JP2017210560A - Method for producing polyarylene sulfide resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyarylene sulfide resin in an apparatus for reaction which reduces elution of a metal material from a contact portion of a reactant or a crude reaction mixture in the apparatus for reaction, and to provide an apparatus for reaction usable in the production method.SOLUTION: There are provided a method for producing a polyarylene sulfide resin using an apparatus for reaction in which at least a part of a contact portion of a reaction or a crude reaction mixture is formed of alloy containing 43-47 mass% or more of chromium, 0.1-2 mass% of molybdenum and the balance nickel and unavoidable impurity; and an apparatus for reaction which is usable in the production method and is formed of the alloy.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a polyarylene sulfide resin using a raw material that is highly corrosive to metals, and more particularly to a reaction apparatus used in the production method and a method for producing a polyarylene sulfide resin using the same. Is.

  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.

  However, PAS resin needs to be polymerized using highly corrosive sulfides, strong alkali components, chlorides, etc. under high-temperature conditions close to 180 ° C to 300 ° C. Corrosion resistance is required.

  For example, various stainless steels have been studied as a metal material used for a liquid contact part of a reaction vessel such as a polymerization vessel (see Patent Documents 1 and 2). However, iron and nickel contained in alloys and stainless steel react with sulfides derived from sulfidizing agents such as sodium sulfide and sodium hydrosulfide when dissolved to produce metal sulfides (iron sulfide and nickel sulfide). It is known to do. This metal sulfide not only inhibits PAS polymerization, but is not removed by the purification process after polymerization because it is unnecessary for the solvent, and remains in the PAS resin product. Deteriorating and mimicking the result of limited use for electrical and electronic parts.

  As a corrosion-resistant metal other than stainless steel, for example, titanium has been proposed (see Patent Document 3). However, titanium also has a problem that the corrosion resistance under high temperature, high pressure, and high alkali is not sufficient, and corrosion tends to proceed after a long period of use.

  Therefore, the use of a material having high corrosion resistance such as zirconium has been proposed as a metal material used for a liquid contact part of a reaction vessel such as a polymerization vessel (see, for example, Patent Document 4). However, even with zirconium having high corrosion resistance, there is a problem that corrosion resistance under high temperature, high pressure and high alkali is not sufficient, and corrosion tends to proceed after long-term use. Zirconium is difficult to process, and when it is applied to polymerization kettles and piping, not only special processing such as explosive processing is required, but there is also a problem of reduced corrosion resistance due to the explosive processing. Therefore, there has been a strong demand for providing a PAS manufacturing facility that uses a metal material that is excellent in workability and corrosion resistance without using zirconium.

JP-A-1-213338 JP-A-9-278888 Japanese Patent Laid-Open No. 61-023627 Japanese Patent Laid-Open No. 2008-081542

  The problem to be solved by the present invention is to at least react a reaction solution containing a polyhaloaromatic compound and a sulfidizing agent in an alkaline atmosphere in a reaction apparatus in the presence of an aprotic polar organic solvent. In a method for producing a polyarylene sulfide resin having a polymerization step for obtaining a crude reaction mixture containing a polyarylene sulfide resin, elution of a metal material from a contact portion with the reaction liquid or the crude reaction mixture in a reaction apparatus is reduced. Another object of the present invention is to provide a method for producing a polyarylene sulfide resin, and a reaction apparatus that can be used in the production method.

  As a result of intensive studies and studies to solve the above problems, the inventor has a chromium content of 43 to 47% by mass or more, a molybdenum content of 0.1 to 2% by mass and It has been found that the above-mentioned problem can be solved by using a nickel alloy for the alloy composed of nickel and inevitable impurities, and the present invention has been completed.

That is, the present invention provides a reaction solution containing a polyhaloaromatic compound and a sulfiding agent in an alkaline atmosphere in a reaction apparatus in the presence of an aprotic polar organic solvent, and at least a polyarylene sulfide resin. A process for producing a polyarylene sulfide resin having a polymerization step to obtain a crude reaction mixture containing
At least part of the contact portion of the reaction apparatus with the reaction solution or the crude reaction mixture is made of a nickel alloy, and
The nickel alloy 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. The present invention relates to a method for producing an arylene sulfide resin.
In the present invention, a reaction solution containing a polyhaloaromatic compound and a sulfidizing agent is reacted in an alkaline atmosphere in the presence of an aprotic polar organic solvent to obtain a crude reaction mixture containing at least a polyarylene sulfide resin. A reaction apparatus for use in a method for producing a polyarylene sulfide resin having a polymerization step,
At least part of the contact portion with the reaction solution or the crude reaction mixture in the reaction apparatus is made of a nickel alloy, and
The nickel alloy has a chromium content of 43 to 47% by mass or more, a molybdenum content of 0.1 to 2% by mass, and the balance composed of nickel and inevitable impurities. It relates to a device.

