WO2019004170A1

WO2019004170A1 - Method for producing polyarylene sulfide resin

Info

Publication number: WO2019004170A1
Application number: PCT/JP2018/024119
Authority: WO
Inventors: 早織奈良; 渡邉　英樹; 将哉角木; 拓茨木; 井上　敏
Original assignee: Dic株式会社
Priority date: 2017-06-29
Filing date: 2018-06-26
Publication date: 2019-01-03
Also published as: JP6866923B2; JPWO2019004170A1

Abstract

Provided is a method for producing a polyarylene sulfide resin that causes a polymerization reaction between a dihalo aromatic compound and a sulfidating agent in the presence of an aliphatic cyclic compound that can be ring-opened by hydrolysis, wherein corrosion of a production apparatus is suppressed and the content of production-apparatus-derived metal atoms in the resulting polyarylene sulfide resin is reduced. More specifically, provided is a method for producing a polyarylene sulfide resin having a dehydrating step (1) for obtaining a mixture by reacting a sulfidating agent containing water and an aliphatic cyclic compound that can be ring-opened by hydrolysis while dehydration is carried out at a pressure in the range of 30 [kPa abs] to atmospheric pressure until the solution temperature reaches a range of 90°C to 150°C, thereafter adding a dihalo aromatic compound, and reacting the solution while heating at a solution temperature in the range of 90°C to 170°C and dehydrating at a pressure in the range of 30 [kPa abs] to 80 [kPa abs].

Description

Method for producing polyarylene sulfide resin

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

Polyarylene sulfide resins represented by polyphenylene sulfide resin (hereinafter sometimes abbreviated as "PPS resin") (hereinafter sometimes abbreviated as "PAS resin") are heat resistant, It has excellent chemical resistance and is widely used for electrical and electronic parts, automobile parts, water heater parts, fibers, film applications, and the like.

As a method for producing a polyarylene sulfide resin, for example, a hydrous alkali metal sulfide or less than 1 mole of N-methylpyrrolidone per mole of the hydrous alkali metal sulfide and a polyhaloaromatic compound are mixed and the mixture is azeotroped There is known a method of obtaining a slurry containing fine particulate anhydrous alkali metal sulfide by dehydration, and then heating the same to carry out a polymerization reaction (see, for example, Patent Documents 1 and 2). According to the above method, it is possible to efficiently produce 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 which induces a side reaction. Although it is necessary to dehydrate highly basic sulfidizing agents at high temperatures, the contact part with the raw material in the reaction equipment such as the reaction vessel is easily corroded. I had to use a member. However, it has still been known that the metal member corrodes and promotes the wear of the metal member. Therefore, there has been a demand for a method for producing a polyarylene sulfide resin which suppresses the consumption of the metal member.

Furthermore, although the obtained polyarylene sulfide resin contains metal atoms derived from the metal member eluted by the consumption of the metal member in the contact portion, it is also difficult to remove these metal atoms in a normal cleaning operation. there were. In particular, in recent years, thinning of molded articles using polyarylene sulfide resin is also progressing, and polyarylene sulfide resin of higher quality than before is required, and metal derived from a reaction device in polyarylene sulfide resin The reduction of atomic content has been an urgent issue.

JP-A-8-231723 WO 2010/058713 brochure

Therefore, the problem to be solved by the present invention is a method for producing a polyarylene sulfide resin in which a dihaloaromatic compound and a sulfidizing agent are subjected to a polymerization reaction in the presence of an aliphatic cyclic compound which can be opened by hydrolysis. It is an object of the present invention to provide a method for suppressing the corrosion of production equipment and reducing the content of metal atoms derived from the production equipment in the resulting polyarylene sulfide resin.

In order to solve the above problems, the present inventors, as a result of hard efforts, dehydrate the sulfidizing agent containing water and the aliphatic cyclic compound which can be opened by hydrolysis in the presence of the dihaloaromatic compound. At that time, it is carried out under reduced pressure, and compared with the case where it is carried out under the atmospheric pressure, that is, compared to the case where it is carried out under atmospheric pressure, corrosion of the contact portion can be reduced. It has been found that the content of the metal atom derived from can be reduced, and the present invention has been completed.

That is, the present invention is a method for producing a polyarylene sulfide resin, wherein a dihaloaromatic compound and a sulfidizing agent are reacted in the presence of an aliphatic cyclic compound that can be opened by hydrolysis.
The liquid temperature of the sulfidizing agent containing water and the aliphatic cyclic compound capable of ring-opening by hydrolysis is from 30 [kPa abs] to at most atmospheric pressure until the liquid temperature is in the range of 90 to 150 ° C. After making it react, making it dehydrate under the pressure of a range, a dihalo aromatic compound is further added, liquid temperature heats to the range of 90 to 170 degreeC, and pressure is 30 [kPa abs] to 80 [ The present invention relates to a method for producing a polyarylene sulfide resin, comprising the dehydration step (1) of obtaining a mixture by reacting while dehydrating in the range of kPa abs] or less.

Furthermore, in the present invention, a step of producing a polyarylene sulfide resin by the above 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 at least one other component selected from the group consisting of a crosslinkable resin having the above and a silane coupling agent, heating to a temperature above the melting point of the polyarylene sulfide resin, and melt kneading The present invention relates to a method for producing a polyarylene sulfide resin composition characterized by

Furthermore, the present invention comprises a polyarylene sulfide resin molded article characterized by comprising a step of producing a polyarylene sulfide resin composition by the above production method, and a step of melt-molding the obtained polyarylene sulfide resin composition. The manufacturing method of

In the method for producing a polyarylene sulfide resin in which a dihaloaromatic compound and a sulfidizing agent are subjected to a polymerization reaction in the presence of an aliphatic cyclic compound capable of ring opening by hydrolysis according to the present invention, corrosion of the production apparatus is suppressed It is possible to provide a method for reducing the content of metal atoms derived from production equipment in the resulting polyarylene sulfide resin.

The method for producing the polyarylene sulfide resin of the present invention is
The liquid temperature of the sulfidizing agent containing water and the aliphatic cyclic compound capable of ring-opening by hydrolysis is from 30 [kPa abs] to at most atmospheric pressure until the liquid temperature is in the range of 90 to 150 ° C. After making it react, making it dehydrate under the pressure of a range, a dihalo aromatic compound is further added, liquid temperature heats to the range of 90 to 170 degreeC, and pressure is 30 [kPa abs] to 80 [ The reaction is characterized by having a dehydration step (1) of obtaining a mixture by reacting while dehydrating in the range of kPa abs] or less. The details will be described below.

