JP2018154693A - Method for producing polyarylene sulfide resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method which suppresses a side reaction in a polymerization reaction and produces less accessory component, and produces a high-molecular-weight polyarylene sulfide resin with good productivity.SOLUTION: A method for producing a polyarylene sulfide resin includes: a step 1 of heating an aliphatic cyclic compound, water and a sulfidation agent so that the aliphatic cyclic compound is 1.5-4.0 mol with respect to 1 mol of the total of sulfur atoms of the sulfidation agent to 200°C or higher and 250°C or lower in the presence of inert gas to obtain a reaction liquid containing 0.1-0.3 mol of alkali metal salt of a hydrolysate of the aliphatic cyclic compound with respect to 1 mol of the total of the sulfur atoms; a step 2 of cooling the reaction liquid obtained in the step 1 to 180°C or higher and lower than 200°C; and a step 3 of dehydrating the reaction liquid obtained in the step 2; and a step 4 of heating the reaction liquid obtained in the step 3 to a temperature in a range of 200°C or higher and 300°C or lower in a closed system to subject the resultant substance to a polymerization reaction; and includes adding a poly-halo-aromatic compound to the resultant substance in either the step 3 or the step 4.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a polyarylene sulfide resin.

  A polyarylene sulfide resin (hereinafter abbreviated as “PAS resin”) represented by polyphenylene sulfide resin (hereinafter abbreviated as “PPS resin”) is excellent in heat resistance, chemical resistance and the like. Widely used in electrical and electronic parts, automotive parts, water heater parts, textiles, film applications, etc.

  As a typical method for producing a PAS resin, a polymerization method called a so-called Phillips method in which an alkali metal sulfide and a dihaloaromatic compound are reacted in an organic amide solvent such as N-methyl-2-pyrrolidone is generally used. Among them, a method for producing a high molecular weight PAS resin with high productivity by using 95% by weight or more of high-purity alkali metal sulfide as a raw material is known (see Patent Document 1). ). However, although this method adds 0.1 to 0.8 mol of water per mol of alkali metal sulfide in order to advance the reaction, the added water causes a side reaction during the polymerization reaction, thereby increasing the molecular weight. There were limits.

JP-A-4-145127

  Therefore, the problem to be solved by the present invention is to provide a method for producing a high molecular weight polyarylene sulfide resin with high productivity while suppressing side reactions during the polymerization reaction to reduce the number of side components.

  As a result of various studies, the inventors of the present invention have obtained a high molecular weight polyarylene sulfide resin by heating an aliphatic cyclic compound, water, and a sulfidizing agent in the absence of a polyhaloaromatic compound. The proportion of the alkali metal salt (SMAB) of the hydrolyzate of the aliphatic cyclic compound to be obtained is important. For this purpose, in the absence of the polyhaloaromatic compound, the aliphatic cyclic compound, water, sulfiding agent It is important to release the water of crystallization present in the sulfidizing agent by heating at a high temperature, polyhaloaromatic compound added after alkali metal salt (SMAB) formation of hydrolyzate of aliphatic cyclic compound As a result, it was found important to suppress the side reaction of water, and the present invention was completed.

That is, the present invention is a method for producing a polyarylene sulfide in which a polyhaloaromatic compound and a sulfidizing agent are reacted in the presence of an aliphatic cyclic compound,
In the presence of an inert gas, the ratio of the aliphatic cyclic compound, water, and sulfidizing agent in the range of 1.5 to 4.0 mol of the aliphatic cyclic compound with respect to 1 mol of the total sulfur atom of the sulfidizing agent. And a reaction liquid containing an alkali metal salt of an aliphatic cyclic compound hydrolyzate in a range of 0.05 to 0.6 mol with respect to a total of 1 mol of the sulfur atoms. (1) to obtain
The step (2) of cooling the reaction solution obtained in the step (1) to a range of 150 ° C. or higher and lower than 200 ° C .;
Dehydrating the reaction solution obtained in step (2) (3),
A polymerization reaction is carried out by adding a polyhaloaromatic compound to the reaction vessel containing the reaction solution obtained in step (3), and heating in a sealed reaction vessel to a range of 200 ° C. or more and 300 ° C. or less. Step (4),
And a process for producing a polyarylene sulfide resin.

  Further, the present invention provides at least one selected from the group consisting of a polyarylene sulfide resin obtained by the production method described above, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a curable resin. The present invention relates to a method for producing a polyarylene sulfide resin composition, comprising a step of melt-kneading one.

  Moreover, this invention relates to the manufacturing method of a polyarylene sulfide resin molded article including the process of shape | molding the polyarylene sulfide resin composition obtained by the said manufacturing method.

  According to the present invention, it is possible to provide a method for producing a high-molecular-weight polyarylene sulfide resin with high productivity while suppressing side reactions during the polymerization reaction and having a small number of side components.

