JP6390083B2 - Process for producing polyarylene sulfide - Google Patents

Description

  The present invention relates to a method for producing a polyarylene sulfide resin by recovering the oligoarylene sulfide discharged in the purification step during the production of the polyarylene sulfide resin and melt-melting the obtained oligoarylene sulfide while circulating.

  Polyarylene sulfide (PAS) resin represented by polyphenylene sulfide (PPS) resin is excellent in heat resistance, chemical resistance, etc., and is widely used in electrical and electronic parts, automotive parts, water heater parts, textiles, film applications, etc. Yes. 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, when an oligoarylene sulfide is melt-polymerized using a polymerization reaction apparatus such as that used in the Philips method, that is, a batch-type reaction kettle, the melt is kept in a molten state (that is, high temperature and high pressure) after the reaction is completed. Since the material is transferred from the polymerization reaction apparatus to the extruder and then subjected to extrusion molding, the production facility becomes complicated and the operation becomes complicated, and the productivity decreases. In addition, even when melt polymerization and extrusion molding are continuously performed using a kneading apparatus conventionally used at the time of molding, such as an extruder or a melt kneader, and an apparatus equipped with a heating mechanism, a long residence time cannot be obtained. Therefore, only the polyarylene fide resin having a low melt viscosity and a low degree of polymerization could be obtained. However, when melt polymerization and extrusion molding are performed continuously, the conventional apparatus cannot avoid increasing the size of the production facility in order to increase the residence time, which increases the apparatus cost and reduces the productivity. there were. In addition, the polyarylene sulfide resin having a low melt viscosity has a problem that a large amount of gas components are generated during the molding process, resulting in a deterioration of the working environment due to odor problems and a decrease in maintainability due to mold contamination.

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 produce a polyarylene sulfide resin having a high molecular weight and a low generated gas with high productivity using oligoarylene sulfide purified and removed as a by-product in the polymerization process of the polyarylene sulfide resin. It is to provide a method.

  As a result of various investigations, the inventors of the present invention have supplied oligoarylene sulfide purified and removed in the polymerization process of polyarylene sulfide resin to a melt-kneading apparatus equipped with a circulation line in a non-oxidizing atmosphere and circulated it. The present inventors have found that a high molecular weight polyarylene sulfide resin can be produced by performing melt kneading while performing melt polymerization to a high degree of polymerization, and thus the present invention has been solved.

  That is, the present invention provides a polyarylene sulfide resin characterized in that oligoarylene sulfide is supplied to a melt kneader equipped with a circulation line, melt kneaded while circulating in a non-oxidizing atmosphere, and melt polymerized. It relates to the manufacturing method.

  ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing polyarylene sulfide resin with high molecular weight and few generated gas can be provided using the oligo arylene sulfide refine | purified and removed as a by-product in the polymerization process of polyarylene sulfide resin.

It is typical sectional drawing which shows schematic structure of the melt-kneading apparatus which concerns on embodiment of this invention.

  The method for producing a polyarylene sulfide resin of the present invention is characterized in that oligoarylene sulfide is supplied to a melt-kneading apparatus equipped with a circulation line, melt-kneaded while circulating in a non-oxidizing atmosphere, and melt-polymerized. And

Details will be described below.
The oligoarylene sulfide (1) used in the present invention, for example, can be produced by 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 an oligoarylene sulfide (1). After obtaining a crude reaction mixture containing the compound (2) represented by the following structural formula (1), the organic polar solvent (3), the polyarylene sulfide (4) and the alkali metal halide (5), the crude reaction The mixture was washed with an organic polar solvent (6) to separate and remove the polyarylene sulfide (4) and the alkali metal halide (5), and the oligoarylene sulfide (1), the compound (2) and the organic polar solvent ( A step (1) of obtaining a reaction mixture (a1) comprising 3).

