JPWO2019004169A1 - Method for producing polyarylene sulfide resin - Google Patents

Abstract

In the method for producing a polyarylene sulfide resin in which a dihaloaromatic compound and a sulfidizing agent are polymerized in the presence of an aliphatic cyclic compound which can be opened by hydrolysis, the corrosion of the production apparatus is suppressed, and Provided is a method for reducing the content of metal atoms derived from a production apparatus in an arylene sulfide resin. More specifically, a dehydration step of reacting a sulfidizing agent containing water with an aliphatic cyclic compound capable of being opened by hydrolysis in the presence of a dihaloaromatic compound while dehydrating under reduced pressure to obtain a mixture ( The present invention provides a method for producing a polyarylene sulfide resin, which has the feature (1).

Description

  The present invention relates to a highly efficient method for producing a linear high molecular weight polyarylene sulfide resin.

  Polyarylene sulfide resin (hereinafter sometimes abbreviated as “PAS resin”) represented by polyphenylene sulfide resin (hereinafter sometimes abbreviated as “PPS resin”) has heat resistance, It has excellent chemical resistance and is widely used for electric and electronic parts, automobile parts, water heater parts, textiles, films and the like.

  As a method for producing a polyarylene sulfide resin, for example, a hydrated alkali metal sulfide or less than 1 mole of N-methylpyrrolidone per mole of the hydrated alkali metal sulfide, and a polyhalo aromatic compound are mixed, and the mixture is azeotropically mixed. A method is known in which a slurry containing fine anhydrous alkali metal sulfide is obtained by dehydration and then heated to cause a polymerization reaction (for example, see Patent Documents 1 and 2). The method is capable of efficiently producing a high-molecular-weight polyarylene sulfide resin by performing a polymerization reaction after removing a small amount of water such as crystal water remaining in a reaction system that induces a side reaction. However, since it is necessary to dehydrate a highly basic sulfidizing agent at a high temperature, the contact parts with the raw materials in a reaction device such as a reaction vessel easily corrode, and therefore, metals such as titanium and zirconium which are resistant to corrosion. Members had to be used. However, it has nevertheless been known that the metal member corrodes and promotes the consumption of the metal member. For this reason, a method for producing a polyarylene sulfide resin that suppresses consumption of the metal member has been required.

  Furthermore, the obtained polyarylene sulfide resin contains metal atoms derived from the metal member eluted due to consumption of the metal member of the contact portion, but it is difficult to remove these metal atoms by a normal cleaning operation. there were. In particular, in recent years, the thickness of molded articles using polyarylene sulfide resin has been reduced, and polyarylene sulfide resin of higher quality than ever has been demanded. Metals derived from a reaction device in polyarylene sulfide resin have been demanded. Reduction of the atomic content has been an urgent issue.

JP-A-8-231723 WO2010 / 058713 pamphlet

  Therefore, an object of the present invention is to provide a method for producing a polyarylene sulfide resin in which a dihalo aromatic compound and a sulfidizing agent are polymerized in the presence of an aliphatic cyclic compound that can be opened by hydrolysis. Another object of the present invention is to provide a method for suppressing corrosion of a production apparatus and reducing the content of metal atoms derived from the production apparatus in the obtained polyarylene sulfide resin.

  The present inventors have made intensive efforts to solve the above-mentioned problems, and as a result, in the presence of a dihalo aromatic compound, dehydrate a sulfidizing agent containing water and an aliphatic cyclic compound which can be opened by hydrolysis. In this case, the operation is performed under reduced pressure, compared with the conventional case, that is, compared with the case where the operation is performed under atmospheric pressure, the corrosion of the contact portion can be reduced, and the production apparatus in the obtained polyarylene sulfide resin The present inventors have found that the content of metal atoms derived can be reduced, and have completed the present invention.

That is, the present invention is a method for producing a polyarylene sulfide resin in which a dihalo aromatic compound and a sulfidizing agent are polymerized in the presence of an aliphatic cyclic compound that can be opened by hydrolysis.
A dehydration step (1) of reacting a sulfidizing agent containing water with an aliphatic cyclic compound capable of being opened by hydrolysis in the presence of a dihaloaromatic compound while dehydrating under reduced pressure to obtain a mixture; And a method for producing a polyarylene sulfide resin.

  Further, the present invention provides a step of producing a polyarylene sulfide resin by the above-mentioned production method, the obtained polyarylene sulfide resin, a filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and two or more functional groups. Having a step of blending with at least one other component selected from the group consisting of a crosslinkable resin having a silane coupling agent, and heating to a melting point or higher of the polyarylene sulfide resin and melting and kneading the mixture. And a method for producing a polyarylene sulfide resin composition.

  Further, the present invention comprises a step of producing a polyarylene sulfide resin composition by the above-mentioned production method, and a step of melt-molding the obtained polyarylene sulfide resin composition, wherein the molded article is a polyarylene sulfide resin molded article. And a method for producing the same.

  In the presence of an aliphatic cyclic compound that can be opened by hydrolysis according to the present invention, a dihalo-aromatic compound and a method for producing a polyarylene sulfide resin that undergoes a polymerization reaction with a sulfidizing agent suppress corrosion of the production apparatus, It is possible to provide a method for reducing the content of metal atoms derived from a production apparatus in the obtained polyarylene sulfide resin.

The method for producing a polyarylene sulfide resin of the present invention includes:
A method for producing a polyarylene sulfide resin in which a dihaloaromatic compound is reacted with a sulfidizing agent in the presence of an aliphatic cyclic compound that can be opened by hydrolysis, comprising: A dehydration step of obtaining a mixture by reacting a sulfidizing agent containing a compound and an aliphatic cyclic compound that can be opened by hydrolysis under reduced pressure while dehydrating. The details will be described below.

・ Dehydration process (1)
The present invention provides a dehydration step in which, in the presence of a dihalo aromatic compound, a sulfidizing agent containing water and an aliphatic cyclic compound capable of being opened by hydrolysis are reacted under reduced pressure while dehydrating to obtain a mixture. (1) is essential.

  The dehydration step (1) is a step of reacting a sulfidizing agent containing water with an aliphatic cyclic compound that can be opened by hydrolysis in the presence of a dihaloaromatic compound while dehydrating. By this step, while effectively removing the amount of water present in the reaction system to the outside, the hydrolysis of the aliphatic cyclic compound is promoted, and at least the anhydrous sulfidizing agent and the aliphatic cyclic compound This is a step of forming a mixture containing an alkali metal salt of a hydrolyzate. In the present invention, by performing the dehydration under reduced pressure, the corrosion at the contact portion with the raw material or the mixture of the reaction apparatus can be reduced as compared with the case where the dehydration is performed under a pressure condition higher than the atmospheric pressure, and the obtained poly is obtained. The content of metal atoms derived from the contact portion in the arylene sulfide resin can be reduced.

