JP5110385B2 - Process for producing carboxyl-containing polyarylene sulfide resin - Google Patents

Description

  The present invention relates to a method for producing a carboxyl-containing polyarylene sulfide resin from which a molded article having excellent impact resistance is obtained. The molded article using the carboxyl-containing polyarylene sulfide resin obtained by the production method of the present invention can be widely used in fields such as electric or electronic parts, automobile parts, and water-bowl parts.

  Polyarylene sulfide resins are excellent in heat resistance and chemical resistance, and are widely used for electrical or electronic parts, automobile parts, machine parts, water heater parts, fibers, films and the like. In recent years, there has been a demand for higher performance or lighter weight of parts in the electric or electronic parts, automobile parts, etc., and it has been necessary to reduce the size or thickness of the parts. It is required to further improve the impact resistance of the obtained molded product. Such a method for improving impact resistance includes a method of melt-kneading a polyarylene sulfide resin and a silane coupling agent such as epoxy silane or a functional group-containing thermoplastic elastomer, and a high molecular weight of the polyarylene sulfide resin. There are known methods for improving the toughness by increasing the size.

  As a method for improving the toughness of the molded product by increasing the molecular weight of the polyarylene sulfide resin, for example, during the polymerization reaction of the polyarylene sulfide resin, the gas phase part of the reaction vessel is cooled to condense part of the gas phase. The polyarylene sulfide resin is made to have a high molecular weight by refluxing to the liquid phase, and after the polymerization reaction, the obtained polyarylene sulfide resin is washed with an organic solvent, and then washed with water to lower the molecular weight. A method for removing components is known (see Patent Document 1). However, although the polyarylene sulfide resin thus obtained has a high molecular weight and can remove low molecular weight components which are impurities and has improved toughness to some extent, the epoxy silane coupling agent and the functional group-containing heat The impact resistance improvement effect when an impact modifier such as a plastic elastomer is added has not yet been sufficient.

Japanese Patent Laid-Open No. 8-253587

  The problem to be solved by the present invention is that, when an impact modifier such as an epoxy silane coupling agent or a functional group-containing thermoplastic elastomer is added to the polyarylene sulfide resin, a significant impact resistance improvement effect is exhibited. An object of the present invention is to provide a production method capable of easily producing a polyarylene sulfide resin for obtaining a polyarylene sulfide resin composition.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have produced an alkali metal sulfide and / or an alkali in the presence of an amide group-containing cyclic hydrocarbon compound when producing a polyarylene sulfide resin. After preparing the reaction slurry by reacting the metal hydrosulfide with the aromatic polyhalogen compound, the content of the amide group-containing cyclic hydrocarbon compound in the reaction slurry is equal to the weight of the amide group-containing cyclic hydrocarbon compound (a1w ) And the weight (Aw) of the polyarylene sulfide resin in the reaction slurry is adjusted to be 0.6 to 1.5 times the ratio ((a1w) / (Aw)). A polyarylene sulfide resin containing a carboxyl group can be easily obtained by distilling off the hydrocarbon compound and washing the polyarylene sulfide resin. The improvement in impact resistance can be achieved by reducing the amount of the compound having a specific structure contained in the polyarylene sulfide resin. This compound having the specific structure is contained in the amide group-containing cyclic hydrocarbon compound in the above production method. By making the amount 0.6 to 1.5 times [(a1w) / (Aw)], it can be easily removed from the polyarylene sulfide resin in the washing step, and the remaining of the specific compound Since the amount is small, a polyarylene sulfide resin can be easily provided with a large number of carboxyl groups in the washing step, a compound that reacts with a carboxyl group and a polyarylene sulfide resin with a carboxyl group, for example, epoxy silane coupling A composition containing an agent or an impact-imparting agent such as a functional group-containing thermoplastic elastomer Found that such a composition excellent in sex, and have completed the present invention.

  That is, the present invention reacts an alkali metal sulfide and / or alkali metal hydrosulfide (a2) with an aromatic polyhalogen compound (a3) in the presence of an amide group-containing cyclic hydrocarbon compound (a1). The first step of obtaining the reaction slurry (1) containing the resulting polyarylene sulfide resin (A), and the content of the amide group-containing cyclic hydrocarbon compound (a1) in the reaction slurry (1) is the first step. The ratio ([a1w) / (Aw) of the weight (a1w) of the amide group-containing cyclic hydrocarbon compound (a1) used in step 1 to the weight (Aw) of the polyarylene sulfide resin (A) obtained in the first step. )] Is adjusted to 0.6 to 1.5 times the reaction slurry (2), and then the amide group-containing cyclic hydrocarbon compound (a1) is distilled off from the reaction slurry (2) to obtain polyarylene. Carboxyl group-containing poly, comprising a second step of obtaining a mixture containing the rufide resin (A) and a third step of washing the mixture with water to obtain a carboxyl group-containing polyarylene sulfide resin (A1). A method for producing an arylene sulfide resin is provided.

  According to the present invention, a polyarylene sulfide resin having a high carboxyl group content can be easily provided. A compound which reacts with the polyarylene sulfide resin obtained by the production method of the present invention and the carboxyl group by having many carboxyl groups, for example, an impact resistance imparting agent such as an epoxy silane coupling agent or a functional group-containing thermoplastic elastomer The composition containing these has excellent impact resistance.

  The carboxyl group-containing polyarylene sulfide resin (A1) obtained by the production method of the present invention has the following structural formula (1)

〔構造式（１）中、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のアルキレン基を表す。〕で表される分子構造を有する化合物（ｘ１）を含有する。この上記記構造式（１）で表される構造を有する化合物（ｘ１）は、カルボキシル基含有ポリアリーレンスルフィド樹脂（Ａ１）を製造する際の副生成物であり、本発明の製造方法は様々な副生成物、不純物のなかでも前記化合物（ｘ１）の含有率を低減させることにより、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を飛躍的に向上させることができる。本発明の製造方法により得られるカルボキシル基含有ポリアリーレンスルフィド樹脂（Ａ１）中の前記化合物（ａ１）の含有率は、例えば、０．１〜１０００質量ｐｐｍの範囲となる。本発明の製造方法で得られるカルボキシル基含有ポリアリーレンスルフィド樹脂（Ａ１）の中でも、カルボキシル基と反応性を有する耐衝撃性改質剤と溶融混合し組成物とする際に、均一性・反応性が良好なものとなり、耐衝撃性改善効果がより顕著なものとなる点から前記化合物（ａ１）の含有率が１〜５００質量ｐｐｍのカルボキシル基含有ポリアリーレンスルフィド樹脂が好ましい。

[In Structural Formula (1), 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, and R ² represents carbon. An alkylene group having 3 to 5 atoms is represented. The compound (x1) which has a molecular structure represented by this is contained. The compound (x1) having the structure represented by the above structural formula (1) is a by-product in producing the carboxyl group-containing polyarylene sulfide resin (A1), and there are various production methods of the present invention. Impact resistance when adding impact modifiers such as epoxy silane coupling agents and functional group-containing thermoplastic elastomers by reducing the content of the compound (x1) among by-products and impurities The improvement effect can be dramatically improved. The content rate of the said compound (a1) in the carboxyl group containing polyarylene sulfide resin (A1) obtained by the manufacturing method of this invention becomes the range of 0.1-1000 mass ppm, for example. Among the carboxyl group-containing polyarylene sulfide resins (A1) obtained by the production method of the present invention, uniformity and reactivity are obtained when melt-mixed with an impact modifier having reactivity with carboxyl groups to obtain a composition. Is preferable, and a carboxyl group-containing polyarylene sulfide resin having a content of the compound (a1) of 1 to 500 ppm by mass is preferable from the viewpoint that the impact resistance improving effect becomes more remarkable.

The specific structure of the compound (x1) depends on the raw materials and polymerization conditions for producing the carboxyl group-containing polyarylene sulfide resin (A1). For example, in the structural formula (1), Y ^{1 represents} a bromine atom. Or a chlorine atom as Y ² having a hydrogen atom, a bromine atom, or a chlorine atom, R ¹ having a hydrogen atom or a methyl group, an ethyl group, a propyl group, a 2-propyl group, or a cyclohexyl group; ² as propylene group, 2-methylethylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, 1,1-dimethylethylene group, pentylene group, 2-methylbutylene group, 1,1-dimethylpropylene group And those having a 2-ethylpropylene group. Among these, as a raw material for producing the carboxyl group-containing polyarylene sulfide resin (A1), for example, the amide group-containing cyclic hydrocarbon compound used in the production method of the present invention is N-methyl-2-pyrrolidone described later, When the group polyhalogen compound is p-dichlorobenzene described later, the compound (a1) has the following structural formula (3):

で表されるものとなる（以下、この化合物を「ＣＰ−ＭＡＢＡ（水素型）」と略記する）。

(Hereinafter, this compound is abbreviated as “CP-MABA (hydrogen type)”).

