) in the raw material. The total amount of sulfur atoms was 1.633 mol parts. Since 1.260 parts by mass (0.005071 mol) of CP-MABA (Na salt type) derived from the filtrate (1) is added to the raw material, CP-MABA (Na salt type) added to the raw material. The ratio of was 0.003106 mol with respect to 1 mol of the sulfur atom contained in the raw material.

From the obtained slurry (4), a white powdery polymer (4) was obtained in the same manner as in Example 1. The melt viscosity was measured and found to be 39 Pa · s.

5. Example 4
A slurry (2) was obtained in the same manner as in Example 1. The obtained slurry (2) was filtered to obtain a filtrate (2) containing a solvent. The main composition of this filtrate (2) was 1.450 wt% of oligomer, 0.650 wt% of CP-MABA (Na salt type), 3.020 wt% of water, and 94.30 wt% of NMP. The filtrate (2) was housed in a container with a tension-tightening lock mechanism, left for 30 minutes, cooled to room temperature, and stored.

The autoclave was charged with 202.3 parts by mass of flaky sodium sulfide (60.75 wt% Na ₂ S), 196.1 parts by mass of NMP, and 183.0 parts by mass of the filtrate (2) taken out from the container. The temperature was raised to 212 ° C. with stirring under a nitrogen stream to distill 54.00 parts by mass of water. Then, the autoclave was sealed and cooled to 180 ° C., and p-DCB 226.9 parts by mass (1.543 mol parts) and NMP 238.8 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 (5).

In addition, a sulfur atom (1.575 mol part) derived from flaky sodium sulfide (60.75 wt% Na ₂ S) and a sulfur atom (0.02455 mol) derived from an oligomer in the above filtrate (2) in the raw material. The total amount of sulfur atoms was 1.600 mol. Since 1.190 parts by mass (0.004790 mol parts) of CP-MABA (Na salt type) derived from the filtrate (2) is added to the raw material, CP-MABA (Na salt type) added to the raw material. The ratio of was 0.002994 mol to 1 mol of the sulfur atom contained in the raw material.

From the obtained slurry (5), a white powdery polymer (5) was obtained in the same manner as in Example 1. The melt viscosity was measured and found to be 44 Pa · s.

6. Example 5
A slurry (5) was obtained in the same manner as in Example 4. The obtained slurry (5) was filtered to obtain a filtrate (3) containing a solvent. The main composition of the filtrate (3) was 1.480 wt% oligomer, 0.790 wt% CP-MABA (Na salt type), 3.090 wt% water, and 94.27 wt% NMP. The filtrate (3) was housed in a container with a tension-tightening lock mechanism, left for 30 minutes, cooled to room temperature, and stored.

The autoclave was charged with flaky sodium sulfide _(60.75wt% Na 2 S) 202.3 parts by mass, the NMP196.1 parts by mass and the filtrate was taken out from the container (3) 183.0 parts by mass. The temperature was raised to 212 ° C. with stirring under a nitrogen stream to distill 54.00 parts by mass of water. Then, the autoclave was sealed and cooled to 180 ° C., and p-DCB 226.9 parts by mass (1.543 mol parts) and NMP 238.8 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 (6).

In addition, a sulfur atom (1.575 mol part) derived from flaky sodium sulfide (60.75 wt% Na ₂ S) and a sulfur atom (0.02505 mol) derived from an oligomer in the above filtrate (3) in the raw material. The total amount of sulfur atoms was 1.600 mol. Since 1.450 parts by mass (0.005836 mol parts) of CP-MABA (Na salt type) derived from the filtrate (3) is added to the raw material, CP-MABA (Na salt type) added to the raw material The ratio of was 0.003648 mol to 1 mol of the sulfur atom contained in the raw material.

From the obtained slurry (6), a white powdery polymer (6) was obtained in the same manner as in Example 1. The melt viscosity was measured and found to be 44 Pa · s.

7. Comparative Example 1
A slurry (7) was obtained in the same manner as in Example 1 except that "the above-mentioned filtrate (1) 370.0 parts by mass" was replaced with "the above-mentioned filtrate (1) 183.0 parts by mass". ..