  The dihalo-aromatic compound used in the present invention acts as a solvent for maintaining the fluidity of the obtained mixture in the dehydration step (1), but can be used as a polymerization raw material in the subsequent polymerization step. Examples of the dihalo aromatic compound used in the present invention include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p , P'-dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenyl sulfone, 4,4'-dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfide and the above Compounds having, as a nuclear substituent, an alkyl group having 1 to 18 carbon atoms in the aromatic ring of each compound.In addition, the halogen atom contained in each of the above compounds is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

  Among the dihalo-aromatic compounds, when efficiently producing a linear polyarylene sulfide resin, p-dichlorobenzene is particularly preferred in that the finally obtained polyarylene sulfide resin has good mechanical strength and good moldability. , M-dichlorobenzene, 4,4'-dichlorobenzophenone and 4,4'-dichlorodiphenylsulfone are preferred, and p-dichlorobenzene is particularly preferred.

  When it is desired to have a branched structure in a part of the polymer structure of the linear polyarylene sulfide resin, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene is added together with the dihaloaromatic compound. , 1,3,5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, or 1,4,6-trihalonaphthalene may be partially used in combination. preferable. The halogen atom contained in each of the above compounds is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. When used together, it is preferable to use the compound in an amount of 0.001 mol or more to 3 mol or less with respect to 100 mol of the dihalo aromatic compound while paying attention to gelation.

  In the dehydration step (1), the amount of the dihalo aromatic compound to be added is preferably from 0.2 mol or more, more preferably from 0.3 mol or more, and preferably from 5. mol to 1 mol of the sulfur atom of the sulfidizing agent. The range is 0 mol or less, more preferably 2.0 mol or less. When it is 0.2 mol or more, it is preferable from the viewpoint of securing the fluidity of the mixture, and when it is 5.0 mol or less, it is preferable from the viewpoint that the total amount of heat required for heating can be suppressed and the productivity is excellent.

  Examples of the sulfidizing agent used in the present invention include alkali metal sulfides, or alkali metal hydrosulfides and alkali metal hydroxides. Generally, an alkali metal sulfide or an alkali metal hydrosulfide is used as a raw material of a polyarylene sulfide resin as a so-called hydrate containing water of crystallization. In this case, the solid content concentration is preferably 10% by mass. A liquid or solid hydrate having a range of 35% by mass or more, preferably 80% by mass or less, more preferably 65% by mass or less is used.

  Examples of the alkali metal sulfide used in the present invention include compounds such as lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide. These may be used alone or in combination of two or more. Among these alkali metal sulfides, sodium sulfide and potassium sulfide are preferable, and sodium sulfide is particularly preferable.

  The alkali metal sulfide can also be obtained by reacting an alkali metal hydrosulfide with an alkali metal hydroxide. Alternatively, an alkali metal sulfide prepared in the same reaction system as in the dehydration step (1) can be used. It does not matter whether or not one prepared in advance in a reaction system different from the dehydration step (1) may be used. Specific examples of the alkali metal hydroxide include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Of these, lithium hydroxide, sodium hydroxide and potassium hydroxide are particularly preferred, and sodium hydroxide is particularly preferred. The alkali metal hydroxide is preferably used as an aqueous solution, and its concentration is preferably in the range of 10% by mass to 50% by mass. Examples of the alkali metal hydrosulfide used in the present invention include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, and cesium hydrosulfide. These may be used alone or in combination of two or more. Among these alkali metal hydrosulfides, sodium bisulfide and potassium bisulfide are preferred, and sodium bisulfide is particularly preferred. Further, an alkali metal hydrosulfide can be obtained by reacting hydrogen sulfide with an alkali metal hydroxide, but one prepared in advance outside the reaction system may be used.

  As the aliphatic cyclic compound used in the present invention, known compounds can be used without particular limitation as long as they can be opened by hydrolysis. Specific examples of such aliphatic cyclic compounds N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, N-methyl-ε-caprolactam, formamide, acetamide, N-methylformamide, N, N Aliphatic amide compounds such as dimethylacetamide, 2-pyrrolidone, ε-caprolactam, hexamethylphosphoramide, tetramethylurea, N-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinonic acid, amide urea , And lactams. Among these, aliphatic cyclic amide compounds, particularly NMP, are preferred from the viewpoint of good reactivity.

  At that time, the amount of the aliphatic cyclic compound to be charged is preferably in the range of 0.01 mol or more to 4.0 mol or less with respect to 1 mol of sulfur atom of the sulfidizing agent. When producing a high-molecular-weight polyarylene sulfide resin, it is preferably in the range of 0.01 or more, preferably 0.9 mol, more preferably 0.1 mol, per mol of sulfur atom of the sulfidizing agent. It is less than 9 moles, more preferably 0.5 mole or less.

  In the dehydration step (1), the dehydration proceeds under reduced pressure. More specifically, in the presence of a dihalo aromatic compound, a sulfidizing agent containing water and an aliphatic cyclic compound that can be opened by hydrolysis are converted to a boiling point of the sulfidizing agent or higher, and The temperature at which the liquid is removed by azeotropic distillation, preferably, the liquid temperature is 90 or higher, more preferably 110 ° C or higher, still more preferably 120 ° C or higher, particularly preferably 130 ° C or higher, and 170 ° C or lower, more preferably 160 ° C or lower. Hereafter, it is still more preferably 150 ° C. or less, particularly preferably while being heated to a range of less than 150 ° C., and the pressure is 30 [kPa abs] or more, preferably 35 [kPa abs] or more, more preferably 40 [kPa abs]. abs] or more, and 80 [kPa abs] or less, preferably 70 [kPa abs] or less, more preferably 60 [kPa abs]. By reducing the pressure to be in a range below include a method comprising a step of performing dehydration. More preferably, in the presence of a dihalo-aromatic compound, a sulfidizing agent containing water and an aliphatic cyclic compound capable of being opened by hydrolysis until the liquid temperature falls within a range from 90 ° C. to 130 ° C. After raising the temperature under the atmospheric pressure, the dehydration is performed at a liquid temperature of preferably higher than 90 ° C, more preferably 110 ° C or higher, more preferably 130 ° C or higher, preferably 170 ° C or lower, more preferably 160 ° C or lower. ° C. or less, more preferably in the range of 150 ° C. or less, and the pressure is preferably 30 [kPa abs] or more, more preferably 35 [kPa abs] or more, more preferably from 40 [kPa abs] or more, 80 kPa abs or less, more preferably 70 kPa abs or less, still more preferably 60 kPa abs or less. How to do while, and the like.