・ Dehydration process (1)
The present invention provides a sulfidizing agent containing water and an aliphatic cyclic compound capable of ring-opening by hydrolysis until the liquid temperature is in the range of 90 ° C. or more to 150 ° C. or less, from 30 kPa abs or more The reaction is carried out while dehydrating under a pressure in the range of atmospheric pressure or less, and a dihaloaromatic compound is further added, and the liquid temperature is heated to a range of 90 ° C. to 150 ° C., and the pressure is 30 [kPa abs] From the above, the reaction is carried out while dehydrating in the range of 80 [kPa abs] or less, and a dehydration step (1) for obtaining a mixture is essential.

The dehydration step (1) is a step of reacting a sulfidizing agent containing water and an aliphatic cyclic compound which can be opened by hydrolysis in the presence of a dihaloaromatic compound while dehydrating. By this step, the water content existing in the reaction system is efficiently removed out of the system, and the hydrolysis of the aliphatic cyclic compound is promoted, and at least an anhydrous sulfidizing agent and the aliphatic cyclic compound are obtained. Forming a mixture comprising an alkali metal salt of the hydrolyzate. In the present invention, by performing dehydration under reduced pressure, corrosion of the reaction apparatus at the contact portion with the raw material or the mixture can be reduced, as compared with the case where the dehydration is performed under atmospheric pressure or higher, The content of metal atoms derived from the contact portion in the arylene sulfide resin can be reduced.

The dihaloaromatic compound used in the present invention acts as a solvent for securing the fluidity of the resulting mixture in the dehydration step (1), but can be used as a polymerization raw material in the subsequent polymerization step. Examples of the dihaloaromatic 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 Examples of the aromatic ring of each compound include a compound having an alkyl group in the range of 1 to 18 carbon atoms as a nuclear substituent.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 above-mentioned dihaloaromatic compounds, p-dichlorobenzene from the viewpoint that the mechanical strength and moldability of the finally obtained polyarylene sulfide resin will be particularly excellent when the linear polyarylene sulfide resin is efficiently produced. M-dichlorobenzene, 4,4'-dichlorobenzophenone and 4,4'-dichlorodiphenyl sulfone are preferred, and p-dichlorobenzene is particularly preferred.

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

In the dehydration step (1), the amount of the dihaloaromatic compound added is preferably 0.2 mol or more, more preferably 0.3 mol or more, preferably 5. It is in the range of 0 mol or less, more preferably 2.0 mol or less. If it is 0.2 mol or more, it is preferable from the viewpoint of securing the fluidity of the mixture, and if it is 5.0 mol or less, the total amount of heat necessary for heating can be suppressed, and it is preferable from the viewpoint of excellent productivity.

As the sulfidizing agent used in the present invention, alkali metal sulfide or alkali metal hydrosulfide and alkali metal hydroxide can be mentioned. In general, alkali metal sulfides and alkali metal hydrosulfides are used as raw materials of polyarylene sulfide resin as so-called hydrates containing crystal water, and in that case, the solid content concentration is preferably 10% by mass. The liquid or solid hydrate is used preferably in the range of 35% by mass or more, preferably 80% by mass or less, more preferably 65% by mass or less.

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.

In addition, although it is also obtained by reacting an alkali metal sulfide with an alkali metal hydrosulfide and an alkali metal hydroxide, it is possible to use one prepared in the same reaction system as the dehydration step (1). You may use what was previously prepared by the reaction system different from dehydration process (1). Specific examples of the alkali metal hydroxide include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide. Among these, lithium hydroxide and sodium hydroxide and potassium hydroxide are particularly preferable, and sodium hydroxide is particularly preferable. 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. Moreover, as an alkali metal hydrosulfide used by this invention, lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide etc. are mentioned, for example. These may be used alone or in combination of two or more. Among these alkali metal hydrosulfides, sodium hydrosulfide and potassium hydrosulfide are preferable, and sodium hydrosulfide is particularly preferable. Furthermore, although an alkali metal hydrosulfide can also be obtained by reacting hydrogen sulfide with an alkali metal hydroxide, 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 ring-opened by hydrolysis, and specific examples of such aliphatic cyclic compounds can be used. As N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, N-methyl-ε-caprolactam, formamide, acetamide, N-methylformamide, N, N Aliphatic cyclic amide compounds such as -dimethylacetamide, 2-pyrrolidone, ε-caprolactam, hexamethylphosphoramide, tetramethylurea, N-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinonic acid, amidourea And lactams. Among these, aliphatic cyclic amide compounds, particularly NMP, are preferable in terms 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 and 4.0 mol or less with respect to 1 mol of sulfur atom of the sulfidizing agent, but it is more preferable. In the case of producing a high molecular weight polyarylene sulfide resin, it is preferably in the range of 0.01 or more, preferably in the range of 0.9 mol, more preferably 0. It is less than 9 moles, more preferably in the range of 0.5 moles or less.

In the dehydration step (1), dehydration is allowed to proceed under reduced pressure. More specifically, the temperature of the solution is 90 ° C. or more, preferably 110 ° C. or more, more preferably 120 ° C. or more, and the sulfidizing agent containing water and the aliphatic cyclic compound capable of ring opening by hydrolysis. While heating to a temperature in the range of 150.degree. C. or less, preferably 140.degree. C. or less, more preferably 130.degree. C. or less, and preferably under a pressure in the range of 30 kPa abs or more to atmospheric pressure or less. After reacting while dehydrating under atmospheric pressure, a dihaloaromatic compound is further added, and the liquid temperature is 90 ° C. or more, preferably 110 ° C. or more, more preferably 120 ° C. or more, still more preferably 130 ° C. or more. While heating to a range of 170 ° C. or less, preferably 160 ° C. or less, more preferably 150 ° C. or less, particularly preferably less than 150 ° C., and bs] or more, preferably 35 [kPa abs or more, more preferably 40 [kPa abs] or more, to 80 [kPa abs] or less, preferably 70 [kPa abs] or less, more preferably 60 [kPa abs] There is a method of dehydrating by reducing the pressure to be in the following range.

