JP6390079B2 - Process for producing branched polyarylene sulfide resin - Google Patents

Description

  The present invention relates to a method for producing a branched polyarylene sulfide resin, in which oligoarylene sulfide discharged in a purification step during the production of the polyarylene sulfide resin is recovered and reused.

  Polyarylene sulfide resins represented by polyphenylene sulfide resins are excellent in heat resistance and chemical resistance, and are widely used in electrical and electronic parts, automobile parts, water heater parts, fibers, films and the like. Particularly in applications such as packing for lithium ion batteries and gasket members, in recent years, high molecular weight PAS resins have been widely used because of their excellent toughness and moldability.

  As an industrial polymerization method of PPS, a method of reacting an alkali metal sulfide such as sodium sulfide and a polyhaloaromatic compound such as p-dichlorobenzene in an N-methyl-2-pyrrolidone (NMP) solvent is generally used. However, it is known that about 2 to 5% of oligoarylene sulfide is produced as a by-product in the PAS polymerization reaction stage (see Non-Patent Document 1, especially page 388, lower right column).

  This oligoarylene sulfide reduces the crystallization rate of polyarylene sulfide resin, causes a delay in the molding cycle during injection molding, increases the amount of gas generated during melting, increases the amount of resin during injection molding, etc. Since it also causes, it is purified and removed in the post-treatment step of PAS polymerization.

  However, the purification and removal of the oligoarylene sulfide leads to a decrease in yield, which requires additional raw materials, which is a factor that presses down on manufacturing costs, and further increases the amount of industrial waste. Several hundred tons (when the amount of oligoarylene sulfide produced is 5%, production of 10,000 tons and industrial waste of 500 tons) caused industrial waste disposal problems.

  Therefore, paying attention to the cyclic oligoarylene sulfide having a repeating unit n = 4 to 13-mer contained in the oligoarylene sulfide, the cyclic oligoarylene sulfide is subjected to ring-opening polymerization as a monomer raw material to synthesize a high molecular weight linear compound. Attention has been focused on the possibility of application development to high-functional materials and functional materials that utilize ring-shaped materials, including methods (Patent Documents 1 and 2).

  However, the by-product of the PAS polymerization includes the following structural formula (1) in addition to the cyclic oligoarylene sulfide.

（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。）で表される化合物（１）（以下、カルボキシアルキルアミノ基含有化合物（１）と表すことがある。）が含まれる。このため、ＰＡＳ重合の副生物からカルボキシアルキルアミノ基含有化合物（１）を有機溶剤洗浄で分離・除去する方法がとられていたが、該化合物（１）は水素型とアルカリ金属塩型とで溶解する有機溶剤種が異なることから、一旦、７０℃で水洗した後に、クロロホルム抽出処理とアルコール再沈殿処理を施して水素型及びアルカリ金属塩型のカルボキシアルキルアミノ基含有化合物（１）を環状オリゴアリーレンスルフィドから分離・除去していた。しかし、この方法は、該化合物（１）を完全除去できるものの、分離・除去操作が煩雑な上、高価な溶剤を多量に使用するため、商業生産的には高コストなプロセスとなる問題があった。また、この分離・除去方法を経て得られた環状オリゴアリーレンスルフィドを開環重合して得られたポリアリーレンスルフィド樹脂は高分子量化されてはいるものの、他の化合物や樹脂との反応性が低いものであった。このため、エポキシシランカップリング剤や官能基含有熱可塑性エラストマーなどの耐衝撃性改質剤を加えた際の耐衝撃性改善効果も十分なものとはいえず、用途や使用法に制限があった。

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, and X represents a hydrogen atom or an alkali metal atom) (hereinafter referred to as a carboxyalkylamino group-containing compound (1)). Is included). For this reason, a method of separating and removing the carboxyalkylamino group-containing compound (1) from the by-product of the PAS polymerization by washing with an organic solvent has been adopted, but the compound (1) is divided into a hydrogen type and an alkali metal salt type. Since the organic solvent species to be dissolved are different, after washing with water at 70 ° C., chloroform extraction treatment and alcohol reprecipitation treatment are performed to obtain hydrogen-type and alkali metal salt-type carboxyalkylamino group-containing compound (1) as a cyclic oligo. It was separated and removed from the arylene sulfide. However, although this method can completely remove the compound (1), the separation / removal operation is complicated, and a large amount of expensive solvent is used. It was. In addition, the polyarylene sulfide resin obtained by ring-opening polymerization of the cyclic oligoarylene sulfide obtained through this separation / removal method has a high molecular weight, but has low reactivity with other compounds and resins. It was a thing. For this reason, the impact resistance improvement effect when adding an impact modifier such as an epoxy silane coupling agent or a functional group-containing thermoplastic elastomer cannot be said to be sufficient, and there is a limit to applications and usage. It was.

Fahey, D.R et.al, Macromolecules, Volume 30, Issue 3, 10 February 1997, Pages 387-393

WO2007 / 034800 pamphlet JP 2011-132323 A

  Therefore, the problem to be solved by the present invention is to use an oligoarylene sulfide purified and removed as a by-product in the polymerization process of the polyarylene sulfide resin, and to provide an impact resistance such as an epoxy silane coupling agent or a functional group-containing thermoplastic elastomer. Provided is a method for producing a high molecular weight branched arylene sulfide resin having excellent reactivity with a modifier.

  As a result of various investigations, the inventors of the present invention have found that by-products purified and removed in the polymerization process of the polyarylene sulfide resin are brought into contact with water at 100 ° C. or higher and pH 6 or higher, the oligoarylene sulfide and the carboxyalkylamino are obtained. The group-containing compound (1) is efficiently separated and a recovered composition containing oligoarylene sulfide at a high concentration is obtained, and this composition is heated in an oxidizing atmosphere to melt polymerize to a high degree of polymerization. As a result, it was found that a branched polyarylene sulfide resin having a high molecular weight can be produced, and the present invention has been solved.

  That is, the present invention melts 0.01 to 20 parts by mass of the compound (1) represented by the following structural formula (1) and 99.99 to 80 parts by mass of the oligoarylene sulfide (2) in an oxidizing atmosphere. The present invention relates to a method for producing a branched polyarylene sulfide resin characterized by polymerization.

（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。）

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, and X represents a hydrogen atom or an alkali metal atom.)

  Using the oligoarylene sulfide purified and removed as a by-product in the polymerization process of the polyarylene sulfide resin according to the present invention, the reactivity with an impact modifier such as an epoxysilane coupling agent or a functional group-containing thermoplastic elastomer is improved. A method for producing an excellent high molecular weight branched polyarylene sulfide resin can be provided.

  The method for producing the branched polyarylene sulfide resin of the present invention comprises 0.01 to 20 parts by mass of the compound (1) represented by the following structural formula (1) and 99.99 to 80 parts by mass of the oligoarylene sulfide (2). Is characterized by melt polymerization in an oxidizing atmosphere.

