JP2017071752A - Method for producing polyarylene sulfide resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyarylene sulfide resin which is reduced in a volatile component during melt molding such as an oligomer, a by-product and an unreacted raw material with good productivity.SOLUTION: A method for producing a polyarylene sulfide resin includes: a step 1 of reacting a polyhaloaromatic compound and a sulfiding agent in an organic polar solvent to obtain a crude reaction mixture containing at least a polyarylene sulfide resin and the organic polar solvent; a step 2 of subjecting the crude reaction mixture obtained in the step 1 to solid-liquid separation to separate a solid content containing at least the polyarylene sulfide resin; and a step 3 of subjecting the solid content separated and obtained in the step 2 to solvent washing, where in the step 3, a slurry or a wet cake to which a solvent is added to the solid content is irradiated with ultrasonic waves.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a polyarylene sulfide resin, a method for producing a polyarylene sulfide resin composition, and a method for producing a polyarylene sulfide resin molded article.

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

  The polyarylene sulfide resin is a method of polymerizing a sulfidizing agent and a polyhaloaromatic compound in an aprotic polar organic solvent such as N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP). The crude reaction product produced by (Phillips method) includes low molecular weight of less than 15 repeating units that cannot be produced in addition to the target polyarylene sulfide resin and the polar organic solvent used in the reaction. Polyarylene sulfide resin (that is, oligomer), 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。）で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有機塩といった副生成物、未反応原料等も含まれる。

Wherein n is 0 to 2, Y ¹ represents a halogen atom, Y ² represents a hydrogen atom or a halogen atom, R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a cyclohexyl group; R ² represents an alkylene group having 3 to 5 carbon atoms, X represents a hydrogen atom or an alkali metal atom.) By-products such as organic salts such as carboxyalkylamino group-containing compounds, unreacted raw materials, etc. included.

  For this reason, the crude reaction product after the polymerization reaction is subjected to a solvent removal treatment using a solid-liquid separation device, and then washed and filtered using a washing solvent, and these oligomers, by-products and unreacted raw materials are repeated. Has been done to remove.

  For example, a method of removing an oligomer component and a non-oligomer component by washing a crude reaction mixture after reaction with NMP and further washing the obtained solid content with water is known (Patent Document 1). Further, the water content in the slurry after the reaction is less than 2% by weight and solid-liquid separated at a specific temperature, and the obtained solid content is heated to a specific temperature. There is also known a method of washing with water after washing with an organic solvent of not more than% by weight and removing the mother liquor (Patent Document 2).

  However, since the polyarylene sulfide resin is insoluble in the solvent, by-products and unreacted raw materials adhering to the surface of the polymer particles can be removed by solvent washing, but the oligomers and by-products contained in the resin are included. It was difficult to remove unreacted raw materials. For this reason, during melt kneading of the polyarylene sulfide resin, the oligomers, by-products and unreacted raw materials contained in the resin are volatilized as volatile components, which not only deteriorates the working environment due to the characteristic sulfur odor, but also melts. It was the cause of clogging of the kneading machine vent (gas venting part) and contamination of the mold and the surface of the molded product.

Japanese Patent Laid-Open No. 7-3022 Japanese Patent Laid-Open No. 11-80355

  Therefore, the problem to be solved by the present invention is that in a polar organic solvent, a polyhaloaromatic compound and (i) an alkali metal sulfide, or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide, Providing a method for producing a polyarylene sulfide resin having reduced volatile components during melt molding, such as oligomers, by-products and unreacted raw materials, with high productivity In particular, the present invention provides a method for purifying polyarylene sulfide resin that more efficiently cleans volatile components at the time of melt molding such as oligomers, by-products and unreacted raw materials, and further volatilizes volatile components at the time of melt molding. An object of the present invention is to provide a polyarylene sulfide resin composition that can be suppressed and a method for producing a molded article.

As a result of various studies, the inventors of the present invention have found that a polyhaloaromatic compound and (i) an alkali metal sulfide or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide are obtained in a polar organic solvent. In the method for producing a polyarylene sulfide resin that reacts with a product,
By increasing the surface area of the granular polyarylene sulfide resin obtained by solid-liquid separation of the crude reaction product after the polymerization reaction by ultrasonic irradiation, it becomes possible to wash the solvent efficiently thereafter, and oligomers and unreacted raw materials It has become clear that undesired components that can become volatile components during melt molding can be efficiently removed, and the present invention has been completed.

That is, the present invention comprises reacting a polyhaloaromatic compound and (i) an alkali metal sulfide or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in a polar organic solvent, Obtaining a crude reaction mixture comprising at least a polyarylene sulfide resin and the polar organic solvent (1),
A step (2) of solid-liquid separating a crude reaction mixture containing at least a polyarylene sulfide resin and the polar organic solvent to recover a solid content containing at least the polyarylene sulfide resin;
A method for producing a polyarylene sulfide resin, which includes a step (3) in which a solvent is added to the solid content obtained in the step (2) to perform washing.
In the step (3), the present invention relates to a method for producing a polyarylene sulfide resin, wherein the slurry or wet cake obtained by adding a solvent to the solid content is irradiated with ultrasonic waves while being cooled.

  The present invention also provides a method for producing a polyarylene sulfide resin composition comprising a step of melt kneading the polyarylene sulfide resin obtained by the above production method with at least one selected from the group consisting of a resin, a filler and an additive. About.

  Furthermore, this invention relates to the manufacturing method of the polyarylene sulfide resin molded article which has the process of shape | molding, after melt-kneading the polyarylene sulfide resin composition obtained by the said manufacturing method.

Furthermore, the present invention is obtained by reacting a polyhaloaromatic compound and (i) an alkali metal sulfide or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in a polar organic solvent. Separating the resulting crude reaction mixture into a solid and a liquid, and recovering a solid content containing at least a polyarylene sulfide resin (2),
A step (3) of performing solvent washing on the solid content obtained in the step (2);
In the step (3), the present invention relates to a method for purifying a polyarylene sulfide resin, wherein the slurry or wet cake obtained by adding a solvent to the solid content is irradiated with ultrasonic waves while being cooled.