  First, in the step (1), at least a polyhaloaromatic compound and an alkali metal sulfide are reacted in an organic polar solvent to obtain an oligoarylene sulfide (1), a compound represented by the structural formula (1). (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 Oligoarylene sulfide (1), compound (2) represented by the following structural formula (1), organic polar solvent (3), polyarylene sulfide (4) by reacting with metal hydrosulfide and alkali metal hydroxide 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 form an oligoarylene sulfide (1), a carboxyalkylamino group-containing compound (2), an organic polar solvent (3), A crude reaction mixture containing arylene sulfide (4) and alkali metal halide (5) is obtained, or oligoarylene sulfide, polyhaloaromatic compound, alkali metal hydrosulfide and alkali metal hydroxide are reacted to form an oligo The form which obtains the crude reaction mixture containing the arylene sulfide (1), the carboxyalkylamino group-containing compound (2), the organic polar solvent (3), the polyarylene sulfide (4) and the 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). Then, the method of producing the reaction mixture (a1) containing the oligoarylene sulfide (1), the carboxyalkylamino group-containing compound (2), the organic polar solvent (3) and (6) is included as the step (1b).

  The polyarylene sulfide (4) and the alkali metal halide (5) are separated and removed from the crude reaction mixture, and the oligoarylene sulfide (1), the carboxyalkylamino group-containing compound (2) and the organic polar solvent (3) are contained. 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 to contain oligoarylene sulfide (1) and carboxyalkylamino group Can be obtained object (2) and an organic polar solvent (3 and 6) the reaction mixture containing the (a1) as the filtrate component.

  As such an organic polar solvent (6), a solvent in which the oligoarylene sulfide (1) is dissolved in the environment where the oligoarylene sulfide (1) is dissolved but the polyarylene sulfide resin (4) is difficult to dissolve is preferable. 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 (1) and the carboxyalkylamino group-containing compound (2) 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), a step of separating the oligo arylene sulfide (1) carboxyalkyl amino group-containing compound (2).

In step (3), separation of oligo arylene sulfide and (1) carboxyalkyl amino group-containing compound (2) does not have to be completely, for example, the reaction mixture (a2), optionally A method of contacting the alkylamino group-containing compound (2) with a solvent in which the oligoarylene sulfide (1) does not dissolve or hardly dissolves after washing with water under conditions in the range of 20 to 100 ° C. as a pretreatment. Is mentioned.

In step (3) Rinsing with water as a pretreatment carried out according to the above need, for example, a method of filtering using the filtration device after stirring water was added to the reaction mixture (a2), obtained by filtration and the A method of adding water again to a filtration residue containing water (hereinafter abbreviated as “water-containing cake”) to make a slurry and then filtering, or filtering by adding water again while the water-containing cake is held in a filter And the like.
A method of bringing the amino group-containing compound (2) into contact with a dissolving solvent can be mentioned.

  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 (1). 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.

In step (3), the reaction mixture containing the oligo arylene sulfide (1) carboxyalkyl amino group-containing compound (2) (a2) is, after the water washing treatment if necessary, oligo arylene sulfide (1) Although not dissolved or difficult to dissolve, the alkylamino group-containing compound (2) is brought into contact with a dissolving solvent.

  Specific examples of the solvent in which the oligoarylene sulfide (1) is insoluble or difficult to dissolve, but the alkylamino group-containing compound (2) dissolves include undesirable side reactions such as decomposition and crosslinking of the oligoarylene sulfide (1). Although it is not particularly limited as long as it does not cause substantially, for example, alcohol, phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, Hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, and cyclopentane, and ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl butyl ketone, and acetophenone Examples include organic solvents such as solvents, carboxylic acid ester solvents such as methyl acetate, ethyl acetate, pentyl acetate, octyl acetate, methyl butyrate, ethyl butyrate, pentyl butyrate, methyl salicylate, ethyl formate, and water. But methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, pentane, hexane, heptane, octane, cyclohexane, cyclopentane, acetone, methyl acetate, ethyl acetate are preferred, methanol, ethanol, propanol, ethylene glycol, Pentane, hexane, heptane, octane, cyclohexane, acetone, ethyl acetate, and water are particularly preferable. These organic solvents can be used as one kind or a mixture of two or more kinds.

  In the step (3), the pressure condition can be normal pressure or pressurized condition. When pressurizing, in order to promote the dissolution of the compound (1) in the solvent while exhibiting an excellent predetermined purification effect, it may be carried out at 0.02 to 0.1 [MPa] (gauge pressure). preferable. 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.

  In step (3), the temperature at which the oligoarylene sulfide (1), the carboxyalkylamino group-containing compound (2) and the solvent are brought into contact with each other is not particularly limited as long as the effects of the present invention are not impaired. Although it should just be the range of 20 degreeC or more, the solubility to the water of a carboxyalkylamino group containing compound (2) becomes more remarkable, and isolation | separation of a carboxyalkylamino group containing compound (2) and an oligo arylene sulfide (1) is more efficient. Therefore, the pressure is higher than 100 ° C., preferably 120 ° C. or higher, more preferably 140 ° C. or higher under pressure. 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.