  According to the present invention, at least a polyarylene sulfide resin is obtained by reacting a reaction solution containing a polyhaloaromatic compound and a sulfidizing agent in an alkaline atmosphere in the reaction apparatus in the presence of an aprotic polar organic solvent. In the method for producing a polyarylene sulfide resin having a polymerization step for obtaining a crude reaction mixture containing polyarylene sulfide, the polyarylene sulfide reduces elution of a metal material from a contact portion with the reaction solution or the crude reaction mixture in a reaction apparatus. A resin production method and a reaction apparatus that can be used in the production method can be provided.

It is a schematic diagram of the superposition | polymerization pot (state with the reaction raw material charged) used in the Example.

  The reaction apparatus used in the present invention is characterized in that the contact portion with the reaction solution or the crude reaction mixture is composed of a nickel alloy.

  Examples of the reaction apparatus include a batch-type reaction vessel (reaction kettle) having a stirring blade inside, a reaction vessel (polymerization line) such as a continuous reaction vessel, a dehydration tank, a washing tank, a separation tank, and a solvent removal tank. And the like, pipes in the purification tower, pipes such as raw material or reaction product transportation pipes, stirring blades, baffle plates, raw material or reaction product storage tanks, and the like.

  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. It is preferable that a heat medium is attached to the side surface of the reaction vessel or the baffle plate (baffle). In particular, it is preferable that the baffle plate is 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.

  Further, for example, the reaction vessel is specifically provided with various measuring devices such as a temperature sensor, a pressure sensor, and a level gauge, and a steam distillation line, a condenser, a decanter, a distillation are provided outside thereof. It is preferable that a liquid return line, an exhaust line, a hydrogen sulfide capturing device and the like 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 reaction solution or the crude reaction mixture means the organic polar solvent, polyhaloaromatic compound (a), sulfidizing agent (b), alkali in the reaction apparatus. It is a part or all of the inner wall surface of the reaction apparatus in contact with the reaction liquid having a catalyst or the like. The reaction solution may be in the form of a slurry. In this case, examples of solids include alkali metal sulfides used as raw materials and alkali metal-containing inorganic salts such as alkali metal chlorides produced by the reaction.

  The reaction apparatus used in the present invention is characterized in that at least a part of the contact part, preferably all the contact part with the reaction solution or the crude reaction product, 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.

  Examples of the method for producing the contact surface with the reaction solution or the crude reaction product composed of the nickel alloy include 1) the nickel alloy rolled plate, 2) the rolling pressure bonding method, the diffusion bonding method, and the explosion pressure bonding method. 3) A clad steel plate manufactured by bonding together a nickel alloy rolled plate and a steel plate such as carbon steel, and 3) a titanium rolled plate on the surface of the carbon steel rolled plate, and a nickel alloy rolled plate 3 A clad steel sheet having a layered structure may be mentioned.

  The method for producing a polyarylene sulfide resin according to the present invention includes a reaction solution containing a polyhaloaromatic compound and a sulfidizing agent in an alkaline atmosphere in the presence of an aprotic polar organic solvent in the reaction apparatus detailed above. To obtain a crude reaction mixture containing at least a polyarylene sulfide resin.

  Examples of the polyhaloaromatic compound used here include 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-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'-diha Diphenyl 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 these, a bifunctional dihaloaromatic compound is preferable because it can efficiently produce a linear high molecular weight polyarylene sulfide resin, and the mechanical strength of the polyarylene sulfide resin finally obtained is particularly preferable. And 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 have a branched structure in a part of the polymer structure of the linear polyarylene sulfide resin, together with the dihaloaromatic compound, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, Alternatively, it is preferable to partially use 1,3,5-trihalobenzene.