  According to the present invention, polyarylene is reacted with a polyhaloaromatic compound and (i) an alkali metal sulfide or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in a polar organic solvent. In a method for producing a sulfide resin, to provide a method for producing a polyarylene sulfide resin having reduced volatile components at the time of melt molding such as oligomers, by-products and unreacted raw materials with high productivity. It is possible to provide a purification method of polyarylene sulfide resin that more efficiently cleans volatile components at the time of melt molding such as products and unreacted raw materials, and furthermore it is possible to suppress volatilization of volatile components at the time of melt molding. A polyarylene sulfide resin composition and a method for producing a molded article can be provided.

The method for producing a polyarylene sulfide resin according to the present invention comprises a polyhaloaromatic compound and (i) an alkali metal sulfide or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in a polar organic solvent. Step (1) to obtain a crude reaction mixture containing at least a polyarylene sulfide resin and the polar organic solvent,
A step (2) of solid-liquid separating a crude reaction mixture containing at least a polyarylene sulfide resin and the polar organic solvent to recover a solid content containing at least the polyarylene sulfide resin;
A method for producing a polyarylene sulfide resin having a step (3) of performing solvent washing on the solid content obtained in the step (2),
In the step (3), the slurry or wet cake obtained by adding a solvent to the solid content is irradiated with ultrasonic waves while being cooled.

  As the step (1), for example, a polyhaloaromatic compound and (i) an alkali metal sulfide or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide are reacted in a polar organic solvent. Any method may be used as long as it is a method for producing a polyarylene sulfide resin by the so-called Philips method.

  Here, the polyhaloaromatic compound used in the present invention is, for example, a halogenated aromatic compound having two or more halogen atoms directly bonded to an aromatic ring, specifically, p-dichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, trichlorobenzene, tetrachlorobenzene, dibromobenzene, diiodobenzene, tribromobenzene, dibromonaphthalene, triiodobenzene, dichlorodiphenylbenzene, dibromodiphenylbenzene, di And dihaloaromatic compounds such as chlorobenzophenone, dibromobenzophenone, dichlorodiphenyl ether, dibromodiphenyl ether, dichlorodiphenyl sulfide, dibromodiphenyl sulfide, dichlorobiphenyl, dibromobiphenyl, and mixtures thereof. These compounds may be block copolymerized. Of these, dihalogenated benzenes are preferred, and those containing p-dichlorobenzene of 80 mol% or more are particularly preferred.

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

  Furthermore, polyhaloaromatic compounds having a functional group having active hydrogen such as amino group, thiol group, hydroxyl group can be mentioned. Specifically, 2,6-dichloroaniline, 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 and 2,4′-diamino-2 ′, 4-dichlorodiphenyl ether Examples thereof include compounds in which the amino group is replaced by a thiol group or a hydroxyl group in a mixture thereof.

  In addition, active hydrogen-containing polyhalo compounds in which the hydrogen atom bonded to the carbon atom forming the aromatic ring in these active hydrogen-containing polyhaloaromatic compounds is substituted with another inert 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 Dihalonitrodiphenyl ethers; dihalonitrodiphenyl sulfones such as 3,3′-dinitro-4,4′-dichlorodiphenyl sulfone; 2,5-dichloro-3-nitropyridine, 2-chloro-3,5 -Mono or dihalonitropyridines such as dinitropyridine; or various dihalonitronaphthalenes.

  The alkali metal sulfide used in the present invention 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. The alkali metal sulfide can also be derived from the reaction between an alkali metal hydrosulfide and an alkali metal hydroxide. Normally, a small amount of alkali metal hydroxide may be added to react with alkali metal hydrosulfide or alkali metal thiosulfate present in a trace amount in the alkali metal sulfide.

  In addition, the alkali metal hydrosulfide used in the present invention includes lithium hydrosulfide, sodium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and mixtures thereof. Such alkali metal hydrosulfides can be used as hydrates, aqueous mixtures or anhydrides.

  In addition, examples of the alkali metal hydroxide used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, etc., but these may be used alone, 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.

  Examples of the polar organic solvent used in the polymerization step (1) of the present invention include formamide, acetamide, N-methylformamide, N, N-dimethylacetamide, tetramethylurea, N-methyl-2-pyrrolidone, 2- Amides such as pyrrolidone, N-methyl-ε-caprolactam, ε-caprolactam, hexamethylphosphoramide, N-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone acid, urea and lactams; sulfolane, dimethyl Examples include sulfolanes such as sulfolane; nitriles such as benzonitrile; ketones such as methyl phenyl ketone and mixtures thereof, among which N-methyl-2-pyrrolidone, 2-pyrrolidone, N-methyl-ε -Caprolactam, epsilon-caprolactam, hexamethyl phosphor Bromide, N- dimethyl propylene urea, 1,3-dimethyl-2-amide having an aliphatic cyclic structure imidazolidinone acids are preferred, more preferably N- methyl-2-pyrrolidone.