In the dehydration step (1), the addition time of the dihaloaromatic compound is not particularly limited, but the dehydration progress is preferably 30% or more, more preferably 40% or more and 70% or less, more preferably More preferably, it is at a point in the range of 60% or less.

The degree of progress of dehydration is determined by measuring the total amount of water in the reaction system before the start of the dehydration step (1) and subtracting the total amount of water in the reaction system after the completion of the desired dehydration step (1) The target moisture content of the distilled water (hereinafter referred to as the target distilled water content) is set, and the present moisture content of the distilled water according to the progress of dehydration in the dehydration step The water content can be measured to obtain “current water content to be distilled” / “target water content to be distilled” × 100 (%). However, since there is a time lag related to exhausting as vapor from the reaction system and distillation and separation in the distillation apparatus, an error range of ± 20% shall be acceptable.

For dehydration, while controlling the liquid temperature and pressure within the above range, open the valve of the pipe leading from the reaction system to the distillation apparatus and distill the mixture of aliphatic cyclic compound, water and dihaloaromatic compound It is done by In the distillation, an aliphatic cyclic compound is isolated, and then a mixed vapor containing water and a dihaloaromatic compound as main components is condensed by a condenser, the water and the dihaloaromatic compound are separated by a decanter or the like, and azeotropic distillation And the like, for example, a method of returning the dihaloaromatic compound into 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, they correspond to the azeotropically distilled amount. If an aliphatic cyclic compound or a dihaloaromatic compound is additionally charged, or after considering the azeotropically distilling amount, an excess of the aliphatic cyclic compound or the dihaloaromatic compound may be charged in advance. Good.

As described above, in the dehydration step (1) of the present invention, water is discharged out of the reaction system by dehydration treatment, and the aliphatic cyclic compound that can be opened by hydrolysis is hydrolyzed, and at the same time, an anhydrous sulfidizing agent Preferably, it is a process in which anhydrous alkali metal sulfide is formed. If excess water is present in the reaction system after dehydration treatment, a large amount of by-products are generated in the subsequent polymerization step to induce growth end termination reaction, and chain extension reaction of polyarylene sulfide resin, As a result, it tends to inhibit viscosity increase or high molecular weight formation. Therefore, it is preferable that the total water content in the reaction system after the dehydration step (1) be as small as possible. Specifically, it is preferably 0. 1 per mol of sulfur atoms of the sulfidizing agent used in the dehydration step (1). The amount of water is in the range of 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 water content in the reaction system" refers to water consumed for hydrolysis of the aliphatic cyclic compound, crystal water remaining in a small amount in the sulfidizing agent, and other water present in the reaction system. It is the total mass of all.

Furthermore, it is preferable that the amount of water existing in the reaction system after the dehydration step (1) be in a range of 0.4 mol or less per 1 mol of sulfur atom of the sulfidizing agent in the reaction system. It is more preferable that the ratio be in the range of 0.4 mol or less from the limit, and it is further preferable that the ratio be in the range of 0.03 mol or more to 0.11 mol or less as a range excellent in the efficiency of dehydration. 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 amount of water in the reaction system, that is, water of crystallization, H ₂ The total amount of water (hereinafter, these are called "crystal water, etc.") actually present in the reaction system as O, etc. is said.

As described above, according to the present invention, by promoting dehydration under reduced pressure, liberation of crystal water in the sulfidizing agent is promoted even at a lower heating temperature, and a reaction system which is a cause of causing a side reaction in the polymerization step Water is efficiently removed, it is also converted to a hydrolyzate of an aliphatic cyclic compound that is considered to exhibit a polymerization promoting action, and as a result, along with the polymerization promotion, side reactions during polymerization are It can be suppressed.

・ Dehydration process (2)
In the present invention, an optional aprotic polar organic solvent may be added to the mixture obtained in the dehydration step (1), and water may be distilled off to carry out dehydration as an optional step. . In the dehydration step (2), the charged amount of the aprotic polar solvent into the reaction system is preferably in the range of 0.5 mol or more and 5 mol or less with respect to 1 mol of sulfur atom of the sulfidizing agent Is preferably added. If the amount of water existing in the reaction system is within the range of less than 0.03 mol with respect to 1 mol of sulfur atom of the sulfidizing agent, the dehydrating efficiency tends to be greatly reduced. After the dehydration step (1), by further performing the dehydration step (2), the amount of water contained in the reaction system at the end of the dehydration step (2) relative to 1 mol of sulfur atoms of the sulfidizing agent The concentration can be adjusted in the range of less than 0.03 mol, preferably in the range of less than 0.03 mol from the detection limit, and more preferably, in the range of from the detection limit or more to 0.01 mol or less.

Dehydration in the dehydration step (2) can be carried out under the conditions where the liquid temperature is in the range of 90 ° C. to 220 ° C., and in the range of 30 kPa abs to 202 kPa abs. Among them, dehydration processing conditions under the same reduced pressure as the dehydration step (1), that is, the liquid temperature is preferably 90 ° C. or more, more preferably 110 ° C. or more, still more preferably 130 ° C. or more to 160 ° C. or less Is preferably 30 kPa abs or more, more preferably 35 kPa abs or more, and still more preferably 40 kPa abs or more, preferably 80 kPa while heating to a temperature of 150 ° C. or less. abs] or less, more preferably 70 [kPa abs] or less, still more preferably 60 [kPa abs] or less From the viewpoint of performing the dehydration while the pressure was reduced it can be efficiently dehydrated at lower liquid temperature.

It is preferable to carry out the dehydration step (2) in the same reaction vessel as the dehydration step (1) from the viewpoint of sharing production facilities and improving productivity, but on the other hand, resin production per unit time 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 Next, according to the present invention, the mixture obtained through the dehydration step (1) is heated in the range of 0.4 mol or less of the existing water content in the reaction system to 1 mol of the dihaloaromatic compound. And a polymerization step to cause a polymerization reaction. When dehydration step (2) is performed after dehydration step (1), the mixture obtained through dehydration step (2) is present in the reaction system relative to 1 mol of dihaloaromatic compound. The polymerization reaction can be carried out by heating in the range of less than 0.03 mol of water content.
In the polymerization step, the polymerization reaction proceeds by heating the mixture obtained through the dehydration step (1) to the dehydration step (2) to a range of 200 ° C. or more and 300 ° C. or less in a closed reaction vessel. Process.

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 210 ° C. or more and 280 ° C. or less, More preferably, the reaction is performed in the range of 215 ° C. or more and 250 ° C. or less.