On the other hand, the sulfidizing agent is, for example, a liquid alkali metal sulfide or a solid hydrous alkali metal sulfide of a compound such as lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, lithium hydrosulfide, sodium hydrosulfide, water Examples thereof include liquid alkali metal hydrosulfides or solid hydrous alkali metal hydrosulfides of compounds such as potassium sulfide, rubidium hydrosulfide and cesium hydrosulfide.
In addition, the sulfidizing agent adjusts the solid alkali metal sulfide by reacting the liquid alkali metal hydrosulfide or the solid hydrated alkali metal hydrosulfide with the alkali metal hydroxide in advance to be used for the reaction. May be.

  Examples of the alkali metal hydroxide used here include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and aqueous solutions having a concentration of 20% by mass or more. Among these, lithium hydroxide, sodium hydroxide, and potassium hydroxide are particularly preferable, and sodium hydroxide is particularly preferable.

  The term “in an alkaline atmosphere” means that the reaction slurry exhibits alkalinity, and it is preferable that the alkali metal hydroxide described above is appropriately added to the reaction slurry as necessary.

  In the above method, an aprotic polar organic solvent can be used. Examples of the organic solvent that can be used here include N-methyl-2-pyrrolidone (hereinafter abbreviated as “NMP”), N-cyclohexyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazo. Cyclic amidoureas such as lydinonic acid, ε-caprolactam, N-methyl-ε-caprolactam; sulfolanes such as sulfolane and dimethylsulfolane; formamide, acetamide, N-methylformamide, N, N-dimethylacetamide, hexamethylphospho Amides such as amide, urea, tetramethylurea, N-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone acid; and lactams; sulfolanes such as sulfolane, dimethylsulfolane; benzonitrile, etc. Nitriles; ketones such as methyl phenyl ketone It is.

  Among these, in particular, those having hydrolyzability, that is, those that react with water present in the reaction system in the presence of a sulfidizing agent to form a hydrolyzate, such as N-methyl-2- Cyclic amidoureas such as pyrrolidone, N-cyclohexyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, N-methyl-ε-caprolactam, sulfolane, dimethylsulfolane, etc. Compounds having an aliphatic cyclic structure that can be opened by hydrolysis of sulfolanes and the like, and among them, N-methyl-2-pyrrolidone is excellent in solubility and has an effect of promoting a polymerization reaction. preferable. The amount of water present in the reaction system is not generally determined depending on the water content of the sulfiding agent used, dehydration conditions, or the like, but is preferably set to 0. The range is 01 to 2 mol. Furthermore, when using a hydrolyzable thing as an aprotic polar organic solvent, the quantity of the water which exists in a reaction system and is used for a hydrolysis becomes equimolar with the quantity of a hydrolyzate. For this reason, in the polymerization step, the amount of the hydrolyzate is not generally determined depending on the water content of the sulfiding agent used, dehydration conditions, and the like. It is preferably present in the range of 01 to 2 mol.

  Among the reactions detailed above, when an alkali metal sulfide is used as a sulfidizing agent, the basic effect is strong, and the contact surface in the reaction apparatus is easily corroded. Therefore, the present invention can be preferably applied.

  In the polymerization reaction of the polyarylene sulfide resin, the alkali metal sulfide is reacted with the polyhaloaromatic compound as a sulfidizing agent in the presence of these aprotic polar organic solvents. Alternatively, in the polymerization reaction of the polyarylene sulfide resin, the alkali metal hydrosulfide and alkali metal hydroxide are reacted with the polyhaloaromatic compound as a sulfidizing agent in the presence of these aprotic polar organic solvents. The polymerization conditions are generally in the range of 200 to 330 ° C., and the pressure should be in such a range as to keep the polymerization solvent and the polymerization monomer polyhaloaromatic compound in a substantially liquid phase. It is selected from the range of 1-20 MPa, preferably from the range of 0.1-2 MPa. The amount of the polyhaloaromatic compound charged is in the range of 0.2 mol to 5.0 mol with respect to 1 mol of the sulfur atom of the sulfiding agent. The amount of aprotic polar organic solvent charged varies depending on the type of compound used and the water content in the system, and although it cannot be specified in general, it maintains the viscosity of the reaction system that allows a uniform polymerization reaction. In order to maintain a certain degree of productivity, the amount is preferably in the range of 1.0 to 6.0 mol per mol of sulfur atom of the sulfidizing agent, From the viewpoint of further increasing, the range of 1.2 to 5.0 mol is more preferable, and the range of 1.5 to 4.5 mol is most preferable.

