JPH06248079A - Production of polyarylene sulfide and resin composition - Google Patents

Abstract

PURPOSE:To produce the subject polymer exhibiting a high reactivity and excellent in adhesion, etc., by reacting an alkaline metal sulfide with a dihalogenoaromatic compound in a polar solvent under a specified condition, then removing liquid components from the reaction solution and subsequently washing the residual solid components with water. CONSTITUTION:(A) An alkaline metal sulfide (preferably sodium sulfide) is initially reacted with (B) a dihalogenoaromatic compound (preferably p- dichlorobenzene, etc.) in the presence of a base (preferably NaOH) in a polar solvent (preferably N-methylpyrrolidone) using the component (A) in an excessive amount based on the component (B) on molar base, preferably using the component (B) in a molar ratio of 0.9 to 0.99mol based on 1mol component (A). After completion of the reaction the liquid components such as the reaction solvent and water are then removed from the reaction solution and the residual solid components are washed with water, thus producing the objective polymer. In addition, the reaction between the components (A) and (B) is carried out preferably at 180 to 280 deg.C for 0.5 to 20hr in an atmosphere of nitrogen.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a polyarylene sulfide (hereinafter referred to as P
Abbreviated as AS), especially polyphenylene sulfide (hereinafter,
The present invention relates to a method for producing PPS) and a PAS obtained by the method, particularly a composition using PPS. More specifically, the present invention is suitable as a material for various molded products and films, fibers, electric / electronic parts, automobile parts, etc., and is excellent in heat resistance, moldability, dimensional stability, etc.,
And PAS having good reactivity, adhesion, adhesiveness and compatibility with other resins and / or inorganic fillers or metals and adhesives, and particularly to a method for producing PPS and a composition containing the PAS Is.

[0002]

2. Description of the Related Art As a conventional method for producing PPS, which is a typical PAS, an alkali metal sulfide represented by sodium sulfide and p-dichlorobenzene are used in an organic amide solvent such as N-methyl-2-pyrrolidone. A method for reacting a representative dihalo aromatic compound is described in Japanese Patent Publication No. 45-3368. In such a reaction, the reaction molar ratio of the alkali metal sulfide to the dihaloaromatic compound is preferably 1.1 to 0.9 in the former and 0.9 to 1.1 in the latter. Are known. In such a case, when the alkali metal sulfide is used in a slight excess with respect to the dihaloaromatic compound, the resulting polymer is M
It is also well known that it becomes a -S- group (M is an alkali metal) and can be acidified to form a terminal mercaptan.

However, even if the alkali metal sulfide is used in excess with respect to the dihaloaromatic compound, only a polymer having a thiolate group or a thiol group having a high reactivity at the end cannot be obtained, and the reactivity of the obtained polymer is low. It was quite low. Then, as a method for producing a highly reactive PPS having a thiolate group or a thiol group at the polymer terminal, PPS and an alkali metal sulfide and / or an alkali metal hydrosulfide are heated at 150 to 230 ° C. in a polar aprotic solvent.
The method (Japanese Patent Application Laid-Open No. 2-140233) was considered. In this method, the isolated PPS is reacted with an alkali metal sulfide or the like, or an alkali metal sulfide or the like is added and reacted in the latter stage of PPS polymerization, and it is sure that the concentration of the thiolate group or the thiol group at the polymer end is increased. You can However, isolated PP
Reacting with S makes the operation complicated and is industrially disadvantageous, and the method of adding alkali metal sulfide or the like in the latter stage of the polymerization is generally difficult to liquefy solid alkali metal sulfide or the like. Therefore, the reaction is carried out continuously, that is, a special apparatus is required for addition at high temperature and under pressure, and addition at around room temperature makes the reaction discontinuous, which makes it difficult to control the polymerization. It is disadvantageous for industrial implementation.