As described above, since the dihaloaromatic compound which is the polymerization raw material is charged azeotropically by distillation in addition to being charged in the dehydration step (1), the dihaloaromatic compound is taken into consideration after considering the amount to be azeotropically distilled off. The compound of the group is previously charged in excess in the dehydration step, or the dihaloaromatic compound is additionally charged until the polymerization step is started, and the ratio of the dihaloaromatic compound in the reaction system is the sulfur atom of the sulfidizing agent It is preferably in the range of 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 to 1 mol. Adjust for reaction.

The amount of water existing in the reaction system at the start of 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 less per 1 sulfur atom of the sulfidizing agent. It is preferably in the range of 0.4 mol or less, more preferably 0.11 mol or less, still more preferably 0.08 mol or less, particularly preferably 0.03 mol or less, most preferably 0.01 mol or less. As the polymerization reaction proceeds, water is produced, so that at the end of the polymerization reaction of the polymerization step, water is produced in the range of 0.1 mol or more and 0.3 mol or less per mol of sulfur atom of the sulfidizing agent. The above range is preferably satisfied after the point at which the conversion of the dihaloaromatic compound exceeds 80% by mole, more preferably after the point at which the conversion of the dihaloaromatic compound exceeds 60% by mole, more preferably immediately after the start of the polymerization.

Here, the conversion of the dihaloaromatic compound is represented by the following formula.
Conversion rate (%) = (charged amount-residual amount) / charged amount × 100
However, "the amount charged" represents the mass of the dihaloaromatic compound charged into the reaction system, and the "remaining amount" represents the mass of the dihaloaromatic 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 added as it is or after adding an acid or a base, under reduced pressure or normal pressure. The solvent is distilled off with water, and the solid after evaporation is washed once or twice or more with a solvent such as water, acetone, methyl ethyl ketone or alcohols, followed by neutralization, water washing, filtration and drying, or After completion of the polymerization reaction, the reaction mixture contains a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons (soluble in the polymerization solvent used, and Solid solvent such as polyarylene sulfide resin and inorganic salt by adding at least a solvent which is a poor solvent to polyarylene sulfide resin as a precipitant The product was precipitated, and these were separated by filtration, washed and dried, or after completion of the polymerization reaction, the reaction mixture was added with a reaction solvent (or an organic solvent having equivalent solubility to a low molecular weight polymer) and stirred. Then, after filtering to remove low molecular weight polymers, washing is performed once or twice or more with a solvent such as water, acetone, methyl ethyl ketone or alcohols, followed by neutralization, water washing, filtration and drying. 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 the air or in an inert gas atmosphere such as nitrogen.

The polyarylene sulfide resin thus obtained can be used as it is for various molding materials and the like, but may be oxidized and crosslinked by heat treatment in air or oxygen-enriched air or under reduced pressure conditions. The temperature of the heat treatment is preferably in the range of 180 ° C. or more to 270 ° C. or less, although it varies depending on the target crosslinking treatment time and the treatment atmosphere. The heat treatment may be carried out in a molten state of the polyarylene sulfide resin at a temperature above the melting point of the polyarylene sulfide resin using an extruder or the like, but the possibility of thermal degradation of the polyarylene sulfide resin is increased. It is preferable to carry out at a temperature of 100 ° C. or less.

-Production device The reaction device used in each of the above steps in the method for producing a polyarylene sulfide resin of the present invention is a raw material, that is, a dihaloaromatic compound, a sulfidizing agent, an alkali catalyst, etc. Part, or all, of the contact portion with the group cyclic compound, the mixture obtained through the dehydration step, and the polymerization reactant including the polyarylene sulfide resin obtained after the polymerization reaction is composed of titanium, zirconium or nickel alloy It is preferable from the viewpoint of corrosion resistance to use the same.

Examples of the reaction apparatus include batch type reaction containers (autoclave, reaction kettle) equipped with stirring blades inside, reaction containers (polymerization line) such as continuous reaction containers, stirring blades, baffles and the like.

For example, the batch type reaction vessel may be any vessel capable of holding the raw material, the mixture or the polymerization reaction inside the reaction vessel, and is composed of, for example, a top cover, a body and a bottom, and if necessary There is a structure having a sealable structure, and a structure having a stirring blade, an axis transmitting power to the stirring blade, a baffle plate, and a temperature control serpentine inside is preferable from the viewpoint of excellent stirring efficiency. Here, as a stirring blade, an anchor type stirring blade, a turbine type stirring blade, a screw type stirring blade, a double helical type stirring blade, etc. are mentioned. It is preferable from the viewpoint of facilitating heat conduction and heat control that the lower end of the baffle plate is installed near the bottom surface of the reaction vessel and the upper end of the baffle plate is extended to the position where it comes out of the liquid surface.

On the other hand, the continuous reaction vessel includes, for example, a tubular reactor in which a plurality of mixing elements without moving parts are fixed, a polymerization line in which the tubular reactors are connected in series, or a plurality of tubulars What forms a continuous annular polymerization line which has a structure which connects a reactor and circulates a part of reaction liquid to the raw material inlet of the said tubular reactor is mentioned. These continuous reaction containers can feed raw materials and transfer reaction liquid by a plunger pump or the like.

In addition, the reaction vessel is further equipped with various measuring devices such as a thermometer, a pressure gauge, a safety valve and the like, and the piping and the open / close valve leading to the steam device outside thereof, a condenser, a decanter, a distillate (a decanter Organic layer component) Distillation equipment such as return line, distillate (water layer component of decanter) distillation line, and pressure reduction valve such as pressure control valve, vacuum pump, hydrogen sulfide capture device, etc. Is preferred.

In the reaction apparatus used in the present invention, at least a part of the contact portion may preferably be composed entirely of the nickel alloy. From the viewpoint of corrosion resistance, the nickel alloy used herein preferably has a chromium content in the range of 43% to 47% by mass, and a molybdenum content in the range of 0.1% to 2% by mass. 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 a trace amount of impurities which are technically difficult to remove. In the present invention, for example, a carbon atom contained in the alloy in a proportion of 3% by mass or less, preferably 1% by mass or less, more preferably the detection limit or less is mentioned.