  Further, in the above method, in the presence of a dihaloaromatic compound, a sulfidizing agent containing water and an aliphatic cyclic compound capable of being opened by hydrolysis to form a liquid having a liquid temperature of 90 ° C or more to 130 ° C or less. When raising the temperature under atmospheric pressure until it is, it is also preferable to confirm the gas phase temperature in the reaction vessel, and after the gas phase temperature in the reaction vessel reaches a temperature 10 ° C. lower than the boiling point of water, It is also preferable to start the dehydration operation after reaching a temperature 5 ° C. lower than the boiling point of the water, more preferably after reaching the boiling point of water. In addition, dehydration starts reducing pressure from atmospheric pressure, and after reaching the above pressure range, within a certain range, for example, within a range of ± 10 [kPa abs], preferably within a range of 5 [kPa abs]. , More preferably within the range of 1 [kPa abs]. In the above method, it is preferable that the decompression operation from the atmospheric pressure to the pressure range be performed promptly. Since the pressure gradient at that time varies depending on the volume of the reaction vessel, the total amount of the raw materials, and the like, it cannot be unconditionally specified, but is preferably in the range of -3 [kPa abs / min] or less, more preferably-. 6 [kPa abs / min] or less. On the other hand, the lower limit is not particularly set, but is preferably -60 [kPa abs / min] or more, more preferably -30 [kPa abs / min] or more, from the viewpoint of preventing the equipment from becoming large.

  In the above method, the liquid temperature is adjusted by measuring the liquid temperature and manually controlling the amount of heat input into the reaction system from the heating device so as to be within a predetermined temperature range, or by performing sequence control or feedback control. It is preferable to perform automatic control by a known automatic control method such as feed forward control. Since the control always involves a time lag, a certain temperature range is allowed between the liquid temperature to be controlled and the actual liquid temperature. The temperature range is preferably in the range of ± 10 ° C, more preferably ± 5 ° C, with respect to the temperature to be maintained.

  In the dehydration, while controlling the liquid temperature and the pressure within the above range, a valve (valve) of a pipe leading from the reaction system to the distillation apparatus is opened, and a mixture of an aliphatic cyclic compound, water, and a dihalo aromatic compound is distilled. It is performed by In the distillation, after the aliphatic cyclic compound is isolated, a mixed vapor mainly composed of water and a dihalo aromatic compound is condensed by a condenser, and water and the dihalo aromatic compound are separated by a decanter or the like, and azeotropic distillation is performed. A method of returning the dihaloaromatic compound to the reaction system. The isolated aliphatic cyclic compound, the aliphatic cyclic compound and the dihaloaromatic compound separated from water are preferably returned to the reaction system, but if not returned, the amount corresponds to the amount azeotropically distilled. An additional amount of the aliphatic cyclic compound or dihalo aromatic compound is added, or the amount of the aliphatic cyclic compound or dihalo aromatic compound may be preliminarily charged in consideration of the amount of azeotropic distillation. Good.

  As described above, in the dehydration step (1) of the present invention, the water is discharged out of the reaction system by the dehydration treatment, and the aliphatic cyclic compound that can be opened by hydrolysis is hydrolyzed, and at the same time, the anhydrous sulfidizing agent is dehydrated. , Preferably, a step of producing anhydrous alkali metal sulfide. If excessive water is present in the reaction system after the dehydration treatment, a large amount of by-products are generated in the subsequent polymerization step to induce a growth terminal termination reaction, and to extend the chain length of the polyarylene sulfide resin. As a result, it tends to hinder viscosity increase or increase in molecular weight. Therefore, the total water content in the reaction system after the dehydration step (1) is preferably as small as possible. Specifically, the total water content is preferably 0.1 to 1 mol of the sulfur atom of the sulfidizing agent used in the dehydration step (1). The water content is more than 1 mol, more preferably 0.6 mol or more, preferably 0.99 mol or less, more preferably 0.96 mol or less. Here, "the total amount of water in the reaction system" refers to water consumed in the hydrolysis of the aliphatic cyclic compound, water of crystallization tracely remaining in the sulfidizing agent, and other water present in the reaction system. It is the total mass of all.

Further, after the dehydration step (1), the amount of water present in the reaction system is preferably in a range of 0.4 mol or less per 1 mol of sulfur atom of the sulfidizing agent in the reaction system. The ratio is more preferably in the range from the limit to 0.4 mol or less, and even more preferably in the range from 0.03 mol or more to 0.11 mol or less as a range excellent in dehydration efficiency. Here, “the amount of water existing in the reaction system” refers to water excluding water consumed for hydrolysis of the aliphatic cyclic compound, out of the total water amount in the reaction system, that is, water of crystallization, H ₂ It refers to the total amount of water actually present in the reaction system as O or the like (hereinafter, these are referred to as “crystal water or the like”).

  As described above, according to the present invention, by promoting dehydration under reduced pressure, liberation of water of crystallization in the sulfidizing agent is promoted even at a lower heating temperature, and the reaction system which causes a side reaction in the polymerization step is caused. As the water is efficiently removed, it is also converted into a hydrolyzate of an aliphatic cyclic compound which is considered to exhibit a polymerization promoting action. As a result, with the promotion of the polymerization, a side reaction during the polymerization is caused. Can be suppressed.

・ Dehydration process (2)
The present invention may optionally include a dehydration step (2) in which an aprotic polar organic solvent is further added to the mixture obtained in the dehydration step (1), and water is distilled off to perform dehydration. . In the dehydration step (2), the amount of the aprotic polar solvent charged into the reaction system is preferably in a range of 0.5 mol or more to 5 mol or less per 1 mol of the sulfur atom of the sulfidizing agent. It is preferable to add them. If the amount of water existing in the reaction system is set to a range of less than 0.03 mol with respect to 1 mol of the sulfur atom of the sulfidizing agent, the dehydration efficiency tends to be extremely reduced. Further, by performing the dehydration step (2) further following the dehydration step (1), the amount of water contained in the reaction system at the end of the dehydration step (2) is reduced with respect to 1 mol of sulfur atom of the sulfidizing agent. , Less than 0.03 mol, preferably from the detection limit to less than 0.03 mol, and more preferably from the detection limit to 0.01 mol.

  The dehydration in the dehydration step (2) can be performed under the condition that the liquid temperature is in a range of 90 ° C. or more to 220 ° C. or less and in a range of 30 kPa abs to 202 kPa abs. Among them, the dehydration treatment conditions under the same reduced pressure as in the dehydration step (1), that is, the liquid temperature is preferably 90 ° C or higher, more preferably 110 ° C or higher, still more preferably 130 ° C or higher, and more preferably 160 ° C or lower, more preferably While heating to be in the range of 150 ° C. or less, and preferably 30 kPa abs or more, more preferably 35 kPa abs or more, still more preferably 40 kPa abs or more, and preferably 80 kPa abs or more. abs], preferably 70 [kPa abs] or less, more preferably 60 [kPa abs] or less. It is preferable to perform dehydration while performing dehydration efficiently at a lower liquid temperature.