In addition, a sulfur atom (1.575 mol part) derived from flaky sodium sulfide (60.75 wt% Na ₂ S) and a sulfur atom (0.04929 mol) derived from an oligomer in the above filtrate (1) in the raw material. In total, the sulfur atom was 1.624 mol parts. Since 1.900 parts by mass (0.007647 mol parts) of CP-MABA (Na salt type) derived from the filtrate (1) is added to the raw material, CP-MABA (Na salt type) added to the raw material The ratio of was 0.004709 mol to 1 mol of the sulfur atom contained in the raw material.

From the obtained slurry (7), a white powdery polymer (7) was obtained in the same manner as in Example 1. The melt viscosity was measured and found to be 32 Pa · s.

8. Comparative Example 2
A slurry (6) was obtained in the same manner as in Example 5. The obtained slurry (6) was filtered to obtain a filtrate (4) containing a solvent. The main composition of this filtrate (4) was 1.490 wt% of oligomer, 0.990 wt% of CP-MABA (Na salt type), 3.020 wt% of water, and 94.04 wt% of NMP. The filtrate (4) was housed in a container with a tension-tightening lock mechanism, left for 30 minutes, cooled to room temperature, and stored.

The autoclave was charged with flaky sodium sulfide _(60.75wt% Na 2 S) 202.3 parts by mass, the NMP196.1 parts by mass and the filtrate was taken out from the container (4) 183.0 parts by mass. The temperature was raised to 212 ° C. with stirring under a nitrogen stream to distill 54.00 parts by mass of water. Then, the autoclave was sealed and cooled to 180 ° C., and p-DCB 226.9 parts by mass (1.543 mol parts) and NMP 238.8 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 (8).

In addition, a sulfur atom (1.575 mol part) derived from flaky sodium sulfide (60.75 wt% Na ₂ S) and a sulfur atom (0.02522 mol) derived from an oligomer in the above filtrate (4) in the raw material. The total amount of sulfur atoms was 1.600 mol. Since 1.810 parts by mass (0.007285 mol) of CP-MABA (Na salt type) derived from the filtrate (4) is added to the raw material, CP-MABA (Na salt type) added to the raw material. The ratio of was 0.004553 mol to 1 mol of sulfur atom contained in the raw material.

From the obtained slurry (8), a white powdery polymer (8) was obtained in the same manner as in Example 1. The melt viscosity was measured and found to be 32 Pa · s.

Claims (5)

Step (1): Polymerization after a polymerization reaction of a polyarylene sulfide resin in which an alkali metal sulfide or an alkali metal hydrosulfide or an alkali metal hydroxide is reacted with a polyhalo aromatic compound in the presence of a polar organic solvent. and wherein the polar organic solvent is solid-liquid separated from the crude reaction mixture obtained in the reaction, the polar organic solvent as a main component, a liquid phase component that is part of at least carboxyalkyl amino group-containing compounds, polyarylene sulfide The solid phase component composed of the reaction mixture containing the resin and alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound is separated, the solid phase component is removed, and the organic polar solvent containing the carboxyalkylamino group-containing compound (a). ) To obtain the process,
Step (2): A step of supplying the organic polar solvent (a) obtained in the step (1) into the reaction vessel.
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. It has a step of polymerizing hydrosulfide and alkali metal hydroxide as raw materials in an organic polar solvent containing a carboxyalkylamino group-containing compound, and in the step (4), the organic polarity containing the raw materials. A method for producing a polyarylene sulfide resin, wherein the ratio of the carboxyalkylamino group-containing compound in the solvent is in the range of 0.004 mol or less with respect to 1 mol of sulfur atoms in the raw material. 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 a manufacturing method of the polyarylene sulfide resin according to claim 1, wherein is represented by the representative.) a hydrogen atom or an alkali metal atom. The method for producing a polyarylene sulfide resin according to claim 1 or 2, wherein the carboxyalkylamino group-containing compound is an alkali metal salt. The method for producing a polyarylene sulfide resin according to any one of claims 1 to 3, wherein the organic polar solvent (a) obtained through the step (1) contains a polyarylene sulfide resin oligomer. The organic polar solvent (a) obtained in the step (1) is stored in a container provided with a sealing mechanism, and the step (2) is performed from the container to the organic polar solvent (a). The method for producing a polyarylene sulfide resin according to any one of claims 1 to 4, which is a step of taking out a) and supplying it into a reaction vessel.