  In the polymerization reaction of the polyarylene sulfide resin in the polymerization (1), the alkali metal sulfide is reacted with the polyhaloaromatic 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 alkali metal hydroxide are reacted with the polyhaloaromatic compound as a sulfidizing agent in the presence of these aprotic polar solvents. The polymerization conditions are not particularly limited as long as they are in the general range employed in the Philips method, but the temperature is preferably in the range of 200 to 330 ° C., and the pressure is substantially in the liquid phase with the polymerization solvent and the polyhaloaromatic compound as the polymerization monomer. The range should be maintained, and in general, the range of 0.1 to 20 MPa is preferable, and the range of 0.1 to 2 MPa is more preferable. The feed amount of each raw material is not particularly limited as long as it is a general range adopted in the Philips method, but the feed amount of the polyhaloaromatic compound is 0.2 mol with respect to 1 mol of the sulfur atom of the sulfidizing agent. The range of -5.0 mol is preferable, the range of 0.8-1.3 mol is more preferable, and the range of 0.9-1.1 mol is particularly preferable. The amount of the polar organic solvent charged is preferably in the range of 1.0 to 6.0 mol, more preferably in the range of 2.5 to 4.5 mol, with respect to 1 mol of the sulfur atom of the sulfidizing agent. The polymerization reaction is preferably performed in the presence of a small amount of water, and the proportion is preferably adjusted as appropriate in consideration of the polymerization method and the molecular weight and productivity of the polymer obtained. Specifically, the dehydration operation is preferably performed in a range of 2.0 mol or less, preferably 1.6 mol or less with respect to 1 mol of the sulfur atom of the sulfidizing agent. In the case where the dehydration operation is carried out at the bottom (for example, the method of “5)” in the following specific embodiment), it is 0.9 mol or less, preferably 0.05-0.3 mol, more preferably 0.01-0. The dehydration operation can also be performed so as to be in the range of 02 mol or less.

As a specific embodiment for polymerizing a sulfidizing agent and a polyhaloaromatic compound in the presence of the polar organic solvent described above, for example,
1) A method using a polymerization aid such as an alkali metal carboxylate or lithium halide,
2) A method using a crosslinking 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 for further polymerization
4) A method in which during the reaction between the alkali metal sulfide and the aromatic dihalogen compound, the gas phase portion of the reaction kettle is cooled to condense part of the gas phase in the reaction kettle and reflux to the liquid phase,
5) In the presence of a polyhaloaromatic compound, an alkali metal sulfide, or a hydrous alkali metal hydrosulfide and an alkali metal hydroxide, and an amide, urea or lactam having an aliphatic cyclic structure are reacted while being dehydrated. Obtained through a step of producing a slurry containing a solid alkali metal sulfide, a step of adding a polar organic solvent such as NMP and dehydrating by distilling off water after producing the slurry, followed by a dehydration step. In the resulting slurry, a polyhaloaromatic compound, an alkali metal hydrosulfide, and an alkali metal salt of an amide, urea or lactam hydrolyzate having an aliphatic cyclic structure are mixed with 1 mol of a polar organic solvent such as NMP. In contrast, polyarylene sulfide having a process of performing polymerization by reacting at a water content of 0.02 mol or less in the reaction system as an essential process. Method for manufacturing a resin.

  Among these, when a polyarylene sulfide resin is produced by the polymerization methods 1) to 4), the production of by-products is increased, and therefore, it can be suitably reduced by the method of the present invention.

  After completion of the polymerization of the polyarylene sulfide resin by the Philips method, a crude reaction mixture containing the polyarylene sulfide resin and the polar organic solvent used for the polymerization is obtained as a crude reaction mixture. In addition, at least a carboxyalkylamino group is contained. A compound may be included, and further, for example, by-products such as oligomers and alkali metal-containing inorganic salts, unreacted raw materials, and water may be included.

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

（式中、Ｘはアルカリ金属原子または水素原子を表す。）で表されるものが得られる傾向にある（この化合物を“ＣＰ−ＭＡＢＡ”と略記する）。

(Wherein X represents an alkali metal atom or a hydrogen atom) tends to be obtained (this compound is abbreviated as “CP-MABA”).

  Moreover, when water exceeds 1 mass% in a crude reaction product, dehydration operation is performed and it is 1 mass% or less with respect to the polar organic solvent used for superposition | polymerization, Preferably it is 0.5 mass% or less. It may be reduced.

  Next, the crude reaction mixture containing at least the polyarylene sulfide resin and the polar organic solvent is subjected to solid-liquid separation to recover a solid content containing at least the polyarylene sulfide resin (step (2)).

The solid-liquid separation is roughly classified into two types, a flash method and a quench method described later.
The flash method is a method in which the solvent in the crude reaction mixture is evaporated to recover the solvent, and at the same time, the solid is recovered. In general, the crude reaction mixture is flashed from a high-temperature and high-pressure state to an atmosphere of normal pressure or reduced pressure. And the solvent is distilled off and recovered, and at the same time, the solid containing the polyarylene sulfide resin is recovered in the form of powder. A preferred embodiment of the flash method is a method in which a high-temperature and high-pressure (usually 250 ° C. or higher, 0.8 MPa or higher) polymerization reaction product obtained in the polymerization step is ejected from a nozzle into an atmosphere such as nitrogen or water vapor at normal pressure. It is done. In the flash method, the solvent can be efficiently recovered by utilizing the heat of vaporization of the solvent when the polymerization reaction product is flushed from a high temperature and high pressure state to a normal pressure state. Efficiency is improved and productivity is improved. Therefore, the temperature and pressure in the polymerization system when flashing are usually 250 ° C. or higher, preferably 255 to 280 ° C. and 0.8 MPa or higher, preferably 1.0 to 5.0 MPa. From this state, the ambient temperature when flashing under reduced pressure or normal pressure is usually in the range of 150 to 250 ° C. When the solvent recovery from the crude reaction mixture is insufficient, the ambient temperature is 150 to 250 ° C. after the flash. The heating may be continued.

  On the other hand, the quench method is a method for recovering particulate polyarylene sulfide resin by cooling the crude reaction mixture. Generally, the crude reaction mixture is gradually cooled from a high-temperature and high-pressure state in the reaction system. In this method, after the polyarylene sulfide resin is crystallized, the solid content containing the polyarylene sulfide resin is recovered as granules by solid-liquid separation by filtration or the like.