  The dehydration step (2) is preferably carried out in the same reaction vessel as in the dehydration step (1), from the viewpoint of sharing production facilities and improving productivity. From the viewpoint of improving the amount, it is also preferable to use a reaction vessel different from the dehydration step (1) or the polymerization step.

-Polymerization step In the present invention, the mixture obtained through the dehydration step (1) is then heated in a range where the amount of water present in the reaction system is 0.4 mol or less per 1 mol of the dihalo aromatic compound. And carrying out a polymerization reaction. When the dehydration step (2) is performed after the dehydration step (1), the mixture obtained through the dehydration step (2) is present in the reaction system with respect to 1 mol of the dihalo aromatic compound. The polymerization reaction can be carried out by heating the water content in a range of less than 0.03 mol.
In the polymerization step, the mixture obtained through the dehydration step (1) and the dehydration step (2) is heated in a sealed reaction vessel to a temperature of 200 ° C. or more and 300 ° C. or less, so that the polymerization reaction proceeds. This is the step of causing

  In the polymerization step, the polymerization reaction conditions are not particularly limited, but a temperature at which the polymerization reaction can easily proceed, that is, a range of 200 ° C or more and 300 ° C or less, preferably a range of 210 ° C or more and 280 ° C or less, More preferably, the reaction is performed at a temperature of 215 ° C or higher and 250 ° C or lower.

  As described above, the dihalo-aromatic compound, which is a polymerization raw material, is charged in the dehydration step (1) and azeotropically distilled by distillation. The aromatic compound is charged in advance in the dehydration step in advance, or an additional dihaloaromatic compound is charged before the polymerization step is started, and the ratio of the dihaloaromatic compound in the reaction system is increased by the sulfur atom of the sulfidizing agent. The amount is preferably 0.8 mol or more, more preferably 0.9 mol or more, preferably 1.2 mol or less, more preferably 1.1 mol or less, particularly preferably equimolar, relative to 1 mol. Adjust to be able to react.

  The amount of water present in the reaction system at the start of the polymerization is preferably as small as possible, for example, in the range of 0.4 mol or less, preferably in the range of the detection limit (mol) or more per 1 mol of sulfur atom of the sulfidizing agent. Therefore, the range is preferably 0.4 mol or less, more preferably 0.11 mol or less, further preferably 0.08 mol or less, particularly preferably 0.03 mol or less, and most preferably 0.01 mol or less. Since water is generated as the polymerization reaction proceeds, water in the range of 0.1 mol or more to 0.3 mol or less per 1 mol of sulfur atom of the sulfidizing agent may be produced at the end of the polymerization reaction in the polymerization step. Preferably, the above range is satisfied from the time when the conversion of the dihalo aromatic compound exceeds 80 mol%, more preferably, from the time when the conversion exceeds 60 mol%, and further preferably, immediately after the start of the polymerization.

Here, the conversion of the dihalo aromatic compound is represented by the following formula.
Conversion rate (%) = (prepared amount−remaining amount) / prepared amount × 100
Here, the “charge amount” indicates the mass of the dihalo aromatic compound charged in the reaction system, and the “residual amount” indicates the mass of the dihalo aromatic compound remaining in the reaction system.

-Post-treatment step The reaction mixture containing the polyarylene sulfide resin obtained by the polymerization reaction can be subjected to a post-treatment step. The post-treatment step may be any known method, and is not particularly limited. For example, after completion of the polymerization reaction, the reaction mixture is first used as it is, or after adding an acid or a base, under reduced pressure or normal pressure. The solvent is distilled off, and then the solid after the solvent is distilled off is washed once or twice or more with a solvent such as water, acetone, methyl ethyl ketone, or alcohols, and further neutralized, washed with water, filtered and dried, or After the completion of the polymerization reaction, a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, or aliphatic hydrocarbons (soluble in the polymerization solvent used, and A solvent which is a poor solvent for at least the polyarylene sulfide resin) is added as a precipitant, and solids such as polyarylene sulfide resin and inorganic salts are added. The product is allowed to settle, and these are separated by filtration, washed, and dried, or after the polymerization reaction is completed, a reaction solvent (or an organic solvent having an equivalent solubility to a low molecular weight polymer) is added to the reaction mixture and stirred. Then, after filtering to remove the low molecular weight polymer, washing once or more with a solvent such as water, acetone, methyl ethyl ketone, or alcohols, and then neutralizing, washing with water, filtering and drying, etc. Can be
In the post-treatment method as exemplified above, the drying of the polyarylene sulfide resin may be performed in vacuum, or may be performed in air or in an inert gas atmosphere such as nitrogen.

  The polyarylene sulfide resin thus obtained can be used for various molding materials as it is, but may be subjected to heat treatment in air or oxygen-enriched air or under reduced pressure conditions to be oxidatively crosslinked. The temperature of this heat treatment is preferably in the range of 180 ° C. or more and 270 ° C. or less, although it varies depending on the target crosslinking treatment time and the atmosphere to be treated. Further, the heat treatment may be performed in a state where the polyarylene sulfide resin is melted at a temperature equal to or higher than the melting point of the polyarylene sulfide resin using an extruder or the like, but the possibility of thermal deterioration of the polyarylene sulfide resin is increased. It is preferable to perform the process at plus 100 ° C. or lower.

-Production apparatus In the method for producing a polyarylene sulfide resin of the present invention, the reaction apparatus used in each of the above steps is a raw material, that is, a dihaloaromatic compound, a sulfidizing agent, an alkali catalyst, or the like, a fat that can be opened by hydrolysis. Group-based cyclic compound, a mixture obtained through a dehydration step, and a part or all of a contact portion with a polymerization reaction product containing a polyarylene sulfide resin obtained after the polymerization reaction, titanium, zirconium, a nickel alloy It is preferable to use those from the viewpoint of corrosion resistance.

  Examples of the reaction device include a batch-type reaction vessel (autoclave, reactor) having a stirring blade therein, a reaction vessel (polymerization line) such as a continuous reaction vessel, a stirring blade, a baffle plate, and the like.