（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。）

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, and X represents a hydrogen atom or an alkali metal atom.)

Details will be described below.
The compound (1) represented by the following structural formula (1) and the oligoarylene sulfide (2) used in the present invention can be produced by, for example, the following steps (1) to (3).

・ Process (1)
In an organic polar 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 the following structural formula (1): After obtaining a crude reaction mixture containing the compound (1), oligoarylene sulfide (2), organic polar solvent (3), polyarylene sulfide (4) and alkali metal halide (5) represented by The mixture is washed with an organic polar solvent (6) to separate and remove the polyarylene sulfide (4) and the alkali metal halide (5), and the compound (1), the oligoarylene sulfide (2) and the organic polar solvent ( A step (1) of obtaining a reaction mixture (a1) comprising 3).

  First, in step (1), at least a polyhaloaromatic compound and an alkali metal sulfide are reacted in an organic polar solvent to obtain a compound (1) represented by the structural formula (1), an oligoarylene sulfide. (2) preparing a crude reaction mixture comprising an organic polar solvent (3), a polyarylene sulfide (4) and an alkali metal halide (5), or at least a polyhaloaromatic compound and an alkali in an organic polar solvent A compound (1) represented by the following structural formula (1) by reacting a metal hydrosulfide and an alkali metal hydroxide, an oligoarylene sulfide (2), an organic polar solvent (3), a polyarylene sulfide (4) And a method for producing a crude reaction mixture containing an alkali metal halide (5) is included as step (1a).

  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, and specifically includes p-dichlorobenzene, o-dioxy. Chlorobenzene, m-dichlorobenzene, trichlorobenzene, tetrachlorobenzene, dibromobenzene, diiodobenzene, tribromobenzene, dibromonaphthalene, triiodobenzene, dichlorodiphenylbenzene, dibromodiphenylbenzene, dichlorobenzophenone, And dihaloaromatic compounds such as dibromobenzophenone, dichlorodiphenyl ether, dibromodiphenyl ether, dichlorodiphenyl sulfide, dibromodiphenyl sulfide, dichlorobiphenyl, dibromobiphenyl, and mixtures thereof. The compound 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.

  Examples of the alkali metal sulfide used in the present invention include lithium sulfide, sodium sulfide, rubidium sulfide, cesium sulfide, and mixtures 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.

  Examples of the organic polar solvent used in the present invention include formamide, acetamide, N-methylformamide, N, N-dimethylacetamide, tetramethylurea, N-methyl-2-pyrrolidone, 2-pyrrolidone, and N-methyl-ε-caprolactam. , Ε-caprolactam, hexamethylphosphoramide, N-dimethylpropyleneurea, amides such as 1,3-dimethyl-2-imidazolidinone, urea and lactams; sulfolanes such as sulfolane and dimethylsulfolane; benzonitrile and the like Nitriles; ketones such as methyl phenyl ketone and mixtures thereof, among which N-methyl-2-pyrrolidone, 2-pyrrolidone, N-methyl-ε-caprolactam, ε-caprolactam, hexamethyl Phosphoramide, N-dimethylpro Ren urea, 1,3-dimethyl-2-amide having an aliphatic cyclic structure imidazolidinone acid.

  In the presence of these organic polar solvents, the polymerization reaction of the polyarylene sulfide resin is carried out by combining the above-mentioned alkali metal sulfide or alkali metal hydrosulfide and alkali metal hydroxide called a sulfidizing agent with a polyhaloaromatic compound. React. The polymerization conditions are generally in the range of 200 to 330 ° C., and the pressure should be in such a range that the polymerization solvent and the polymerization monomer polyhaloaromatic compound are substantially retained in the liquid layer. It is selected from the range of 1-20 MPa, preferably from the range of 0.1-2 MPa.

  As one of the specific embodiments of the method for producing the polyarylene sulfide resin used in the present invention, 1) For example, an alkali metal sulfide or a hydrous alkali metal hydrosulfide and an alkali metal hydroxide in the presence of a polyhaloaromatic compound. And a amide, urea or lactam having an aliphatic cyclic structure to react while dehydrating to produce a slurry containing solid alkali metal sulfide, and after producing the slurry, polar organic such as NMP A step of adding a solvent, distilling off water and then dehydrating, and then in a slurry obtained through the dehydration step, a polyhaloaromatic compound, an alkali metal hydrosulfide, and an amide having the above aliphatic cyclic structure, The amount of water existing in the reaction system with respect to 1 mol of a polar organic solvent such as NMP is 0.0% of the alkali metal salt of urea or lactam hydrolyzate. Method for producing a polyarylene sulfide resins having a step of performing polymerization by reacting a molar below as essential production steps.

Other specific methods for polymerizing an alkali metal sulfide or alkali metal hydrosulfide and an aromatic polyhalogen compound in the presence of an amide group-containing cyclic hydrocarbon compound include:
2) A method of using a polymerization aid such as an alkali metal carboxylate or lithium halide,
3) A method using a crosslinking agent such as an aromatic polyhalogen compound,
4) A method in which a polymerization reaction is carried out in the presence of a small amount of water, followed by addition of water and further polymerization.
5) During the reaction between the alkali metal sulfide and the aromatic dihalogen compound, a method of cooling the gas phase part of the reaction vessel to condense a part of the gas phase in the reaction vessel and refluxing it to the liquid phase, etc. .
Among these, the method 1) is preferred because it produces little by-products and can easily obtain a linear and high molecular weight polyarylene sulfide resin at low cost.

  In the present invention, an oligoarylene sulfide, a polyhaloaromatic compound and an alkali metal sulfide are reacted to produce a carboxyalkylamino group-containing compound (1), an oligoarylene sulfide (2), an organic polar solvent (3), a polyarylene. A crude reaction mixture containing sulfide (4) and alkali metal halide (5) is obtained, or oligoarylene sulfide, polyhaloaromatic compound, alkali metal hydrosulfide and alkali metal hydroxide are reacted to produce carboxyalkyl The form which obtains the crude reaction mixture containing the amino group-containing compound (1), oligoarylene sulfide (2), organic polar solvent (3), polyarylene sulfide (4) and alkali metal halide (5) is also included.

  In the production of the polyarylene sulfide resin, as a raw material for producing the polyarylene sulfide resin, for example, when the organic polar 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 (1 ′)

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

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

  Subsequently, in the step (1), the crude reaction mixture obtained in the step (1a) is washed with an organic polar solvent (6) to separate and remove the polyarylene sulfide (4) and the alkali metal halide (5). And it has as a process (1b) the method of manufacturing the reaction mixture (a1) containing a carboxyalkylamino group containing compound (1), an oligoarylene sulfide (2), an organic polar solvent (3), and (6).