Therefore, in recent years, a method of improving the adhesiveness by modifying the surface of a PPS molded product has been considered. For example, there is a method of activating the surface of a molded article by irradiating the molded article of PPS with ultraviolet rays to improve the adhesiveness (Japanese Patent Laid-Open No. 3-97028). Since this method is certainly easy to operate and the apparatus is inexpensive, it is good for improving a small amount of molded products, but it is industrially disadvantageous because of poor productivity in mass production. In addition, JP-A-5
JP-A-7-187327 also proposes a method of subjecting the surface of a PAS resin film to corona discharge or plasma treatment. However, these methods have a problem that the production process is complicated and inefficient, and the film surface is significantly deteriorated. Another surface modification method for polymer molded articles is a chemical modification method using an acid or the like. For example, JP-A-63-8954 discloses a method using a mixed solution of chromic anhydride and sulfuric acid and a solution of a Friedel-Crafts reaction catalyst dissolved in an organic solvent.
Japanese Patent No. 118342 discloses a method of using a treating agent composed of chlorosulfonic acid and dichloroethane, but these have a problem in safety and hygiene because they use a powerful drug which is harmful to the human body, and therefore, such as wastewater treatment. There are some problems and it is difficult to implement industrially.

In addition, methods of using various additives have been proposed to improve the adhesiveness or paintability of PAS typified by PPS and the adhesiveness to metals. For example,
JP-A-2-208363 discloses a PAS resin composition obtained by polymerizing a monomer having at least one ethylenically unsaturated bond in the presence of PAS, and JP-A-2-272063 discloses a carnauba wax. A PPS resin composition containing is disclosed. However, in either case, the effect was insufficient or the heat resistance of the additive was inferior to that of PPS. .

[0006]

SUMMARY OF THE INVENTION In view of the above problems, the present inventors have found that when improving the adhesiveness of PAS, etc.
By devising the method for producing AS, studies were conducted to provide PAS with high reactivity.

[0007]

[Means for Solving the Problems] The inventors of the present invention have made extensive studies to achieve the above object and found that a thiolate group or a thiol group having a high reactivity is used even in a system in which the alkali metal sulfide is excessive in the method for producing PAS. Although it was recognized that the number did not increase, addition of a base to such a reaction system (system in which the alkali metal sulfide was excessive with respect to the dihalogenoaromatic compound) dramatically increased the reactivity of the thiolate group or The desired reaction is achieved by increasing the number of thiol groups and, in addition, after this reaction, the step of distilling off the liquid component from the reaction solution (second step) and the step of washing the residual solid component with water (third step). The present invention has been completed by finding that a highly flexible polymer, that is, a polymer having good adhesiveness is obtained.

That is, according to the present invention, when a polyarylene sulfide is obtained by reacting an alkali metal sulfide with a dihalogeno aromatic compound in a polar solvent, the first step is to convert the alkali metal sulfide to the dihalogeno aromatic compound in a polar solvent. A step of reacting by adding a base in excess with respect to the above, and adding a base to cause a reaction, a second step: a step of distilling a liquid component from the reaction solution after completion of the reaction, a third step: a step of washing residual solid components with water The present invention relates to a method for producing a polyarylene sulfide, which comprises three steps, and a resin composition containing the polyarylene sulfide.

One of the requirements in the first step in the method of the present invention
That is, adding alkali metal hydroxide, which is a base, to a system in which alkali metal sulfide is present is to react with alkali metal hydrosulfide and alkali metal thiosulfate, which are present in trace amounts as impurities in alkali metal sulfide. What is often done is, for example, JP-A-62-177027.
It is also known from the description of the issue. However, in this case, an extremely small amount is added in order to react the alkali metal hydrosulfide and the alkali metal thiosulfate present as impurities in the used alkali metal sulfide with the alkali metal hydroxide to replace the total amount with the alkali metal sulfide. However, it is not intended to add excess alkali metal hydroxide to the alkali metal sulfide.

As described above, it is recognized that a system having an excess of alkali metal sulfide with respect to a dihalogeno aromatic compound does not increase the number of highly reactive thiolate groups or thiol groups. It has been discovered for the first time by the present inventors that the addition of a base in a system in which the metal is in excess of the dihalogenoaromatic compound) and the presence thereof causes a dramatic increase in the number of highly reactive thiolate groups or thiol groups. Therefore, the present invention is based on such knowledge.