  For example, the batch-type reaction vessel may be any vessel capable of holding a raw material, a mixture, or a polymerization reactant inside the reaction vessel, and includes, for example, an upper lid, a body, and a bottom, and optionally includes A structure having a stirring blade, a shaft for transmitting power to the stirring blade, a baffle (baffle), and a temperature control snake tube is preferable from the viewpoint of excellent stirring efficiency. Here, examples of the stirring blade include an anchor-type stirring blade, a turbine-type stirring blade, a screw-type stirring blade, and a double helical-type stirring blade. It is preferable that the baffle (baffle) is installed at a position where the lower end is close to the bottom surface of the reaction vessel and on the other hand, is at a position where the upper end is out of the liquid level, from the viewpoint of facilitating heat conduction and heat control.

  On the other hand, the continuous reaction vessel includes, for example, a tubular reactor in which a plurality of mixing elements having no moving parts are fixed inside, and a polymerization line in which the tubular reactors are connected in series, or a plurality of tubular reactors. One that connects the reactors and forms a continuous cyclic polymerization line having a structure in which a part of the reaction solution is recirculated to the raw material inlet of the tubular reactor. In these continuous reaction vessels, feed of raw materials and transfer of a reaction solution can be performed by a plunger pump or the like.

  The reaction vessel is further provided with various measuring devices such as a thermometer, a pressure gauge, and a safety valve. Outside the piping, a piping and an on-off valve, a condenser, a decanter, and a distillate (a decanter) are provided. A distillation device such as an organic layer component return line and a distillate (water layer component of the decanter) distillation line, and a pressure reducing device such as a pressure regulating valve, a vacuum pump, and a hydrogen sulfide capturing device must be provided. Is preferred.

  The reaction device used in the present invention may be configured such that at least a part, preferably all, of the contact portion is made of the nickel alloy. The nickel alloy used here preferably has a chromium content of 43% by mass or more and 47% by mass or less and a molybdenum content of 0.1% by mass or more and 2% by mass or less from the viewpoint of corrosion resistance. And the remainder is an alloy composed of nickel and unavoidable impurities. Tungsten, iron, cobalt and copper preferably have a content below the detection limit. In the present invention, the term "unavoidable impurities" means trace impurities that are technically difficult to remove. In the present invention, for example, carbon atoms contained in the alloy at a ratio of 3% by mass or less, preferably 1% by mass or less, more preferably a detection limit or less are exemplified.

Molding processing etc. The polyarylene sulfide resin obtained by the production method of the present invention described in detail above is a filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, a crosslinkable resin having two or more functional groups, and A polyarylene sulfide resin composition through a step of blending with at least one other component selected from the group consisting of silane coupling agents, heating to a temperature equal to or higher than the melting point of the polyarylene sulfide resin, and melt-kneading; It can be.

  The filler is not particularly limited, but examples include a fibrous filler and an inorganic filler. Examples of the fibrous filler include fiber such as glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium sulfate, calcium silicate, and natural fiber such as wollastonite. Can be used. In addition, as the inorganic filler, barium sulfate, calcium sulfate, clay, viroferrite, bentonite, sericite, zeolite, mica, mica, talc, atalpargite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, etc. Can be used. In addition, various additives such as a release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust preventive, a flame retardant, and a lubricant can be added as additives during the molding process.

  Further, the thermoplastic resin other than the polyarylene sulfide resin, which is blended in the polyarylene sulfide resin composition of the present invention, includes polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, and polyethersulfone. , Polyether ether ketone, polyether ketone, polyarylene, polyethylene, polypropylene, polytetrafluoroethylene, polydifluoroethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, liquid crystal polymer, etc. It may be used as a polyarylene sulfide resin composition containing a synthetic resin. The blending ratio of the thermoplastic resin other than the polyarylene sulfide resin is preferably at least 1 part by mass, more preferably at least 3 parts by mass, even more preferably at least 5 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin. Preferably it is 300 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 45 parts by mass or less. When the content of the thermoplastic resin other than the polyarylene sulfide resin is within these ranges, an effect of further improving heat resistance, chemical resistance, and mechanical properties can be obtained.

  As the elastomer blended in the polyarylene sulfide resin composition of the present invention, a thermoplastic elastomer may be used. Examples of the thermoplastic elastomer include a polyolefin-based elastomer, a fluorine-based elastomer, and a silicone-based elastomer. In addition, in this specification, a thermoplastic elastomer is classified into an elastomer instead of the thermoplastic resin.

  The elastomer (particularly, a thermoplastic elastomer) preferably has a functional group capable of reacting with a hydroxy group or an amino group. This makes it possible to obtain a resin composition that is particularly excellent in terms of adhesiveness, impact resistance, and the like. Examples of such a functional group include an epoxy group, a carboxy group, an isocyanate group, an oxazoline group, and a compound represented by the formula: R (CO) O (CO)-or R (CO) O- (where R is a group having 1 or more carbon atoms). And an alkyl group in the range of 8 or less.). The thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerizing an α-olefin with a vinyl polymerizable compound having the above functional group. Examples of the α-olefin include α-olefins having 2 to 8 carbon atoms, such as ethylene, propylene and butene-1. Examples of the vinyl polymerizable compound having a functional group include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylate and alkyl esters thereof, maleic acid, fumaric acid, itaconic acid and the like. Other examples include α, β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono or diesters and acid anhydrides thereof), and glycidyl (meth) acrylate. Among these, an epoxy group, a carboxy group, and a formula: R (CO) O (CO)-or R (CO) O- (where R is an alkyl group having 1 to 8 carbon atoms) The ethylene-propylene copolymer and the ethylene-butene copolymer having at least one kind of functional group selected from the group consisting of groups represented by the following formulas are preferred from the viewpoint of improvement in toughness and impact resistance.

  The blending ratio of the elastomer cannot be specified unconditionally because it varies depending on the type and use thereof. For example, it is preferably 1 part by mass or more, more preferably 3 parts by mass or more, based on 100 parts by mass of the polyarylene sulfide resin. The range is preferably from 5 parts by mass or more, preferably 300 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 45 parts by mass or less. When the content of the elastomer is in these ranges, more excellent effects can be obtained in terms of securing heat resistance and toughness of the molded article.

  The crosslinkable resin blended in the polyarylene sulfide resin composition has two or more functional groups. Examples of the functional group include an epoxy group, a phenolic hydroxyl group, an amino group, an amide group, a carboxy group, an acid anhydride group, and an isocyanate group. Examples of the crosslinkable resin include an epoxy resin, a phenol resin, and a urethane resin.

  The compounding amount of the crosslinkable resin is preferably at least 1 part by mass, more preferably at least 3 parts by mass, still more preferably at least 5 parts by mass, preferably at most 300 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin. , More preferably 100 parts by mass or less, still more preferably 30 parts by mass or less. When the blending amount of the crosslinkable resin is in these ranges, the effects of improving the rigidity and heat resistance of the molded product can be particularly remarkably obtained.