  The polyarylene sulfide (4) and the alkali metal halide (5) are separated and removed from the crude reaction mixture, and contain a carboxyalkylamino group-containing compound (1), an oligoarylene sulfide (2), and an organic polar solvent (3). There is no restriction | limiting in particular in the method of obtaining reaction mixture (a1), for example, after removing a part or most part of organic polar solvent (3) by solid-liquid separation operations, such as distillation, as needed, it is organic in the obtained slurry. The polyarylene sulfide (4) and the alkali metal halide (5) are mixed by mixing the polar solvent (6) and bringing them into contact with each other in the range of 10 to 200 ° C, preferably 50 to 150 ° C, more preferably 80 to 130 ° C. The solid component containing is separated by a simple filtration operation, the carboxyalkylamino group-containing compound (1), oligo arylsulfur Can be obtained de (2) and an organic polar solvent (3 and 6) the reaction mixture containing the (a1) as the filtrate component.

  Such an organic polar solvent (6) is preferably a solvent in which the oligoarylene sulfide (2) is dissolved but the polyarylene sulfide resin (4) is difficult to dissolve in an environment where the oligoarylene sulfide (2) is dissolved. The arylene sulfide resin (4) is more preferably a solvent that does not dissolve. Although the pressure at the time of making the said slurry and organic polar solvent (6) contact may be either normal pressure or pressurization, it is preferable to carry out under the pressurization of the range of 0.1-0.5 [MPa]. As the organic polar solvent (6) to be used, those which do not substantially cause undesirable side reactions such as decomposition and crosslinking of the polyarylene sulfide resin (4) are preferable. For example, pentane, hexane, heptane, octane, cyclohexane, cyclopentane, benzene , Hydrocarbon solvents such as toluene and xylene, halogen solvents such as chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene and 2,6-dichlorotoluene, diethyl ether, tetrahydrofuran Ether solvents such as diisopropyl ether, formamide, acetamide, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, tetramethylurea, N-methyl-2-pyrrolidone, 2-pi Amides such as lidone, N-methyl-ε-caprolactam, ε-caprolactam, hexamethylphosphoramide, N-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone, urea and lactams, dimethyl sulfoxide, Examples include polar solvents such as trimethyl phosphoric acid, N, N-dimethylimidazolidinone, and methyl ethyl ketone.

  Although there is no restriction | limiting in particular in the atmosphere at the time of making the said slurry and organic polar solvent (6) contact, Polyarylene sulfide resin (4) and organic polar solvent (6) are oxidized according to conditions, such as temperature and time at the time of making contact. When it deteriorates, it is desirable to carry out in a non-oxidizing atmosphere.

・ Process (2)
In the step (2), following the step (1), the organic polar solvent is separated from the reaction mixture (a1) by solid-liquid separation, and the oligoarylene sulfide (2) and the carboxyalkylamino group-containing compound (1) are contained. In this step, a reaction mixture (a2) is obtained.
The method for removing the organic polar solvents (3) and (6) from the reaction mixture (a1) obtained as the filtrate component is, for example, a so-called flash method in which the solvent is recovered by evaporating the solvent and simultaneously recovering the solid matter. The removal of the solvent using a film can be exemplified. When removing the organic polar solvent, the ratio of the solid (non-volatile content) is 20 to 100 [mass%], preferably 20 to 99.99 [mass%], more preferably 30 to 90 [mass%]. It is desirable to remove the solvent. Although the temperature at which the solvent is removed by heating depends on the characteristics of the solvent used, it cannot be limited uniquely. However, the temperature can usually be selected from 20 to 150 ° C, preferably from 40 to 120 ° C. In addition, the pressure for removing the solvent is preferably normal pressure or lower, which makes it possible to remove the solvent at a lower temperature.

・ Process (3)
Step (3), following step (2), the reaction mixture (a2) at 100 ° C. ultra and pH6 above, by contacting with water, carboxyalkyl amino group-containing compound (1) and oligo arylene sulfide (2) is a step of separating.

The reaction mixture (a2), after washing with water under the conditions of the range of 20 to 100 ° C. as the pre-treatment if necessary, at 100 ° C. Katsu Yue pH6 above, is contacted with water.
The washing treatment performed as required, for example, a method of filtering using the filtration device after stirring water was added to the reaction mixture (a2), the filter residue (hereinafter containing water obtained by filtration above " Abbreviated as “water-containing cake”), and a method of adding water again to form a slurry and then filtering, or a method of adding water again and filtering while the water-containing cake is held in a filter.

  From the viewpoint of washing efficiency, the amount of water added in the washing treatment performed as necessary is in the range of 2 to 10 times the theoretical yield of the finally obtained oligoarylene sulfide (2). Preferably, the above amount of water is divided into 2 to 10 times, preferably 2 to 4 times, and then subjected to water washing. The temperature of the water during the water washing treatment is preferably in the range of 50 to 90 ° C. from the viewpoint of good washing efficiency, and particularly preferably in the range of 70 to 90 ° C.

  The water washing process performed as needed can be performed a plurality of times as a batch process. When performing several times, it wash | cleans at 50-90 degreeC, for example. When the water washing is repeated a plurality of times, the temperature condition may be the same or different.

Carboxyalkyl amino group-containing compound (1) and the reaction mixture containing the oligo arylene sulfide (a2) is, after the water washing treatment if necessary, under pressure, at 100 ° C. ultra and pH6 or more, in contact with water Let

  The pressurizing condition is in the range of 0.02 to 0.1 [MPa], and in order to promote the dissolution of the compound (1) in water while exhibiting an excellent predetermined purification effect, the pressure is set to 0. It is preferable to carry out at 02-0.1 [MPa]. As an atmosphere to be pressurized, a mixed gas with an inert gas such as nitrogen gas, argon gas, or neon gas may be used from the viewpoint of safety, but air is most preferable from the viewpoint of economy.

  The temperature at which the carboxyalkylamino group-containing compound (1), oligoarylene sulfide and water are brought into contact with each other under pressure is such that the solubility of the carboxyalkylamino group-containing compound (1) in water becomes more pronounced. Since separation of contained compound (1) and oligoarylene sulfide can be performed more efficiently, it is over 100 ° C, preferably 120 ° C or higher, more preferably 140 ° C or higher. Moreover, the upper limit of the temperature in this case is not particularly limited, but is 200 ° C. or lower, more preferably 180 ° C. or lower.

When the carboxyalkylamino group-containing compound (1), oligoarylene sulfide and water are brought into contact with each other under pressure, acid or base is added to adjust the pH to 6 or more, preferably 6.5 to 11.5. It is preferable to control the solubility of the compound (1) in water and the like.
In particular, when a base is added at the time of hot water washing above 100 ° C. and the pH after hot water washing is adjusted to 9.5 to 11.5, the acidic type terminal (H type terminal) of the carboxyalkylamino group-containing compound (1) Is converted to a basic type terminal (Na type terminal), so that the solubility of the carboxyalkylamino group-containing compound (1) in water is further increased, which is preferable.