The method for producing polyarylene sulfide of the present invention is a method for producing polyarylene sulfide in which a polyhaloaromatic compound and a sulfidizing agent are reacted in the presence of an aliphatic cyclic compound,
In the presence of an inert gas, the ratio of the aliphatic cyclic compound, water, and sulfidizing agent in the range of 1.5 to 4.0 mol of the aliphatic cyclic compound with respect to 1 mol of the total sulfur atom of the sulfidizing agent. And a reaction liquid containing an alkali metal salt of an aliphatic cyclic compound hydrolyzate in a range of 0.05 to 0.6 mol with respect to a total of 1 mol of the sulfur atoms. (1) to obtain
The step (2) of cooling the reaction solution obtained in the step (1) to a range of 150 ° C. or higher and lower than 200 ° C .;
Dehydrating the reaction solution obtained in step (2) (3),
A step (4) in which the reaction liquid obtained in the step (3) is subjected to a polymerization reaction by heating to a range of 200 ° C. or more and 300 ° C. or less in a closed system;
Having
A polyhaloaromatic compound is added in at least one step selected from the group consisting of step (3) and step (4).

・ Process (1)
In the production method of the present invention, in the presence of an inert gas, the aliphatic cyclic compound, water, and sulfidizing agent are mixed with 1.5 to 4 aliphatic cyclic compounds with respect to a total of 1 mol of sulfur atoms of the sulfidizing agent. It is heated to a range of 200 ° C. or more at a ratio of 0.0 mol, and an alkali metal salt of an aliphatic cyclic compound hydrolyzate (hereinafter sometimes referred to as SMAB) is added to 1 mol of the total sulfur atom. And a step (1) of obtaining a reaction liquid containing in the range of 0.05 to 0.6 mol.

  In the step (1), first, an aliphatic cyclic compound, water and a sulfidizing agent are charged into a reactor as essential raw material components and mixed. Examples of the sulfidizing agent include alkali metal sulfides and alkali metal hydrosulfides. Of these, alkali metal sulfides and alkali metal hydrosulfides are preferably used from the viewpoint of efficiently generating SMAB. When the alkali metal sulfide and the alkali metal hydrosulfide are used in combination, the alkali metal sulfide is in the range of 80 to 99.9% by mass, preferably 90%, based on the total of the alkali metal sulfide and the alkali metal hydrosulfide. It is preferable to use in a ratio of ˜99% by mass and the balance being alkali metal hydrosulfide. In the step (1), the introduction of the inert gas may be performed when the raw material components are charged, or may be performed during heating described later.

  At that time, the charged amount of the aliphatic cyclic compound is preferably in the range of 1.5 to 4.0 mol with respect to 1 mol of the total sulfur atoms of the sulfidizing agent. From the viewpoint of further increasing, the range of 2.0 to 3.5 mol is more preferable.

  The amount of water charged is in the range of 0.05 to 0.6 mol, preferably 0.1 to 0, with respect to the total 1 mol of sulfur atoms in the reaction solution obtained in step (1). Although it is not particularly limited as long as it can be produced in the range of 3 mol, for example, the total water content in the reaction system in step (1) is preferably 0.05 with respect to the total 1 mol of sulfur atoms of the sulfidizing agent. The amount of water contained in the raw material (for example, as crystallization water in the sulfidizing agent) (in the present invention, “sulfidation” so that it is in the range of ~ 0.6 mol, more preferably in the range of 0.1 to 0.3. It is preferable to add water at the time of preparation after subtracting “the amount of water in the agent”.

  In step (1), the mixture charged in the reactor and containing the aliphatic cyclic compound, water and the sulfidizing agent as essential raw material components is then heated in the presence of an inert gas. The heating conditions are not particularly limited, but when the total water content in the reaction system at the time of charging exceeds the above range, an equipment such as distillation is attached to the reaction vessel so as to be within the above range, The reaction can be carried out by heating under reduced pressure. However, when the total water content in the reaction system at the time of preparation is within the above range, it is more preferable to heat and react in a closed system from the viewpoint of improving productivity. As temperature conditions, it heats so that it may become the range of 200 degreeC or more. Since Step 1 does not involve a polymerization reaction, there is no need to consider the melting point or decomposition temperature of the polyarylene sulfide resin, and there is no need to set the upper limit of the temperature condition. From the viewpoint of ensuring the corrosiveness and design strength of the part, it is preferably in the range of 300 ° C. or lower. Examples of the inert gas include nitrogen gas, argon gas, and helium gas.

  Here, as the aliphatic cyclic compound used in the present invention, known aliphatic cyclic compounds can be used without particular limitation as long as they can be ring-opened by hydrolysis. Specific examples of N-methyl-2-pyrrolidone (hereinafter 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-imidazolidinone acid, amidourea And lactams. Among these, an aliphatic cyclic amide compound, particularly NMP, is preferable from the viewpoint of good reactivity.

  Specific examples of the alkali metal sulfide used in the present invention include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and the like. 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. These alkali metal sulfides may be anhydrous or may be so-called hydrates containing water of crystallization. Moreover, although an alkali metal sulfide can be obtained by reacting an alkali metal hydrosulfide and an alkali metal hydroxide, those prepared in advance outside the reaction system may be used. Specific examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Among these, lithium hydroxide, 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 the concentration is preferably in the range of 10 to 50% by mass.