  Examples of the silane coupling agent blended in the polyarylene sulfide resin composition of the present invention include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxy) Cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and the like.

  The amount of the silane compound is, for example, preferably at least 0.01 part by mass, more preferably at least 0.1 part by mass, preferably at most 10 parts by mass, more preferably at most 10 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin. The range is 5 parts by mass or less. When the compounding amount of the silane compound is in these ranges, an effect of improving the compatibility between the polyarylene sulfide resin and the other components can be obtained.

  The polyarylene sulfide resin composition of the present invention may further contain other additives such as a release agent, a coloring agent, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust inhibitor, a flame retardant and a lubricant. . The amount of the additive is preferably, for example, in the range of 1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the polyarylene sulfide resin.

  The polyarylene sulfide resin composition can be obtained, for example, in the form of a compound in the form of pellets by a method of melt-kneading the polyarylene sulfide resin obtained by the above method and the other components. The temperature of the melt-kneading is, for example, preferably in the range of 250 ° C. or higher, more preferably 290 ° C. or higher, preferably 350 ° C. or lower, more preferably 330 ° C. or lower. Melt kneading can be performed using a twin screw extruder or the like.

The polyarylene sulfide resin composition according to the present embodiment may be melt-formed by various melt processing methods such as injection molding, extrusion molding, compression molding, and blow molding, alone or in combination with the other components. Thus, it can be processed into a molded product having excellent heat resistance, molding workability, dimensional stability and the like. Since the polyarylene sulfide resin composition of the present invention has a low metal content, it enables easy production of a high-quality molded product, particularly a thin-walled molded product having excellent insulation properties.

  The polyarylene sulfide resin and the composition thereof obtained by the production method of the present invention also have various properties such as heat resistance and dimensional stability inherent to the polyarylene sulfide resin. Electrical and electronic parts such as molded parts, automotive parts such as lamp reflectors and various electrical parts, interior materials such as buildings, aircraft and automobiles, and precision parts such as OA equipment parts, camera parts and clock parts It is widely useful as a material for various molding processes such as injection molding or compression molding, extrusion molding of composites, sheets, pipes or the like, or pultrusion molding, or as a material for fibers or films.

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

(Measurement of metal atom content)
100 mg of PPS resin was weighed into a platinum crucible, and 2 ml of concentrated sulfuric acid was added. This was placed on an electric heater and subjected to thermal decomposition until no white smoke of sulfuric acid was generated. Thereafter, the crucible containing the decomposition product was placed in an electric furnace, and was thermally decomposed at 800 ° C. for 3 hours, and completely incinerated. The crucible was cooled and the contents were washed into a volumetric flask with 10 ml of 1N hydrochloric acid. Thereafter, the flask was washed with 5 ml of distilled water once every 5 times into a 100 ml measuring flask, and the measuring flask was filled up with distilled water to prepare a 100 ml diluted solution. Using an ICP emission spectrophotometer (“Optical Emission Spectrometer Optima 4300 DV” manufactured by Perkin Elmer Co., Ltd.), the obtained diluent was used to measure the metal ion content, excluding sodium ions used as a polymerization raw material. , Metal ion content. The detection limit is 0.01 ppm.

(Measurement method of melt viscosity)
The melt viscosity (η) of the PPS resin was maintained at 300 ° C., 1.96 MPa, L / D = 10 (mm) / 1 (mm) for 6 minutes using a flow tester (“CFT500D” manufactured by Shimadzu Corporation). This is a value measured later.

(Quantification of phenol (by-product) amount)
10 g of the obtained PPS slurry and 0.2 g of an internal standard substance (chlorobenzene) are weighed and diluted with 15 g of acetone. The obtained diluted solution was treated with ultrasonic waves for 5 minutes, and subjected to solid-liquid separation with a centrifuge. Thereafter, 1 μL of the supernatant was collected and measured by gas chromatography.

  The measurement with a gas chromatograph is performed by gas chromatography “GC2014” manufactured by Shimadzu Corporation (column: column “G300” manufactured by Chemicals Evaluation and Research Institute, carrier gas: helium), measurement column conditions: held at 140 ° C. for 5 minutes → 3 ° C. / Minute, and the temperature was raised to 200 ° C. → held at 200 ° C. for 20 minutes). To determine the phenol concentration, a calibration curve was first prepared with a standard sample. Next, the peak area having the same retention time as the standard sample was obtained from the chromatogram obtained by measuring the supernatant prepared above. The concentration in the measurement solution was determined from the peak area and the calibration curve, and the number of moles of the phenol per mole of the sulfidizing agent (1 mole of the total charged sulfur atoms) was calculated as a percentage (hereinafter, “mol% / S”). ).

(Quantification of water content)
The water content was measured by Karl Fischer titration using a Karl Fischer moisture meter (AQV-300 manufactured by Hiranuma Sangyo Co., Ltd.). The detection limit is 6.0 × 10 ⁻⁶ mol per mol of sulfur atom.

(Example 1)
・ Dehydration process (1)
Equipped with a thermometer, a heating device, a titanium impeller and a pressure gauge, a raw material (NMP) storage tank, a decompression device (a pressure regulating valve, a vacuum pump and a device for collecting the scattered hydrogen sulfide), and a distillation device (a rectification tower, a condenser) P-dichlorobenzene (hereinafter, referred to as an autoclave) having an inner wall (liquid contact part) made of a nickel alloy (Ni-Cr-Mo alloy containing 45% by mass of chromium, 1% by mass of molybdenum, and the balance of nickel) connected to the autoclave. , Abbreviated as p-DCB) 220.5 parts by mass (1.50 parts by mol), 29.7 parts by mass of NMP (0.3 parts by mol), 45 wt% NaSHaq. 123.6 parts by mass (1.5 mol parts) and 48 wt% NaOHaq. 125.0 g (1.5 mol part) was charged, and the liquid temperature was raised to 128 ° C. (gas temperature in the autoclave: 96 ° C.) under a nitrogen atmosphere with stirring while the autoclave was sealed.

  Next, the valve of the pipe leading from the autoclave to the distillation apparatus was opened to start dehydration, and the valve of the pipe leading to the decompression apparatus was opened. The valve was opened at atmospheric pressure at a rate of -6.6 [kPa abs] / min. While reducing the pressure to [kPa abs], the liquid temperature was gradually increased from 128 ° C. to 147 ° C. at a rate of 0.1 ° C./min, and finally 47 [kPa abs] and the liquid temperature was 147 ° C. for 4 hours. And dehydrated. The mixed steam of water and p-DCB discharged from the rectification column is condensed by a condenser, and water and p-DCB are separated by a decanter. At any time, water is distilled out of the system, and p-DCB is placed in an autoclave. I put it back. During that time, the amount of distilled water was 123.5 parts by mass, the inside of the autoclave after the dehydration reaction was in a slurry state in which a fine anhydrous sodium sulfide composition was dispersed in DCB, and the remaining amount of existing moisture was determined by the autoclave. It was 0.3 mole per mole of sulfur atoms present therein.