  In particular, in the step (3), when the carboxyalkylamino group-containing compound (1), the oligoarylene sulfide and water are brought into contact with each other under pressure, an acid or a base is added to adjust the pH to 6 or more, preferably 6. It is preferable to control the solubility of the compound (1) in water and the like by adjusting to a range of 5 to 11.5. 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 (2) is the base. Since it is converted into a sex type terminal (Na type terminal), the solubility of the carboxyalkylamino group-containing compound (2) in water is further enhanced, 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.

  In the step (3), water molecules are also present as liquids in the amount of the solvent used when the oligoarylene sulfide (1), the carboxyalkylamino group-containing compound (2) and the solvent are brought into contact with each other under pressure. There is no particular limitation as long as it is an amount. If the pressure of the solvent in the closed system reaches the saturated vapor pressure at that temperature under the pressurized condition, the solvent exists as a liquid. In the present invention, the carboxyalkylamino group-containing compound (2) In order to be efficiently soluble in the solvent, the range of 100 to 1000 parts by mass is preferable with respect to 100 parts by mass of the carboxyalkylamino group-containing compound (2), and more preferably in the range of 100 to 1000 parts by mass. A range of ˜800 parts by mass is more preferable.

  In the present invention, the contact of the carboxyalkylamino group-containing compound (2), the oligoarylene sulfide and water under a pressurized condition may be performed continuously, or may be performed batchwise.

  In the present invention, the container used when contacting the oligoarylene sulfide (1), the carboxyalkylamino group-containing compound (2) and the solvent under pressure can dissolve the compound (2) 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 step (3), oligo arylene sulfide (1) and said carboxyalkyl amino group-containing compound the reaction mixture containing (2) (a2) is, after the water washing treatment if necessary, oligo arylene sulfide (1) Is not soluble or difficult to dissolve, but the alkylamino group-containing compound (2) is brought into contact with a solvent to be dissolved, and then filtered as necessary, and ion-exchanged water is added and filtered again in the range of 20 to 90 ° C. Then, the carboxyalkylamino group-containing compound (2) converted to the basic type terminal (Na type terminal) is separated as a liquid layer, and the oligoarylene sulfide (1) is recovered as a solid content. However, including the way the reaction mixture solids obtained by solid-liquid separation from the (a2) oligo arylene sulfide (1) a high concentration. The solid-liquid separation operation is performed once or a plurality of times, and is preferably a composition (α) containing 0.0040 to 40% by mass of the carboxyalkylamino group-containing compound (1) and 100.00 to 60% by mass of the oligoarylene sulfide. Is preferably carried out until the composition (α) contains 0.01 to 20% by mass of the carboxyalkylamino group-containing compound (1) and 99.99 to 80% by mass of the oligoarylene sulfide.
When the carboxyalkylamino group-containing compound (1) in the composition (α) is in the range of 20% by mass or less, the reactivity during the melt polymerization of the polyarylene sulfide resin is improved, while 0.01% by mass or less. If it is in the range, it is preferable because excessive solid-liquid separation is unnecessary and productivity is improved.

  The recovered composition (α) containing the oligoarylene sulfide (1) at a high concentration may be dried as it is to obtain a powder, or further washed with water several times, followed by solid-liquid separation. It may be dried to obtain a powder. 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 (1), the following structural formula (2)

（ただし、式中、Ａｒはアリーレン構造を表し、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）

(In the formula, Ar represents an arylene structure, and m = 2 to 50, preferably 4 to 13.) The cyclic polyarylene sulfide (2a) represented by 50% by mass or more, preferably 70% by mass. % Or more, more preferably 80% by mass or more and 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.

-Manufacturing method of PAS This invention melt-polymerizes using what was obtained as a composition ((alpha)) containing oligo arylene sulfide (1) as a raw material through the said process (1)-(3). Thus, a polyarylene sulfide resin can be produced.