  Examples of the acid used here include hydrochloric acid, sulfuric acid, carbonic acid, and acetic acid. Among these, carbonic acid and acetic acid are preferable. Examples of the basic compound used 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. Examples of the pH measurement method include a method of measuring the pH of a filtrate obtained by filtering the slurry when an acid is added to the slurry.

  Further, the amount of water used when the carboxyalkylamino group-containing compound (1), the oligoarylene sulfide (2) and water are brought into contact with each other under pressure is not particularly limited as long as water molecules are present as a liquid. No. If the pressure of the water in the closed system reaches the saturated vapor pressure at that temperature under the pressurized condition, the water exists as a liquid. In the present invention, the carboxyalkylamino group-containing compound (1) In order to efficiently dissolve in water, the range of 100 to 1000 parts by mass, more preferably the range of 100 to 1000 parts by mass, is more preferable with respect to 100 parts by mass of the carboxyalkylamino group-containing compound (1). A range of ˜800 parts by mass is more preferable.

In the present invention, the contact of the carboxyalkylamino group-containing compound (1), the oligoarylene sulfide and the water under pressure may be performed continuously or in a batch manner.
In the present invention, the container used when the carboxyalkylamino group-containing compound (1), oligoarylene sulfide (2) and water are brought into contact under pressure can dissolve the compound (1) in the liquid layer. The container has a mixing function that can be sealed or can be sealed, and may be any container that can achieve the object of the present invention, but has a stirring blade inside the container and is used for filtration at the bottom. Examples thereof include a sealed type provided with a filter or a container having a mixing function capable of being sealed.

In the carboxyalkyl amino group-containing compound (1) and oligo arylene sulfide (2) the reaction mixture containing (a2), after performing the water washing treatment if necessary, under pressure, 100 ° C. ultra and pH6 more After contacting with water and then cooling to room temperature, it is filtered if necessary, and ion-exchanged water is added and filtered again in the range of 20 to 90 ° C. to form a basic type terminal (Na type terminal) as a liquid layer. The carboxyalkylamino group-containing compound (1) converted to) is separated, and the oligoarylene sulfide (2) is recovered as a solid content. However, the reaction mixture in this way solids obtained by solid-liquid separation from (a2) other containing oligo arylene sulfide (2) in a high concentration, without separation carboxyalkyl amino group-containing compound (1) Therefore, the solid-liquid separation operation is performed until the composition (α) containing 0.01 to 20% by mass of the carboxyalkylamino group-containing compound (1) and 99.99 to 80% by mass of the oligoarylene sulfide is obtained. It is preferable to carry out once or a plurality of times. When the carboxyalkylamino group-containing compound (1) in the composition (α) is in a range exceeding 20% by mass, when used as part of the raw material of the polyarylene sulfide resin, the polyarylene sulfide resin is melt polymerized. On the other hand, in order to make it less than 0.01% by mass, excessive solid-liquid separation is required, which causes a decrease in productivity.

  The recovered composition (α) containing the oligoarylene sulfide (2) at a high concentration may be dried as it is to obtain a powder, and further subjected to several water washing treatments, followed by solid-liquid separation. It may be dried to obtain a powder. Although there is no restriction | limiting in particular in the amount of water used for the water-washing process performed after hot water washing over 100 degreeC, It is the range of 2-10 times with respect to the theoretical yield of oligoarylene sulfide (2). Drying is performed by heating to a temperature at which water substantially evaporates. Drying may be performed under vacuum, or may be performed in air or in an inert atmosphere such as nitrogen.

  In the oligoarylene sulfide (2), the following structural formula (2)

（ただし、式中ｍ＝２〜５０、好ましくは４〜１３である。）で表される環式ポリアリーレンスルフィド（２ａ）を５０質量％以上、好ましくは７０質量％以上、より好ましくは８０質量％以上から１００質量％以下、好ましくは９５質量％以下、より好ましくは９０質量％以下の範囲といった高純度で含有する。なお、残りの成分としては下記構造式（３）および（４）

(Wherein m = 2 to 50, preferably 4 to 13). The cyclic polyarylene sulfide (2a) represented by the formula is 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass. % To 100% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less. The remaining components include the following structural formulas (3) and (4)

（式中、Ｙ_１ハロゲン原子を表す。）で表される２量体ないし３量体成分などが０質量％以上、好ましくは５質量％以上、より好ましくは１０質量％以上から、５０質量％以下、好ましくは３０質量％以下、より好ましくは２０質量％以下の範囲となる割合で挙げられる。

The dimer or trimer component represented by the formula (wherein Y ₁ represents a halogen atom) is 0% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and 50% by mass. Hereinafter, the proportion is preferably 30% by mass or less, more preferably 20% by mass or less.

Production method of PAS The present invention undergoes steps (1) to (3) described above, whereby 0.01 to 20 parts by mass of compound (1) represented by structural formula (1) and oligoarylene sulfide (2) 99. A branched polyarylene sulfide resin can be produced by melt polymerization in an oxidizing atmosphere using a material (α) containing .99 to 80 parts by mass as a raw material. The compound (1) and oligoarylene sulfide (2) produced separately are blended so as to be 0.01 to 20 parts by mass of the compound (1) and 99.99 to 80 parts by mass of the oligoarylene sulfide (2). In addition, melt polymerization can be performed in an oxidizing atmosphere.

  In the present invention, the melt polymerization may be carried out in a state where the oligoarylene sulfide is melted at a temperature equal to or higher than the melting point of the oligoarylene sulfide using an extruder or the like. It is preferable to carry out at a temperature of ℃ or less. However, melting | fusing point here refers to what was measured based on JISK7121 using the differential scanning calorimeter (DSC apparatus Pyris Diamond made from Perkin Elmer).

  In the present invention, melt polymerization is performed in an oxidizing atmosphere from the viewpoint of increasing the degree of branching and obtaining a high degree of polymerization. In the present invention, the oxidizing atmosphere refers to a range where the oxygen concentration in the gas phase is 5% by volume or more and 30% by volume or less, preferably 10% by volume or more and 25% by volume or less. It is most preferable from the viewpoint of productivity.

  In the present invention, the melt polymerization is preferably performed under a condition that does not substantially contain a solvent. The condition that substantially does not contain a solvent means that the solvent is 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 100 parts by mass relative to the total of 100 parts by mass of the compound (1) and the oligoarylene sulfide (2). It means that it is in the range of 1 part by mass or more, 0 part by mass or more, preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more.

  In addition, in addition to 0.01 to 20 parts by mass of the compound (1) represented by the structural formula (1) and 99.99 to 80 parts by mass of the oligoarylene sulfide (2) as a raw material for melt polymerization in the present invention, Polyarylene sulfide resin (β) in the range of 50 parts by mass or less, preferably 0 to 50 parts by mass, more preferably 0 to 10 parts by mass with respect to a total of 100 parts by mass of the compound (1) and oligoarylene sulfide (2). ).