Molding, etc. The polyarylene sulfide resin obtained by the manufacturing method of the present invention described in detail above includes a filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, a crosslinkable resin having two or more functional groups, At least one other component selected from the group consisting of silane coupling agents is compounded, and heated to a temperature equal to or higher than the melting point of the polyarylene sulfide resin, and then melt-kneaded through the process of polyarylene sulfide resin composition It can be done.

Although it does not restrict | limit especially as a filler, For example, a fibrous filler, an inorganic filler, etc. are mentioned. Examples of fibrous fillers include glass fibers, carbon fibers, silane glass fibers, ceramic fibers, aramid fibers, metal fibers, fibers such as potassium titanate, silicon carbide, calcium sulfate and calcium silicate, and natural fibers such as wollastonite Can be used. In addition, as the inorganic filler, barium sulfate, calcium sulfate, clay, viroferrite, bentonite, sericite, zeolite, mica, mica, mica, talc, atalpulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, etc. It can be used. In addition, various additives such as a mold release agent, a colorant, a heat resistant stabilizer, an ultraviolet light stabilizer, a foaming agent, a rust inhibitor, a flame retardant, a lubricant and the like can be contained as an additive during molding processing.

Furthermore, as thermoplastic resins other than the said polyarylene sulfide resin mix | blended with the polyarylene sulfide resin composition of this invention, polyester, a polyamide, a polyimide, a polyether imide, a polycarbonate, a polyphenylene ether, a polysulfone, a polyether sulfone , Polyetheretherketone, polyetherketone, polyarylene, polyethylene, polypropylene, polytetrafluorinated ethylene, polydifluorinated ethylene, polystyrene, ABS resin, epoxy resin, silicone resin, silicone resin, phenolic resin, urethane resin, liquid crystal polymer, etc. You may use as a polyarylene sulfide resin composition which mix | blended the synthetic resin. The proportion of the thermoplastic resin other than the polyarylene sulfide resin is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more with respect to 100 parts by mass of the polyarylene sulfide resin. The amount is preferably 300 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 45 parts by mass or less. When the content of the thermoplastic resin other than the polyarylene sulfide resin is in these ranges, the effect of further improving the heat resistance, the chemical resistance and the mechanical physical properties can be obtained.

As an elastomer mixed with the polyarylene sulfide resin composition of the present invention, it is mentioned that a thermoplastic elastomer is used. Examples of thermoplastic elastomers include polyolefin elastomers, fluorine elastomers and silicone elastomers. In the present specification, thermoplastic elastomers are classified not into the thermoplastic resin but into elastomers.

The elastomer (especially the thermoplastic elastomer) preferably has a functional group capable of reacting with a hydroxy group or an amino group. Thereby, the resin composition which was especially excellent in points, such as adhesiveness and impact resistance, can be obtained. Such functional groups include epoxy group, carboxy group, isocyanate group, oxazoline group, and the formula: R (CO) O (CO)-or R (CO) O- (wherein R represents one or more carbon atoms) And a group represented by the following 8 alkyl groups: The thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerization of an α-olefin and a vinyl polymerizable compound having the above functional group. Examples of the α-olefins include α-olefins in the range of 2 to 8 carbon atoms such as ethylene, propylene and butene-1. Examples of the vinyl polymerizable compound having a functional group include, for example, α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid esters and alkyl esters thereof, maleic acid, fumaric acid, itaconic acid and the like Other α, β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono- or di-esters and acid anhydrides thereof), glycidyl (meth) acrylates and the like can be mentioned. Among these, an epoxy group, a carboxy group, and a formula: R (CO) O (CO)-or R (CO) O-(wherein R represents an alkyl group having a carbon number of 1 to 8). Ethylene-propylene copolymers and ethylene-butene copolymers having at least one functional group selected from the group consisting of groups represented by) are preferable from the viewpoint of improvement in toughness and impact resistance.

The proportion of the elastomer varies depending on the type and application, but can not be generally defined, but for example, preferably 1 part by mass or more, more preferably 3 parts by mass or more, with respect to 100 parts by mass of the polyarylene sulfide resin. The amount is preferably in the range of 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, an even more excellent effect can be obtained in securing the heat resistance and the 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 epoxy group, phenolic hydroxyl group, amino group, amido group, carboxy group, acid anhydride group, and isocyanate group. As a crosslinkable resin, an epoxy resin, a phenol resin, and a urethane resin are mentioned, for example.

The compounding amount of the crosslinkable resin is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, preferably 300 parts by mass or less with respect to 100 parts by mass of the polyarylene sulfide resin. It is more preferably in the range of 100 parts by mass or less, still more preferably 30 parts by mass or less. When the compounding amount of the crosslinkable resin is in these ranges, the effect of improving the rigidity and heat resistance of the molded article can be particularly remarkably obtained.

As a silane coupling agent blended with the polyarylene sulfide resin composition of the present invention, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxy) Examples include cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane.

The compounding amount of the silane compound is, for example, preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 10 parts by mass or less, more preferably 100 parts by mass of the polyarylene sulfide resin. It is a range of 5 parts by mass or less. When the compounding quantity of a silane compound exists in these ranges, the effect of the compatibility improvement with polyarylene sulfide resin and said other component is acquired.

The polyarylene sulfide resin composition of the present invention may further contain other additives such as a mold release agent, a colorant, a heat resistant stabilizer, an ultraviolet light stabilizer, a foaming agent, a rust inhibitor, a flame retardant and a lubricant. . It is preferable that the compounding quantity of an additive is the range of 1 mass part or more and 10 mass parts or less with respect to 100 mass parts of polyarylene sulfide resin, for example.

The polyarylene sulfide resin composition can be obtained, for example, in the form of a pellet-like compound or the like 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 more, more preferably 290 ° C. or more, preferably 350 ° C. or less, more preferably 330 ° C. or less. Melt-kneading can be performed using a twin-screw extruder etc.

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 materials such as the other components. Thus, it can be processed into a molded article excellent in heat resistance, moldability, 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 high-quality molded articles, particularly thin-walled molded articles excellent in insulation.