  Specific examples of the alkali metal hydrosulfide used in the present invention include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide and the like. 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. Moreover, although an alkali metal hydrosulfide can be obtained by reacting hydrogen sulfide with an alkali metal hydroxide, one prepared in advance outside the reaction system may be used.

  The sulfidizing agent used as a raw material in the step (1) is such that the amount of water in the sulfidizing agent is in the range of 0 mol (anhydride) to 0.55 mol with respect to 1 mol in total of sulfur atoms. It is preferable to use those, and it is more preferable to use those in the range of 0.01 to 0.29 mol. The use of a water content in the sulfidizing agent within the above range is not only preferable from the viewpoint of suppressing side reactions during polymerization and increasing the molecular weight of the PAS resin. In this case, the amount of SMAB produced can be adjusted by adjusting the amount of water charged, which eliminates the need for distillation operation. As a result, the occupation time of the reaction vessel used for the polymerization can be saved, which is preferable from the viewpoint of improving productivity. In addition, when the sulfidizing agent used as a raw material in the step (1) contains a water content exceeding the above range in the sulfidizing agent, it is within the above range in advance other than the reaction vessel used for the polymerization reaction (outside the reaction system). It is preferable to use after adjusting the amount of water. Moreover, when using a solid thing as an alkali metal sulfide, use the solid thing whose particle diameter (number average particle diameter of at least 50 points | pieces by the equivalent circle diameter by a microscope method) is the range of 10-800 micrometers. It is more preferable to use a solid material having a particle diameter in the range of 50 to 500 μm. However, since the alkali metal sulfide has deliquescence, the particles may be partially bonded to each other.

  Thus, in the step (1), prior to the polymerization reaction step, a sulfidizing agent, particularly an alkali metal sulfide, an aliphatic cyclic compound, water, and an alkali metal hydrosulfide, in the absence of a polyhaloaromatic compound in advance. Is heated in a temperature range of 200 ° C. or higher, so that the water is crystallized in the sulfidizing agent, so that liberation is promoted, and the water in the system that causes side reactions in the polymerization process is efficiently removed. It is considered that it has been converted to a hydrolyzate of an aliphatic cyclic compound that is considered to exhibit a polymerization accelerating action, and as a result, it has been possible to promote a high molecular weight of the PAS resin while suppressing side reactions during polymerization. .

・ Process (2)
The reaction solution obtained in step (1) is cooled. In this case, the temperature range of the reaction solution is in the range of 150 ° C. to less than 200 ° C., preferably in the range of 180 ° C. to 199 ° C., from the viewpoint that SMAB is efficiently generated and exists stably. The temperature difference between the temperature after heating the reaction solution in step (1) and the temperature after cooling the reaction solution in step (2) is not particularly limited, but is 50 to 80 ° C. from the viewpoint of productivity. It is preferable that it is the range of these. The cooling condition may be either an open system or a closed system, and is not particularly limited, but it is preferable to react in a closed system from the viewpoint of improving productivity.

・ Process (3)
The reaction solution obtained in step (2) is dehydrated. More specifically, water is distilled off while heating the reaction solution obtained in the step (2). In the step (3), the heating temperature for performing the dehydration treatment is not particularly limited as long as water can be distilled off. However, from the viewpoint of improving the dehydration efficiency and improving the productivity, the temperature is 180 to 220 ° C. The range is preferable, in particular, the range of 190 to 210 ° C is more preferable, the range of the gauge pressure is 0.0 to 0.3 MPa, and the range of 0.0 to 0.2 MPa is more preferable. Water is distilled off by isolating a mixture of an aliphatic cyclic compound and water under the above temperature and pressure conditions by distillation, condensing the mixed vapor with a condenser, separating the mixture with a decanter, etc. In the case of adding a polyhaloaromatic compound in the step (3), a mixture of an aliphatic cyclic compound, water and a polyhaloaromatic compound under the temperature and pressure conditions described above can be mentioned. After isolating the aliphatic cyclic compound by distilling the water, the vapor mixture of water and polyhaloaromatic compound is condensed in a condenser, and water and polyhaloaromatic compound are separated by decanter and azeotropic distillation. A method of returning the produced polyhaloaromatic compound into the reaction system can be mentioned.

In the step (3), the aliphatic cyclic compound may be added at a ratio of 0.5 to 5 moles with respect to 1 mole of sulfur atoms in the sulfidizing agent.
The amount of water contained in the reaction solution at the end of the step (3) is preferably in a range of the detection limit to 0.04 mol or less with respect to 1 mol in total of sulfur atoms of the sulfidizing agent. More preferably, it is in the range of the detection limit to 0.01 mol.