  Although there is no restriction | limiting in particular in cooling time, Usually 0.1 to 3 degree-C / min is a preferable range. Further, there is no need to slowly cool at the same speed in the whole process of the slow cooling step, and the range is 0.1 ° C./min to 1 ° C./min until the polyarylene sulfide resin granules crystallize, and thereafter A method of cooling at a rate of 1 ° C./min or more is also preferable. Finally, it is preferable to recover the solid content including the polyarylene sulfide resin by cooling to 70 ° C. or higher, preferably 100 ° C. or higher and 200 ° C. or lower, and then solid-liquid separation. Solid-liquid separation in the Quench method is a method in which after separation using a centrifugal separator such as filtration or screw decanter, water is directly added to the obtained filtration residue to form a slurry, and then solid-liquid separation is repeated. For example, a method of removing the remaining solvent by heating the filtered residue in a non-oxidizing atmosphere can be used.

  The flash method is preferable because solids can be recovered relatively easily, and the quench method is easy to control the particle size of the polyarylene sulfide resin and the by-products and unreacted in the polymer particles during crystallization. This is preferable because impurities such as raw materials can be hardly taken up.

Subsequently, washing is performed by adding a solvent to the solid content obtained in the step (2) (step (3)).
The solid content obtained through the step (2) mainly contains polyarylene sulfide resin, and impurities such as by-products and unreacted raw materials are mainly included in the polyarylene sulfide resin and remain. Will be. Examples of the components remaining after inclusion (hereinafter sometimes referred to as residues) include, for example, carboxyalkylamino group-containing compounds, other by-products such as oligomers and organic salts such as alkali metal-containing inorganic salts, and unreacted products. Raw materials may be included. These cause volatilization during melt molding.

  For this reason, the solid content obtained in the step (2) is washed by bringing it into contact with a washing solvent (hereinafter referred to as a washing solvent), and then the solid containing the polyarylene sulfide resin is separated by filtration or the like. The liquid phase component is separated from the liquid phase component by liquid separation. In that case, in the step (1), when the crude reaction mixture further contains a carboxyalkylamino group-containing compound, the carboxyalkylamino group-containing compound can be separated as a liquid phase component. At this time, by-products such as oligomers and organic salts such as alkali metal-containing inorganic salts and unreacted raw materials may be separated as the liquid phase component in addition to the carboxyalkylamino group-containing compound.

  In step (3), solid-liquid separation was obtained by, for example, a method of adding a solvent to the solid content obtained by separation in step (2) and stirring the mixture, followed by filtration using a filtration device, as described above. A method of adding a solvent to a filtration residue containing a solvent (hereinafter abbreviated as “solvent-containing cake”) to make a slurry and then filtering, or adding a solvent again while the solvent-containing cake is held in a filter and filtering. And the like.

  The washing solvent used in the step (3) is preferably mixed with the polar organic solvent used in the polymerization in the step (1), and is selected according to the characteristics of the polar organic solvent. Those which do not substantially cause undesirable side reactions such as cross-linking are preferable, for example, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol and other alcohol / phenol solvents, chloroform, Halogen solvents such as bromoform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene, 2,6-dichlorotoluene, pentane, hexane, heptane, octane, cyclohexane, cyclopentane, benzene , Hydrocarbon solvents such as toluene, xylene, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl butyl ketone, acetophenone, methyl acetate, ethyl acetate, pentyl acetate, octyl acetate, methyl butyrate, ethyl butyrate Examples thereof include carboxylic acid ester solvents such as pentyl butyrate, methyl salicylate, ethyl formate, and the like, among which methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, chloroform, methylene chloride, 1,2 -Dichloroethane, pentane, hexane, heptane, octane, cyclohexane, cyclopentane, acetone, methyl acetate, ethyl acetate, water are preferred, methanol, ethanol, propanol, ethylene group Call, chloroform, methylene chloride, 1,2-dichloroethane, acetone, ethyl acetate, water is particularly preferred, methanol, acetone, water and even more preferably, water is particularly preferred. These solvents can be used as one kind or a mixture of two or more kinds.

  There are no particular restrictions on the atmosphere in which the solid content is brought into contact with the cleaning solvent, but if the polyarylene sulfide resin or the cleaning solvent is oxidatively deteriorated depending on conditions such as the temperature and time of contact, it is non-oxidized. It is desirable to carry out in a sex atmosphere. There is no particular restriction on the temperature at which the solid content is brought into contact with the washing solvent, but it is preferable to carry out under atmospheric pressure. Therefore, the upper limit temperature is preferably set to be equal to or lower than the reflux temperature under atmospheric pressure of the solvent used. When using the preferable solvent mentioned above, 20-150 degreeC, for example, Preferably 30-100 degreeC can be illustrated as a specific temperature range.

  The method of bringing the solid content into contact with the washing solvent is not particularly limited as long as a known general method is used. For example, the solid-liquid separation described above is performed after mixing the solid content and the solvent and stirring as necessary. Any method can be used, such as a method for recovering the solid content by performing an operation, a method for showering the solvent on the solid content on various filters, and a method based on the principle of the Soxhlet extraction method. Although there is no restriction | limiting in particular in the usage-amount of the washing | cleaning solvent at the time of making solid content and a washing | cleaning solvent contact, For example, the range of 0.1-100 times is preferable on a mass basis with respect to the theoretical yield of polyarylene sulfide resin. In the case of such a ratio range, the solid content and the cleaning solvent can be easily mixed uniformly, and the polar organic solvent can be efficiently separated from the solid content. When contact between the solid content and the cleaning solvent is repeated, a smaller ratio may be used, and a sufficient effect is often obtained.

Below, the aspect of the washing | cleaning which used water as a washing | cleaning solvent is explained in full detail.
When washing with water as a solvent (hereinafter referred to as “water washing”), the amount of water added to the solid content is 2 to 10 times on a mass basis with respect to the theoretical yield of the polyarylene sulfide resin finally obtained. It is preferable from the point of washing | cleaning efficiency, and it is preferable to divide the said quantity of water into 2-10 times, Preferably it divides | segments into 2-4 times, and uses for water washing. The water washing is preferably performed in a nitrogen or air atmosphere in a solvent temperature range of 50 ° C. to 100 ° C. and a cleaning efficiency of 70 ° C. to 90 ° C., in particular. The water washing can be repeated once or a plurality of times. When water washing is repeated a plurality of times, the atmosphere and temperature conditions may be the same or different.