  In the present invention, melt polymerization is supplied to a melt-kneading apparatus equipped with a circulation line, and melt-kneading is performed while circulating in a non-oxidizing atmosphere, and the oligo-arylene sulfide is melted at a temperature equal to or higher than the melting point of the oligo-arylene sulfide. However, since the possibility of the thermal deterioration of the oligoarylene sulfide increases, it is preferable to carry out at a melting point plus 100 ° C. 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).

The melting time may be determined by plotting the relationship between the melting time and the melt viscosity of the resin in a preliminary experiment or the like and appropriately adjusting the melt viscosity to be within a predetermined range.
The melt kneading apparatus used in the present invention is not particularly limited as long as the melt kneading apparatus includes a circulation line and can perform melt polymerization while circulating the melt kneaded product. It is preferable to have a circulation line that can be transferred to.

  A method for producing a polyarylene sulfide resin using the melt kneader used in the present invention will be specifically described with reference to the drawings.

  The weighed composition (α) containing the oligoarylene sulfide (1) is charged from the charging port 1 and supplied to the melt kneader 2. The composition (α) containing the supplied oligoarylene sulfide (1) has a flight 3 for propelling the raw material installed in the melt kneader 2, and the flight 3 is engaged with each other in a biaxial manner. A kneaded product (melt polymer) is obtained by kneading with the screw 4. The kneaded product (melt polymer) is supplied to the melt kneader 2 through the circulation line 5 from the supply port 6 and circulated. At that time, the melt-kneaded material is once discharged from the discharge port 7 sent in the screw front end direction, and then supplied to the melt kneader 2 through the circulation line 5 and from the supply port 6 that can move again in the rear end direction. preferable. At the start of melt kneading, it is preferable that the valve 11 installed at the supply port 6 is closed and the circulation line 5 is filled with the kneaded material and then opened after being circulated. After the melt-kneading, the obtained molten polymer passes through the discharge port 7, passes through the discharge line 8, and is discharged through a discharge nozzle (not shown) or a die head.

  Here, the melt kneader 2 used in the present invention may be either a single screw type or a twin screw type. The melt kneader 2 preferably has a rotation speed of 25 to 300 rpm and an extrusion rate of 1 to 100 kg / hr. The melt-kneading apparatus used in the present invention is provided with a circulation line 5 in the melt-kneader 2 and circulates the kneaded material through this line to lengthen the residence time and sufficiently advance the melt polymerization reaction. It is. The residence time at this time may be appropriately adjusted as described above, but is in the range of 5 to 120 minutes, and a gear pump (not shown) provided in the circulation line 5 so that the residence time is within this range. What is necessary is just to set capacity, the pipe diameter of a circulation line, etc.

  As described above, the present invention advances the kneading and reaction while circulating the kneaded product (melt polymer), so that not only can the melt polymerization reaction be controlled easily, but also an apparatus of the same scale as the normally used melt polymerization apparatus. Thus, a polyarylene sulfide resin having a high molecular weight and a small amount of generated gas can be produced with high productivity.

  In the present invention, the melt polymerization is performed in a non-oxidizing atmosphere from the viewpoint of preventing a oxidative crosslinking reaction and obtaining a high degree of polymerization. In the present invention, the non-oxidizing atmosphere means an atmosphere having a gas phase oxygen concentration of less than 5% by volume, preferably less than 2% by volume, more preferably substantially free of oxygen, that is, nitrogen, helium, argon, etc. Indicates an inert gas atmosphere.

  In the present invention, the melt polymerization is preferably performed under a condition that does not substantially contain a solvent. The condition that the solvent is not substantially contained is that the solvent is 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 100 parts by mass of the composition (α) containing the oligoarylene sulfide (1). 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 the present invention, 50 parts by mass or less, preferably 0 to 50 parts by mass, more preferably 0 to 10 parts by mass with respect to 100 parts by mass of the composition (α) containing oligoarylene sulfide (1) as a raw material for melt polymerization. The heat treatment can be performed under the condition containing the polyarylene sulfide resin (β) within the range of.

  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 polyarylene sulfide resin of the present invention obtained by melt polymerization using the melt kneading apparatus can be directly fed directly to a melt kneader for producing a resin composition. Adding a solvent that dissolves the reaction product to the reaction product to prepare a solution, and taking out the reaction product from the reaction apparatus in the state of the solution does not only improve productivity, but also increases the reactivity. Since it becomes favorable, 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.