  In the production method of the present invention, not only the compound (x1) but also the following structural formula (2)

〔構造式（２）中、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、Ｘはアルカリ金属原子を、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のアルキレン基を表す。〕で表される分子構造を有する化合物（ｘ２）のカルボキシル基含有ポリアリーレンスルフィド樹脂（Ａ１）中の含有率を低減させることができる。具体的には、例えば、前記化合物（ｘ１）及び前記化合物（ｘ２）の合計の含有率を、前記カルボキシル基含有ポリアリーレンスルフィド樹脂（Ａ１）中、２〜１８００ｐｐｍとなる範囲、特に５０〜１２００質量ｐｐｍとなる範囲にすることができる。このような範囲となることで耐衝撃性の改善効果が顕著なものとなる。

[In Structural Formula (2), Y ¹ represents a halogen atom, Y ² represents a hydrogen atom or a halogen atom, X represents an alkali metal 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. ] The content rate in the carboxyl group-containing polyarylene sulfide resin (A1) of the compound (x2) having a molecular structure represented by the formula (I) can be reduced. Specifically, for example, the total content of the compound (x1) and the compound (x2) is in a range of 2 to 1800 ppm in the carboxyl group-containing polyarylene sulfide resin (A1), particularly 50 to 1200 mass. The range can be ppm. By being in such a range, the impact resistance improvement effect becomes remarkable.

The specific structure of the compound (x2) includes, for example, a bromine atom or a chlorine atom as Y ¹ in the structural formula (2), a hydrogen atom, a bromine atom, or a chlorine atom as Y ² , and R ¹ Has a hydrogen atom or a methyl group, an ethyl group, a propyl group, a 2-propyl group, or a cyclohexyl group, and R ² is a propylene group, a 2-methylethylene group, a butylene group, a 1-methylpropylene group, or 2-methylpropylene. And those having a group, 1,1-dimethylethylene group, pentylene group, 2-methylbutylene group, 1,1-dimethylpropylene group, 2-ethylpropylene group, and the like.

  As in the case of the compound (x1), as a raw material for producing the carboxyl group-containing polyarylene sulfide resin (A1), for example, an amide group-containing cyclic hydrocarbon compound is N-methyl-2-pyrrolidone, alkali metal sulfide and sodium sulfide. When the aromatic polyhalogen compound is p-dichlorobenzene, the compound (x2) has the following structural formula (4):

で表されるものとなる（以下、「ＣＰ−ＭＡＢＡ（Ｎａ型）」と略記する）。

(Hereinafter abbreviated as “CP-MABA (Na type)”).

  Here, a method for quantifying the contents of the compound (x1) and the compound (x2) is shown below. First, the compound (x1) is quantified by mixing the carboxyl group-containing polyarylene sulfide resin (A1) obtained by the production method of the present invention with ion-exchanged water and a 0.4% by mass alkaline aqueous solution. A mixture which is sufficiently slurried by mixing water is heated to 220 ° C. in a pressure vessel equipped with a stirrer to extract the compound (x1), and its content is abbreviated as “HPLC”. )).

  Next, the compound (x2) is quantified by mixing a carboxyl group-containing polyarylene sulfide resin (A1) with ion-exchanged water and heating it to 220 ° C. in a pressure vessel equipped with a stirrer. Thus, there is a method in which both the compound (x1) and the compound (x2) are extracted, the total content thereof is quantified by HPLC, and the difference from the content of the compound (x1) is taken.

  From the contents of the compound (x1) and the compound (x2) thus determined and the mass of the carboxyl group-containing polyarylene sulfide resin (A1) used for the measurement, the carboxyl group-containing polyarylene sulfide resin (A1) The contents of the compound (x1) and the compound (x2) in the content can be determined.

  On the other hand, among the carboxyl group-containing polyarylene sulfide resins (A1) obtained by the production method of the present invention, the carboxyl group-containing polyarylene sulfide (A1), which is the main component of the carboxyl group-containing polyarylene sulfide resin (A1), is aromatic. It has a resin structure having a structure in which a ring and a sulfur atom are bonded as a repeating unit and having a carboxyl group in its molecular structure. Specifically, the following structural formula (5)

(In formula, R < ¹ > and R < ² > represents a hydrogen atom, a C1-C4 alkyl group, a nitro group, an amino group, a phenyl group, a methoxy group, an ethoxy group, and a carboxyl group each independently.
Is a resin having a repeating unit as a structural site represented by:

Here, in the structural part represented by the structural formula (5), in particular, R ¹ and R ² in the formula are hydrogen atoms from the viewpoint of the mechanical strength of the carboxyl group-containing polyarylene sulfide resin (A1). It is preferable that there are, and in that case, those bonded at the para position represented by the following structural formula (6) and those bonded at the meta position represented by the following structural formula (7) are exemplified.

  Among these, in particular, the heat resistance of the polyarylene sulfide resin (A1) is that the sulfur atom bond to the aromatic ring in the repeating unit is a structure bonded at the para position represented by the structural formula (6). It is preferable in terms of crystallinity.

  Further, the carboxyl group-containing polyarylene sulfide resin (A1) is not only the structural portion represented by the structural formula (5) but also the following structural formulas (8) to (11).

May be included in 30 mol% or less of the total with the structural site represented by the structural formula (5). In particular, in the present invention, from the viewpoint of heat resistance and mechanical strength of the carboxyl group-containing polyarylene sulfide resin (A1), the structural site represented by the structural formulas (8) to (11) is 10 mol% or less. preferable. When the carboxyl group-containing polyarylene sulfide resin (A1) includes structural sites represented by the structural formulas (8) to (11), the bonding mode thereof includes a random copolymer and a block copolymer. Any of these may be used.

  The carboxyl group-containing polyarylene sulfide resin (A1) has the following structural formula (12) in its molecular structure.

May have a trifunctional structural site represented by the formula (1) or a naphthyl sulfide bond, but is preferably 3 mol% or less, particularly 1 mol%, based on the total number of moles with other structural sites. The following is preferable.

  Examples of the carboxyl group-containing polyarylene sulfide resin (A1) include a crosslinked carboxyl group-containing polyarylene sulfide resin and a so-called linear carboxyl group-containing polyarylene sulfide resin having a substantially linear structure. Is mentioned. Here, when the molecular weight of the cross-linked carboxyl group-containing polyarylene sulfide resin and the molecular weight of the linear carboxyl group-containing polyarylene sulfide resin are compared under the same conditions of melt viscosity, the latter linear type carboxyl group-containing polyarylene resin is obtained. Since the arylene sulfide resin has a higher molecular weight, it has better toughness.

  Since the carboxyl group-containing polyarylene sulfide resin (A1) obtained by the production method of the present invention has a carboxyl group in its molecular structure, when melt mixed with an impact modifier having reactivity with the carboxyl group. The uniformity and reactivity of the resin become good, and the impact resistance improvement effect is dramatically improved. The carboxyl group content is particularly in the range of 15 μmol / g to 100 μmol / g, particularly 15 μmol / g to 70 μmol / g in the carboxyl group-containing polyarylene sulfide resin (A1) from the point that this improvement effect becomes remarkable. More preferably, it is in the range.

  In addition, the carboxyl group-containing polyarylene sulfide resin (A1) obtained by the production method of the present invention preferably has a melt viscosity measured at 300 ° C. in the range of 50 poise to 40,000 poise. As described above, in the present invention, even with a polyarylene sulfide resin having a low melt viscosity, excellent impact resistance can be exhibited, so that the parts in electric / electronic parts, automobile parts, etc. can be downsized or thinned. Can be supported. Among these ranges, the range of 100 poise to 10,000 poise is preferable from the viewpoint of a good balance between the impact resistance of the molded product and the fluidity during molding.

  The production method of the present invention comprises reacting an alkali metal sulfide and / or alkali metal hydrosulfide (a2) with an aromatic polyhalogen compound (a3) in the presence of an amide group-containing cyclic hydrocarbon compound (a1). The first step of obtaining the reaction slurry (1) containing the polyarylene sulfide resin (A) obtained in the above, and the content of the amide group-containing cyclic hydrocarbon compound (a1) in the reaction slurry (1) Ratio [(a1w) / () of the weight (a1w) of the amide group-containing cyclic hydrocarbon compound (a1) used in the step and the weight (Aw) of the polyarylene sulfide resin (A) obtained in the first step. Aw)] is adjusted to 0.6 to 1.5 times the weight of the reaction slurry (2), and then the amide group-containing cyclic hydrocarbon compound (a1) is distilled off from the reaction slurry (a2). Polya A second step of obtaining a mixture containing Rensurufido resin (A), the washed with water and the mixture, characterized in that it contains a third step of obtaining a carboxyl group-containing polyarylene sulfide resin (A1).

  In the first step of the present invention, polymerization is performed by reacting the alkali metal sulfide or alkali metal hydrosulfide (a2) with the aromatic polyhalogen compound (a3) in the presence of the amide group-containing cyclic hydrocarbon compound (a1). Let At this time, the amide group-containing cyclic hydrocarbon compound (a1) is hydrolyzed at the time of polymerization to obtain a ring-opened product of the compound, and this ring-opened product is reacted with an aromatic polyhalogen compound. )

〔構造式（２）中、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、Ｘはアルカリ金属原子を、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のアルキレン基を表す。〕で表される分子構造を有する化合物（ｘ２）を生成させ、これをポリアリーレンスルフィドの成長末端に付加させることにより、分子末端にカルボン酸塩を有するポリアリーレンスルフィドを製造することができる。該カルボン酸塩は、最終的に精製段階で酸処理を施されてカルボン酸に変換されることになる。

[In Structural Formula (2), Y ¹ represents a halogen atom, Y ² represents a hydrogen atom or a halogen atom, X represents an alkali metal 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. A polyarylene sulfide having a carboxylate at the molecular end can be produced by generating a compound (x2) having a molecular structure represented by the following formula and adding it to the growth end of the polyarylene sulfide. The carboxylate is finally subjected to an acid treatment in a purification step to be converted into a carboxylic acid.