  When washing with water, many traces of organic salts such as alkali metal-containing inorganic salts and carboxyalkylamino group-containing compounds are removed by washing, but the polyarylene sulfide resin separated by filtration contains traces of alkali metals. Organic salts such as inorganic salts and carboxyalkylamino group-containing compounds may remain. In this case, solid-liquid separation after further contact with water in the range of 100 to 275 ° C. (hereinafter sometimes referred to as “hot water washing”), remaining alkali metal-containing inorganic salt and carboxyalkylamino group-containing Water containing an organic salt such as a compound can be extracted and filtered to obtain a solid content containing a polyarylene sulfide resin.

  The temperature of the hot water washing is preferably in the range of 120 to 275 ° C., for example, because the extraction efficiency of organic salts such as alkali metal-containing inorganic salts and carboxyalkylamino group-containing compounds is good. More specifically, it is preferable to perform the extraction treatment with hot water at 140 to 260 ° C. under the condition that the pressure of the gas phase in the reactor is 0.2 to 4.6 MPa. By such hydrothermal treatment, the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound that have been included and remained in the polyarylene sulfide resin can be extracted into water more efficiently, and then the alkali metal-containing compound can be extracted. An aqueous solution containing an organic salt such as an inorganic salt and a carboxyalkylamino group-containing compound can be removed by filtration to obtain a solid content containing a polyarylene sulfide resin.

  A specific method for performing such hot water washing is a method of washing the polyarylene sulfide resin filtered after the water washing with stirring under water under a predetermined pressure condition and temperature condition in a pressure vessel. It is done. The amount of water at the time of hot water washing is preferably 1.5 times to 10 times the mass of polyarylene sulfide from the viewpoint of good extraction efficiency of the carboxyalkylamino group-containing compound. The hot water cleaning may be performed in two or more times. For example, when the hot water washing is repeated twice, it is preferable to perform filtration between the first hot water washing and the second hot water washing to remove the carboxyalkylamino group-containing compound extracted by the first hot water washing. . Moreover, after carrying out hot water washing once, it may filter and may carry out an above described water washing. This operation also promotes the removal of the carboxyalkylamino group-containing compound. Moreover, although the conditions of the 1st hot water washing | cleaning process and the 2nd hot water washing | cleaning process can be selected arbitrarily from said conditions, the temperature of the 1st hot water washing | cleaning process is in the range of 120 to 200 degreeC, for example. The temperature is set to a certain temperature, and the highly alkaline filtrate is first removed by filtration, and then the temperature of the second hot water washing step is higher than the temperature of the first hot water washing step, for example, in the range of 150 ° C. to 275 ° C. It is preferable to set the temperature at a certain temperature from the viewpoint of chemical resistance of the apparatus used in the hot water cleaning.

  In the hot water washing, acid or base can be added to adjust pH before hot water washing, hot water washing or after hot water washing. In particular, in the carboxyalkylamino group-containing compound, X is an alkali metal. Since it becomes an atom and is easily extracted into water, it is preferable to control so that the pH after hot water washing is in the range of 11.0 or more and less than 13.0. Examples of the acid used at that time include hydrochloric acid, sulfuric acid, carbonic acid, acetic acid, and oxalic acid. Among these, carbonic acid, acetic acid, and oxalic acid are preferable. Further, carbon dioxide gas may be introduced and contacted at normal pressure or under pressure. On the other hand, examples of the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, or sodium carbonate, ammonium carbonate, sodium phosphate, and the like. Among these, sodium hydroxide is preferable.

  For water washing or hot water washing, it is possible to use a water washing tank having a stirrer or a centrifuge for solid-liquid separation, but it has a stirring blade inside the container and a filter for filtration at the bottom. Can be carried out in a container having a mixing function. It is also possible to use a water washing tank having a stirrer or a centrifuge for solid-liquid separation even in hot water washing exceeding 100 ° C., but it has a stirring blade inside the container and has a bottom part. It can be carried out in a sealed container provided with a filter for filtration or in a container having a mixing function capable of being sealed. In the present invention, water washing or hot water washing may be performed continuously or in a batch manner.

  In the step (3), the ultrasonic irradiation is performed on the wet cake after the solvent is washed, or the slurry obtained by adding the solvent to the solid content or the liquid phase component is reduced by solid-liquid separation of the slurry by filtration or the like. While doing. As a result, the polyarylene sulfide resin contained in the solid content can be crushed into granules or particles having a smaller particle diameter, the residue in the polyarylene sulfide resin can be extracted, and the cleaning solvent can be efficiently used Can be contacted. Therefore, it is preferable to remove the residue by performing at least one solvent washing on the solid content after ultrasonic irradiation.

When performing ultrasonic irradiation, the irradiation energy is not particularly limited as long as it is an energy capable of pulverizing granules or particles composed of the polyarylene sulfide resin contained in the solid content, but 1.0 × 10 ^{5 to} 1.0 × It is preferably 10 ¹⁰ [W / m ³ ], and more preferably in the range of 1.0 × 10 ^{7 to} 1.0 × 10 ⁹ [W / m ³ ]. When performing ultrasonic irradiation, the frequency may remain the same or different frequencies may be sequentially irradiated. In that case, the frequency is increased from a low frequency to a high frequency, or conversely, from a high frequency to a low frequency. And the frequency can be lowered, or they can be alternated. The ultrasonic irradiation may be performed once or divided into a plurality of times. In the case of performing a plurality of times, the number of times may be performed until the dispersion is completed, but is preferably 2 to 100 times, and preferably 2 to 10 times. Is more preferable. When ultrasonic cleaning is performed a plurality of times, it is preferable to perform at least one solvent cleaning for a single ultrasonic irradiation, and then perform this multiple times as a set.