The polar solvent used in the method of the present invention includes:
Organic polar solvents that are substantially liquid at the reaction temperature and pressure, particularly organic polar aprotic solvents, are preferred. Specifically, formamide, acetamide, N-
Methylformamide, N, N-dimethylacetamide,
N, N-dimethylformamide, N-ethylpropionamide, N, N-dipropylbutyramide, 2-pyrrolidone, N-methyl-2-pyrrolidone, ε-caprolactam, N-methyl-ε-caprolactam, N, N ′. -Ethylenedi-2-pyrrolidone, hexamethylphosphoramide, tetramethylurea, amides such as 1,3-dimethyl-2-imidazolidinone, urea and lactams; sulfolane, dimethylsulfolane, 1-methyl-1-oxosulfolane , Sulfolanes such as 1-phenyl-1-oxosulfolane; nitriles such as benzonitrile; ketones such as methylphenylketone; 1-methyl-1-oxophosphane, 1-normal-propyl-1-oxophosphane, Cyclic organophosphorus compounds such as 1-phenyl-1-oxophosphane and the like And a mixture of et. Among these solvents, amides and lactams are preferable, and N-methylpyrrolidone is particularly preferable.

Examples of the alkali metal sulfide used in the method of the present invention include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide. These may be used alone or in combination of two kinds. The above may be mixed and used. The above-mentioned alkali metal sulfide may be used in any form of anhydrate, hydrate and aqueous solution. When using a hydrate or aqueous solution, it is better to carry out dehydration operation before the reaction as described later. Among the above alkali metal sulfides, sodium sulfide and potassium sulfide are preferable, and sodium sulfide is particularly preferable.

These alkali metal sulfides can be obtained by reacting an alkali metal hydrosulfide with an alkali metal base or hydrogen sulfide with an alkali metal base, but they may be prepared in the reaction system or outside the reaction system. You may use the thing.

Examples of the alkali metal hydrosulfide include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, and cesium hydrosulfide. These may be used alone or in combination of two or more. You may mix and use. The above-mentioned alkali metal hydrosulfide may be an anhydride, a hydrate, or an aqueous solution, but when using a hydrate or an aqueous solution, as in the case of the alkali metal sulfide, as described below, It is better to perform dehydration operation before the reaction. Among the above alkali metal hydrosulfides, sodium hydrosulfide and potassium hydrosulfide are preferable, and sodium hydrosulfide is particularly preferable.

These alkali metal hydrosulfides can be obtained by reacting hydrogen sulfide with an alkali metal base, but it does not matter whether they are prepared in the reaction system or used outside the reaction system. .

Examples of the alkali metal base include alkali metal hydroxide. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide, which may be used alone or in combination with 2
You may mix and use 1 or more types. Among the above alkali metal hydroxide compounds, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is particularly preferable.

The dihalogeno-aromatic compound used in the present invention is, as long as it has an aromatic nucleus and two halo substituents in the nucleus, and is reacted with a sulfiding agent (alkali metal sulfide) to give a heavy compound. It can be arbitrary as long as it can be integrated. Therefore, the aromatic nucleus may have various substituents that do not inhibit the reaction with the sulfidizing agent, in addition to the case where the aromatic nucleus is composed of only aromatic hydrocarbon.

Specifically, examples of the dihalogeno aromatic compound used in the present invention are as follows. p-dichlorobenzene, m-dichlorobenzene,
2,5-dichlorotoluene, p-dibromobenzene,
1,4-dichloronaphthalene, 1-methoxy-2,5-
Dichlorobenzene, 4,4'-dichlorobiphenyl,
3,5-dichlorobenzoic acid, 2,4-dichlorobenzoic acid, 2,5-dichloronitrobenzene, 2,4-dichloronitrobenzene, 2,5-dichloroaniline, 2,4
-Dichloroaniline, 2,4-dichloroanisole,
p, p'-dichlorodiphenyl ether, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl sulfone, 4,4'-dichlorodiphenyl sulfoxide, 4,4'-dichlorodiphenyl sulfide, etc. .
Among them, p-dichlorobenzene, m-dichlorobenzene, 4,4′-dichlorobenzophenone and 4,4 ′
Dichlorodiphenyl sulfone is particularly preferably used. Copolymers containing two or more different reaction units can be obtained by an appropriate selected combination of dihalogeno aromatic compounds. When p-dichlorobenzene and 4,4'-dichlorobenzophenone or 4,4'-dichlorophenylsulfone are used in combination, a copolymer containing these units can be obtained.