  Examples of the amide group-containing cyclic hydrocarbon compound (a1) used here include N-methyl-2-pyrrolidone, N-ethylpyrrolidone, N-methyl-ε-caprolactam, N-ethyl-ε-caprolactam, and 1,3-dimethyl. -2-imidazolidinone, N, N′-ethylene-2-pyrrolidone, 2-pyrrolidone, ε-caprolactam, and the like, and mixtures thereof. Among these, N-methyl- 2-pyrrolidone is particularly preferred.

  In addition to these amide group-containing cyclic hydrocarbon compounds (a1), N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, formamide, acetamide, hexamethylphosphoramide, tetramethylurea, etc. These chain organic amide solvents and polar solvents other than amide solvents such as diphenylsulfone can be used in combination.

  Among the alkali metal sulfides or alkali metal hydrosulfides (a2), examples of the alkali metal sulfide include hydrates such as lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide. They may be used alone or in combination of two or more. Among these, sodium sulfide and potassium sulfide are preferable from the viewpoint of good reactivity, and in particular, it is preferable to use them as hydrates during actual polymerization because they are easily available. In particular, hydrous sodium sulfide is particularly preferred from the viewpoint of excellent reactivity.

  Examples of the hydrated alkali metal hydrosulfide include hydrates such as lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, etc., and these may be used alone or 2 You may mix and use a seed | species or more. Among these, hydrated sodium hydrosulfide and potassium hydrosulfide are preferable from the viewpoint of good reactivity, and in particular, they are preferably used as these hydrated substances during actual polymerization because they are easily available. In particular, hydrous sodium hydrosulfide is preferable from the viewpoint of excellent reactivity.

  Examples of the aromatic polyhalogen compound (a3) include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 2,5-dichlorotoluene, p-dibromobenzene, 1,4-dichloronaphthalene, 1- Methoxy-2,5-dichlorobenzene, 4,4'-dichlorobiphenyl, 4,4'-dibromobiphenyl, 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2 , 4-dichloroaniline, 2,5-dichloroaniline, 3,5-dichloroaniline, 4,4'-dichlorophenyl ether, 4,4'-dichlorodiphenyl sulfoxide, 4,4'-dichlorophenyl ketone, and other aromatic dihalogen compounds , 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, etc. Androgenic compounds, 1,2,4,5 aromatic tetracarboxylic halogen compounds tetra chlorobenzene, and as well as similar thereto can be mixtures thereof. Among them, those containing an aromatic dihalogen compound substituted at the para position represented by p-dichlorobenzene as a main component are preferable, and p-dichlorobenzene is more preferable.

  In order to increase the carboxyl group content in the carboxyl group-containing polyarylene sulfide resin (A1) obtained by the production method of the present invention, 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 3 , 5-dichlorobenzoic acid, 3-nitro-4-chlorobenzoic acid and the like are preferably used, and an alkali metal hydroxide may be added during the polymerization reaction. The timing of adding the alkali metal hydroxide is preferably carried out after the time when the reaction rate of the aromatic dihalogen compound becomes 50% or more.

A specific method of polymerizing the alkali metal sulfide or alkali metal hydrosulfide (a2) and the aromatic polyhalogen compound (a3) in the presence of the amide group-containing cyclic hydrocarbon compound (a1) is, 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 polyhalogen compound (a3), 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) A hydrous alkali metal sulfide, an amide group-containing cyclic hydrocarbon compound (a1) and an aromatic polyhalogen compound (a3) of less than 1 mol per 1 mol of the hydrous alkali metal sulfide are mixed and subjected to a dehydration reaction. To obtain a mixture containing a solid alkali metal sulfide, an alkali metal salt of a hydrolyzate of an amide group-containing cyclic hydrocarbon compound, an alkali metal hydrosulfide, and an aromatic polyhalogen compound (a3), and then the mixture Further heating and polymerizing,
Etc.

  Among these, the method 5) above is preferable because the production of by-products is small and the linear and high molecular weight carboxyl group-containing polyarylene sulfide resin (A1) can be easily obtained at low cost. . Examples of the alkali metal hydroxide used in the method 5) include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. These may be used alone or in combination of two or more. Among these, lithium hydroxide, sodium hydroxide, and potassium hydroxide are preferable because they are easily available, and sodium hydroxide is particularly preferable.

  The temperature during the dehydration in 5) is preferably in the range of 80 ° C. to less than 200 ° C. from the viewpoint of excellent dehydration efficiency.

  In the dehydration reaction in the above method 5), a small amount of alkali metal hydroxide may be added in excess in order to remove impurities present in a trace amount in the hydrated alkali metal hydrosulfide. Moreover, the temperature conditions at the time of performing above-described polymerization should just be temperature conditions higher than the temperature at the time of the said dehydration reaction, Specifically, it is preferable that it is 200-300 degreeC.

  In the method 5), the compounding amount of the amide group-containing cyclic hydrocarbon compound (a1) is preferably in the range of 0.02 mol to 0.9 mol with respect to 1 mol of the hydrated alkali metal hydrosulfide. At the time of polymerization, it is possible to effectively suppress the formation of by-products, and in the range of 0.03 mol to 0.6 mol, particularly 0.04 mol to 0.4 mol from the viewpoint of expressing an appropriate reaction rate. It is preferable that it exists in the range.

  The blending amount of the aromatic polyhalogen compound (a3) is preferably in the range of 0.2 mol to 5.0 mol with respect to 1 mol of the hydrated alkali metal sulfide. When the amount of the aromatic polyhalogen compound (a3) is increased, the dehydration efficiency during the dehydration reaction is improved, while the complexity of removing the excess aromatic polyhalogen compound (a3) increases. . Therefore, the range of 0.3 to 2.0 mol is particularly preferable from the viewpoint of these balances.

  The reaction slurry (1) containing the polyarylene sulfide resin (A) is obtained in the first step described above. In the second step, the content of the amide group-containing cyclic hydrocarbon compound (a1) in the reaction slurry (1) is set to the weight (a1w) of the amide group-containing cyclic hydrocarbon compound (a1) used in the first step. ) And the weight (Aw) of the polyarylene sulfide resin (A) obtained in the first step, adjusted to a weight of 0.6 to 1.5 ((a1w) / (Aw)). After the reaction slurry (2) is obtained, the amide group-containing cyclic hydrocarbon compound (a1) is distilled off from the reaction slurry (a2) to obtain a mixture containing the polyarylene sulfide resin (A).

  By adjusting the content of the amide group-containing cyclic hydrocarbon compound (a1) in the reaction slurry (1) to be 0.6 to 1.5 times the weight of [(a1w) / (Aw)]. The amide group-containing cyclic hydrocarbon compound (a1) penetrates into the polyarylene sulfide resin (A) and is represented by the structural formula (1) and structural formula (2) inside the polyarylene sulfide resin (A). The inventors believe that the oligomers to be dissolved can be eluted on the surface of the polyarylene sulfide resin (A), and these oligomers are also easily removed when washed and removed with water in the third step described later. Yes. These oligomers are alkaline, and the washing water becomes alkaline due to the migration of the oligomer into the washing water used for washing, but the oligomer is eluted on the surface of the polyarylene sulfide resin (A) and is easily removed by washing. Yes, the washing water does not change to alkaline at an early stage when the washing water is replaced and repeatedly washed. Accordingly, the efficiency of the washing process can be improved, and the washing water does not change to alkaline at an early stage of washing. Therefore, the carboxylic acid metal salt of the polyarylene sulfide resin (A) can be easily converted into carboxylic acid by the water used for washing. The polyarylene sulfide resin (A1) having a large number of carboxyl groups can be efficiently obtained.

  When the content of the amide group-containing cyclic hydrocarbon compound (a1) in the reaction slurry (1) is less than 0.6 times the weight of [(a1w) / (Aw)], the oligomer is converted into a polyarylene sulfide resin (A). This is not preferable because it is difficult to elute on the surface of the material and becomes difficult to remove when washed with water and removed in the third step described later. Further, when the content of the amide group-containing cyclic hydrocarbon compound (a1) in the reaction slurry (1) is larger than 1.5 of [(a1w) / (Aw)], the amide group-containing cyclic hydrocarbon compound is distilled off. A long time is required, which is not preferable because it is not economical. In the second step, the content of the amide group-containing cyclic hydrocarbon compound (a1) in the reaction slurry (1) is determined based on the weight (a1w) of the amide group-containing cyclic hydrocarbon compound (a1) used in the first step. The weight of the polyarylene sulfide resin (A) obtained in the first step (Aw) is adjusted to 0.7 to 1.4 times the weight (A1w) / (Aw)]. Is preferred.

  In the second step, the content of the amide group-containing cyclic hydrocarbon compound (a1) in the reaction slurry (1) is adjusted to 0.6 to 1.5 times the weight of [(a1w) / (Aw)]. For example, when the content of the amide group-containing cyclic hydrocarbon compound (a1) in the reaction slurry (1) obtained in the first step is smaller than [(a1w) / (Aw)] 0.6 times The amide group-containing cyclic hydrocarbon compound (a1) may be added to the reaction slurry (1). Further, when the content of the amide group-containing cyclic hydrocarbon compound (a1) in the reaction slurry (1) is larger than 1.5 times [(a1w) / (Aw)], for example, the reaction slurry (1) to the amide The group-containing cyclic hydrocarbon compound (a1) is distilled off.