As a specific embodiment for polymerizing the sulfidizing agent and the polyhaloaromatic compound in the presence of the above aprotic polar organic solvent, for example,
1) A method using a polymerization aid such as an alkali metal carboxylate or lithium halide,
2) A method using a crosslinking agent such as an aromatic polyhalogen compound,
3) A method in which a polymerization reaction is carried out in the presence of a small amount of water and then water is added for further polymerization,
4) A method in which during the reaction between the alkali metal sulfide and the aromatic dihalogen compound, the gas phase portion of the reaction kettle is cooled to condense part of the gas phase in the reaction kettle and reflux to the liquid phase,
5) Hydrolyzable polar organic compounds such as amides, ureas or lactams having an alkali cyclic structure, and alkali metal sulfides or hydrous alkali metal hydrosulfides and alkali metal hydroxides in the presence of polyhaloaromatic compounds. A step of producing a slurry containing solid alkali metal sulfide by reacting with a solvent while dehydrating, and after producing the slurry, an aprotic polar organic solvent such as NMP is further added, and water is distilled off. In the slurry obtained through the step of dehydration and then through the dehydration step, polyhaloaromatic compound, alkali metal hydrosulfide, alkali metal of hydrolyzate of amide, urea or lactam having the above aliphatic cyclic structure Polymerization is performed by reacting a salt with 1 mol of an aprotic polar organic solvent such as NMP at a water content existing in the reaction system of 0.02 mol or less. Method for producing a polyarylene sulfide resin having a degree as an essential production step thereof.

  The crude reaction mixture obtained after the completion of the polymerization of the polyarylene sulfide resin contains at least the polyarylene sulfide resin, and may further contain an alkali metal-containing inorganic salt and the aprotic polar organic solvent.

  The crude reaction mixture thus obtained is then subjected to a solid-liquid separation step. In the solid-liquid separation step, the aprotic polar organic solvent is solid-liquid separated from the obtained crude reaction mixture, and the liquid phase component mainly composed of the aprotic polar organic solvent, the polyarylene sulfide resin and the alkali metal This is a step of separating a solid phase component composed of a reaction mixture containing the contained inorganic salt and removing the solid phase component to obtain a liquid phase component mainly composed of a polar organic solvent. The solid-liquid separation is roughly classified into two types, a flash method and a quench method described later. The flash method is a method of recovering a solvent by evaporating the solvent and simultaneously recovering a solid, and is generally performed by heating to 130 to 200 ° C. under reduced pressure to distill off the solvent. The solvent temperature immediately after recovering the solvent by the flash method is generally in the range of 130 to 200 ° C. However, usually, for the operation under room temperature (for example, 20 ° C., the same applies hereinafter), a heat retention measure described later is performed. Tends to be cooled to a range of 90 to 190 ° C.

  On the other hand, the quench method is a method for recovering particulate polyarylene sulfide resin by cooling the polymerization reaction product. Generally, the reaction slurry is cooled in a reaction kettle while adding a poor solvent as necessary. And a method of solid-liquid separation after crystallizing the polyarylene sulfide resin. Solid-liquid separation in the Quench method is a method in which after separation using a centrifugal separator such as filtration or screw decanter, water is directly added to the obtained filtration residue to form a slurry, and then solid-liquid separation is repeated. For example, a method of removing the remaining solvent by heating the filtered residue in a non-oxidizing atmosphere can be used. Although the solvent temperature immediately after solvent recovery by the quench method is in the range of 130 to 200 ° C., it is usually cooled to the range of 90 to 190 ° C. even if the heat retention measures described below are taken for work in a room temperature environment. There is a tendency. The flash method is preferable because solids can be collected relatively easily, and the quench method is easy to control the particle size of the polyarylene sulfide resin, and the polymer particles contain alkali metal-containing inorganic salts and other salts during crystallization. Since it becomes difficult to take in impurities, it is preferable in that a high-purity polymer is obtained.

  As described above, after the polymerization reaction is performed, the solid reaction component obtained by subjecting the crude reaction mixture to the solid-liquid separation step, a polymerization reaction product is obtained, and then a known post-treatment step is performed to obtain a polyarylene sulfide resin. Can be manufactured.