  As the ultrasonic irradiation device, any known device that can generate and emit ultrasonic waves can be used without particular limitation. For example, an ultrasonic homogenizer, an ultrasonic cleaner, an ultrasonic dispersion device, A sonic reaction device, an ultrasonic generator, or the like can be used. More specifically, there are “UP series” and “UIP series” manufactured by Heelscher Co., Ltd., an ultrasonic reactor SR series manufactured by Shinshin Sangyo Co., Ltd., and the like.

  The amount of the solvent in the slurry or wet cake irradiated with the ultrasonic waves is preferably in the range of 3 to 10 times, more preferably in the range of 4 to 6 times in terms of mass unit with respect to the solid content. If it is the said range, since an ultrasonic wave will be easily transmitted in a slurry or a wet cake, and this can reduce irradiation energy and irradiation amount, it is preferable from a viewpoint of productivity improvement. The temperature of the slurry or wet cake to be irradiated with the ultrasonic wave is not particularly limited as long as the solvent can maintain fluidity without being solidified or evaporated, but it is usually performed in the range of 1 to 60 ° C. Preferably, it is more preferably carried out in the range of 10 to 55 ° C., more preferably at room temperature. When the temperature is higher than room temperature, a heated solvent may be used, or a container containing a slurry or a wet cake may be heated using an oil bath, a water bath, microwave irradiation, or the like. On the other hand, during irradiation, the container containing the slurry or wet cake is cooled by a known method such as a cooling device containing a sufficient amount of cooling water, ice or refrigerant so that the amount of solvent in the slurry or wet cake does not boil. .

  Aggregation of polyarylene sulfide resin granules or particles may be prevented by known methods such as stirring and dispersion before ultrasonic irradiation, during ultrasonic irradiation, or after ultrasonic irradiation.

  By the ultrasonic irradiation, the polyarylene sulfide resin contained in the solid content can be crushed into granules or particles having a smaller particle diameter, preferably in the range of 1 to 150 (μm), more preferably 5 to 5. It may have a median diameter (d50) in the range of 100 (μm), more preferably in the range of 10-50 (μm), and most preferably in the range of 20-40 (μm).

  The polyarylene sulfide resin obtained through the step (3) can then be dried to prepare a powdery or granular polyarylene sulfide resin. In addition, heat crosslinking may be performed in air or oxygen-enriched air or under reduced pressure conditions for oxidative crosslinking. The temperature of this heat treatment is preferably in the range of 180 ° C. to 270 ° C., although it varies depending on the target crosslinking treatment time and the atmosphere to be treated. In addition, the heat treatment may be performed in a state where the polyarylene sulfide resin is melted at a temperature equal to or higher than the melting point of the polyarylene sulfide resin using an extruder or the like. It is preferable to carry out at +100 degrees C or less.

  The polyarylene sulfide resin obtained by the present invention can be used as a polyarylene sulfide resin composition combined with various fillers in order to further improve performance such as strength, heat resistance, and dimensional stability. Although it does not restrict | limit especially as a filler, For example, a fibrous filler, an inorganic filler, etc. are mentioned. Examples of the fibrous filler include glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium sulfate, calcium silicate, and other natural fibers such as wollastonite. Can be used. Inorganic fillers include barium sulfate, calcium sulfate, clay, viroferrite, bentonite, sericite, zeolite, mica, mica, talc, talpulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, etc. Can be used. In addition, various additives such as a mold release agent, a colorant, a heat stabilizer, a UV stabilizer, a foaming agent, a rust inhibitor, a flame retardant, and a lubricant can be added as additives during molding.

  Furthermore, the polyarylene sulfide resin obtained according to the present invention can be appropriately selected from polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyether depending on the application. Synthetic resins such as ketone, polyarylene, polyethylene, polypropylene, polytetrafluoroethylene, polydifluoroethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, liquid crystal polymer, or polyolefin rubber Further, a resin such as an elastomer such as fluorine rubber or silicone rubber may be blended and used as a polyarylene sulfide resin composition.

  The polyarylene sulfide resin and the composition obtained by the production method of the present invention are heat-resistant, moldability, dimensional stability, etc. by various known melt molding such as injection molding, extrusion molding, compression molding and blow molding. Can be processed into an excellent molded product.

  The polyarylene sulfide resin obtained by the production method of the present invention has few volatile components and can further increase the melt viscosity, in addition to various performances such as heat resistance and dimensional stability inherent to the polyarylene sulfide resin, The mechanical strength can be further improved, and the molded products include, for example, electrical and electronic parts such as connectors, printed circuit boards and sealing molded products, automobile parts such as lamp reflectors and various electrical components, and various constructions. Various materials such as injection molding or compression molding of interior parts such as objects, aircraft and automobiles, precision parts such as OA equipment parts, camera parts and watch parts, or extrusion molding or pultrusion molding of composites, sheets, pipes, etc. It is widely useful as a material for molding or as a material for fibers or films.