  In the present invention, the content of the amide group-containing cyclic hydrocarbon compound (a1) in the reaction slurry (1) is the weight (a1w) of the amide group-containing cyclic hydrocarbon compound (a1) used in the first step, The weight is adjusted to 0.6 to 1.5 times the ratio [(a1w) / (Aw)] to the weight (Aw) of the polyarylene sulfide resin (A) obtained in the first step. The unit of the content of the amide group-containing cyclic hydrocarbon compound (a1) in the reaction slurry (1) at this time is the unit of the weight of the amide group-containing cyclic hydrocarbon compound (a1) and the polymer obtained in the first step. It is the same unit as the unit of weight of the arylene sulfide resin (A).

  For example, after the first step, the distillation of the amide group-containing cyclic hydrocarbon compound (a1) is performed by flushing the reaction slurry (1) from a high temperature and high pressure state to an atmosphere under normal pressure or reduced pressure. The method, a method in which the amide group-containing cyclic hydrocarbon compound (a1) is distilled off by heating under reduced pressure, the reaction slurry (1) is cooled in a reaction kettle, and the polyarylene sulfide resin (A) is crystallized. Thereafter, the filtration residue obtained by filtration can be heated by a non-oxidizing atmosphere to remove the remaining amide group-containing cyclic hydrocarbon compound (a1).

  After obtaining the reaction slurry (2) in the second step, the amide group-containing cyclic hydrocarbon compound (a1) is distilled off from the reaction slurry (a2) to obtain a mixture containing the polyarylene sulfide resin (A). . Examples of the distillation method include the above-described distillation method.

  In the third step, the mixture obtained in the second step is washed with water to obtain a carboxyl group-containing polyarylene sulfide resin (A1). By this water washing (washing step), the carboxylic acid metal salt of the polyarylene sulfide resin (A) can be converted to carboxylic acid, and the carboxyl group-containing polyarylene sulfide resin (A1) can be obtained. The method of washing with water is, for example, a method of adding water to the mixture and stirring the mixture, followed by filtration using a filtration device, and a filtration residue containing moisture obtained by the filtration described above (hereinafter abbreviated as “hydrated cake”) again. Examples include a method of filtering after adding water to form a slurry, 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 to the mixture obtained in the second step during washing is in the range of 2 to 10 times the theoretical yield of the polyarylene sulfide (A1) finally obtained. 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 washing is preferably in the range of 50 ° C. to 90 ° C. from the viewpoint of good washing efficiency, and particularly preferably in the range of 70 ° C. to 90 ° C.

  The water washing performed in the third step can be performed a plurality of times as a batch process. When performing multiple times, after washing | cleaning at 50 to 90 degreeC, for example, it can also wash | clean with water (hot water) more than this temperature. The compound (a2) can be efficiently removed by washing with hot water. In particular, when the compound (x2) remains in the resin, it is changed to the compound (x1) by the acid treatment described later, and the content of the compound (x1) is increased. It is important to sufficiently reduce the content of the compound (x2). The temperature of the hot water used here is preferably in the range of 120 to 275 ° C., for example, from the viewpoint of good extraction efficiency of the compound (x2). 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 compound (x2) contained in the polyarylene sulfide resin (A) can be efficiently extracted into water, and then the compound (x2) is removed by filtration. be able to.

  A specific method for performing such a hot water treatment is a method in which the polyarylene sulfide resin (A) obtained in the second step is washed in water in a pressure vessel with stirring under predetermined pressure and temperature conditions. Can be mentioned. The heating and stirring time is preferably 10 minutes to 300 minutes.

  The amount of hot water when performing the hydrothermal treatment is preferably 1.5 times to 10 times the mass of the polyarylene sulfide (A) from the viewpoint of good extraction efficiency of the compound (x2). This amount of hot water may be divided into two or more times and washed with hot water. 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 compound (x2) extracted by the first hot water washing. Moreover, after performing hot water washing once, it may filter and may carry out water washing. By this operation, the removal of the compound (x2) is further promoted. Moreover, although the conditions of the 1st hot water washing process and the 2nd hot water washing process can be selected arbitrarily from said conditions, the temperature of the 1st hot water washing process is the temperature which exists in the range of 120 to 200 degreeC, for example. After setting and removing the highly alkaline filtrate first, the temperature of the second hot water washing step is set to a temperature higher than the temperature of the first hot water washing step, for example, a temperature in the range of 150 ° C. to 275 ° C. It is preferable to set and implement from the viewpoint of chemical resistance of the apparatus used in the hot water washing step.

  In this hot water washing step, the compound (x2) contained in the particles of the carboxyl group-containing polyarylene sulfide resin (A1) is efficiently extracted by heating and stirring above the boiling point of water in the pressure vessel, Subsequently, the said compound (x2) extracted in the filtrate is removed by filtering. For example, the temperature of the hot water washing is preferably 120 ° C. to 275 ° C. The extraction efficiency of the compound (x2) can be improved at 120 ° C. or higher, and the composition is difficult to melt at 275 ° C. or lower and the melt becomes a mass after cooling. This is preferable because it is suppressed. Among these, it is more preferable that it exists in the range of 140 to 260 degreeC. The superheated stirring time is preferably 10 minutes to 300 minutes, and if it is 10 minutes or more, the extraction efficiency of the compound (x2) is improved, and if it is 300 minutes or less, productivity can be improved and economic efficiency is improved. The amount of water is preferably 1.5 times to 10 times the weight of the resin, and when it is 1.5 times or more, the fluidity of the slurry is improved and the extraction efficiency of the compound (x2) is improved by heating uniformly. In the case of 10 times or less, it is preferable that the amount of heat necessary for heating the slurry is easily suppressed within an economical range.

  By washing with water in the third step of the present invention, the carboxylic acid metal salt of the polyarylene sulfide resin (A) can be converted into a carboxyl group to obtain a carboxyl group-containing polyarylene sulfide resin (A1). In the production method, the reactivity, crystallization rate, alkali metal content, etc. of the carboxyl group-containing polyarylene sulfide resin (A1) are further adjusted by adjusting the pH by adding acid or base during hot water washing. It can be controlled, and the pH after hot water washing is preferably controlled to be in the range of 6.5 to 11.5. When the pH after hot water washing is 6.5 or more, the compound (x2) does not easily change to the compound (x1) and is easily extracted into water, and thus is easy to remove and contains a compound having reactivity with the carboxyl group and a carboxyl group A molded article obtained by melt-molding a composition containing the polyarylene sulfide resin (A1) is preferable because it has improved flexural strength and impact resistance and has a high elastic modulus. In addition, when the pH after hot water washing is 11.5 or less, the amount of the basic compound in the composition is easily reduced, so the compound having reactivity with the carboxyl group and the polyarylene sulfide resin (A1) are melted. This is preferable because the crystallization speed of the mixture obtained by kneading is unlikely to be slow.

Among these, by adding an acid during hot water washing to adjust the pH after hot water washing to 6.5 to 8.5, the crystallization rate of the polyarylene sulfide resin (A1) can be increased, When a base is added at the time of washing with water and the pH after washing with hot water is adjusted to 9.5 to 11.5, the compound (x1) is easily changed to the compound (x2) and is easily removed and is reactive with the carboxyl group. This is preferable because the impact resistance of a molded product obtained by melt-kneading the polyarylene sulfide resin (A1) with the compound having the above is improved. 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.

  The method of acid treatment may be a method of acid-treating the obtained slurry after carrying out the hot water washing, or filtering after the hot water washing, adding ion exchange water and filtering again. A method of acidifying after slurrying the obtained hydrous cake, or a method of filtering after washing with hot water, adding ion-exchanged water and filtering again, and then subjecting the polyarylene sulfide resin that is a solid content to acid treatment, etc. Can be mentioned. Among these, filtration after hot water filtration, adding ion exchange water and filtering again, slurrying the hydrous cake obtained, or acid treatment, or filtration after hot water wash, adding ion exchange water and again The method of acid-treating polyarylene sulfide which is a solid content after filtration is preferable from the viewpoint of excellent removal efficiency of the CP-MABA (Na type).

  The temperature condition of the acid treatment may be in the range of 5 ° C to 100 ° C, but it is particularly 15 ° C to 80 ° C from the viewpoint of increasing the amount of carboxylic acid in the polyarylene sulfide resin and preventing the molecular weight from being reduced by the acid. Temperature is preferred.

  The pH during the acid treatment is preferably controlled in the range of 4.0 to 7.0 after the acid treatment from the viewpoint of increasing the carboxyl group content in the carboxyl group-containing polyarylene sulfide resin (A1). . In particular, it is preferably in the range of 5.5 to 6.5 from the viewpoint of preventing a decrease in reactivity due to the remaining of excess acid (acid not used for conversion from molecular terminal Na to molecular terminal H). Examples of the method for measuring pH include a method of measuring the pH of a filtrate obtained by filtering the slurry when an acid is added to the slurry. The polyarylene sulfide, which is a solid content after filtration, is acidified. When processing, the method of measuring the pH of the washing | cleaning filtrate which mixed all the filtrates obtained by repeating washing | cleaning using the aqueous solution of predetermined | prescribed acid concentration can be mentioned.

  Examples of the acid used for the acid treatment include formic acid, acetic acid, oxalic acid, phthalic acid, hydrochloric acid, phosphoric acid, sulfuric acid, and carbonic acid.

  The carboxyl group-containing polyarylene sulfide resin (A1) obtained by the production method of the present invention can be made into a composition by adding an impact modifier (B) having reactivity with a carboxyl group. Specifically, the impact modifier (B) is an epoxy silane coupling agent (b1) or a thermoplastic elastomer (b2) having a functional group reactive with a carboxyl group in the molecular structure. It is preferable from the point that the effect of improving the impact resistance of the molded product becomes remarkable.