The base to be added is the above-mentioned alkali metal base, and examples thereof include the above-mentioned alkali metal hydroxide. Sodium hydroxide is particularly preferable as the alkali metal hydroxide.

Production of PAS in the present invention (first step)
In the case of reacting an alkali metal sulfide with a dihalogenoaromatic compound, it is necessary to first satisfy the conditions of using the alkali metal sulfide in an excessive molar ratio with respect to the dihalogenoaromatic compound and adding a base.

The amount of water present in the polymerization reaction system is 0.5 to 5 mol with respect to the alkali metal sulfide (sulfiding agent),
Preferably 0.6-2.0 mol, more preferably 0.7-
It is 1.5 Moro. In the method of the present invention, when the water content in the system is less than the above range, it is difficult to carry out the polymerization reaction.

The order of adding the respective raw materials to the polar solvent is not particularly limited, but preferably, a sulfidizing agent such as an alkali metal sulfide and a base such as an alkali metal hydroxide are mixed in advance in a polar solvent, and the mixture is added from the beginning. Hydration water or water of crystallization contained, or water produced is dehydrated by a dehydration operation such as azeotropic distillation to prepare a mixed solution in which the amount of water in the system is adjusted. It is desirable to react with a dihalogeno aromatic compound in a molar ratio of less than 1. Simultaneously satisfying both conditions of using the dihalogeno aromatic compound in a molar ratio of less than 1 with respect to the sulfidizing agent and adding a base is significantly different from the conventional production method of polyarylene sulfide. However, it is not enough to satisfy either condition.

The proportions of the various components used in the present invention differ depending on the reaction conditions such as reaction temperature and reaction time and therefore cannot be specified unconditionally. However, the dihalogeno aromatic compound is used in a molar ratio of less than 1 with respect to the alkali metal sulfide, and There is no particular limitation as long as the condition that a base is added is satisfied, but the dihalogeno aromatic compound is 0.
85 to 0.999 mol, preferably 0.88 to 0.99
It is 5 mol, more preferably 0.90 to 0.99 mol. The amount of the base or alkali metal base added to the reaction solution is 0.005 with respect to 1 mol of the alkali metal sulfide.
It is at least mol, preferably at least 0.01 mol, and more preferably at least 0.02 mol.

The polar solvent is used in a molar ratio of 1 to 20 with respect to the alkali metal sulfide (sulfiding agent),
It is preferably in the range of 2-10. When the amount of the solvent is less than 1, the reaction may be non-uniform, which is not preferable, and when the amount exceeds 20, it is not preferable in that the productivity is lowered.

Next, the first preferred embodiment among the embodiments of the present invention.
Explaining with an example of the method in the step, first, an alkali metal sulfide and an alkali metal hydroxide are mixed in a polar solvent. After heating if necessary, after performing dehydration operation by azeotropic distillation, etc., add a dihalogeno aromatic compound,
It is usually heated to a temperature of 60 to 300 ° C., preferably 150 to 300 ° C., and more preferably 180 to 280 ° C.
The polymerization reaction is carried out by heating for ~ 40 hours, preferably 0.5-20 hours. Since this reaction temperature varies depending on the type of dihalogeno aromatic compound used, it cannot be specified unconditionally,
If it is lower than 60 ° C, the reaction rate is slow and the reaction may be non-uniform, while if it is higher than 300 ° C, the produced polymer is deteriorated. The reaction time depends on the type and amount of the starting materials used, or the reaction temperature, and therefore cannot be specified unconditionally, but if the reaction time is less than 0.1 hours, the polymer produced is likely to have a low molecular weight, and 40 hours is required. Beyond that, productivity falls.

This polymerization reaction is usually carried out with nitrogen, helium,
It is preferably carried out in an atmosphere of an inert gas such as argon, and nitrogen is particularly preferred from the viewpoints of economy and ease of handling.

The reaction pressure is not particularly limited because it cannot be unconditionally specified because it depends on the types and amounts of the starting materials and solvents used, the reaction temperature, and the like.

The reaction may be a one-step reaction carried out at a constant temperature, a multi-step reaction in which the temperature is raised stepwise, or a reaction in which the temperature is continuously changed.