  Here, the polyarylene sulfide resin (β) is not particularly limited as long as it does not impair the effects of the present invention. For example, the polyarylene sulfide (4) and the alkali separated and removed in the step (1b) are used. The metal halide (5) can be recovered, and a product obtained by subjecting to a known purification step such as contact with water and filtration of the alkali metal halide (5) can be used.

  The reaction product containing the branched polyarylene sulfide resin of the present invention obtained by melt polymerization can be directly produced in a melt kneader or the like to produce a resin composition. It is not only excellent in productivity but also good in reactivity to prepare a lysate by adding a solvent in which the reaction product is dissolved in and removing the reaction product from the reaction apparatus in the state of the lysate. Therefore, it is preferable. The addition of the solvent in which the reaction product is dissolved is preferably performed after the melt polymerization, but it may be performed in the later stage of the reaction of the melt polymerization, or as described above, the molten mixture (reaction product) is cooled and solid state After obtaining the mixture, the polymerization reaction may be further advanced by heating the mixture under pressure, reduced pressure, or atmospheric pressure in a non-oxidizing atmosphere. The step of preparing the lysate may be performed in a non-oxidizing atmosphere. Further, the temperature for heating and dissolving may be in the range of the melting point or higher of the solvent in which the reaction product dissolves, preferably in the range of 200 to 350 ° C, more preferably in the range of 210 to 250 ° C, under pressure. It is preferable to carry out with.

  The blending ratio of the solvent in which the reaction product is used for preparing the dissolved product is preferably 90 to 1000 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the reaction product containing the polyarylene sulfide resin. It is the range of 200-400 mass parts.

  As a solvent in which the reaction product dissolves, for example, a solvent used as a polymerization reaction solvent in solution polymerization such as a Philips method can be used. Examples of preferred solvents include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and ε-caprolactam. , Aliphatic cyclic amide compounds such as N-methyl-ε-caprolactam, amide compounds such as hexamethylphosphoric triamide (HMPA), tetramethylurea (TMU), dimethylformamide (DMF), and dimethylacetamide (DMA), polyethylene Examples include etherified polyethylene glycol compounds such as glycol dialkyl ether (having a degree of polymerization of 2000 or less and an alkyl group having 1 to 20 carbon atoms), and sulfoxide compounds such as tetramethylene sulfoxide and dimethyl sulfoxide (DMSO). . Examples of other usable solvents include benzophenone, diphenyl ether, diphenyl sulfide, 4,4′-dibromobiphenyl, 1-phenylnaphthalene, 2,5-diphenyl-1,3,4-oxadiazole, 2,5- Diphenyloxazole, triphenylmethanol, N, N-diphenylformamide, benzyl, anthracene, 4-benzoylbiphenyl, dibenzoylmethane, 2-biphenylcarboxylic acid, dibenzothiophene, pentachlorophenol, 1-benzyl-2-pyrrolidione, 9- Fluorenone, 2-benzoylnaphthalene, 1-bromonaphthalene, 1,3-diphenoxybenzene, fluorene, 1-phenyl-2-pyrrolidinone, 1-methoxynaphthalene, 1-ethoxynaphthalene, 1,3-diphenylacetate 1,4-dibenzoylbutane, phenanthrene, 4-benzoylbiphenyl, 1,1-diphenylacetone, o, o'-biphenol, 2,6-diphenylphenol, triphenylene, 2-phenylphenol, thianthrene, 3-phenoxy Benzyl alcohol, 4-phenylphenol, 9,10-dichloroanthracene, triphenylmethane, 4,4′-dimethoxybenzophenone, 9,10-diphenylanthracene, fluoranthene, diphenylphthalate, diphenyl carbonate, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 4-bromodiphenyl ether, pyrene, 9,9'-bifluorene, 4,4'-isopropylidene-diphenol, epsilon-caprolactam, N-cyclohexyl- Examples thereof include one or more solvents selected from the group consisting of 2-pyrrolidone, diphenylisophthalate, diphenyl-terephthalate and 1-chloronaphthalene.

The melted product taken out from the reaction apparatus is preferably subjected to post-treatment and then melt-kneaded with other components to prepare a resin composition because the reactivity becomes better. The method for post-treatment of the lysate is not particularly limited, and examples thereof include the following methods.
Treatment (1) The solution is used as it is, or after adding an acid or a base, the solvent is distilled off under reduced pressure or normal pressure, and then the solid after the solvent is distilled off is used for water and the solution. Wash once or twice with a solvent (or an organic solvent having an equivalent solubility in a low molecular weight polymer), acetone, methyl ethyl ketone, and alcohols, then neutralize, wash with water, filter and dry. Method.
Treatment (2) Solvent such as water, acetone, methyl ethyl ketone, alcohol, ether, halogenated hydrocarbon, aromatic hydrocarbon, and aliphatic hydrocarbon (soluble in the solvent of the lysate, and at least (A solvent which is a poor solvent for polyarylene sulfide resin) is added as a precipitating agent to precipitate a solid product containing polyarylene sulfide resin and inorganic salt, and the solid product is filtered, washed and How to dry.
Treatment (3) After adding the solvent (or an organic solvent having an equivalent solubility with respect to the low molecular weight polymer) used in the dissolved material to the dissolved material and stirring, and then filtering to remove the low molecular weight polymer , Washing with a solvent selected from water, acetone, methyl ethyl ketone, alcohol and the like once or twice, followed by neutralization, washing with water, filtration and drying.

  In the post-treatment methods exemplified in the above treatments (1) to (3), the polyarylene sulfide resin may be dried in a vacuum, or in an inert gas atmosphere such as air or nitrogen. You may do it. The branched polyarylene sulfide resin can be further oxidized and crosslinked by performing a heat treatment in an oxidizing atmosphere having an oxygen concentration in the range of 5 to 30% by volume or under reduced pressure.

-Polyarylene sulfide resin The polyarylene sulfide resin obtained by the production method of the present invention has a melt viscosity (V6) measured at 300 ° C in the range of 20 to 5,000 [Pa · s]. However, melt viscosity (V6) measured at 300 ° C. is an orifice having a temperature / 300 ° C., a load of 1.96 MPa, an orifice length and an orifice diameter of 10/1 using a flow tester. Represents the melt viscosity after holding for 6 minutes.

  The polyarylene sulfide resin obtained by the production method of the present invention has a non-Newtonian index in the range of 1.26 to 2.50, preferably in the range of 1.30 to 2.20, more preferably 1 The range is from 50 to 2.0. Such a branched polyarylene sulfide resin is excellent in mechanical properties, fluidity, and abrasion resistance. However, the non-Newtonian index (N value) is measured by measuring the shear rate and shear stress using a capillograph at 300 ° C, the ratio of the orifice length (L) to the orifice diameter (D), and L / D = 40. These are values calculated using the following formula.