  As described above, the production method of the present invention uses a melt kneader equipped with a simple mechanism called a circulation line to easily and easily produce a polyarylene sulfide resin having a high molecular weight and a small amount of generated gas from an oligoarylene sulfide. It can be manufactured with good performance. As a result, it is possible to prevent an increase in the size of production equipment and complexity of operation, and not only improve the odor problem at the time of molding, but also prevent mold contamination and improve maintainability.

-Polyarylene sulfide resin The physical properties of the polyarylene sulfide resin obtained by the production method of the present invention such as melt viscosity, non-Newton's index, mass average molecular weight, and spread of molecular weight distribution are not particularly specified, but preferably Is as follows.
(Melt viscosity)
The melt viscosity (V6) measured at 300 ° C. is preferably in the range of 5 to 1,000 [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.

(Non-Newtonian index)
The non-Newtonian index is preferably in the range of 0.90 to 1.25, more preferably in the range of 0.95 to 1.15, and further in the range of 0.95 to 1.10. More preferred. Such a 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 mathematical formula (I).

［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.

(Mass average molecular weight)
The mass average molecular weight is preferably in the range of 10,000 to 1,000,000, more preferably in the range of 20,000 to 500,000, and most preferably in the range of 40,000 to 100,000.

(Expansion of molecular weight distribution)
The spread of the molecular weight distribution, that is, the ratio of the weight average molecular weight to the number average molecular weight (mass average molecular weight / number average molecular weight) is preferably 2.5 or more, and more preferably 3.0 or more.

  Furthermore, the polyarylene sulfide resin obtained by the production method of the present invention is a mold release agent, a colorant, a heat stabilizer, and an ultraviolet light stabilizer as long as they do 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.

  In addition, the polyarylene sulfide resin obtained by the production method of the present invention has a high degree of polymerization and is not only excellent in mechanical strength due to its high molecular weight, but also has an epoxy silane coupling agent and a functional group-containing thermoplastic. Excellent reactivity with impact modifiers such as elastomers, and similar to conventional polyarylene sulfide resins, heat resistance and molding by various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding. Molded products with excellent processability and dimensional stability can be obtained. For example, electrical and electronic parts such as connectors, printed circuit boards, and sealing molded products, automotive parts such as lamp reflectors and various electrical components, and various buildings Injection molding / compression molding products such as interior materials such as aircraft and automobiles, precision parts such as OA equipment parts, camera parts and watch parts, Rui is widely available as an extrusion molding, pultrusion molded articles such as fibers, film, sheet pipe.

  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 mass reduction rate 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 mass at 320 ° C. based on the sample mass at 100 ° C. The mass reduction rate was calculated. A lower mass reduction rate (%) during heating indicates that the generated gas is suppressed.

(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) is 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. It calculated using Formula (I).

[Production Example 1]
(Production of polyphenylene sulfide resin containing oligophenylene sulfide)
In an autoclave equipped with a stirring blade to which a pressure gauge, a thermometer, and a condenser are connected, 1294.2 parts by mass of flaky sodium sulfide (60.3% by mass Na ₂ S) and N-methyl-2-pyrrolidone (NMP) 3000.0 The mass part was charged. While stirring under a nitrogen stream, the temperature was raised to 209 ° C. to distill 309.6 parts by mass of water (the amount of water remaining was 11.3 mol per mol of sodium sulfide). Thereafter, the autoclave was sealed and cooled to 180 ° C., and 1479.0 parts by mass of paradichlorobenzene (p-DCB) and 1200.0 parts by mass 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 18.9 parts by mass of oxalic acid dihydrate in NMP6630 parts by mass was injected under pressure, stirred for 30 minutes, and then cooled.

  The total amount of the resulting reaction slurry was filtered at 120 ° C., 3200 parts by mass of NMP was added, and the cake was washed and filtered. The amount of NMP filtrate was 5360 parts by mass. 10000 parts by mass of ion exchanged water at 70 ° C. was added to the total amount of the NMP-containing cake thus obtained and stirred for 10 minutes, followed by filtration. The cake after washing was added with 10000 parts by mass of ion exchanged water at 70 ° C. To the obtained water-containing cake, 10000 parts by mass of ion-exchanged water was added and stirred for 10 minutes, followed by filtration. To the cake after filtration, 10000 parts by mass of ion-exchanged water at 70 ° C. was added to perform cake washing. After repeating this operation once more, it was dried at 120 ° C. for 4 hours to obtain a PPS resin having a melt viscosity (V6) of 63 Pa · s and a yield of 969 parts by mass.