・ Process (4)
In the step (4), the reaction solution obtained through the step (3) is sealed in a sealed system, that is, in a sealed reaction vessel with respect to the reaction vessel containing the reaction solution obtained in the step (3). In this step, the polymerization reaction is carried out by heating to a temperature in the range of from ℃ to 300 ℃.

  The reaction conditions of step (4) are not particularly limited, but the temperature at which the polymerization reaction can proceed easily, that is, the range of 200 ° C. or more and 300 ° C. or less, preferably the range of 210 ° C. or more and 280 ° C. or less, More preferably, the reaction is preferably performed in the range of 215 ° C. or more and 250 ° C. or less.

  The polyhaloaromatic compound can be added in at least one step selected from the group consisting of step (3) and step (4). That is, in step (3), the polyhaloaromatic compound may be added, in step (4), the polyhaloaromatic compound may be added and then heated, or after heating, the polyhaloaromatic compound may be added. Alternatively, the polyhaloaromatic compound may be added while heating.

  Specific examples of the polyhaloaromatic compound used in the present invention include, for example, p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3, 5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6-trihalonaphthalene, 2,5-dihalotoluene, 1,4-dihalo Naphthalene, 1-methoxy-2,5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalo Halonitrobenzene, 2,4-dihaloanisole, p, p'-dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenylsulfone 4,4' dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfide, and a compound having an aromatic ring in the alkyl group having 1 to 18 carbon atoms of each of the above compounds as nuclear substituents. Moreover, it is desirable that the halogen atom contained in each compound is a chlorine atom or a bromine atom.

  Among the polyhaloaromatic compounds, a bifunctional dihaloaromatic compound is preferable from the viewpoint that the present invention can efficiently produce a linear high molecular weight PAS resin. From the viewpoint of good mechanical strength and moldability, p-dichlorobenzene, m-dichlorobenzene, 4,4′-dichlorobenzophenone and 4,4′-dichlorodiphenyl sulfone are preferable, and p-dichlorobenzene is particularly preferable. When it is desired to give a branched structure to a part of the polymer structure of the linear PAS resin, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, or 1 together with the dihaloaromatic compound. , 3,5-trihalobenzene is preferably used in combination.

In addition, a copolymer containing two or more different reactive units can be obtained by appropriately selecting and combining polyhaloaromatic compounds. For example, p-dichlorobenzene and 4,4′-dichlorobenzophenone, Use in combination with 4′-dichlorodiphenylsulfone is particularly preferred because a polyarylene sulfide having excellent heat resistance can be obtained.
The amount of the polyhaloaromatic compound charged is not particularly limited, but since the amount charged is directly subjected to the polymerization reaction, the total amount of sulfur atoms in the amount of the sulfidizing agent used in step (1) is used from the viewpoint of productivity or economy. It is preferably used in a proportion of 0.8 to 1.2 mol per mol, and more preferably in an equimolar proportion. As a method of adding the polyhaloaromatic compound to the reaction liquid in the step (3) to the step (4), a method of adding the amount necessary for preparation in a lump, a method of adding in two or more portions, May be any of the methods of dropping continuously.

  In this step (3) or (4), a lithium salt compound may be added to the reaction system and the reaction may be performed in the presence of lithium ions. Specific examples of the lithium salt compound that can be used here include, for example, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium carbonate, lithium hydrogen carbonate, lithium sulfate, lithium hydrogen sulfate, lithium phosphate, and phosphoric acid. Lithium hydrogen, lithium dihydrogen phosphate, lithium nitrite, lithium sulfite, lithium chlorate, lithium chromate, lithium molybdate, lithium formate, lithium acetate, lithium oxalate, lithium malonate, lithium propionate, lithium butyrate, iso Lithium butyrate, lithium maleate, lithium fumarate, lithium butanedioate, lithium valerate, lithium hexanoate, lithium octoate, lithium tartrate, lithium stearate, lithium oleate, lithium benzoate, lithium phthalate, benzenesulfur Inorganic lithium salt compounds such as lithium phosphate, lithium p-toluenesulfonate, lithium sulfide, lithium hydrosulfide, lithium hydroxide; lithium methoxide, lithium ethoxide, lithium propoxide, lithium isopropoxide, lithium butoxide, lithium And organic lithium salt compounds such as phenoxide. Among these, lithium chloride and lithium acetate are preferable, and lithium chloride is particularly preferable. The lithium salt compound can be used as an anhydride, a hydrate, or an aqueous solution. When the lithium salt compound is added to the reaction system in steps (3) to (4) and the reaction is performed in the presence of lithium ions, the amount used is the amount of the sulfur atom of the sulfidizing agent used in step (1). It is preferable to use the polyarylene sulfide resin in a proportion that is preferably in the range of 0.01 mol or more and less than 0.9 mol with respect to 1 mol in total because the polyarylene sulfide resin can be made higher in molecular weight.