  The epoxy silane coupling agent (b1) only needs to contain one or more epoxy groups per molecule. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- Examples include (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane. It is preferable that content of the said epoxy silane coupling agent (b1) exists in the range of 0.01 mass part-3 mass parts with respect to 100 mass parts of carboxyl group-containing polyarylene sulfide resin (A1). In the case of 0.01 parts by mass or more, the addition effect of the epoxy silane coupling agent (b1) is expressed, and the compound having reactivity with the carboxyl group and the carboxyl group-containing polyarylene sulfide resin (A1) are melt-molded. The obtained molded product is preferable because it has improved bending strength and impact resistance and has a high elastic modulus. The amount of 3 parts by mass or less is preferable because an increase in viscosity due to reaction with the polyarylene sulfide resin composition is suppressed. Among these, the range of 0.1 to 1 part by mass is particularly preferable from the viewpoint of the balance of bending strength, elastic modulus, impact resistance, and viscosity of the molded product.

  The thermoplastic elastomer (b2) having a functional group having reactivity with a carboxyl group used in the present invention specifically includes an epoxy group, an amino group, a hydroxyl group, a carboxyl group, a mercapto group, an isocyanate group, and an oxazoline. Or the following structural formula (13), structural formula (14)

(In Structural Formula (13) and Structural Formula (14), R represents an alkyl group having 1 to 8 carbon atoms.) A heat having at least one functional group selected from the group consisting of partial structures represented by Mention may be made of plastic elastomers. Among these, an epoxy group, a carboxyl group, or the following structural formula (13) and structural formula (14)

(In Structural Formula (13) and Structural Formula (14), R represents an alkyl group having 1 to 8 carbon atoms.) The thermoplastic elastomer having a partial structure represented by carboxyl group-containing polyarylene sulfide resin (A1 ) Is melted and kneaded to react well, and the molded product obtained by melt molding is particularly preferable from the viewpoint of excellent bending strength and impact resistance and high bending elastic modulus.

  The impact modifier (B) having reactivity with the carboxyl group can be obtained, for example, by copolymerization of α-olefins and vinyl polymerizable compounds having the functional group. Examples of the α-olefins include α-olefins having 2 to 8 carbon atoms such as ethylene, propylene, and butene-1. Examples of the vinyl polymerizable compounds having the functional group include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid esters and alkyl esters thereof, maleic acid, fumaric acid, and itaconic acid. Other unsaturated dicarboxylic acids having 4 to 10 carbon atoms and mono- and diesters thereof, α, β-unsaturated dicarboxylic acids such as acid anhydrides and derivatives thereof, glycidyl (meth) acrylate, and the like.

  As described above, among these, an epoxy group, a carboxyl group, or the following structural formula (13) or structural formula (14) in the molecule.

（構造式（１３）、構造式（１４）中、Ｒは炭素原子数１〜８のアルキル基、または芳香環を表す。）で表される部分構造からなる群から選ばれる少なくとも１種の官能基を有するエチレン−プロピレン共重合体、またはエチレン−ブテン共重合体が靭性や耐衝撃性の向上のため好ましい。さらに、分子内にエポキシ基、カルボキシル基を含有するものが好ましく、特に分子内にエポキシ基を有するものが好ましい。

(In Structural Formula (13) and Structural Formula (14), R represents an alkyl group having 1 to 8 carbon atoms or an aromatic ring). At least one functional selected from the group consisting of partial structures represented by An ethylene-propylene copolymer or an ethylene-butene copolymer having a group is preferable for improving toughness and impact resistance. Further, those having an epoxy group or a carboxyl group in the molecule are preferred, and those having an epoxy group in the molecule are particularly preferred.

The carboxyl group-containing polyarylene sulfide resin (A1) obtained by the production method of the present invention can contain an inorganic filler (C). By blending the inorganic filler (C), a composition having high rigidity and high heat stability can be obtained. The inorganic filler (C) is, for example, a powdery filler such as carbon black, calcium carbonate, silica, and titanium oxide, a plate-like filler such as talc and mica, a granular filler such as glass beads, silica beads, and a glass balloon. Examples thereof include fibrous fillers such as glass fiber, carbon fiber, and wollastonite fiber, and glass flakes.
The content of the inorganic filler (C) is preferably 1 to 300 parts by mass with respect to 100 parts by mass of the carboxyl group-containing polyarylene sulfide resin (A1). In the above case, the mechanical properties of the molded product obtained by melt molding are improved, and when it is 300 parts by mass or less, the fluidity during melt molding is improved, which is preferable. Among these ranges, the range of 5 to 200 parts by mass is particularly preferable from the viewpoint of the balance between the mechanical properties of the molded product and the fluidity during melt molding.

  The carboxyl group-containing polyarylene sulfide resin (A1) obtained by the production method of the present invention includes a mold release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust inhibitor, a flame retardant, and a lubricant as additives. It can be included. Further, similarly, synthetic resins and elastomers as described below can be mixed and used. These synthetic resins include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, polyethylene, polypropylene, polytetrafluoroethylene, polydifluoride. Ethylene fluoride, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, liquid crystal polymer, and the like. Examples of thermoplastic elastomers include polyolefin elastomers, fluorine elastomers, and silicone elastomers.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

[Synthesis of standard substance: CP-MABA (hydrogen type)]
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).

The isolated CP-MABA is abbreviated as a nuclear magnetic resonance apparatus (hereinafter abbreviated as “proton NMR” and “C ¹³ -NMR”) and a liquid chromatogram-mass spectrometer (hereinafter abbreviated as “LC-MS”). ), The structure was analyzed, and the structure of the following structural formula (3) was determined.

[Synthesis of standard substance: CP-MABA (Na type)]
After producing CP-MABA (hydrogen type) in the same manner as in [Synthesis of CP-MABA (hydrogen type)], the CP-MABA (hydrogen type) is added to a sodium hydroxide aqueous solution at pH 10 and stirred. The water was distilled off to obtain CP-MABA (Na type).

The isolated CP-MABA (Na type) was structurally analyzed by proton NMR, C ¹³ -NMR, and LC-MS, and confirmed to have the structure of the following structural formula (4).

[CP-MABA (hydrogen type), CP-MABA (Na type) quantification method]
The quantification of CP-MABA (hydrogen type) or CP-MABA (Na type) with respect to the total mass of the carboxyl group-containing polyarylene sulfide resin (A) and the compound (a1) was performed as follows.

  (1) A methanol solution of CP-MABA (hydrogen type) or CP-MABA (Na type) synthesized by the above synthesis method is prepared so as to have the following four levels: 1000 ppm, 100 ppm, 10 ppm, 1 pmm, Retention time and peak area were measured by HPLC for each concentration of standard sample solution, and a calibration curve showing the relationship between peak area and concentration was prepared.

(2) Quantification of CP-MABA (hydrogen type) After adding 150 g of ion-exchanged water to 50 g of the polyarylene sulfide resin composition and thoroughly stirring it, the temperature is raised to 220 ° C. in a pressure vessel equipped with a stirrer. Warmed and extracted with stirring for 30 minutes. This extract was measured by HPLC, and the concentration in the extract was obtained from the peak area and calibration curve with the same retention time as that of the standard sample, and the concentration in the polyarylene sulfide resin composition (hereinafter referred to as “CP-MABA (hydrogen type)”. Abbreviated as “content”).

(3) Quantification of CP-MABA (Na-type) After adding 140 g of ion-exchanged water and 10 g of a 0.1 mol / L sodium hydroxide aqueous solution to 50 g of the polyarylene sulfide resin composition and thoroughly stirring it, In a pressure vessel with a stirrer, the temperature was raised to 220 ° C., and the mixture was stirred for 30 minutes for extraction. The concentration in the polyarylene sulfide resin composition was calculated by the same method as described above. Since CP-MABA (hydrogen type) is extracted by changing to CP-MABA (Na type) under alkaline conditions, this concentration is the same as that of CP-MABA (hydrogen type) and CP-MABA (Na type) originally present. It means the total concentration (hereinafter abbreviated as “total CP-MABA content”). Therefore, from the difference between this concentration and the concentration of CP-MABA (hydrogen type) determined by the method of (2) above, the concentration of CP-MABA (Na type) (hereinafter referred to as “CP-MABA (Na type) content”). Abbreviated.) Was calculated.

[Calculation method of removal efficiency of CP-MABA (Na type)]
[Removal amount of CP-MABA (Na type) in each washing step / Amount of total CP-MABA (Na type) removed in washing step] × 100 (%)

[Method for quantifying carboxyl group of carboxyl group-containing polyarylene sulfide resin (A)]
The quantitative method is that a polyarylene sulfide resin composition is pressed at 350 ° C. and then rapidly cooled to prepare a film showing amorphous properties, and a Fourier transform infrared spectrometer (hereinafter abbreviated as “FT-IR apparatus”). The measurement was performed. Determined the relative intensity of the absorption of 1705 cm ^-1 for absorption of 630.6Cm ^-1 of infrared absorption spectrum, additional content of carboxyl group in the measurement sample using a calibration curve prepared by the method described later (hereinafter "carboxyl Abbreviated as "total content of groups"). The content of the carboxyl group is indicated by the number of moles in 1 g of the resin composition, and the unit is expressed in μmol / g. From the difference between the carboxyl group content of the polyarylene sulfide resin composition thus determined and the concentration of CP-MABA (hydrogen type) determined by the above method, the carboxyl group of the carboxyl group-containing polyarylene sulfide resin (A) Content (hereinafter abbreviated as “carboxyl group content in polymer”) was calculated. The calibration curve was created by adding a predetermined amount of 4-chlorophenylacetic acid to 3 g of polyarylene sulfide resin containing carboxylate at the molecular end without acid treatment and mixing well, and then creating a film in the same manner as above. Then, measurement was performed with an FT-IR apparatus, and a calibration curve in which the relative intensity ratio of the absorption to the carboxyl group content was plotted was prepared. The higher the carboxyl group content in the polyarylene sulfide resin, the more excellent the impact resistance is obtained when an impact modifier such as an epoxysilane coupling agent or a functional group-containing thermoplastic elastomer is added. It can be said that.