The polymer produced in the reaction of the first step is obtained by first distilling off the reaction solvent and the liquid component such as water from the reaction system containing the solid component such as the produced polymer and the produced salt, and then removing the polymer from water or an organic solvent. It is preferable to wash with. Distilling off the liquid component from the reaction solution after the reaction means that the liquid component (the liquid component showing a liquid state at 25 ° C.) contained in the solid component after the distillation is 5% by weight or less, preferably 2% by weight or less. State. Distillation method to achieve such a state,
It is a method of heating to a temperature at which the liquid component vaporizes, depressurizing, or a combination of both.
(Hereinafter, this method is generally referred to as desolvation.) The timing of desolvation may be immediately after the completion of the reaction, without adding anything, or after adding the acid. Further, after completion of the reaction, the solvent may be removed by washing with water or solvent. However, from the viewpoint of the efficiency of solvent recovery or the convenience of the process, it is preferable to remove the solvent immediately after completion of the reaction with a small amount of acid or without adding any acid.

The solid component containing the desolvated polymer may be washed by a usual method. That is, water or warm water, or methanol, ethanol, acetone, or ether is used so that unreacted raw materials or by-produced salts can be removed.
It is washed with a relatively low boiling point organic solvent such as tellurium or THF. It is effective to remove the adhering sodium hydroxide etc. without using an acid when removing the solvent and to use a relatively dilute aqueous solution for cleaning, and change the terminal thiolate to a thiol. You can also do it. As the acid to be used, it is preferable to use dilute hydrochloric acid, dilute phosphoric acid, dilute acetic acid or the like from the viewpoints of easy handling and economy. The polymer thus isolated is dried by heating to a temperature at which a solvent such as water evaporates. Drying may be performed under vacuum, or may be performed in air or in an atmosphere of an inert gas such as nitrogen.

Polymer thus obtained (uncrosslinked)
Has a melt flow rate of 200 to 6000 (g / 10
Minutes) preferably 300 to 4000 (g / 10 minutes), more preferably 500 to 2500 (g / 10 minutes). The obtained polymer can be used as it is for various molding materials, etc., but it can be thickened by heat treatment in air or oxygen-enriched air or under reduced pressure. After carrying out, it may be used for various molding materials and the like. This heat treatment temperature cannot be specified unconditionally because it varies depending on the treatment time and the atmosphere to be treated, but it is usually preferably 180 ° C. or higher and lower than the melting point of the polymer. If the heat treatment temperature is lower than 180 ° C., the rate of thickening is very slow and the productivity is poor, and if it is higher than the melting point of the polymer, the operation is substantially impossible. Further, since heat treatment may lower the reactivity and the like, excessive heat treatment is not preferable in view of high reactivity which is the object of the present invention and the provision of adhesiveness therewith.

The polymer obtained in the present invention may of course be used alone, but it can also be used as a mixture with PAS produced by a known method by taking advantage of its high reactivity and adhesiveness. It is possible. The mixing ratio of the polymer obtained in the present invention and PAS produced by a known method varies depending on the purpose and is arbitrary as long as high reactivity and the like can be obtained.
The polymer obtained by the present invention is injection-molded as it is,
By various melt processing methods such as extrusion molding, compression molding and blow molding, a molded product having excellent heat resistance, moldability and dimensional stability can be obtained. However, in order to further improve performances such as strength, heat resistance and dimensional stability, it is also possible to use it in combination with various fillers within a range not impairing the object of the present invention.

Examples of the filler include fibrous filler and inorganic filler. As the fibrous filler, glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide,
Fibers such as calcium sulfate and calcium silicate and natural fibers such as wollastonite can be used. Further, as the inorganic filler, barium sulfate, calcium sulfate, clay, biferrite, bentonite, sericite, zeolite, mica, mica, talc, atalpulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads and the like. Can be used.