The polyarylene sulfide resin obtained by the production method of the present invention and the composition thereof also have various properties such as the inherent heat resistance and dimensional stability of the polyarylene sulfide resin, and thus, for example, connectors, printed boards and seals Electrical and electronic parts such as molded parts, automobile parts such as lamp reflectors and various electric parts, interior materials for various buildings, aircrafts and automobiles, or precision parts such as office equipment parts, camera parts and watch parts It is widely useful as a material for various molding processes such as injection molding or compression molding, or extrusion molding of composites, sheets, pipes and the like, or pultrusion, or as materials for fibers or films.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

(Measurement of metal atom content)
In a platinum crucible, 100 mg of PPS resin was weighed, and 2 ml of concentrated sulfuric acid was added. This was placed on an electric heater, and thermal decomposition was performed until white smoke of sulfuric acid did not come out. Thereafter, the decomposition product-containing crucible was placed in an electric furnace, thermally decomposed at 800 ° C. for 3 hours, and completely incinerated. The crucible was cooled and the contents were flushed out into the measuring flask with 10 ml of 1N hydrochloric acid. Then, it was washed out once with 5 ml of distilled water over 5 times into a 100 ml measuring flask, and the measuring flask was made up with distilled water to make a 100 ml dilution. The resulting diluted solution was measured for metal ion content using an ICP emission spectrophotometer ("Optical Emission Spectrometer Optima 4300 DV" manufactured by Perkin-Elmer, Inc.) to remove sodium ion used as a polymerization raw material , Metal ion content was described. The detection limit is 0.01 ppm.

(Measuring method of melt viscosity)
The melt viscosity (η) of the PPS resin was held at 300 ° C., 1.96 MPa, L / D = 10 (mm) / 1 (mm) for 6 minutes using a flow tester (“CFT 500 D” manufactured by Shimadzu Corporation) It is the 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 solid-liquid separation was performed by a centrifuge. Thereafter, 1 μL of the supernatant was collected and measured by gas chromatography.

Measurement by gas chromatograph is performed by Shimadzu gas chromatography “GC 2014” (column: column “G300” manufactured by Chemical Substances Evaluation Research Corporation, carrier gas: helium, measurement column conditions: 140 ° C. for 5 minutes → 3 ° C.) Temperature / 200 ° C. for 20 minutes). In order to determine the phenol concentration, first, a standard curve was prepared with a standard sample. Next, a peak area of the same retention time as that of the standard sample was obtained from the chromatogram obtained by measuring the supernatant prepared above. The concentration in the solution was determined from the peak area and the calibration curve, and the number of moles of phenol was calculated as a percentage per 1 mole of sulfide agent (1 mole of sulfur atoms in total) (hereinafter "mol% / S" ).

(Quantification of water content)
The water content was measured by a Karl Fischer volumetric titration method using a Karl Fischer moisture measuring device (AQV-300 manufactured by Hiranuma Sangyo Co., Ltd.). The detection limit is 6.0 × 10 ⁻⁶ mol with respect to 1 mol of sulfur atom.

Example 1
・ Dehydration process (1)
Thermometer, heating device, titanium stirring blade and pressure gauge, raw material (pDCB) storage tank, raw material (NMP) storage tank, decompression device (pressure control valve, vacuum pump and recovery device of scattered hydrogen sulfide) and distillation To an autoclave made of a nickel alloy (Ni-Cr-Mo alloy containing 45% by mass of chromium, 1% by mass of molybdenum and 1% by mass of molybdenum) connected to the apparatus (refraction column, condenser and decanter) respectively , NMP 29.7 parts by mass (0.3 molar parts), 45 wt% NaSHaq. 123.6 parts by mass (1.5 molar parts) and 48 wt% NaOH aq. 125.0 g (1.5 mol parts) was charged at room temperature, and while the autoclave was sealed, the temperature was raised to a liquid temperature of 90 ° C. under a nitrogen atmosphere while stirring.

Thereafter, the valve of the pipe leading from the autoclave to the distillation apparatus was opened, dehydration was started under atmospheric pressure, and the temperature was raised to a liquid temperature of 128 ° C. Condensate the mixed vapor of water and p-DCB discharged from the rectification column with a condenser, separate the water and p-DCB with a decanter, and if necessary, distill the water out of the system, p-DCB into the autoclave It returned.

When the amount of distilled water reaches 60 parts by mass and reaches 60% of the target amount of distilled water (the target distilled water content is 123.5 parts by mass), p − 220.5 parts by mass (1.50 parts by mole) of dichlorobenzene (hereinafter, abbreviated as p-DCB) was pumped out from a pipe by opening a valve leading to the raw material storage tank, and charged into an autoclave.

Next, while continuing the dewatering, open the valve of the piping that leads to the decompression device, and reduce the pressure from atmospheric pressure to 47 [kPa abs] at a rate of -6.6 [kPa abs] / min. The temperature was gradually raised at a rate of 0.1 ° C./min to 147 ° C., and dehydration was carried out while maintaining a solution temperature of 147 ° C., finally 47 kPa abs. Condensate the mixed vapor of water and p-DCB discharged from the rectification column with a condenser, separate the water and p-DCB with a decanter, and if necessary, distill the water out of the system, p-DCB into the autoclave It returned. When the total amount of total water distilled out of the system by dehydration reached 123.5 parts by mass, the valve of the pipe from the autoclave to the distillation apparatus was closed to complete the dehydration. The dehydration time was 96 minutes in total. The inside of the autoclave after the dehydration reaction was in a slurry state in which fine particulate anhydrous sodium sulfide composition was dispersed in DCB, and the remaining amount of water was 0.3 mol per 1 sulfur atom in the autoclave.

Polymerization Step The autoclave containing the mixture obtained in the dehydration step was placed under a nitrogen atmosphere, and the valve was closed to seal the reaction system. The liquid temperature was set to 160 ° C., 415.8 parts by mass (4.2 mol parts) of NMP previously set in the raw material storage tank was opened by a valve leading to the raw material storage tank, pumped out from the piping and charged in the autoclave . Then, the temperature was raised to 220 ° C. and stirred for 2 hours, and then the temperature was raised to 250 ° C. and stirred for 1 hour. The final pressure was 373 [kPa abs]. Then, it cooled to room temperature.

Post-Treatment Step After cooling, the obtained slurry was poured into 3000 parts by mass of water, stirred at 80 ° C. for 1 hour, and 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, and after filtration, it was dried overnight at 120 ° C. in a hot air dryer to obtain 154 parts by weight 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.