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

[Example 1]
(Process 1)
In a 150 liter autoclave with a stirring blade to which a pressure gauge, a thermometer, a condenser, a decanter, and a rectifying column are connected, p-dichlorobenzene (hereinafter abbreviated as “p-DCB”) 33.222 kg (226 mol), NMP2. 280 kg (23 mol), 47.33% by weight NaSH aqueous solution 27.300 kg (230 mol as NaSH), and 49.21 wt% NaOH aqueous solution 18.533 g (228 mol as NaOH) were charged under a nitrogen atmosphere with stirring. The temperature was raised to 173 ° C. over 5 hours to distill 27.300 kg of water, and then the autoclave was sealed. The p-DCB distilled azeotropically during dehydration was separated with a decanter and returned to the autoclave as needed. In the autoclave after the completion of the dehydration, the finely divided anhydrous sodium sulfide composition was dispersed in p-DCB. Since the NMP content in this composition was 0.069 kg (0.7 mol), 97 mol% (22.3 mol) of the charged NMP was a ring-opened product of NMP (4- (methylamino) It was shown to be hydrolyzed to the sodium salt of butyric acid (hereinafter abbreviated as “SMAB”). The amount of SMAB in the autoclave was 0.097 mol per mol of sulfur atoms present in the autoclave. When the total amount of NaSH and NaOH charged is changed to anhydrous Na2S, the theoretical dehydration amount is 27.921 g, so out of the remaining water amount 621 g (34.5 mol) in the autoclave, 401 g (22.3 mol) is NMP. Is consumed in the hydrolysis reaction between OH and NaOH, and is not present in the autoclave as water, and the remaining 220 g (12.2 mol) remains in the autoclave in the form of water or crystal water. It was. The amount of water in the autoclave was 0.053 mol per mol of sulfur atoms present in the autoclave.

  After completion of the dehydration step, the internal temperature was cooled to 160 ° C., NMP 47.492 kg (479 mol) was charged, and the temperature was raised to 185 ° C. The amount of water in the autoclave was 0.025 mol per 1 mol of NMP charged in step 2. When the gauge pressure reached 0.00 MPa, the valve connected to the rectifying column was opened, and the temperature was raised to an internal temperature of 200 ° C. over 1 hour. At this time, the cooling and the valve opening were controlled so that the rectification tower outlet temperature was 110 ° C. or lower. The distilled vapor of p-DCB and water was condensed by a condenser and separated by a decanter, and p-DCB was returned to the autoclave. The amount of distilled water was 179 g (9.9 mol), the water content in the autoclave was 41 g (2.3 mol), 0.005 mol per 1 mol of NMP charged after dehydration, and 1 mol of sulfur atoms present in the autoclave. It was 0.010 mol. The amount of SMAB in the autoclave was 0.097 mol per mol of sulfur atoms present in the autoclave, as in dehydration. Subsequently, the temperature was raised from an internal temperature of 200 ° C. to 230 ° C. over 3 hours and stirred at 230 ° C. for 3 hours, and then heated to 250 ° C. and stirred for 1 hour to obtain a crude reaction mixture. The gauge pressure at an internal temperature of 200 ° C. was 0.03 MPa, and the final gauge pressure was 0.30 MPa.

(Process 2)
After gradually cooling to 120 ° C. over 3 hours, it was transferred to a flat plate filter and filtered under pressure at 120 ° C. The obtained wet cake was transferred to a desolventizer and desolvated to obtain a solid content (1).

(Process 3)
360 g of hot water at 70 ° C. was added to 120 g of the solid content (1) after solvent removal, and the mixture was slurried and stirred for 10 minutes. The stirred slurry was filtered, and the wet cake was washed with 240 g of hot water at 70 ° C. Pure water was added to the wet cake, and the slurry was adjusted to 300 g.

Subsequently, ultrasonic irradiation was performed for 15 minutes with an ultrasonic disperser ("UP400S" manufactured by Hielscher, 0.5 cycle amplitude 45%). The irradiation energy was 50 [W / m ³ ]. During the ultrasonic irradiation, the container containing the slurry was cooled with a sufficient amount of ice while suppressing boiling.

  Next, after the slurry irradiated with ultrasonic waves was filtered, the wet cake was washed with 240 g of hot water at 70 ° C. Pure water was added to the wet cake to adjust the slurry to 300 g.

  Thereafter, the prepared slurry was charged into an autoclave and washed with hot water at 195 ° C. for 30 minutes. Further, the hot-washed slurry was filtered, and the wet cake was washed with 240 g of hot water at 70 ° C. The washed wet cake was dried in an oven at 120 ° C. for 4 hours to obtain a PPS resin (1).

  The obtained PPS resin (1) had a melt viscosity of 240 Pa · s and a median diameter (d50) of particles of 37 μm. On the other hand, all the filtrates used for washing were collected and the amount of CP-MABA was measured. The amount of extracted CP-MABA was 33 μmol / g.

[Example 2]
After obtaining a crude reaction mixture in the same manner as in Example 1 (Step 1), the bottom valve of a 150 liter autoclave was opened, and the crude reaction mixture was transferred to a desolventizer to remove the solvent to obtain a solid content (2). .

(Process 3)
360 g of hot water at 70 ° C. was added to 120 g of the solid content (2) after solvent removal, and the mixture was slurried and stirred for 10 minutes. The stirred slurry was filtered, and the wet cake was washed with 240 g of hot water at 70 ° C. Pure water was added to the wet cake, and the slurry was adjusted to 600 g.

Subsequently, ultrasonic irradiation was performed for 15 minutes with an ultrasonic disperser ("UP400S" manufactured by Hielscher, 0.5 cycle amplitude 45%). The irradiation energy was 40 [W / m ³ ].

Thereafter, in the same manner as in Example 1, PPS resin (2) was obtained.
The obtained PPS resin (2) had a melt viscosity of 220 Pa · s, and a particle median diameter (d50) of 29 μm. On the other hand, all the filtrates used for washing were collected and the amount of CP-MABA was measured. The amount of CP-MABA in the extracted filtrate component was 30 μmol / g.

[Example 3]
In the same manner as in Example 1, a solid content (3) was obtained.

(Process 3)
360 g of warm water at 70 ° C. was added to 120 g of the solid content (3) after the solvent removal, and the mixture was slurried and stirred for 10 minutes. The stirred slurry was filtered, and the wet cake was washed with 240 g of hot water at 70 ° C. Pure water was added to the wet cake, and the slurry was adjusted to 200 g.

Subsequently, ultrasonic irradiation was performed for 15 minutes with an ultrasonic disperser ("UP400S" manufactured by Hielscher, 0.5 cycle amplitude 45%). The irradiation energy was 40 [W / m ³ ].