(Recovery of reaction mixture containing oligophenylene sulfide and CP-MABA)
5360 parts by mass 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 183.5 parts by mass of a brown solid residue. The mass of this residue after drying for 1 hour in a 150 ° C. vacuum dryer was 75.2 parts by mass (including 50.9 parts by mass of oligophenylene sulfide and 24.320 parts by mass of Na-type CP-MABA). The nonvolatile content was 41.0 wt%. 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 mass 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)
183.5 parts by mass of the solid residue obtained in Production Example 1 and 1000 parts by mass of ion-exchanged water were charged into an autoclave, and the pH was adjusted to 10.6 by adding a 48% NaOH aqueous solution, followed by stirring at 180 ° C. for 60 minutes. Went. After cooling to room temperature, filtration was performed, and cake washing was performed by adding 1000 parts by mass of ion-exchanged water at 70 ° C. to the cake after filtration. The pH of the filtrate was 10.0, the amount of Na-type CP-MABA in the filtrate was 24.315 parts by mass, 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 powdery mixture (A-1) containing 50.9 parts by mass of oligophenylene sulfide and 0.005 parts by mass of CP-MABA was obtained. It was. The melting point of the powdery mixture (A-1) was Tm204 ° C.

[Example 1]
(Production of PPS resin by melt polymerization)
The PPS resin was produced using a melt-kneading apparatus (“compounder 15” manufactured by DSM Explore) shown in FIG. The powdery mixture (A-1) was weighed and charged into a melt-kneading apparatus filled with a nitrogen atmosphere from the charging port (1). Thereafter, the mixture was melt-kneaded in a nitrogen atmosphere at a kneading temperature of 320 ° C. and a rotation speed of 250 rpm, and the melt-kneaded material was retained for 1 hour while circulating through the circulation line (5). After the melt-kneading, the melt-kneaded product was extruded into a strand shape from the discharge nozzle via the discharge port (7) and the discharge line (9). The obtained strand was cooled to room temperature (23 degreeC), and PPS resin (1) was obtained. The obtained PPS resin (1) had a melting point Tm of 282 (° C.), a melt viscosity V6 of 580 (Pa · s), a non-Newtonian index of 1.23, and a heating mass reduction rate (%) of 0.05%. there were.

[Reference Example 2]
(Separation of CP-MABA)
183.5 parts by mass of the solid residue obtained in Production Example 1, 1000 parts by mass of chloroform, and 1000 parts by mass of ion-exchanged water were charged into an autoclave, and a 48% NaOH aqueous solution was added to adjust the aqueous phase to pH 13. After the chloroform was distilled off under reduced pressure from the chloroform phase from which the oligophenylene sulfide was extracted, 100 parts by mass of chloroform was again added to the solid residue and dissolved at room temperature. This was slowly added dropwise to 1000 parts by mass of methanol with stirring, and the precipitate was filtered. The obtained cake was dried with a 60 ° C. vacuum dryer for 1 hour, and then 50.9 parts by mass of white powdery oligophenylene sulfide (A-2) was obtained. The amount of Na-type CP-MABA in the aqueous phase was 24.320 parts by mass, and the extraction rate was 100%. The melting point of the powdery product (A-2) was Tm204 ° C.

[Example 2]
(Production of PPS resin by melt polymerization)
PPS resin (2) was obtained in the same manner as in Example 1 except that the powdered product (A-2) was used instead of the powdery mixture (A-1). The obtained PPS resin (2) had a melting point Tm of 281 (° C.), a melt viscosity V6 of 600 (Pa · s), a non-Newtonian index of 1.23, and a mass reduction rate upon heating of 0.05 (%). It was.

[Comparative Example 1]
The powder mixture (A-1) is melt-kneaded using a twin-screw kneading extruder (laboro plast mill manufactured by Toyo Seiki Seisakusho) at a nitrogen component atmosphere, a resin component discharge rate of 20 g / min, a screw rotation speed of 120 rpm, and a set temperature of 320 ° C The resulting liquid was cooled to room temperature (23 ° C.) to obtain a solid (3). The obtained solid (3) remained an oligophenylene sulfide having a melting point Tm of 204 (° C.).