(Reference Example 1)
・ Dehydration process (1)
Thermometer, heating device, titanium stirring blade and pressure gauge, raw material (NMP) storage tank, decompression device (pressure control valve, vacuum pump and recovery device of scattered hydrogen sulfide) and distillation device (refining column, condenser) P-Dichlorobenzene (below) in an autoclave made of a nickel alloy (a Ni-Cr-Mo alloy containing 45% by mass of chromium, 1% by mass of molybdenum and 1% by mass of molybdenum) connected to each of , 22. 5 parts by mass (1.50 parts by mol) of p-DCB, 29.7 parts by mass (0.3 parts by mol) of NMP, 45 wt% NaSHaq. 123.6 parts by mass (1.5 molar parts) and 48 wt% NaOH aq. 125.0 g (1.5 mol parts) was charged, and while the autoclave was sealed, the temperature was raised to a liquid temperature of 128 ° C. under a nitrogen atmosphere while stirring.

Next, open the valve of the pipe leading from the autoclave to the distillation device, start dehydration, and open the valve of the pipe leading to the decompression device, and from the atmospheric pressure 47 at a rate of -6.6 [kPa abs] / min. While the pressure is reduced to [kPa abs], the temperature of the liquid is gradually raised from 128 ° C. to 147 ° C. at a rate of 0.1 ° C./min, and finally 47 kPa abs, liquid temperature 147 ° C. for 4 hours Dehydrated. Condensate the mixed vapor of water and p-DCB discharged from the rectification column with a condenser, separate the water and p-DCB with a decanter, and if necessary, distill the water out of the system, p-DCB into the autoclave It returned. Meanwhile, the amount of distilled water is 123.5 parts by mass, and the inside of the autoclave after the dehydration reaction is in a slurry state where the particulate anhydrous sodium sulfide composition is dispersed in DCB, and the remaining amount of water is the autoclave It was 0.3 mole per mole of sulfur atom present therein.

(Comparative example 1)
"Next, while continuing the dewatering, open the valve of the piping that leads to the decompression device, and reduce the pressure from atmospheric pressure to 47 [kPa abs] at a rate of -6.6 [kPa abs] / min and The temperature of the solution was gradually raised to 147 ° C. at a rate of 0.1 ° C./min, and finally the portion was dehydrated while maintaining the solution temperature of 147 ° C. at 47 kPa abs. ”
"Then, while continuing the dewatering, the temperature of the liquid, which had once dropped, was gradually raised at a rate of 0.1 ° C / min to 173 ° C and finally dehydrated while maintaining the liquid temperature of 173 ° C under atmospheric pressure. The same operation as in Example 1 was carried out except that the above was adopted.

In the dehydration step (1), when the total amount of total water distilled out of the system by dehydration reached 123.5 parts by mass, the valve of the pipe from the autoclave to the distillation apparatus was closed to complete the dehydration. The inside of the autoclave after the dehydration reaction was in a slurry state in which a particulate anhydrous sodium sulfide composition was dispersed in DCB, and the remaining amount of water was 0.31 mol per 1 mol of sulfur atoms present in the autoclave.

Further, after the post-treatment step, the melt viscosity of the obtained PPS resin was 65 Pa · s, the amount of phenol produced was 0.1 mol%, and the total metal content of chromium, molybdenum and nickel was 23 ppm.

(Comparative example 2)
"Next, while continuing the dewatering, open the valve of the piping that leads to the decompression device, and reduce the pressure from atmospheric pressure to 47 [kPa abs] at a rate of -6.6 [kPa abs] / min and The temperature of the solution was gradually raised to 147 ° C. at a rate of 0.1 ° C./min, and finally the portion was dehydrated while maintaining the solution temperature of 147 ° C. at 47 kPa abs. ”
"Then, while continuing the dewatering, the temperature of the liquid, which had once dropped, was gradually raised at a rate of 0.1 ° C / min to 147 ° C, and finally dehydrated while maintaining the liquid temperature of 147 ° C under atmospheric pressure. Basically, the same procedure as in Example 1 was carried out except that the above was adopted.

However, in the dehydration step (1), when the dehydration time reached 96 minutes in total, the valve of the pipe from the autoclave to the distillation apparatus was closed to complete the dehydration. The total amount of total water distilled out of the system by dehydration was 49.4 parts by mass. The inside of the autoclave after the dehydration reaction was in a slurry state in which particulate anhydrous sodium sulfide composition was dispersed in DCB, and the remaining amount of water was 3 moles per 1 sulfur atom 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 could not be measured for melt viscosity. 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 to be “an autoclave whose inner wall (wetted part) is a nickel alloy (Ni-Cr-Mo alloy containing 45% by mass of chromium, 1% by mass of molybdenum and the remainder of nickel)” is
The same procedure as in Example 1 was performed except that "the inner wall (wetted portion) was an autoclave made of titanium".

In the dehydration step (1), when the total amount of total water distilled out of the system by dehydration reached 123.5 parts by mass, the valve of the pipe from the autoclave to the distillation apparatus was closed to complete the dehydration. The inside of the autoclave after the dehydration reaction was in the form of a slurry in which fine particulate anhydrous sodium sulfide composition was dispersed in DCB, and the remaining amount of water was 0.29 mol per mol of sulfur atoms present in the autoclave.

Further, after the post-treatment step, the melt viscosity of the obtained PPS resin was 67 Pa · s, the amount of phenol produced was 0.08 mol%, and the metal content of titanium was below the detection limit value.

(Comparative example 3)
The part to be “an autoclave whose inner wall (wetted part) is a nickel alloy (Ni-Cr-Mo alloy containing 45% by mass of chromium, 1% by mass of molybdenum and the remainder of nickel)” is
The same procedure as in Comparative Example 1 was followed except that "the inner wall (wetted portion) was an autoclave made of titanium".

In the dehydration step (1), when the total amount of total water distilled out of the system by dehydration reached 123.5 parts by mass, the valve of the pipe from the autoclave to the distillation apparatus was closed to complete the dehydration. The inside of the autoclave after the dehydration reaction was in the form of a slurry in which fine particulate anhydrous sodium sulfide composition was dispersed in DCB, and the remaining amount of water was 0.27 moles per mole of sulfur atoms present in the autoclave.

Further, after the post-treatment step, the melt viscosity of the obtained PPS resin was 65 Pa · s, the amount of phenol produced was 0.09 mol%, and the metal content of titanium was 5 ppm.

(Comparative example 4)
The part to be “an autoclave whose inner wall (wetted part) is a nickel alloy (Ni-Cr-Mo alloy containing 45% by mass of chromium, 1% by mass of molybdenum and the remainder of nickel)” is
The same procedure as in Comparative Example 2 was followed except that "the inner wall (wetted portion) was an autoclave made of titanium".