  In the production method of the present invention, the amount of water at the start of polymerization in step (4) is preferably as small as possible. For example, it is preferably in the range of detection limit to 0.08 mol per 1 mol of the total sulfur atoms. More preferably, it is in the range of detection limit to 0.05 mol. Since water is generated as the polymerization reaction proceeds, it is preferable that 0.1 to 0.3 mol of water is generated per 1 mol of the total sulfur atoms at the end of the polymerization reaction in step (4). It is preferable that the above range is satisfied after the time when the conversion of the group compound exceeds 80 mol%, more preferably after the time when it exceeds 60 mol%, and more preferably immediately after the start of polymerization.

Here, the conversion rate of the polyhaloaromatic compound is represented by the following formula.
Conversion rate (%) = (preparation amount−remaining amount) / preparation amount × 100
However, the “charge amount” represents the mass of the polyhaloaromatic compound charged into the reaction system, and the “remaining amount” represents the mass of the polyhaloaromatic compound remaining in the reaction system.

-Post-treatment process The reaction mixture containing the polyarylene sulfide resin obtained by the polymerization reaction can be subjected to a post-treatment process. The post-treatment step may be a known method, and is not particularly limited. For example, after completion of the polymerization reaction, the reaction mixture is first left as it is, or an acid or a base is added, and then the pressure is reduced or normal pressure. The solvent is distilled off with, and the solid after the solvent is distilled off is washed once or twice with a solvent such as water, acetone, methyl ethyl ketone, alcohols, and further neutralized, washed with water, filtered and dried, or After completion of the polymerization reaction, the reaction mixture is water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons and other solvents (soluble in the polymerization solvent used, and At least a polyarylene sulfide resin, a solvent that is a poor solvent) is added as a precipitating agent to form a solid such as a polyarylene sulfide resin or an inorganic salt. The product is allowed to settle and filtered, washed and dried, or after the polymerization reaction is completed, the reaction mixture (or an organic solvent having an equivalent solubility in a low molecular weight polymer) is added to the reaction mixture and stirred. Thereafter, the low molecular weight polymer is removed by filtration, followed by washing once or more with a solvent such as water, acetone, methyl ethyl ketone, alcohols, etc., followed by neutralization, washing with water, filtration and drying. It is done.
In the post-treatment method as exemplified above, the polyarylene sulfide resin may be dried in a vacuum, or in an inert gas atmosphere such as air or 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 this heat treatment is preferably in the range of 180 ° C. to 270 ° C., although it varies depending on the target crosslinking treatment time and the atmosphere to be treated. In addition, 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. It is preferable to carry out at +100 degrees C or less.

Production apparatus The reaction apparatus used in each of the above steps in the production method of the polyarylene sulfide resin of the present invention is configured such that the contact portion with the raw material, the reaction liquid, or the product obtained after the reaction is made of titanium, zirconium, or a nickel alloy. It is preferable to use what has been used.

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

  For example, the batch-type reaction vessel may be any vessel that can hold the reaction liquid or the crude reaction mixture inside the reaction vessel, and includes, for example, an upper lid portion, a body portion, and a bottom portion, and, if necessary, A structure having a sealable structure is mentioned, and a structure having a stirring blade, a shaft for transmitting power to the stirring blade, a baffle plate, and a temperature control serpentine 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 stirring blade. The baffle plate (baffle) is preferably installed so that the lower end is located near the bottom of the reaction vessel and the upper end is located so as to come out of the liquid level from the viewpoint of easy heat conduction and thermal control.

  In addition, for example, the reaction vessel specifically includes various measuring devices such as a thermometer, a pressure gauge, and a safety valve, and a steam distillation line, a condenser, a decanter, a distillate is provided outside the reaction vessel. It is preferable that a return line, an exhaust line, a hydrogen sulfide capturing device and the like (referred to as equipment such as distillation in the present invention) are provided.

  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, and a polymerization line in which the tubular reactors are connected in series or a plurality of tubular reactors. Examples include those that connect a reactor and form a continuous cyclic polymerization line having a structure in which a part of the reaction liquid is circulated to the raw material inlet of the tubular reactor. These continuous reaction vessels can feed the raw materials and transfer the reaction liquid by a plunger pump or the like.

  In the reaction apparatus used in the present invention, the “contact portion with the raw material, reaction solution or product obtained after the reaction” refers to the above-mentioned raw materials, ie, organic polar solvent, polyhaloaromatic compound, sulfide, inside the reaction apparatus. It is a part or all of the inner wall surface of the reaction apparatus in contact with the mixture of the agent, alkali catalyst, etc., and the product obtained after the polymerization reaction. The raw material, the reaction solution or the product obtained after the reaction may be in the form of a slurry. In that case, the solid material may be an alkali metal sulfide, an alkali metal hydrosulfide used as a raw material, or an alkali metal chloride generated by the reaction. Alkali metal-containing inorganic salts such as products are also included.

  The reaction apparatus used in the present invention may be configured such that at least a part of the contact part, preferably all of the contact part, is composed of the nickel alloy. The nickel alloy used here is an alloy having a chromium content of 43 to 47% by mass or more, a molybdenum content of 0.1 to 2% by mass, and the balance of nickel and inevitable impurities in terms of corrosion resistance. is there. Tungsten, iron, cobalt and copper are preferably those having a content below the detection limit.