Example 1
A 150-liter autoclave with a stirring blade and a bottom valve connected with a pressure gauge, thermometer, condenser, decanter and p-dichlorobenzene 33.472 kg (228 mol), N-methyl-2-pyrrolidone 2.508 kg (25 mol), 47 The mixture was charged with 27.185 kg (230 mol) of 4% NaSH and 18.236 kg (223 mol) of 49% NaOH, heated to 173 ° C. under a nitrogen atmosphere with stirring, and 27.188 kg of water was distilled off. Was sealed. At that time, p-dichlorobenzene distilled by azeotropic distillation was separated by a decanter and returned to the kettle as needed. After completion of dehydration, the internal temperature was cooled to 160 ° C., 47.246 kg (477 mol) of N-methyl-2-pyrrolidone was added, the temperature was raised to 230 ° C. and stirred for 1 hour, and then the temperature was raised to 250 ° C., 1 The reaction slurry (1) containing polyarylene sulfide resin (A) was obtained by stirring for a period of time. The final pressure was 0.33 MPa. The weight of the obtained polyarylene sulfide resin (A) was 23.6 kg. Therefore, the ratio of N-methyl-2-pyrrolidone / polyarylene sulfide resin is 2.1 by weight.

After completion of the reaction, the internal temperature of the autoclave was cooled from 250 ° C to 235 ° C. After reaching 235 ° C., the bottom valve of the autoclave was opened and flushed with a 150 liter vacuum stirrer / dryer equipped with a stirring blade (desolventizer jacket temperature: 175 ° C.) in a reduced pressure state to extract N-methyl-2-pyrrolidone. By this flushing, the content of N-methyl-2-pyrrolidone in the reaction slurry ( 1 ) is 0.6 to the weight ratio (2.1) of the N-methyl-2-pyrrolidone / polyarylene sulfide resin in the reaction slurry. 1.5 times the 33.1kg next is 1.4 times to enter (1.2 6 to 3.15 times), to obtain a reaction slurry (2).

  After completion of the flash, the reaction slurry (2) [mixture of polyarylene sulfide, residual N-methyl-2-pyrrolidone and salts] was sampled from a 150 liter vacuum stirring dryer, and cooled to room temperature. Thereafter, 181 g of the reaction slurry (2) was dried in a vacuum dryer at 150 ° C./5 Torr for 3 hours so that the polyarylene sulfide in the sampled reaction slurry (2) was 52 g to remove N-methyl-2-pyrrolidone. And a mixture containing polyarylene sulfide resin was obtained.

  To this mixture was added 296 g of ion exchanged water at 70 ° C. and stirred for 10 minutes, followed by filtration. The cake after filtration was added 208 g of ion exchanged water at 70 ° C. to perform cake washing (water washing treatment). The obtained hydrous cake and 156 g of ion-exchanged water were charged in a 0.5 liter autoclave and stirred at 150 ° C. for 30 minutes (first hot water treatment). After cooling to room temperature, filtration was performed, and 208 g of ion-exchanged water at 70 ° C. was added to the cake after filtration to wash the cake. The obtained hydrous cake and 208 g of ion-exchanged water were again charged into a 0.5 liter autoclave and stirred at 220 ° C. for 30 minutes (second hot water treatment). After cooling to room temperature, filtration was performed, and cake washing was performed by adding 156 g of ion-exchanged water at 70 ° C. to the cake after filtration. Thereafter, 156 g of normal temperature carbonated water (pH = 4.0) was added to wash the cake, and 156 g of ion-exchanged water at 70 ° C. was added to wash the cake. The obtained water-containing cake was dried with a hot air circulating dryer at 120 ° C. for 6 hours to obtain a white powdery carboxyl group-containing polyarylene sulfide resin.

  The amount of CP-MABA (Na type) removed by the water washing treatment was 6.0 μmol / g based on the weight of the obtained carboxyl group-containing polyarylene sulfide resin (the same applies hereinafter). The amount of CP-MABA (Na type) removed by the first hot water treatment was 20.3 μmol / g based on the weight of the obtained carboxyl group-containing polyarylene sulfide resin (the same applies hereinafter). The amount of CP-MABA (Na type) removed by the second hot water treatment was 24.1 μmol / g based on the weight of the obtained carboxyl group-containing polyarylene sulfide resin (the same applies hereinafter). The amount of the carboxyl group in the carboxyl group-containing polyarylene sulfide resin was 20.3 μmol / g based on the weight of the obtained carboxyl group-containing polyarylene sulfide resin (the same applies hereinafter).

Example 2
A reaction slurry (1) was obtained in the same manner as in Example 1. From the reaction end temperature of 250 ° C., the autoclave bottom valve was opened and flushed to a 150 liter vacuum agitation dryer with a stirring blade (desolventizer jacket temperature 70 ° C.) in a reduced pressure state to extract N-methyl-2-pyrrolidone. . By this flushing, the content of N-methyl-2-pyrrolidone in the reaction slurry ( 1 ) is 0.6 to the weight ratio (2.1) of the N-methyl-2-pyrrolidone / polyarylene sulfide resin in the reaction slurry. 1.5 times the 40.2kg next is 1.7 times to enter (1.2 6 to 3.15 times), to obtain a reaction slurry (2).

  After completion of the flash, the reaction slurry (2) [mixture of polyarylene sulfide, residual N-methyl-2-pyrrolidone and salts] was sampled from a 150 liter vacuum stirring dryer, and cooled to room temperature. Thereafter, 197 g of the reaction slurry (2) was dried in a vacuum dryer at 150 ° C./5 Torr so that the polyarylene sulfide in the sampled reaction slurry (2) was 52 g to remove N-methyl-2-pyrrolidone. And a mixture containing polyarylene sulfide resin was obtained.

  To this mixture was added 296 g of ion exchanged water at 70 ° C. and stirred for 10 minutes, followed by filtration. The cake after filtration was added 208 g of ion exchanged water at 70 ° C. to perform cake washing (water washing treatment). The obtained hydrous cake and 156 g of ion-exchanged water were charged in a 0.5 liter autoclave and stirred at 150 ° C. for 30 minutes (first hot water treatment). After cooling to room temperature, filtration was performed, and 208 g of ion-exchanged water at 70 ° C. was added to the cake after filtration to wash the cake. The obtained hydrous cake and 208 g of ion-exchanged water were again charged into a 0.5 liter autoclave and stirred at 220 ° C. for 30 minutes (second hot water treatment). After cooling to room temperature, filtration was performed, and cake washing was performed by adding 156 g of ion-exchanged water at 70 ° C. to the cake after filtration. Thereafter, 156 g of normal temperature carbonated water (pH = 4.0) was added to wash the cake, and 156 g of ion-exchanged water at 70 ° C. was added to wash the cake. The obtained water-containing cake was dried with a hot air circulating dryer at 120 ° C. for 6 hours to obtain a white powdery carboxyl group-containing polyarylene sulfide resin.

  The amount of CP-MABA (Na type) removed by the water washing treatment in the same manner as in Example 1, the amount of CP-MABA (Na type) removed by the first hot water treatment, and the second hot water treatment. The amount of CP-MABA (Na type) and the amount of carboxyl groups in the carboxyl group-containing polyarylene sulfide resin were measured. Table 1 shows the measurement results.

Example 3
A reaction slurry (1) was obtained in the same manner as in Example 1. From the reaction end temperature of 250 ° C., the bottom valve of the autoclave was opened and the pressure was maintained in a reduced pressure state, and a 150 liter vacuum agitation dryer with a stirring blade in which 10 kg of N-methyl-2-pyrrolidone at room temperature was applied (desolventizer jacket temperature 175 ° C. ) To remove N-methyl-2-pyrrolidone. By this flushing, the content of N-methyl-2-pyrrolidone in the reaction slurry ( 1 ) is 0.6 to the weight ratio (2.1) of the N-methyl-2-pyrrolidone / polyarylene sulfide resin in the reaction slurry. 1.5 times the 47.3kg next is 2.0 times to enter (1.2 6 to 3.15 times), to obtain a reaction slurry (2).

  After completion of the flash, the reaction slurry (2) [mixture of polyarylene sulfide, residual N-methyl-2-pyrrolidone and salts] was sampled from a 150 liter vacuum stirring dryer, and cooled to room temperature. Thereafter, 212 g of the reaction slurry (2) was dried for 3 hours in a vacuum dryer at 150 ° C./5 Torr so that the polyarylene sulfide in the sampled reaction slurry (2) was 52 g to remove N-methyl-2-pyrrolidone. And a mixture containing polyarylene sulfide resin was obtained.