-Polymerization step The autoclave containing the mixture obtained in the dehydration step was placed under a nitrogen atmosphere, the valve was closed, and the reaction system was sealed. The liquid temperature was set to 160 ° C., and 415.8 parts by mass (4.2 mol parts) of NMP previously set in the raw material storage tank was extruded by a pump from a pipe by opening a valve communicating with the raw material storage tank, and charged in an autoclave. . Then, the temperature was raised to 220 ° C., and the mixture was stirred for 2 hours. Then, the temperature was raised to 250 ° C., and the mixture was stirred for 1 hour. The final pressure was 373 [kPa abs]. Then, it cooled to room temperature.

-Post-treatment process After cooling, the obtained slurry was poured into 3000 parts by mass of water, stirred at 80 ° C for 1 hour, and then filtered. The cake was again stirred with 3000 parts by mass of warm water for 1 hour, washed, and filtered. This operation was repeated four times, followed by filtration and drying in a hot air dryer at 120 ° C. overnight to obtain 154 parts by mass of a white powdery PPS.
The melt viscosity of this polymer was 66 Pa · s, the amount of phenol produced was 0.08 mol%, and the total metal content of chromium, molybdenum and nickel was below the detection limit.

(Comparative Example 1)
Next, the valve of the pipe leading to the distillation apparatus from the autoclave was opened, dehydration was started, and the valve of the pipe leading to the pressure reducing apparatus was opened. From the atmospheric pressure at a rate of -6.6 [kPa abs] / min. While reducing the pressure to 47 kPa abs, the liquid temperature was gradually raised from 128 ° C. to 147 ° C. at a rate of 0.1 ° C./min. Dehydrated for hours. "
Next, the valve of the pipe leading from the autoclave to the distillation apparatus is opened, dehydration is started, and the liquid temperature is gradually raised from 128 ° C. to 173 ° C. at a rate of 0.1 ° C./min under atmospheric pressure. Finally, the solution was dehydrated at 173 ° C. for 4.5 hours under atmospheric pressure. ”

  During the dehydration step (1), the amount of distilled water was 123.5 parts by mass, and the interior of the autoclave after the dehydration reaction was in a slurry state in which the particulate anhydrous sodium sulfide composition was dispersed in DCB. The remaining amount was 0.3 mol per mol of sulfur atoms present in the autoclave.

  After the post-treatment step, the obtained PPS resin had a melt viscosity of 65 Pa · s, a phenol generation amount of 0.09 mol%, and a total metal content of chromium, molybdenum and nickel of 23 pm.

(Comparative Example 2)
Next, the valve of the pipe leading to the distillation apparatus from the autoclave was opened, dehydration was started, and the valve of the pipe leading to the pressure reducing apparatus was opened. From the atmospheric pressure at a rate of -6.6 [kPa abs] / min. While reducing the pressure to 47 kPa abs, the liquid temperature was gradually raised from 128 ° C. to 147 ° C. at a rate of 0.1 ° C./min. Dehydrated for hours. "
Next, the valve of the pipe leading from the autoclave to the distillation apparatus is opened, dehydration is started, and the liquid temperature is gradually raised from 128 ° C. to 147 ° C. at a rate of 0.1 ° C./min under atmospheric pressure. Finally, dehydration was performed at atmospheric pressure and a liquid temperature of 147 ° C. for 4 hours. ”

  During the dehydration step (1), the amount of distilled water was 49.5 parts by mass, and the inside of the autoclave after the dehydration reaction was in a slurry state in which the particulate anhydrous sodium sulfide composition was dispersed in DCB. The remaining amount was 3 moles per mole of sulfur atoms present in the autoclave.

  However, after the post-treatment step, a white powdery PPS resin was not obtained, and a low-viscosity product remained. The product had a low viscosity, and the melt viscosity could not be measured. The amount of phenol produced was 0.5 mol%, and the total metal content of chromium, molybdenum and nickel was 0.1 ppm.

(Example 2)
The part whose “inner wall (liquid contact portion) is made of a nickel alloy (Ni-Cr-Mo alloy containing 45 mass% of chromium, 1 mass% of molybdenum, and the balance of nickel)” is
The procedure was carried out in the same manner as in Example 1 except that "the inner wall (liquid contact portion) was made of titanium autoclave".

  During the dehydration step (1), the amount of distilled water was 123.5 parts by mass, and the interior of the autoclave after the dehydration reaction was in a slurry state in which the particulate anhydrous sodium sulfide composition was dispersed in DCB. The remaining amount was 0.29 mol per mol of sulfur atoms present in the autoclave.

  After the post-treatment step, the obtained PPS resin had a melt viscosity of 67 Pa · s, a phenol production amount of 0.08 mol%, and a metal content of titanium below the detection limit.

(Comparative Example 3)
The part whose “inner wall (liquid contact portion) is made of a nickel alloy (Ni-Cr-Mo alloy containing 45 mass% of chromium, 1 mass% of molybdenum, and the balance of nickel)” is
The procedure was performed in the same manner as in Comparative Example 1, except that "the inner wall (liquid contact portion) was made of titanium autoclave".

  During the dehydration step (1), the amount of distilled water was 123.5 parts by mass, and the interior of the autoclave after the dehydration reaction was in a slurry state in which the particulate anhydrous sodium sulfide composition was dispersed in DCB. The remaining amount was 0.27 mol per mol of sulfur atoms present in the autoclave.

After the post-treatment step, the obtained PPS resin had a melt viscosity of 65 Pa · s, a phenol generation amount of 0.09 mol%, and a metal content of titanium of 5 ppm.

(Comparative Example 4)
The part whose “inner wall (liquid contact portion) is made of a nickel alloy (Ni-Cr-Mo alloy containing 45 mass% of chromium, 1 mass% of molybdenum, and the balance of nickel)” is
The procedure was performed in the same manner as in Comparative Example 2 except that the inner wall (liquid contact part) was made of titanium.

  During the dehydration step (1), the amount of distilled water was 50.2 parts by mass, and the interior of the autoclave after the dehydration reaction was in a slurry state in which the particulate anhydrous sodium sulfide composition was dispersed in DCB. The remaining amount was 2.8 moles per mole of sulfur atoms present in the autoclave.