  In the present invention, the term “inevitable impurities” means a very small amount of impurities that are technically difficult to remove. In the present invention, for example, carbon atoms contained in the alloy at a ratio of 1% by mass or less, preferably the detection limit or less can be mentioned.

-Molding process, etc. The polyarylene sulfide resin obtained by the production method of the present invention described in detail above is subjected to various heat processing methods such as injection molding, extrusion molding, compression molding, blow molding, heat resistance, molding processability, and dimensions. It can be processed into a molded article excellent in stability and the like.

  Further, the polyarylene sulfide resin obtained by the present invention can be used as a polyarylene sulfide resin composition combined with various fillers in order to further improve performance such as strength, heat resistance, and dimensional stability. I can do it. Although it does not restrict | limit especially as a filler, For example, a fibrous filler, an inorganic filler, etc. are mentioned. Examples of the fibrous filler include glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium sulfate, calcium silicate, and other natural fibers such as wollastonite. Can be used. Inorganic fillers include barium sulfate, calcium sulfate, clay, viroferrite, bentonite, sericite, zeolite, mica, mica, talc, talpulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, etc. Can be used. Further, various additives such as a mold release agent, a colorant, a heat stabilizer, a UV stabilizer, a foaming agent, a rust inhibitor, a flame retardant, and a lubricant can be added as additives during the molding process.

  Furthermore, the polyarylene sulfide resin obtained according to the present invention can be appropriately selected from polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyether depending on the application. Synthetic resins such as ketone, polyarylene, polyethylene, polypropylene, polytetrafluoroethylene, polydifluoroethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, liquid crystal polymer, or polyolefin rubber Alternatively, it may be used as a polyarylene sulfide resin composition containing an elastomer such as fluorine rubber or silicone rubber.

  Since the polyarylene sulfide resin obtained by the production method of the present invention also has various performances such as heat resistance and dimensional stability inherent in the polyarylene sulfide resin, for example, a connector, a printed circuit board, a sealing molded product, etc. Injection molding of automobile parts such as electrical / electronic parts, lamp reflectors and various electrical parts, interior materials such as various buildings, aircraft and automobiles, or precision parts such as OA equipment parts, camera parts and watch parts, or It is widely useful as a material for various molding processes such as compression molding, extrusion molding of composites, sheets, pipes, etc., or pultrusion molding, or as a material for fibers or films.

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

(Measurement of melt viscosity (V6) of PPS resin)
The manufactured PPS resin is held for 6 minutes using a flow tester “CFT-500D” manufactured by Shimadzu Corporation at 300 ° C., load: 1.96 × 10 ⁶ Pa, L / D = 10 (mm) / 1 (mm). Was measured after.

(Production rate of alkali metal salt (SMAB) of hydrolyzate of aliphatic cyclic compound)
Na2S, NMP, and water were charged into a 1 L autoclave, and the temperature was raised to a certain temperature. Then, it cooled to 200 degreeC and prepared DCB. The valve was slightly opened at 200 ° C., and the remaining water was extracted from the autoclave. The extracted water was diluted with acetone, and the water content was measured. Since the amount of water consumed and the SMAB production rate are equal, the SMAB production rate was calculated from the following formula.
SMAB generation rate (%) = (charged water amount (g) −missed water amount (g)) / charged water amount (g) × 100

(Quantification of the amount of phenol (by-product))
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 separated with a centrifuge. Thereafter, 1 μL of the supernatant was collected and measured with a gas chromatograph.

  Measurement by gas chromatograph is performed by Shimadzu Gas Chromatography “GC2014” (column: Column “G300” manufactured by Chemicals Evaluation and Research Institute, carrier gas: helium, measurement column condition: 140 ° C. held for 5 minutes → 3 ° C. The temperature was increased to 200 ° C./minute and maintained at 200 ° C. for 20 minutes. In order to obtain the phenol concentration, a calibration curve was first prepared with a standard sample. Next, the peak area having 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 measurement solution was determined from the peak area and the calibration curve, and the number of moles of phenol per mole of sulfidizing agent (total mole of charged sulfur atoms) was calculated as a percentage (hereinafter referred to as “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.).

[Example 1]
The inner wall (wetted part) connecting the pressure gauge, thermometer, raw material transport piping, steam distillation line, condenser, decanter, distillation column, distillate return line, exhaust line, hydrogen sulfide trap is made of titanium, In a 1 L autoclave with a stirring blade, 128.42 g (Na ₂ S: 1.64 mol) of 1.1% Na ₂ S, 7.47 g (NaSH: 0.06 mol) of 45% NaSH, and 0 water .55 g (total amount of water: 0.20 mol) and 301.55 g of NMP were charged, and nitrogen substitution was performed. After the preparation, the autoclave was sealed, heated to 250 ° C. over 3 hours with stirring, and then cooled to 195 ° C. or lower. Thereafter, 249.90 g (DCB: 1.70 mol) of p-dichlorobenzene (hereinafter abbreviated as “p-DCB”) melted at 80 ° C. from the outside through the raw material transport pipe into the autoclave is collectively added and held for 1 hour. did. The amount of water in the system was measured and found to be 0.02 mol. Next, the valves of the steam distillation line and the distillate return line are opened, the temperature is raised to 220 ° C., the residual water in the system is distilled off during the temperature raising, and then the valve is closed to seal the autoclave. And kept at 220 ° C. for 3 hours. Further, the temperature was raised to 250 ° C., reacted at 250 ° C. for 1 hour, and then cooled to room temperature.