  To this mixture was added 296 g of ion exchanged water at 70 ° C. and stirred for 10 minutes, followed by filtration. The cake after filtration was added 208 g of ion exchanged water at 70 ° C. to perform cake washing (water washing treatment). The obtained hydrous cake and 156 g of ion-exchanged water were charged in a 0.5 liter autoclave and stirred at 150 ° C. for 30 minutes (first hot water treatment). After cooling to room temperature, filtration was performed, and 208 g of ion-exchanged water at 70 ° C. was added to the cake after filtration to wash the cake. The obtained hydrous cake and 208 g of ion-exchanged water were again charged into a 0.5 liter autoclave and stirred at 220 ° C. for 30 minutes (second hot water treatment). After cooling to room temperature, filtration was performed, and cake washing was performed by adding 156 g of ion-exchanged water at 70 ° C. to the cake after filtration. Thereafter, 156 g of normal temperature carbonated water (pH = 4.0) was added to wash the cake, and 156 g of ion-exchanged water at 70 ° C. was added to wash the cake. The obtained water-containing cake was dried with a hot air circulating dryer at 120 ° C. for 6 hours to obtain a white powdery carboxyl group-containing polyarylene sulfide resin.

  The amount of CP-MABA (Na type) removed by the water washing treatment in the same manner as in Example 1, the amount of CP-MABA (Na type) removed by the first hot water treatment, and the second hot water treatment. The amount of CP-MABA (Na type) and the amount of carboxyl groups in the carboxyl group-containing polyarylene sulfide resin were measured. Table 1 shows the measurement results.

Example 4
A reaction slurry (1) was obtained in the same manner as in Example 1. From the reaction end temperature of 250 ° C., the bottom valve of the autoclave was opened and the vacuum pressure was kept at 150 ° C. with a stirring blade impregnated with 20 kg of normal temperature N-methyl-2-pyrrolidone (desolventizer jacket temperature 175 ° C. ) To remove N-methyl-2-pyrrolidone. By this flushing, the content of N-methyl-2-pyrrolidone in the reaction slurry ( 1 ) is 0.6 to the weight ratio (2.1) of the N-methyl-2-pyrrolidone / polyarylene sulfide resin in the reaction slurry. 1.5 times the 63.8kg next is 2.7 times to enter (1.2 6 to 3.15 times), to obtain a reaction slurry (2).

  After completion of the flash, the reaction slurry (2) [mixture of polyarylene sulfide, residual N-methyl-2-pyrrolidone and salts] was sampled from a 150 liter vacuum stirring dryer, and cooled to room temperature. Thereafter, 249 g of the reaction slurry (2) was dried in a vacuum dryer at 150 ° C./5 Torr so that the polyarylene sulfide in the sampled reaction slurry (2) was 52 g to remove N-methyl-2-pyrrolidone. And a mixture containing polyarylene sulfide resin was obtained.

  To this mixture was added 296 g of ion exchanged water at 70 ° C. and stirred for 10 minutes, followed by filtration. The cake after filtration was added 208 g of ion exchanged water at 70 ° C. to perform cake washing (water washing treatment). The obtained hydrous cake and 156 g of ion-exchanged water were charged in a 0.5 liter autoclave and stirred at 150 ° C. for 30 minutes (first hot water treatment). After cooling to room temperature, filtration was performed, and 208 g of ion-exchanged water at 70 ° C. was added to the cake after filtration to wash the cake. The obtained hydrous cake and 208 g of ion-exchanged water were again charged into a 0.5 liter autoclave and stirred at 220 ° C. for 30 minutes (second hot water treatment). After cooling to room temperature, filtration was performed, and cake washing was performed by adding 156 g of ion-exchanged water at 70 ° C. to the cake after filtration. Thereafter, 156 g of normal temperature carbonated water (pH = 4.0) was added to wash the cake, and 156 g of ion-exchanged water at 70 ° C. was added to wash the cake. The obtained water-containing cake was dried with a hot air circulating dryer at 120 ° C. for 6 hours to obtain a white powdery carboxyl group-containing polyarylene sulfide resin.

  The amount of CP-MABA (Na type) removed by the water washing treatment in the same manner as in Example 1, the amount of CP-MABA (Na type) removed by the first hot water treatment, and the second hot water treatment. The amount of CP-MABA (Na type) and the amount of carboxyl groups in the carboxyl group-containing polyarylene sulfide resin were measured. The measurement results are shown in Table 1.

Example 5
A reaction slurry (1) was obtained in the same manner as in Example 1. From the reaction end temperature of 250 ° C., the autoclave bottom valve was opened and flushed to a 150 liter vacuum agitation dryer with a stirring blade (desolventizer jacket temperature 70 ° C.) in a reduced pressure state to extract N-methyl-2-pyrrolidone. . After flushing, 5 kg of N-methyl-2-pyrrolidone at room temperature was charged into the kettle. The content of N-methyl-2-pyrrolidone in the reaction slurry (1) is adjusted by the weight ratio of N-methyl-2-pyrrolidone / polyarylene sulfide resin in the reaction slurry by charging the flash and N-methyl-2-pyrrolidone ( 2.1) of 0.6 to 1.5 fold range (1.2 6 ~3. 44.9kg next is 1.9 times to enter the 15-fold) to obtain a reaction slurry (2).

  The reaction slurry (2) was transferred to a 150 liter vacuum stirring dryer. Thereafter, the reaction slurry (2) [mixture of polyarylene sulfide, residual N-methyl-2-pyrrolidone and salts] was sampled from a 150 liter vacuum stirring dryer, and cooled to room temperature. Next, 207 g of the reaction slurry (2) was dried in a vacuum dryer at 150 ° C./5 Torr for 3 hours so that the polyarylene sulfide in the sampled reaction slurry (2) was 52 g, and N-methyl-2-pyrrolidone Removal was performed to obtain a mixture containing polyarylene sulfide resin.

  To this mixture was added 296 g of ion exchanged water at 70 ° C. and stirred for 10 minutes, followed by filtration. The cake after filtration was added 208 g of ion exchanged water at 70 ° C. to perform cake washing (water washing treatment). The obtained hydrous cake and 156 g of ion-exchanged water were charged in a 0.5 liter autoclave and stirred at 150 ° C. for 30 minutes (first hot water treatment). After cooling to room temperature, filtration was performed, and 208 g of ion-exchanged water at 70 ° C. was added to the cake after filtration to wash the cake. The obtained hydrous cake and 208 g of ion-exchanged water were again charged into a 0.5 liter autoclave and stirred at 220 ° C. for 30 minutes (second hot water treatment). After cooling to room temperature, filtration was performed, and cake washing was performed by adding 156 g of ion-exchanged water at 70 ° C. to the cake after filtration. Thereafter, 156 g of normal temperature carbonated water (pH = 4.0) was added to wash the cake, and 156 g of ion-exchanged water at 70 ° C. was added to wash the cake. The obtained water-containing cake was dried with a hot air circulating dryer at 120 ° C. for 6 hours to obtain a white powdery carboxyl group-containing polyarylene sulfide resin.

  The amount of CP-MABA (Na type) removed by the water washing treatment in the same manner as in Example 1, the amount of CP-MABA (Na type) removed by the first hot water treatment, and the second hot water treatment. The amount of CP-MABA (Na type) and the amount of carboxyl groups in the carboxyl group-containing polyarylene sulfide resin were measured. Table 1 shows the measurement results.

Example 6
A reaction slurry (1) was obtained in the same manner as in Example 1. From the reaction end temperature of 250 ° C., the bottom valve of the autoclave was opened and the pressure was maintained in a reduced pressure state, and a 150 liter vacuum agitation dryer with a stirring blade in which 10 kg of N-methyl-2-pyrrolidone at room temperature was applied (desolventizer jacket temperature 175 ° C. ) To remove N-methyl-2-pyrrolidone. By this flushing, the content of N-methyl-2-pyrrolidone in the reaction slurry ( 1 ) is 0.6 to the weight ratio (2.1) of the N-methyl-2-pyrrolidone / polyarylene sulfide resin in the reaction slurry. 1.5 times the 47.3kg next is 2.0 times to enter (1.2 6 to 3.15 times), to obtain a reaction slurry (2).

After completion of the flash, the reaction slurry (2) [mixture of polyarylene sulfide, residual N-methyl-2-pyrrolidone and salts] was dried for 3.5 hours in a 150 liter vacuum stirring dryer (desolventizer jacket temperature 175 ° C.). N-methyl-2-pyrrolidone was removed. After completion of the solvent removal, the powdered polyarylene sulfide and salt mixture was cooled to room temperature and sampled. Next, 17.3 kg of a mixture of polyarylene sulfide, residual N-methyl-2-pyrrolidone and salts, and 47.3 ion-exchanged water 47.3 at 70 ° C. so that the sampled polyarylene sulfide is 8.3 kg. The filter was charged and stirred for 10 minutes for washing. Thereafter, the mixture was filtered, and cake washing was performed by adding 33.2 kg of ion exchange water at 70 ° C. to the cake after filtration. The obtained water-containing cake and 16.6 kg of ion-exchanged water were charged into a 0.3 m 2 flat plate filter and stirred at 150 ° C. for 30 minutes (first hot water treatment). Thereafter, filtration was performed, and cake washing was performed by adding 33.2 kg of ion exchange water at 70 ° C. to the cake after filtration. Next, the obtained liquid-containing cake and 24.9 kg of ion-exchanged water were charged into a 70-liter autoclave and stirred at 220 ° C. for 30 minutes (second hot water treatment). After cooling to room temperature, it was filtered with a centrifugal filter, and 24.9 kg of ion-exchanged water at 70 ° C. was added to the cake after filtration to wash the cake. Thereafter, 24.9 kg of carbonated water (pH = 4.0) at room temperature was added to wash the cake, and 24.9 kg of ion-exchanged water at 70 ° C. was added to wash the cake. The obtained water-containing cake was dried with a hot air circulating dryer at 120 ° C. for 6 hours to obtain a white powdery carboxyl group-containing polyarylene sulfide resin.