［ただし、ＳＲは剪断速度（秒^−１）、ＳＳは剪断応力（ダイン／ｃｍ^２）、そしてＫは定数を示す。］Ｎ値は１に近いほどＰＰＳは線状に近い構造であり、Ｎ値が高いほど分岐が進んだ構造であることを示す。

[Wherein SR represents a shear rate (second ⁻¹ ), SS represents a shear stress (dyne / cm ² ), and K represents a constant. The closer the N value is to 1, the closer the PPS is to a linear structure, and the higher the N value is, the more branched the structure is.

  Furthermore, the branched polyarylene sulfide resin obtained by the production method of the present invention has a mass average molecular weight in the range of 15,000 to 1,500,000, preferably in the range of 30,000 to 750,000, more preferably 60. , 150,000 to 150,000.

  The molecular weight distribution of the branched polyarylene sulfide resin obtained by the production method of the present invention is broadened, that is, the ratio of the mass average molecular weight to the number average molecular weight (mass average molecular weight / number average molecular weight) is 2.5 or more, preferably 3. It is a range of 0 or more.

  The branched polyarylene sulfide resin obtained by the production method of the present invention uses, as a raw material, a composition containing a high concentration of oligoarylene sulfide, in which the carboxyalkylamino group-containing compound (1) is reduced. In addition, it is possible to suppress the gas component generated during the melt molding process and to improve the odor and prevent mold contamination.

  The branched polyarylene sulfide resin obtained by the production method of the present invention is similar to the conventional polyarylene sulfide resin in that it does not depart from the object of the present invention. Known and commonly used additives such as an agent, a foaming agent, a rust preventive agent, a flame retardant, a lubricant, a coupling agent, and a filler can be contained. Furthermore, the following synthetic resins and elastomers can also be mixed and used. These synthetic resins include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, polyarylene, polyethylene, polypropylene, polytetrafluoroethylene, Examples thereof include poly (difluoroethylene), polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, and liquid crystal polymer. Examples of the elastomer include polyolefin rubber, fluorine rubber, and silicone rubber.

  Further, the branched polyarylene sulfide resin obtained by the production method of the present invention is excellent in reactivity with an impact modifier such as an epoxy silane coupling agent or a functional group-containing thermoplastic elastomer, and is a conventional polyarylene. Like the sulfide resin, it can be made into a molded product excellent in heat resistance, molding processability, dimensional stability, etc. by various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding. Electrical / electronic parts such as connectors / printed boards / encapsulated molded parts, automotive parts such as lamp reflectors / electrical parts, interior materials for various buildings, aircraft / automobiles, OA equipment parts / camera parts / watch parts Injection molding and compression molding products such as precision parts, etc., or extrusion molding and pultrusion molding products such as fibers, films, sheets, and pipes It is a wide range of possible use this in.

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

(CP-MABA quantification method)
The amount of CP-MABA was calculated by measuring the concentration of CP-MABA in the liquid by HPLC.
Sample preparation: When CP-MABA was contained in an organic solvent, the solvent was distilled off with an evaporator, and then a HPLC mobile phase was added to the residue and dissolved to prepare a measurement sample. When CP-MABA was contained in the aqueous solution, it was prepared by adding the mobile phase as it was.
The measurement sample was subjected to HPLC measurement, and the concentration in the liquid was determined and calculated from the peak area and calibration curve of the same retention time as the standard sample prepared by the following method.

(Synthesis of standard substance: CP-MABA)
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).

(Measurement of weight loss during heating)
Using a Rigaku differential thermal balance TG8120, weigh 10 mg of sample, raise the temperature from 50 ° C. to 400 ° C. at 20 ° C./min, and measure the decrease in sample weight at 320 ° C. based on the sample weight at 100 ° C. The weight loss rate was calculated.

(Melting point measurement)
Using a Perkin Elmer DSC apparatus, the temperature was raised from 50 ° C. to 350 ° C. at 20 ° C./min, and the endothermic peak temperature (Tm) that appeared when the polymer melted was measured.

(Melt viscosity (V6))
Using a flow tester (Shimadzu Corporation Koka-type flow tester “CFT-500D type”), the temperature / 300 ° C., the load 1.96 MPa, the orifice length / orifice diameter ratio is 10/1. The melt viscosity (Pa · s) after holding for 6 minutes was measured using an orifice.
(Non-Newton index measurement method)
The non-Newtonian index (N value) was measured by measuring the shear rate and the shear stress using a capillograph at 300 ° C., the ratio of the orifice length (L) to the orifice diameter (D), and L / D = 40. Calculated using the formula.
SR = K · SS ^N
However, SR represents a shear rate (second −1), SS represents a shear stress (dyne / cm 2), and K represents a constant. The closer the N value is to 1, the closer the PPS resin is to a linear structure, and the higher the N value is, the more branched the structure is.

(Reactivity evaluation method)
The PPS resin was pulverized with a small pulverizer and then sieved using a test sieve of Japanese Industrial Standard Z8801 with an aperture of 0.5 mm. With respect to 100 parts by mass of the PPS resin that passed through the sieve, 0.5 part by mass of 3-glycidoxypropyltrimethoxysilane was blended and mixed uniformly, and then the melt viscosity V6 was measured. The degree of increase in viscosity was calculated as a magnification from the ratio of melt viscosity V6 after addition / melt viscosity V6 before addition. The higher the degree of increase in viscosity, the higher the reactivity and the better.

[Production Example 1]
(Production of polyphenylene sulfide resin containing oligophenylene sulfide)
In a 1 liter autoclave with a stirring blade connected with a pressure gauge, a thermometer, and a condenser, 129.42 g of flaked sodium sulfide (60.3% by weight Na ₂ S) and N-methyl-2-pyrrolidone (NMP) 300. 0 g was charged. While stirring in a nitrogen stream, the temperature was raised to 209 ° C. to distill 30.96 g of water (the amount of water remaining was 1.13 mol per mol of sodium sulfide). Thereafter, the autoclave was sealed and cooled to 180 ° C., and 147.90 g of paradichlorobenzene (p-DCB) and 120.0 g of NMP were charged. The temperature was raised by pressurizing to 0.1 MPa with a gauge pressure using nitrogen gas at a liquid temperature of 150 ° C. The reaction was allowed to proceed with stirring at a liquid temperature of 260 ° C. for 3 hours, and the upper part of the autoclave was sprinkled to cool it. Next, the temperature was lowered and cooling of the upper part of the autoclave was stopped. The upper part of the autoclave was kept constant during cooling to prevent the liquid temperature from dropping. The maximum pressure during the reaction was 0.85 MPa. After the reaction, the mixture was cooled, and at a temperature of 170 ° C., a solution containing 1.89 g (0.015 mol) of oxalic acid dihydrate in 0.663 kg of NMP was injected under pressure, stirred for 30 minutes, and then cooled.