[Comparative Example 2]
Instead of the powdery mixture (A-1), the same operation as in Comparative Example 1 was performed except that the powdery product (A-2) was used to obtain a solid (4). The obtained solid (6) remained an oligophenylene sulfide having a melting point Tm of 204 (° C.).

DESCRIPTION OF SYMBOLS 1 Input port 2 Melt kneader 3 Flight 4 Screw 5 Circulation line 6 Supply port 7 Discharge port 8 Discharge line 9 Motor 10 Valve 11 Valve

Claims (10)

Supplying the oligoarylene sulfide (1) to a melt-kneading apparatus equipped with a circulation line, performing melt-kneading while circulating in a non-oxidizing atmosphere, and performing melt polymerization;
The oligoarylene sulfide (1) has the 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;
The oligoarylene sulfide (1) is an oligoarylene sulfide purified and removed in the polymerization step of the polyarylene sulfide resin;
A process for producing a polyarylene sulfide resin characterized by The melt kneading apparatus, a manufacturing method of claim 1 Symbol placement of polyarylene sulfide resin is obtained with a circulation line that can migrate to the melt kneaded product again rear direction of the material sent to the screw tip direction. The method for producing a polyarylene sulfide resin according to claim 1 or 2 , wherein the polyarylene sulfide resin obtained by the production method has a non-Newtonian index in the range of 0.90 to 1.25. 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 polyarylene sulfide resin according to any one of claims 1 to 3 , wherein a measured value after being held for 6 minutes using an orifice of 10/1 is in a range of 5 to 1,000 [Pa · s]. Manufacturing method. In addition to the oligoarylene sulfide (1), 0.01-20 parts by mass of the compound (2) represented by the following structural formula (1 ′) and 99.99-80 parts by mass of the oligoarylene sulfide (1) are circulated. The method for producing a polyarylene sulfide resin according to any one of claims 1 to 4, wherein the polyarylene sulfide resin is supplied to a melt kneader equipped with a line, melt kneaded while circulating in a non-oxidizing atmosphere, and melt polymerized.

(In the formula, X represents a hydrogen atom or an alkali metal atom.)   In addition to the oligoarylene sulfide (1) and the compound (2), the polyarylene sulfide resin in a ratio of 50 parts by mass or less with respect to 100 parts by mass of the total of the oligoarylene sulfide (1) and the compound (2). The method for producing a polyarylene sulfide resin according to claim 5, wherein the melt polymerization is carried out under conditions including The oligoarylene sulfide (1) and the compound (2) are prepared by removing the reaction mixture purified and removed in the polyarylene sulfide resin polymerization step by using an alcohol / phenol solvent, a hydrocarbon solvent, a ketone solvent, a carboxylic acid ester system. at least one contact is allowed method for producing a polyarylene sulfide resin obtained are those according to claim 5 or 6 Symbol mounting and selected from the solvents and the group consisting of water. The oligoarylene sulfide (1) and the compound (2) are:
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 an oligoarylene sulfide (1). After obtaining a crude reaction mixture containing the compound (2), organic polar solvent (3), polyarylene sulfide (4) and alkali metal halide (5), the crude reaction mixture was treated with the organic polar solvent (6). Washing to separate and remove the polyarylene sulfide (4) and the alkali metal halide (5), the reaction mixture (a1) containing the oligoarylene sulfide (1), the compound (2) and the organic polar solvent (3) (1) to obtain
A step (2) of solid-liquid separation of the organic polar solvent from the reaction mixture (a1) to obtain a reaction mixture (a2) containing the oligoarylene sulfide (1) and the compound (2);
By contacting the reaction mixture (a2) with at least one selected from the group consisting of an alcohol / phenol solvent, a hydrocarbon solvent, a ketone solvent, a carboxylic acid ester solvent and water, the oligoarylene sulfide (1) and Separating the compound (2) (3),
The method for producing a polyarylene sulfide resin according to any one of claims 5 to 7, which is obtained by the step (4) of recovering the separated oligoarylene sulfide (1). It said alcohol phenol based solvents, hydrocarbon solvents, ketone solvents, at least one selected from the group consisting of carboxylic acid ester solvent and water, according to claim 7, which is 100 ° C. or more and pH6 more water A method for producing a polyarylene sulfide resin. Method for producing a polyarylene sulfide resin of the solid-liquid in the step (2) separating the mounting serial to claim 8 in which the polar organic solvent separated is removed by flushing.

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