Thereafter, in the same manner as in Example 1, PPS resin (3) was obtained.
The obtained PPS resin (3) had a melt viscosity of 216 Pa · s, and the median diameter (d50) of the particles was 29 μm. On the other hand, all the filtrates used for washing were collected and the amount of CP-MABA was measured. The amount of CP-MABA in the extracted filtrate component was 26 μmol / g.

[Comparative Example 1]
A PPS resin (4) was obtained in the same manner as in Example 1 except that ultrasonic irradiation was not performed.
The melt viscosity of the obtained PPS resin (4) was 202 Pa · s, and the median diameter (d50) of the particles was 174.3 μm. On the other hand, the CP-MABA content of the extracted filtrate component was 12.0 μmol / g.

[Measurement of melt viscosity of PPS resin]
The PPS resin was measured using an elevated flow tester “CFT-500D” manufactured by Shimadzu Corporation at 300 ° C. under a load of 1.96 × 10 ⁶ Pa and L / D = 10 mm / 1 mm for 6 minutes.

[Measurement of particle size distribution of PPS resin]
0.03 g of PPS resin was sampled, and particle size distribution measurement was performed using a laser scattering / diffraction particle size distribution analyzer (Nikkiso Microtrac MT 3300EXII) to determine the volume-based (Mv) median diameter (d50).

[Measurement method of CP-MABA]
All filtrate components used for washing were collected and measured by the following method.
The CP-MABA concentration in the aqueous solution was calculated by performing HPLC measurement of the adjusted measurement sample, obtaining the concentration in the solution from the peak area and calibration curve of the same retention time as the standard sample prepared by the following method.

(HPLC measurement)
Equipment: Shimadzu LC-10Avp series
Column: Kanto Chemical Mightysil RP-18GP 150-4.6
Detector: Shimadzu SPD-M10P Photodiode array (detection wavelength: 254 nm)

(Sample preparation)
CP-MABA in an aqueous solution was prepared by adding the mobile phase as it was.

(Standard sample: CP-MABA synthesis)
83.4 g (1.0 mol) of 48% NaOH aqueous solution and 297.4 g (3.0 mol) of N-methyl-2-pyrrolidone were charged in a pressure vessel equipped with a stirrer and stirred at 230 ° C. for 3 hours. After the stirring was completed, the valve was opened with the temperature kept at 230 ° C., the pressure was released, and the pressure was reduced 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 sealed again and the temperature was reduced to about 200 degreeC.

  147.0 g (1.0 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 completion of this stirring, 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. Unreacted p-dichlorobenzene remained as an insoluble matter and was removed by filtration.

  Next, hydrochloric acid was added to the aqueous solution as the filtrate to adjust the pH of the aqueous solution to 4. At this time, brown oily CP-MABA (hydrogen type) was formed 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 its ring-opened product, 4-methylaminobutyric acid (hereinafter abbreviated as “MABA”), the aqueous phase was discarded. The chloroform phase was washed twice with water.

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

  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 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% aqueous NaOH solution was added to the remaining aqueous solution to adjust the pH of the aqueous solution to 4. As a result, the hydrochloride of CP-MABA was neutralized, and brown oily CP-MABA (hydrogen type) 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).

Claims (9)

In a polar organic solvent, a polyhaloaromatic compound and (i) an alkali metal sulfide, or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide are reacted to form at least a polyarylene sulfide resin. Obtaining a crude reaction mixture comprising the polar organic solvent (1),
A step (2) of solid-liquid separating a crude reaction mixture containing at least a polyarylene sulfide resin and the polar organic solvent to recover a solid content containing at least the polyarylene sulfide resin;
A method for producing a polyarylene sulfide resin, which includes a step (3) in which a solvent is added to the solid content obtained in the step (2) to perform washing.
In the step (3), the slurry or wet cake obtained by adding a solvent to the solid content is irradiated with ultrasonic waves while cooling, a method for producing a polyarylene sulfide resin.   The method for producing a polyarylene sulfide resin according to claim 1, wherein in the step (3), the solid content after being irradiated with ultrasonic waves is subjected to solvent washing at least once. In the step (1), the crude reaction mixture containing at least the polyarylene sulfide resin and the polar organic solvent further contains a carboxyalkylamino group-containing compound,
And the manufacturing method of the polyarylene sulfide resin of Claim 1 or 2 which collect | recovers the remaining carboxyalkylamino group containing compound from the polyarylene sulfide resin contained in solid content in a process (3).   The polyarylene sulfide resin obtained through the step (3) is in the form of granules or particles having a median diameter (d50) in the range of 1 to 150 (µm). Method for producing arylene sulfide resin.   5. The amount of solvent in the slurry or wet cake irradiated with ultrasonic waves in the step (3) is in the range of 3 to 10 times in terms of mass unit with respect to the solid content. 5. A method for producing a polyarylene sulfide resin. The method for producing a polyarylene sulfide resin according to any one of claims 1 to 5, wherein the irradiation energy of ultrasonic waves is in the range of 1.0 x 10 ^{5 to} 1.0 x 10 ¹⁰ (W / m ³ ).   A polyarylene having a step of melt-kneading the polyarylene sulfide resin obtained by the production method according to any one of claims 1 to 6 with at least one selected from the group consisting of a filler, an additive and a resin. A method for producing a sulfide resin composition.   The manufacturing method of the polyarylene sulfide resin molded article which has the process of shape | molding, after melt-kneading the polyarylene sulfide resin composition obtained by the manufacturing method of the said Claim 7. A crude reaction mixture obtained by reacting a polyhaloaromatic compound and (i) an alkali metal sulfide or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide in a polar organic solvent. A step (2) of solid-liquid separation to recover a solid content containing at least the polyarylene sulfide resin;
Having a step (3) of washing by adding a solvent to the solid content obtained in the step (2),
In the step (3), the slurry or wet cake obtained by adding a solvent to the solid content is irradiated with ultrasonic waves while cooling, a method for purifying a polyarylene sulfide resin.