  However, after the post-treatment step, a white powdery PPS resin was not obtained, and a low-viscosity product remained. The product had a low viscosity, and the melt viscosity could not be measured. The amount of phenol produced was 0.5 mol%, and the metal content of titanium was 2 ppm.

(Example 3)
The part "The temperature was increased to 128 ° C. in a nitrogen atmosphere with stirring while the autoclave was sealed,"
"The temperature was raised to 105 ° C. in a nitrogen atmosphere with stirring while the autoclave was sealed," and
Next, the valve of the pipe leading to the distillation apparatus from the autoclave was opened, dehydration was started, and the valve of the pipe leading to the pressure reducing apparatus was opened. From the atmospheric pressure at a rate of -6.6 [kPa abs] / min. While reducing the pressure to 47 kPa abs, the liquid temperature was gradually raised from 128 ° C. to 147 ° C. at a rate of 0.1 ° C./min. Dehydrated for hours. "
Next, the valve of the pipe leading to the distillation apparatus from the autoclave was opened, dehydration was started, and the valve of the pipe leading to the pressure reducing apparatus was opened. From the atmospheric pressure at a rate of -6.6 [kPa abs] / min. While reducing the pressure to 32 kPa abs, the liquid temperature was gradually raised from 105 ° C. to 115 ° C. at a rate of 0.1 ° C./min. And dehydrated for hours. "

  During the dehydration step (1), the amount of distilled water was 123.5 parts by mass, and the interior of the autoclave after the dehydration reaction was in a slurry state in which the particulate anhydrous sodium sulfide composition was dispersed in DCB. The remaining amount was 0.3 mol per mol of sulfur atoms present in the autoclave.

  After the post-treatment step, the melt viscosity of the obtained PPS resin was 62 Pa · s, the amount of phenol produced was 0.1 mol%, and the total metal content of chromium, molybdenum and nickel was below the detection limit. Was.

(Example 4)
Next, the valve of the pipe leading to the distillation apparatus from the autoclave was opened, dehydration was started, and the valve of the pipe leading to the pressure reducing apparatus was opened. From the atmospheric pressure at a rate of -6.6 [kPa abs] / min. The liquid temperature was gradually increased from 128 ° C. to 147 ° C. at a rate of 0.1 ° C./min while the pressure was reduced to 47 kPa abs, and finally the liquid temperature was 47 kPa abs and 147 ° C. for 4 hours. And dehydrated. "
Next, the valve of the pipe leading to the distillation apparatus from the autoclave was opened, dehydration was started, and the valve of the pipe leading to the pressure reducing apparatus was opened. From the atmospheric pressure at a rate of -6.6 [kPa abs] / min. While reducing the pressure to 70 kPa abs, the liquid temperature was gradually increased from 128 ° C. to 155 ° C. at a rate of 0.1 ° C./min. And dehydrated for hours. "

  During the dehydration step (1), the amount of distilled water was 123.5 parts by mass, and the interior of the autoclave after the dehydration reaction was in a slurry state in which the particulate anhydrous sodium sulfide composition was dispersed in DCB. The remaining amount was 0.3 mol per mol of sulfur atoms present in the autoclave.

  After the post-treatment step, the obtained PPS resin had a melt viscosity of 65 Pa · s, a phenol production amount of 0.09 mol%, and a total metal content of chromium, molybdenum and nickel below the detection limit. Was.

Claims (12)

A method for producing a polyarylene sulfide resin in which a dihalo aromatic compound and a sulfidizing agent are polymerized in the presence of an aliphatic cyclic compound that can be opened by hydrolysis.
A dehydration step (1) of reacting a sulfidizing agent containing water with an aliphatic cyclic compound that can be opened by hydrolysis in the presence of a dihaloaromatic compound while dehydrating under reduced pressure to obtain a mixture is performed. A method for producing a polyarylene sulfide resin, comprising:   In the dehydration step (1), in the presence of a dihaloaromatic compound, a sulfidizing agent containing water and an aliphatic cyclic compound that can be opened by hydrolysis are mixed with a liquid temperature of 90 ° C to 130 ° C. After raising the temperature under the atmospheric pressure until the temperature falls within the range, the dehydration is performed by raising the liquid temperature to a range from more than 90 ° C to 170 ° C and a pressure from 30 kPa abs to 80 kPa abs. The production method according to claim 1, further comprising a step of obtaining the mixture by performing the reaction at a temperature and reduced pressure.   The production method according to claim 1, wherein the dihaloaromatic compound is in a range of 0.2 mol or more to 5.0 mol or less based on 1 mol of the total sulfur atoms of the sulfidizing agent.   2. The method according to claim 1, wherein the amount of water present in the reaction system after the completion of the dehydration step (1) is in a range of 0.4 mol or less based on 1 mol of the total sulfur atoms of the sulfidizing agent.   The production method according to claim 1, wherein the amount of the aliphatic cyclic compound is in the range of 0.01 mol or more and 0.9 mol or less based on 1 mol of the total sulfur atoms of the sulfidizing agent.   The production method according to claim 1, wherein the sulfidizing agent is an alkali metal sulfide, or an alkali metal hydrosulfide and an alkali metal hydroxide.   The production method according to claim 1, wherein after completion of the dehydration step (1), the mixture is a slurry containing an anhydrous solid sulfidizing agent.   Next, a polymerization step of subjecting the mixture obtained through the dehydration step (1) to a polymerization reaction by heating the mixture in a range where the amount of water present in the reaction system is 0.4 mol or less per 1 mol of the dihalo aromatic compound is performed. The method according to claim 1, wherein Next, an aprotic polar organic solvent is further added to the mixture obtained through the dehydration step (1), and water is distilled off to perform dehydration step (2).
2. The method according to claim 1, further comprising a polymerization step of polymerizing the mixture obtained in the dehydration step (2) at a water content of less than 0.03 mol in the reaction system with respect to 1 mol of the dihaloaromatic compound. The manufacturing method as described.   The contact portion of the reaction device in the dehydration step (1) with a raw material or a mixture obtained after the reaction is made of at least one material selected from the group consisting of titanium, zirconium and a nickel alloy. The manufacturing method as described.   A process for producing a polyarylene sulfide resin by the production method according to claim 1, wherein the obtained polyarylene sulfide resin has a filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and two or more functional groups. A step of blending with at least one other component selected from the group consisting of a crosslinkable resin and a silane coupling agent, heating to a temperature equal to or higher than the melting point of the polyarylene sulfide resin, and melt-kneading. A method for producing a polyarylene sulfide resin composition.   A method for producing a polyarylene sulfide resin composition, comprising: a step of producing a polyarylene sulfide resin composition by the production method according to claim 11; and a step of melt-molding the obtained polyarylene sulfide resin composition. Method.