  The amount of CP-MABA (Na type) removed by the water washing treatment in the same manner as in Example 1, the amount of CP-MABA (Na type) removed by the first hot water treatment, and the second hot water treatment. The amount of CP-MABA (Na type) and the amount of carboxyl groups in the carboxyl group-containing polyarylene sulfide resin were measured. Table 1 shows the measurement results.

Comparative Example 1
A reaction slurry (1) was obtained in the same manner as in Example 1. From the reaction end temperature of 250 ° C., the bottom valve of the autoclave was opened, and it was flushed with a 150 liter vacuum agitation dryer with a stirring blade (desolventizer jacket temperature of 175 ° C.) in a reduced pressure state to extract N-methyl-2-pyrrolidone. . By this flushing, the content of N-methyl-2-pyrrolidone in the reaction slurry ( 1 ) is 0.6 to the weight ratio (2.1) of the N-methyl-2-pyrrolidone / polyarylene sulfide resin in the reaction slurry. 1.5 times the 23.6kg next is 1.0 times that do not fall (1.2 6 to 3.15 times), to obtain a reaction slurry (2).

  After completion of the flash, a comparative reaction slurry (2) [mixture of polyarylene sulfide, residual N-methyl-2-pyrrolidone and salts] was sampled from a 150 liter vacuum stirring dryer, and cooled to room temperature. Thereafter, 160 g of the comparative reaction slurry (2) was dried in a 150 ° C./5 Torr vacuum dryer for 3 hours so that the polyarylene sulfide in the sampled comparative reaction slurry (2) was 52 g, and N-methyl -2-Pyrrolidone was removed to obtain a mixture containing polyarylene sulfide resin.

  To this mixture was added 296 g of ion exchanged water at 70 ° C. and stirred for 10 minutes, followed by filtration. The cake after filtration was added 208 g of ion exchanged water at 70 ° C. to perform cake washing (water washing treatment). The obtained hydrous cake and 156 g of ion-exchanged water were charged in a 0.5 liter autoclave and stirred at 150 ° C. for 30 minutes (first hot water treatment). After cooling to room temperature, filtration was performed, and 208 g of ion-exchanged water at 70 ° C. was added to the cake after filtration to wash the cake. The obtained hydrous cake and 208 g of ion-exchanged water were again charged into a 0.5 liter autoclave and stirred at 220 ° C. for 30 minutes (second hot water treatment). After cooling to room temperature, filtration was performed, and cake washing was performed by adding 156 g of ion-exchanged water at 70 ° C. to the cake after filtration. Thereafter, 156 g of normal temperature carbonated water (pH = 4.0) was added to wash the cake, and 156 g of ion-exchanged water at 70 ° C. was added to wash the cake. The obtained water-containing cake was dried with a hot air circulating dryer at 120 ° C. for 6 hours to obtain a white powdery carboxyl group-containing polyarylene sulfide resin.

  The amount of CP-MABA (Na type) removed by the water washing treatment in the same manner as in Example 1, the amount of CP-MABA (Na type) removed by the first hot water treatment, and the second hot water treatment. The amount of CP-MABA (Na type) and the amount of carboxyl groups in the carboxyl group-containing polyarylene sulfide resin were measured. The measurement results are shown in Table 2.

Comparative Example 2
A reaction slurry (1) was obtained in the same manner as in Example 1. From the reaction end temperature of 250 ° C., the bottom valve of the autoclave was opened, and it was flushed with a 150 liter vacuum agitation dryer with a stirring blade (desolventizer jacket temperature of 175 ° C.) in a reduced pressure state to extract N-methyl-2-pyrrolidone. . By this flushing, the content of N-methyl-2-pyrrolidone in the reaction slurry ( 1 ) is 0.6 to the weight ratio (2.1) of the N-methyl-2-pyrrolidone / polyarylene sulfide resin in the reaction slurry. 1.5 times the 23.6kg next is 1.0 times that do not fall (1.2 6 to 3.15 times), to obtain a reaction slurry (2).

  After completion of the flash, the comparative reaction slurry (2) [mixture of polyarylene sulfide, residual N-methyl-2-pyrrolidone and salts] was added to a 3.5-liter vacuum stir dryer (desolventizer jacket temperature 175 ° C.) to 3.5. After drying for a while, N-methyl-2-pyrrolidone was removed. After completion of the solvent removal, the powdered polyarylene sulfide and salt mixture was cooled to room temperature and sampled. Next, 17.3 kg of a mixture of polyarylene sulfide, residual NN-methyl-2-pyrrolidone and salts, and 47.3 ion-exchanged water 47.3 at 70 ° C. were added so that the sampled polyarylene sulfide was 8.3 kg. The mixture was charged into a 3 m2 flat plate filter and washed by stirring for 10 minutes. Thereafter, cake was washed by adding 33.2 kg of ion exchange water at 70 ° C. to the cake after filtration. The obtained water-containing cake and 16.6 kg of ion-exchanged water were charged into a 0.3 m 2 flat plate filter and stirred at 150 ° C. for 30 minutes (first hot water treatment). Thereafter, filtration was performed, and cake washing was performed by adding 33.2 kg of ion exchange water at 70 ° C. to the cake after filtration. Next, the obtained liquid-containing cake and 24.9 kg of ion-exchanged water were charged into a 70-liter autoclave and stirred at 220 ° C. for 30 minutes (second hot water treatment). After cooling to room temperature, it was filtered with a centrifugal filter, and 24.9 kg of ion-exchanged water at 70 ° C. was added to the cake after filtration to wash the cake. Thereafter, 24.9 kg of carbonated water (pH = 4.0) at room temperature was added to wash the cake, and 24.9 kg of ion-exchanged water at 70 ° C. was added to wash the cake. The obtained water-containing cake was dried with a hot air circulating dryer at 120 ° C. for 6 hours to obtain a white powdery carboxyl group-containing polyarylene sulfide resin.

  The amount of CP-MABA (Na type) removed by the water washing treatment in the same manner as in Example 1, the amount of CP-MABA (Na type) removed by the first hot water treatment, and the second hot water treatment. The amount of CP-MABA (Na type) and the amount of carboxyl groups in the carboxyl group-containing polyarylene sulfide resin were measured. The measurement results are shown in Table 2.

Claims (4)

Polyarylene sulfide resin obtained by reacting alkali metal sulfide and / or alkali metal hydrosulfide (a2) with aromatic polyhalogen compound (a3) in the presence of amide group-containing cyclic hydrocarbon compound (a1) A first step of obtaining a reaction slurry (1) containing (A);
The content of the amide group-containing cyclic hydrocarbon compound (a1) relative to the weight (Aw) of the polyarylene sulfide resin (A) obtained in the first step in the reaction slurry (1) was used in the first step. Ratio [(a1w) / (Aw)] of the weight (a1w) of the amide group-containing cyclic hydrocarbon compound (a1) and the weight (Aw) of the polyarylene sulfide resin (A) obtained in the first step. After adjusting to 0.6 to 1.5 times to obtain a reaction slurry (2), the amide group-containing cyclic hydrocarbon compound (a1) is distilled off from the reaction slurry (2) to obtain a polyarylene sulfide resin ( A second step to obtain a mixture containing A);
And a third step of obtaining the carboxyl group-containing polyarylene sulfide resin (A1) by washing the mixture with water, and a method for producing a carboxyl group-containing polyarylene sulfide resin. The content of the amide group-containing cyclic hydrocarbon compound (a1) relative to the weight (Aw) of the polyarylene sulfide resin (A) obtained in the first step in the reaction slurry (1) as the reaction slurry (2) is as follows. The ratio of the weight (a1w) of the amide group-containing cyclic hydrocarbon compound (a1) used in the first step to the weight (Aw) of the polyarylene sulfide resin (A) obtained in the first step [( The method for producing a carboxyl group-containing polyarylene sulfide resin according to claim 1, wherein a reaction slurry obtained by adjusting the a1w) / (Aw)] to 0.7 to 1.4 is used. The content of the amide group-containing cyclic hydrocarbon compound (a1) relative to the weight (Aw) of the polyarylene sulfide resin (A) obtained in the first step in the reaction slurry (1) as the reaction slurry (2) is as follows. The ratio of the weight (a1w) of the amide group-containing cyclic hydrocarbon compound (a1) used in the first step to the weight (Aw) of the polyarylene sulfide resin (A) obtained in the first step [( The method for producing a carboxyl group-containing polyarylene sulfide resin according to claim 1, wherein a reaction slurry obtained by adjusting the a1w) / (Aw)] to 0.67 to 1.29 is used. N-methyl-pyrrolidone as the amide group-containing cyclic hydrocarbon compound (a1), sodium hydrosulfide as the alkali metal sulfide and / or alkali metal hydrosulfide (a2), and P as the aromatic polyhalogen compound (a3) The method for producing a carboxyl group-containing polyarylene sulfide resin according to claim 1, wherein -dichlorobenzene is used.