In the dehydration step (1), when the dehydration time reached 96 minutes in total, the valve of the pipe from the autoclave to the distillation apparatus was closed to complete the dehydration. The total amount of total water distilled out of the system by dehydration was 50.2 parts by mass. The inside of the autoclave after the dehydration reaction was in a slurry state in which a particulate anhydrous sodium sulfide composition was dispersed in DCB, and the remaining amount of water 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 could not be measured for melt viscosity. The amount of phenol produced was 0.5 mol%, and the metal content of titanium was 2 ppm.

(Example 3)
"Then, the valve of the pipe leading from the autoclave to the distillation apparatus is opened, dehydration is started under atmospheric pressure, and the temperature is raised to a liquid temperature of 128 ° C."
"After that, the valve of the pipe leading from the autoclave to the distillation apparatus was opened, dehydration was started under atmospheric pressure, and the liquid temperature was raised to 105 ° C.",
"Next, while continuing the dewatering, open the valve of the piping that leads to the decompression device, and reduce the pressure from atmospheric pressure to 47 [kPa abs] at a rate of -6.6 [kPa abs] / min and The temperature of the solution was gradually raised to 147 ° C. at a rate of 0.1 ° C./min, and finally the portion was dehydrated while maintaining the solution temperature of 147 ° C. at 47 kPa abs. ”
"Next, while continuing the dewatering, open the valve of the piping that leads to the decompression device, and reduce the pressure from atmospheric pressure to 32 [kPa abs] at a rate of -6.6 [kPa abs] / min and The temperature of the solution was gradually raised at a rate of 0.1 ° C./min to 115 ° C., and dehydration was carried out while maintaining the solution temperature of 115 ° C. finally at 32 [kPa abs]. The same procedure as in Example 1 was performed.

In the dehydration step (1), when the total amount of total water distilled out of the system by dehydration reached 123.5 parts by mass, the valve of the pipe from the autoclave to the distillation apparatus was closed to complete the dehydration. The inside of the autoclave after the dehydration reaction was in a slurry state in which a particulate anhydrous sodium sulfide composition was dispersed in DCB, and the remaining amount of water was 0.3 mol per 1 sulfur atom present in the autoclave.

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

(Example 4)
"Next, while continuing the dewatering, open the valve of the piping that leads to the decompression device, and reduce the pressure from atmospheric pressure to 47 [kPa abs] at a rate of -6.6 [kPa abs] / min and The temperature of the solution was gradually raised to 147 ° C. at a rate of 0.1 ° C./min, and finally the portion was dehydrated while maintaining the solution temperature of 147 ° C. at 47 kPa abs. ”
"Next, while continuing the dewatering, open the valve of the piping that leads to the decompression device, and reduce the pressure from atmospheric pressure to 70 [kPa abs] at a rate of -6.6 [kPa abs] / min and The temperature of the solution was gradually raised at a rate of 0.1 ° C./min to 155 ° C., and dehydration was carried out while maintaining the solution temperature of 155 ° C. finally at 70 [kPa abs]. It went in the same way as 1.

Also, after the post-treatment step, the melt viscosity of the obtained PPS resin is 65 Pa · s, the amount of phenol produced is 0.09 mol%, and the total metal content of chromium, molybdenum and nickel is below the detection limit value The

Claims

A method for producing a polyarylene sulfide resin, which comprises reacting a dihaloaromatic compound and a sulfidizing agent in the presence of an aliphatic cyclic compound which can be opened by hydrolysis.
The liquid temperature of the sulfidizing agent containing water and the aliphatic cyclic compound capable of ring-opening by hydrolysis is from 30 [kPa abs] to at most atmospheric pressure until the liquid temperature is in the range of 90 to 150 ° C. After making it react, making it dehydrate under the pressure of a range, a dihalo aromatic compound is further added, liquid temperature heats to the range of 90 to 170 degreeC, and pressure is 30 [kPa abs] to 80 [ A method for producing a polyarylene sulfide resin, comprising the dehydration step (1) of obtaining a mixture by reacting while dehydrating in the range of kPa abs] or less.
The method according to claim 1, wherein the dihaloaromatic compound is added at a time when the degree of progress of dehydration is in the range of 30% to 70%.
The production method according to claim 1, wherein the amount of the dihaloaromatic compound is in the range of 0.2 mol or more and 5.0 mol or less with respect to 1 mol in total of the sulfur atoms of the sulfidizing agent.
The production method according to claim 1, wherein the water content existing in the reaction system after completion of the dehydration step (1) is in the range of 0.4 mol or less with respect to 1 mol in total of sulfur atoms of the sulfidizing agent.
The production method according to claim 1, wherein the aliphatic cyclic compound is in the range of 0.01 mol or more and 0.9 mol or less with respect to 1 mol in total of the 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 method according to claim 1, wherein the mixture is a slurry containing an anhydrous solid sulfidizing agent after completion of the dehydration step (1).
Next, a polymerization process is carried out by heating the mixture obtained through the dehydration step (1) in the range of the amount of water existing in the reaction system to 0.4 mol or less with respect to 1 mol of the dihaloaromatic compound, The production method according to claim 1, comprising.
Next, to the mixture obtained through the dehydration step (1), an aprotic polar organic solvent is further added, water is distilled off, and dehydration is performed (2),
Subsequently, the mixture obtained in the dehydration step (2) is subjected to a polymerization reaction in which the water content existing in the reaction system is less than 0.03 mol with 1 mol of the dihaloaromatic compound. Manufacturing method described.
The dewatering step (1), wherein the contact part of the reaction apparatus with the raw material or the mixture obtained after the reaction is composed of at least one material selected from the group consisting of titanium, zirconium and a nickel alloy. Manufacturing method described.
A process for producing a polyarylene sulfide resin by the production method according to claim 1, the obtained polyarylene sulfide resin, a filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and two or more functional groups. At least one other component selected from the group consisting of a crosslinkable resin and a silane coupling agent is blended, heated to a temperature equal to or higher than the melting point of the polyarylene sulfide resin, and melt-kneaded. Process for producing a polyarylene sulfide resin composition
A process for producing a polyarylene sulfide resin molded article, comprising the steps of producing a polyarylene sulfide resin composition by the production method according to claim 11 and melt-molding the obtained polyarylene sulfide resin composition. Method.