  The total amount of the obtained reaction slurry was filtered at 120 ° C., 320 g of NMP was added, and the cake was washed and filtered. The amount of NMP filtrate was 536 g. 1 L of 70 ° C. ion-exchanged water was added to the total amount of the NMP-containing cake thus obtained and stirred for 10 minutes, followed by filtration. The cake was washed by adding 1 L of 70 ° C. ion-exchanged water to the cake after filtration. 1 L of ion-exchanged water was added to the obtained water-containing cake and stirred for 10 minutes, followed by filtration. The cake after filtration was added with 1 L of ion-exchanged water at 70 ° C. This operation was repeated once, followed by drying at 120 ° C. for 4 hours to obtain a PPS resin having a melt viscosity (V6) of 63 Pa · s and a yield of 96.9 g.

(Recovery of reaction mixture containing oligophenylene sulfide and CP-MABA)
536 g of the NMP filtrate was charged into a 1 L eggplant flask, and NMP was removed by distillation at 150 ° C. under reduced pressure using a rotary evaporator to obtain 18.35 g of a brown solid residue. The weight of this residue after drying for 1 hour in a 150 ° C. vacuum dryer is 7.52 g (including 5.09 g of oligophenylene sulfide and 2.4320 g of Na-type CP-MABA), and the non-volatile content of the solid residue is 41.0 wt. %Met. However, oligophenylene sulfide and CP-MABA were quantified by the following method.
(Quantitative method of oligophenylene sulfide and CP-MABA)
Chloroform, ion-exchanged water, and 48% NaOH aqueous solution were added to the reaction mixture containing oligophenylene sulfide and CP-MABA recovered from the NMP filtrate to adjust the aqueous phase to pH13. From the chloroform phase from which oligophenylene sulfide was extracted, chloroform was distilled off under reduced pressure to obtain oligophenylene sulfide. The amount of oligophenylene sulfide was calculated | required by weighing the weight after drying an extraction residue with a 150 degreeC vacuum dryer for 1 hour. The amount of CP-MABA was determined by quantifying the aqueous phase with HPLC.

[Reference Example 1]
(Separation of CP-MABA)
18.35 g of the solid residue obtained in Production Example 1 and 100 g of ion-exchanged water were charged into a 0.5 liter autoclave, pH was adjusted to 10.6 by adding a 48% NaOH aqueous solution, and the mixture was stirred at 180 ° C. for 60 minutes. Went. After cooling to room temperature, the mixture was filtered, and 100 g of ion exchange water at 70 ° C. was added to the cake after filtration to wash the cake. The pH of the filtrate was 10.0, the amount of Na-type CP-MABA in the filtrate was 2.4315 g, and the extraction rate was 99.98%. The cake after washing the cake was dried with a vacuum dryer at 60 ° C. for 1 hour, and then a milky white powder mixture (A-1) containing 5.09 g of oligophenylene sulfide and 0.0005 g of CP-MABA was obtained. The melting point of the powdery mixture (A-1) was Tm204 ° C.

[Example 1]
(Production of branched PPS resin by melt polymerization under oxidizing atmosphere)
3.0 g of the powdery mixture (A-1) was weighed, sandwiched between Teflon (registered trademark) sheets, and heated and melted in a 320 ° C. hot air dryer in an air atmosphere for 1 hour to polymerize. After cooling to room temperature, a branched PPS resin was obtained. Table 1 shows the melting point Tm (° C.), the melt viscosity V6 (Pa · s), the non-Newtonian index, the weight loss rate during heating (%), and the reactivity (magnification) of the obtained branched PPS resin.

[Reference Example 2]
(Separation of CP-MABA)
The same operation as in Reference Example 1 was performed except that “stirring at 180 ° C. for 60 minutes” was changed to “stirring at 170 ° C. for 60 minutes”. The pH of the filtrate was 10.0, the amount of Na-type CP-MABA in the filtrate was 2.4223 g, and the extraction rate was 99.6%. A milky white powdery mixture (A-2) containing 5.09 g of oligophenylene sulfide and 0.0097 g of CP-MABA was obtained. The melting point of the powdery mixture (A-2) was Tm204 ° C.

[Example 2]
(Production of branched PPS resin by melt polymerization under oxidizing atmosphere)
A branched PPS resin was obtained in the same manner as in Example 1, except that the powder mixture (A-2) was used instead of the powder mixture (A-1). Table 1 shows the melting point Tm (° C.), the melt viscosity V6 (Pa · s), the non-Newtonian index, the weight loss rate during heating (%), and the reactivity (magnification) of the obtained branched PPS resin.

[Reference Example 3]
(Separation of CP-MABA)
The same operation as in Reference Example 1 was performed except that “stirring at 180 ° C. for 60 minutes” was changed to “stirring at 150 ° C. for 10 minutes”. The pH of the filtrate was 10.0, the amount of Na-type CP-MABA in the filtrate was 2.3348 g, and the extraction rate was 96%. A milky white powdery mixture (A-3) containing 5.09 g of oligophenylene sulfide and 0.0972 g of CP-MABA was obtained. The melting point of the powdery mixture (A-3) was Tm204 ° C.

Example 3
(Production of branched PPS resin by melt polymerization under oxidizing atmosphere)
A branched PPS resin was obtained in the same manner as in Example 1 except that the powder mixture (A-3) was used instead of the powder mixture (A-1). Table 1 shows the melting point Tm (° C.), the melt viscosity V6 (Pa · s), the non-Newtonian index, the weight loss rate during heating (%), and the reactivity (magnification) of the obtained branched PPS resin.

[Reference Example 4]
(Separation of CP-MABA)
The same operation as in Reference Example 1 was performed except that “stirring at 180 ° C. for 60 minutes” was changed to “stirring at 120 ° C. for 10 minutes”. The pH of the filtrate was 10.0, the amount of Na-type CP-MABA in the filtrate was 1.8727 g, and the extraction rate was 77%. A milky white powdery mixture (A-4) containing 5.09 g of oligophenylene sulfide and 0.5593 g of CP-MABA was obtained. The melting point of the powdery mixture (A-4) was Tm196 ° C.

Example 4
(Production of branched PPS resin by melt polymerization under oxidizing atmosphere)
A branched PPS resin was obtained in the same manner as in Example 1 except that the powder mixture (A-4) was used instead of the powder mixture (A-1). Table 1 shows the melting point Tm (° C.), the melt viscosity V6 (Pa · s), the non-Newtonian index, the weight loss rate during heating (%), and the reactivity (magnification) of the obtained branched PPS resin.