To 100 g of the resulting polymerization slurry, 400 g of ion exchanged water at 70 ° C. was added and stirred for 10 minutes, followed by filtration. To the cake after filtration, 600 g of ion exchanged water at 70 ° C. was added to perform cake washing. To the obtained water-containing cake, 400 g of ion-exchanged water at 70 ° C. was added and stirred for 10 minutes, followed by filtration. To the cake after filtration, 600 g of ion-exchanged water at 70 ° C. was added to perform cake washing. This operation was repeated twice. The obtained water-containing cake was dried at 120 ° C. for 4 hours using a hot air dryer to obtain a white powdery polymer.

  The polymer obtained had a melt viscosity of 224 Pa · s. The SMAB production rate was 90%. The amount of phenol as a by-product was 0.03 mol% / S.

[Example 2]
It was based on Example 1 except the point heated up to 200 degreeC over 3 hours, making it stir after preparation. The amount of water in the system after the addition of DCB was measured and found to be 0.05 mol.
The resulting polymer had a melt viscosity of 129 Pa · s. The SMAB production rate was 74%. The amount of phenol as a by-product was 0.08 mol% / S.

[Comparative Example 1]
The inner wall (wetted part) to which a pressure gauge and a thermometer were connected was made of titanium, and 128.42 g (Na ₂ S: 1.64 mol) of Na ₂ S with a moisture content of 1.1% was added to a 1 L autoclave with a stirring blade. (Solid form with an average particle size of 300 μm), 7.47 g of 45% NaSH (NaSH: 0.06 mol), 0.55 g of water (total amount of water: 0.20 mol), p-dichlorobenzene (hereinafter, p- DCB) was charged with 249.90 g (DCB: 1.70 mol) and 301.55 g of NMP, and nitrogen substitution was performed. After the preparation, the temperature was raised to 200 ° C. over 3 hours with stirring. The water content in the system was measured and found to be 0.10 mol. Then, it heated up to 220 degreeC and hold | maintained at 220 degreeC for 3 hours. Then, it heated up to 250 degreeC and hold | maintained at 250 degreeC for 1 hour.

  To 100 g of the resulting polymerization slurry, 400 g of ion exchanged water at 70 ° C. was added and stirred for 10 minutes, followed by filtration. To the cake after filtration, 600 g of ion exchanged water at 70 ° C. was added to perform cake washing. To the obtained water-containing cake, 400 g of ion-exchanged water at 70 ° C. was added and stirred for 10 minutes, followed by filtration. To the cake after filtration, 600 g of ion-exchanged water at 70 ° C. was added to perform cake washing. This operation was repeated twice. The obtained water-containing cake was dried at 120 ° C. for 4 hours using a hot air dryer to obtain a white powdery polymer.

  The polymer obtained had a melt viscosity of 41 Pa · s. The SMAB reaction rate was 51%. The amount of phenol as a by-product was 0.38 mol% / S.

[Comparative Example 2]
"The inner wall (wetted part) connecting the pressure gauge, thermometer, raw material transport piping, steam distillation line, condenser, decanter, distillation column, distillate return line, exhaust line, and hydrogen sulfide trap is made of titanium. In a 1 L autoclave with a stirring blade, 128.42 g (Na ₂ S: 1.64 mol) of Na ₂ S having a moisture content of 1.1%, 7.47 g (NaSH: 0.06 mol) of 45% NaSH, and water 0.55 g (total amount of water: 0.20 mol), 301.55 g of NMP were charged, and nitrogen substitution was performed. ”The parts“ pressure gauge, thermometer, raw material transport pipe, steam distillation line, condenser, decanter, distillation column, distillate return line, the exhaust line, 128.42G moisture 1.1% Na ₂ S in 1L autoclave made of the inner wall which are linked to hydrogen sulfide capture device (wetted parts) titanium (Na ₂ S: .64 mol), 7.47 g of 45% NaSH (NaSH: 0.06 mol), 2.20 g of water (total amount of water: 0.80 mol), and 301.55 g of NMP were charged, and nitrogen substitution was performed. Except for the point, it conformed to Example 1. The amount of water in the system after the addition of DCB was measured and found to be 0.05 mol.
The obtained polymer had a melt viscosity of 82 Pa · s. The SMAB production rate was 88%. The amount of phenol as a by-product was 0.23 mol% / S.