  The post-treatment step required thereafter is not particularly limited. For example, (a) the reaction mixture is first left as it is, or an acid or a base is added, and then the solvent is distilled off under reduced pressure or normal pressure. Next, the solid after evaporation of the solvent is washed once or twice or more with a solvent such as water, a reaction solvent (or an organic solvent having an equivalent solubility in a low-molecular polymer), acetone, methyl ethyl ketone, alcohols, and the like. Neutralization, washing with water, filtration and drying, or (b) solvent (use of water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons, etc. in the reaction mixture A solvent that is soluble in the polymerization solvent and is a poor solvent for at least polyarylene sulfide) as a precipitant. A method of precipitating solid products such as sulfides and inorganic salts and filtering them off, washing and drying, or (c) an organic solvent having an equivalent solubility in a reaction solvent (or low molecular weight polymer in the reaction mixture) ) And stirred, filtered to remove the low molecular weight polymer, then washed once or more with a solvent such as water, acetone, methyl ethyl ketone, alcohols, etc., then neutralized, washed with water, filtered and dried (D) A method of adding water to the reaction mixture and washing with water, filtering, and if necessary, adding an acid when washing with water, acid-treating and drying, (e) After completion of the polymerization reaction, the reaction mixture And, if necessary, washing with a reaction solvent once or twice or more, washing with water, filtration and drying, and the like.

   In the post-treatment methods as exemplified in the above (a) to (e), the polyarylene sulfide resin may be dried in a vacuum or in an inert gas atmosphere such as air or nitrogen. May be.

  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.

  The polyarylene sulfide resin obtained by the production method of the present invention described in detail above is blended with other resins, fillers, and additives by a known method and melt-kneaded above the melting point of the polyarylene sulfide resin. It can be processed into a molded product having excellent heat resistance, molding processability, dimensional stability and the like by various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding via pellets.

  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.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Calculation method of erosion degree]
The dimensional change and weight change of the test piece were measured, and the degree of erosion was calculated from the following formula.

単位は、バッフル２枚の試験前重量（ｇ）、バッフル２枚の試験後重量（ｇ）、密度（ｇ／ｃｍ^３）、バッフル２枚の表面積（ｃｍ²）、試験時間（ｈ）、１０ｍｍ＝１ｃｍで換算、とする。

The unit is the weight before the test of 2 baffles (g), the weight after the test of 2 baffles (g), the density (g / cm ³ ), the surface area of 2 baffles (cm ² ), the test time (h), 10 mm. = Conversion with 1 cm.

[How to create a test piece]
Dimension: Vertical 25 (mm) x Horizontal 25 (mm) x Thickness 2 (mm) are prepared and welded to each other at the center. Dimensions: Vertical 50 (mm) x Width 25 (mm) x Thickness 2 (mm) test pieces were prepared.

[Measurement of melt viscosity]
(Measurement of melt viscosity of PPS resin)
Using the KPS flow tester (CFT-500D) manufactured by Shimadzu Corporation for the manufactured PPS resin, under the conditions of 300 ° C., load: 1.96 × 10 ⁶ Pa, L / D = 10 mm / 1 mm,
The value measured after holding for 6 minutes was taken as the melt viscosity (V6).

[Method of adjusting erosion test solution]
An erosion test solution was prepared by the following procedure. 135.68 g (Na ₂ S: 1.7 mol) of anhydrous Na ₂ S (manufactured by Nagao Co., Ltd., “Na ₂ S: 1.7 mol), 4.33 g of water (water: 0.24 mol), NMP in the autoclave Was replaced with nitrogen. Next, the temperature was raised to 200 ° C. over 3 hours while stirring. After reaching 200 ° C., it was rapidly cooled to room temperature to obtain a slurry solution containing NMP hydrolyzate (SMAB: 0.24 mol).

Example 1
The test piece was prepared using “MC alloy” (Ni—Cr—Mo alloy (45% by mass of chromium, 1% by mass of molybdenum and nickel balance)) manufactured by Hitachi Metals MMC Superalloy Co., Ltd. The prepared test piece was soaked in the erosion test solution. Then, nitrogen substitution was implemented and the autoclave was sealed. The sealed autoclave was put in an oven, heated to 250 ° C., and maintained at 250 ° C. for 170 hours. After 170 hours, the autoclave was removed and cooled to room temperature. After cooling, the autoclave was opened, the test piece was taken out, washed with water, the weight and dimensions of the test piece were measured, and the degree of erosion was calculated according to the above formula. As a result, the erosion degree was 0.003 mm / year.

(Comparative Example 1)
It carried out similarly to Example 1 except having used the test piece created using the zirconium instead of "MC alloy." As a result of calculating the erosion degree, the erosion degree was 0.127 mm / year.