[Reference Example 5]
(Separation of CP-MABA)
The same operation as in Reference Example 1 was performed except that “stirring at 180 ° C. for 60 minutes” was changed to “stirring at 100 ° C. for 10 minutes”. The pH of the filtrate was 10.0, the amount of Na-type CP-MABA in the filtrate was 1.4325 g, and the extraction rate was 58.9%. A milky white powdery mixture (A-5) containing 5.09 g of oligophenylene sulfide and 0.9995 g of CP-MABA was obtained. The melting point of the powdery mixture (A-5) was Tm184 ° C.

Example 5
(Production of branched PPS resin by melt polymerization under oxidizing atmosphere)
A branched PPS resin was obtained in the same manner as in Example 1, except that the powder mixture (A-5) was used instead of the powder mixture (A-1). Table 1 shows the melting point Tm (° C.), the melt viscosity V6 (Pa · s), the non-Newtonian index, the weight loss rate during heating (%), and the reactivity (magnification) of the obtained branched PPS resin.

[Comparative Reference Example 1]
(Separation of CP-MABA)
18.35 g of the solid residue obtained in Production Example 1 and 100 g of ion-exchanged water were charged into a 0.5 liter autoclave, and the mixture was stirred at 70 ° C. for 10 minutes without adjusting the pH. After cooling to room temperature, the mixture was filtered, and 100 g of ion exchange water at 70 ° C. was added to the cake after filtration to wash the cake. The pH of the filtrate was 3.2, the amount of Na-type CP-MABA in the filtrate was 0.5107 g, and the extraction rate was 21%. The cake after cake washing was dried with a vacuum dryer at 60 ° C. for 1 hour, and then a brown powdery mixture (A-6) containing 5.09 g of oligophenylene sulfide and 1.9213 g of CP-MABA was obtained. The melting point of the powdery mixture (A-6) did not show a clear peak.

[Comparative Example 1]
(Production of PPS resin by melt polymerization under oxidizing atmosphere)
A PPS resin was obtained in the same manner as in Example 1 except that the powdery mixture (A-6) was used instead of the powdery mixture (A-1). Table 1 shows the melting point Tm (° C.), melt viscosity V6 (Pa · s), non-Newton's index, weight reduction rate (%) and reactivity (magnification) of the obtained PPS resin.

[Comparative Reference Example 2]
(Separation of CP-MABA)
To 18.35 g of the solid residue obtained in Production Example 1, 100 g of chloroform and 100 g of ion-exchanged water were added, and a 48% NaOH aqueous solution was added to adjust the aqueous phase to pH 13. Chloroform was distilled off under reduced pressure from the chloroform phase from which oligophenylene sulfide was extracted, and 10 g of chloroform was again added to the solid residue and dissolved at room temperature. This was slowly added dropwise to 100 g of methanol while stirring, and the precipitate was filtered. The obtained cake was dried in a vacuum dryer at 60 ° C. for 1 hour to obtain 5.09 g (A-7) of a white powder of oligophenylene sulfide. The amount of Na-type CP-MABA in the aqueous phase was 2.4320 g, and the extraction rate was 100%. The melting point of the powdery mixture (A-7) was Tm204 ° C.

[Comparative Example 2]
(Production of branched PPS resin by melt polymerization under oxidizing atmosphere)
A branched PPS resin was obtained in the same manner as in Example 1, except that the powder mixture (A-7) was used instead of the powder mixture (A-1). Table 1 shows the melting point Tm (° C.), the melt viscosity V6 (Pa · s), the non-Newtonian index, the weight loss rate during heating (%), and the reactivity (magnification) of the obtained branched PPS resin.

Claims (6)

Melt polymerization of 0.01 to 20 parts by mass of the compound (1) represented by the following structural formula (1) and 99.99 to 80 parts by mass of the oligoarylene sulfide (2) in an oxidizing atmosphere;
In addition to the compound (1) and the oligoarylene sulfide (2), the polyarylene sulfide resin is further contained at a ratio of 50 parts by mass or less with respect to 100 parts by mass in total of the compound (1) and the oligoarylene sulfide (2). Melt polymerization under conditions,
Before hear compound (1) and oligo arylene sulfide (2) are those obtained polyarylene sulfide reaction mixture was purified removed in the polymerization step of the resin is contacted with 100 ° C. or more and pH6 more water about,
And the said oligo arylene sulfide (2) is following Structural formula (2)

(Wherein m = 2 to 50. Ar is a phenylene group) The cyclic polyarylene sulfide (2a) represented by the range of 50% by mass to 100% by mass and the following structural formula ( 3) or (4)

Containing a dimer or trimer component represented by the formula (wherein Y ₁ represents a halogen atom) in a proportion ranging from 0% by mass to 50% by mass;
A process for producing a branched polyarylene sulfide resin characterized by

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, and X represents a hydrogen atom or an alkali metal atom.)   The method for producing a branched polyarylene sulfide resin according to claim 1, wherein the polyarylene sulfide resin obtained by the production method has a non-Newtonian index in the range of 1.26 to 2.50.   The polyarylene sulfide resin obtained by the above production method has a melt viscosity at 300 ° C. (however, using a flow tester, the temperature / 300 ° C., the load 1.96 MPa, the orifice length / orifice diameter ratio) The method for producing a branched polyarylene sulfide resin according to claim 1 or 2, wherein a measured value after holding for 10 minutes using an orifice of 10/1 is in a range of 20 to 5,000 [Pa · s]. . Before hear compound (1) and oligo arylene sulfide (2)
In an organic polar solvent, the structural formula (1) is obtained by reacting a polyhaloaromatic compound with (i) an alkali metal sulfide or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide. After obtaining a crude reaction mixture containing the compound (1), oligoarylene sulfide (2), organic polar solvent (3), polyarylene sulfide (4) and alkali metal halide (5) represented by The mixture is washed with an organic polar solvent (6) to separate and remove the polyarylene sulfide (4) and the alkali metal halide (5), and the compound (1), the oligoarylene sulfide (2) and the organic polar solvent ( A step (1) of obtaining a reaction mixture (a1) comprising 3),
(2) a step of solid-liquid separation of the organic polar solvent from the reaction mixture (a1) to obtain a reaction mixture (a2) containing the compound (1) and oligoarylene sulfide (2);
A step (3) of separating the compound (1) represented by the structural formula (1) and the oligoarylene sulfide (2) by contacting the reaction mixture (a2) with water at a temperature higher than 100 ° C. and pH 6 or higher. ,
The method for producing a branched polyarylene sulfide resin according to any one of claims 1 to 3, which is obtained by the step (4) of recovering the separated oligoarylene sulfide (2).   The branch according to claim 4, wherein the reaction mixture (a2) is obtained by subjecting the organic polar solvent to solid-liquid separation from the reaction mixture (a1) and then washing with water in the range of 100 to 250 ° C. For producing type polyarylene sulfide resin.   The method for producing a branched polyarylene sulfide resin according to any one of claims 4 and 5, wherein in the step (2), solid-liquid separation is performed by separating and removing the polar organic solvent by flushing.