[Comparative Example 3]
"The inner wall (wetted part) connecting the pressure gauge, thermometer, raw material transport piping, steam distillation line, condenser, decanter, distillation column, distillate return line, exhaust line, and hydrogen sulfide trap is made of titanium. In a 1 L autoclave with a stirring blade, 128.42 g (Na ₂ S: 1.64 mol) of Na ₂ S having a moisture content of 1.1%, 7.47 g (NaSH: 0.06 mol) of 45% NaSH, and water 0.55 g (total amount of water: 0.20 mol) and 301.55 g of NMP were charged, and nitrogen substitution was performed, and then the temperature was raised to 250 ° C. over 3 hours with stirring, then to 195 ° C. or lower. Thereafter, 249.90 g (DCB: 1.70 mol) of p-dichlorobenzene (hereinafter abbreviated as p-DCB) was added all at once from the outside into the autoclave through the raw material transport pipe and held for 1 hour. The internal wall (contact) connecting the pressure gauge, thermometer, raw material transport piping, steam distillation line, condenser, decanter, distillation column, distillate return line, exhaust line, and hydrogen sulfide capture device. (Liquid part) is made of titanium, in a 1 L autoclave equipped with a stirring blade, 194.7 g (1.64 mol as NaSH) aqueous solution of 47.23 mass% NaSH and 132.5 g (1. 5 as NaOH) of 49.21 mass% NaOH aqueous solution (63 mol) (total amount of water: 9.45 mol), NMP (25.25 g) and DCB (249.90 g) were charged and nitrogen substitution was performed, and then the mixture was heated to 173 ° C. over 5 hours while stirring. Next, it was cooled to 160 ° C. Then, 342.63 g of NMP was added all at once from the outside into the autoclave through the raw material transport pipe and held for 1 hour. Example compliant to 1. When the amount of water in the system after DCB addition was measured, it was 0.1 mol.
The polymer obtained had a melt viscosity of 221 Pa · s. The SMAB production rate was 90%. The amount of phenol as a by-product was 0.06 mol% / S.

Claims (9)

A process for producing a polyarylene sulfide in which a polyhaloaromatic compound and a sulfidizing agent are reacted in the presence of an aliphatic cyclic compound,
In the presence of an inert gas, the ratio of the aliphatic cyclic compound, water, and sulfidizing agent in the range of 1.5 to 4.0 mol of the aliphatic cyclic compound with respect to 1 mol of the total sulfur atom of the sulfidizing agent. And a reaction liquid containing an alkali metal salt of an aliphatic cyclic compound hydrolyzate in a range of 0.05 to 0.6 mol with respect to a total of 1 mol of the sulfur atoms. (1) to obtain
The step (2) of cooling the reaction solution obtained in the step (1) to a range of 150 ° C. or higher and lower than 200 ° C .;
Dehydrating the reaction solution obtained in step (2) (3),
A step (4) in which the reaction liquid obtained in the step (3) is subjected to a polymerization reaction by heating to a range of 200 ° C. or more and 300 ° C. or less in a closed system;
Having
A method for producing a polyarylene sulfide resin, comprising adding a polyhaloaromatic compound in at least one step selected from the group consisting of step (3) and step (4).   2. The polyarylene sulfide resin according to claim 1, wherein the total water content in the reaction system in step (1) is in the range of 0.05 to 0.6 mol with respect to a total of 1 mol of sulfur atoms of the sulfidizing agent. Manufacturing method.   The production method according to claim 1, wherein the water content in the sulfidizing agent in step (1) is a ratio in the range of 0 to 0.55 mol with respect to 1 mol of sulfur atoms in total.   In step (4), the amount of water contained in the reaction solution obtained in step (3) is a ratio in the range of 0.05 mol or less with respect to 1 mol of the total sulfur atoms of the sulfidizing agent. Or the manufacturing method of the polyarylene sulfide resin of 2.   The polyarylene according to any one of claims 1 to 4, wherein step (3) is a step of distilling off water while heating the reaction solution obtained in step (2) in the range of 180 to 230 ° C. A method for producing a sulfide resin.   6. The method for producing a polyarylene sulfide resin according to any one of claims 1 to 5, wherein steps (1) and (2) are both performed in a sealed reaction vessel.   The process according to any one of claims 1 to 6, wherein in step (3), the polyhaloaromatic compound is added in a range of 0.9 to 1.1 mol with respect to a total of 1 mol of sulfur atoms of the sulfidizing agent. A process for producing a polyarylene sulfide resin.   The polyarylene sulfide resin obtained by the production method according to any one of claims 1 to 7, an inorganic filler, a thermoplastic resin other than the polyarylene sulfide resin, an elastomer, and a curable resin. A method for producing a polyarylene sulfide resin composition comprising a step of melt-kneading at least one other component selected.   The manufacturing method of a polyarylene sulfide resin molded article including the process of shape | molding the polyarylene sulfide resin composition obtained by the manufacturing method of the said Claim 8.