(Comparative Example 2)
It carried out similarly to Example 1 except having used the test piece created using titanium instead of "MC alloy." As a result of calculating the erosion degree, the erosion degree was 0.020 mm / year.

(Example 2)
As shown in FIG. 1, a pressure gauge (not shown) and a thermometer (not shown) are connected, a stirring blade (1), a shaft (2) for transmitting power from outside the reaction vessel, and two baffles (3a, 3b), an autoclave (4) equipped with a heating medium (not shown) was used as the reaction apparatus. In addition, the contact part with the reaction liquid or the crude reaction mixture, that is, the stirring blade, the shaft, two baffles, and the inner wall of the autoclave are all “MC Alloy” (Ni-Cr—Mo alloy (45% by mass of chromium) manufactured by Hitachi Metals, Ltd. 1% by mass of molybdenum and the remainder of nickel)).

In the autoclave, 135.68 g of anhydrous Na ₂ S (Na ₂ S: 1.7 mol), p-dichlorobenzene (hereinafter abbreviated as p-DCB) 247.40 g of p-DCB (p-DCB: 1. 68 mol), 4.33 g of water (water: 0.24 mol), and 317.90 g of NMP were charged, and nitrogen substitution was performed. For the erosion degree test, the two baffles (3a, 3b) were placed below the liquid level (5) so that all of them were immersed in the reaction solution.

  Next, while stirring, the temperature was raised from 200 ° C. for 3 hours, from 200 ° C. to 220 ° C. over 2 hours and a half, and kept at 220 ° C. for 2 hours.

Thereafter, the temperature was raised to 250 ° C. over 30 minutes and held at 250 ° C. for 1 hour.
During the polymerization reaction, the inside of the autoclave was in the form of a slurry in which solids (anhydrous Na ₂ S, NaCl) were precipitated in NMP.

  The slurry-like crude reaction mixture was taken out from the autoclave. The crude reaction mixture taken out was added to 400 g of the polymerization slurry obtained by adding 400 g of ion exchange water at 70 ° C. and stirred for 10 minutes, followed by filtration. The cake was filtered by adding 600 g of ion exchange water at 70 ° C. to the cake after filtration. . 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 obtained polymer had a melt viscosity of 110 Pa · s. The same operation as described above was repeated three times, and the degree of erosion was measured after removing the baffle. The erosion degree was 0.02 mm / year. The erosion evaluation based on JIS K0100-1990 “Industrial Water Corrosion Test Method” was judged as “good” by “complete corrosion resistance”.

DESCRIPTION OF SYMBOLS 1 ... Stirring blade 2 ... Shaft 3a, 3b ... Baffle 4 ... Reaction kettle 5 ... Liquid level

Claims (6)

In the reaction apparatus, in the presence of an aprotic polar organic solvent, the reaction solution containing the polyhaloaromatic compound and the sulfidizing agent is reacted in an alkaline atmosphere to obtain a crude reaction mixture containing at least the polyarylene sulfide resin. A method for producing a polyarylene sulfide resin having a polymerization step to obtain,
At least part of the contact portion with the reaction solution or the crude reaction mixture in the reaction apparatus is made of a nickel alloy, and
The nickel alloy 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.
A process for producing a polyarylene sulfide resin characterized by   The manufacturing method of Claim 1 which contains a solid anhydrous alkali metal sulfide as a sulfidation agent in the said superposition | polymerization process.   The production method according to claim 1 or 2, wherein the aprotic polar organic solvent is hydrolyzable.   In the said polymerization process, the hydrolyzate of an aprotic polar organic solvent exists in the range of 0.01-2 mol with respect to 1 mol of sulfur atoms of a sulfidizing agent in reaction container. The manufacturing method as described in any one of these.   In the said superposition | polymerization process, the water in reaction container exists in the range of 0.01-2 mol with respect to 1 mol of sulfur atoms of a sulfidation agent, The manufacturing method as described in any one of Claims 1-4. A polymer having a polymerization step of reacting a reaction solution containing a polyhaloaromatic compound and a sulfidizing agent in an alkaline atmosphere in the presence of an aprotic polar organic solvent to obtain a crude reaction mixture containing at least a polyarylene sulfide resin. A reaction apparatus for use in a method for producing an arylene sulfide resin,
At least part of the contact portion with the reaction solution or the crude reaction mixture in the reaction apparatus is made of a nickel alloy, and
The nickel alloy 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.
A reaction apparatus characterized by the above.

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