Further, a small amount of a release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust preventive, a flame retardant, an additive as an additive in the molding process within a range not departing from the object of the present invention, A lubricant and a coupling agent can be contained. Further, similarly, the following synthetic resins and elastomers can be mixed and used. These synthetic resins include polyester, polyamide, polyimide, polyetherimide,
Polycarbonate, polyphenylene ether, polysulfone, polyether sulfone, polyether ether ketone, polyether ketone, polyarylene, polyethylene, polypropylene, polytetrafluoride ethylene, polydifluoride ethylene, polystyrene, ABS resin, epoxy resin, silicone resin , Phenol resin, urethane resin, liquid crystal polymer, etc., and the elastomer includes polyolefin rubber, fluororubber, silicone rubber, etc.

Since the PAS obtained by the production method of the present invention is extremely rich in reactivity, various properties such as adhesiveness and adhesiveness with other resins and / or inorganic fillers, metals and adhesives are remarkable. improves. Therefore, the PAS or the composition containing the PAS obtained in the present invention can be used, for example, in electric / electronic parts such as connectors, printed circuit boards, and encapsulation molded articles, automobile parts such as lamp reflectors and various electric component parts, and various buildings. Interior materials for objects and aircraft, automobiles,
Alternatively, heat resistance, molding processability, and dimensions in various molding processing fields such as injection molding and compression molding of precision parts such as OA equipment parts, camera parts, and watch parts, or extrusion molding and pultrusion molding of composite sheets and pipes. It is used as a molding material or fiber or film having excellent stability.

[0036]

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

The various physical properties were measured according to the following methods. (1) Melt flow rate ASTM method D-1238-74 (315.5 ° C., 5 kg
Load).

(2) Determination of thiolate group or thiol group at the end of PPS: JP-A-62-187731 and JP-A-2-140.
It was carried out according to the method described in Japanese Patent No. The details will be described below.

(A) Principle

[0040]

[Chemical 1]

(B) Operation After the completion of the polymerization reaction, the reaction slurry is cooled to room temperature, and a part of the reaction slurry is immediately sampled, poured into water to precipitate the polymer, separated by filtration, and thoroughly washed with pure water, and then diluted hydrochloric acid water. The terminal thiolate group was changed to a thiol group by treatment with, and washed with pure water for 30 minutes, further washed with acetone for 30 minutes, and dried under reduced pressure at room temperature in a vacuum dryer to obtain a sample. Immediately after that, about 10 mg to 1 g of a sample was precisely weighed, placed in a sealed stopper type test tube, and 2.5 ml of an acetone solution containing 2.5 ml of acetone and 50 mol of iodoacetamide was added.
ml was added, the container was sealed, and heated at 100 ° C. for 1 hour. Then, the mixture was cooled with water, opened, and the liquid phase portion was separated, and the absorbance at 360 nm, that is, the absorbance at I ₂ was measured using an ultraviolet absorptiometer. Thiol model compound

[0042]

[Chemical 2]

The thiol group concentration at the terminal was calculated from the absorbance from the calibration curve prepared using. The sample amount is
The thiol group concentration in the acetone solution is 0.1 to 0.3 (μ
It is preferable to select an appropriate value within the range of mol / cc) in order to reduce the error. In addition, the same sample was analyzed three times and the average value of the terminal thiol group concentration was obtained.

(3) Evaluation of Adhesiveness 40 parts by weight of polymer, 35 parts by weight of glass fiber and 25 parts by weight of calcium carbonate were melt-kneaded at 320 ° C. using an extruder to form pellets, and then 50 mm by an injection molding machine. × 2
A 5 mm test piece was prepared. Cross-sectional area of sample piece 25m
An epoxy-based adhesive was attached to the m × 25 mm portion, sample pieces were laid on each other crosswise, the adhesive was cured, and then the adhesive strength was measured. As the glass fiber,
Asahi Fiber Glass Co., Ltd. 03-MA497 was used. Further, as the adhesive, a mixture of Epicron EP-850 manufactured by Dainippon Ink and Chemicals, Inc. and laccamide EA-631 was used and cured at 150 ° C. for 1 hour.

(4) Goggles test A conductive paste is applied to the surface of the molded product in a thickness of about 30 μm, dried at 150 ° C. for about 30 minutes, and scratches are made in a grid pattern at 1 mm intervals. went. In addition, the conductive paste is made by Asahi Chemical Research Institute, Cabon Paste.
TU-30SK diluted with butyl cellosolve to 60% by weight was used.

Example 1 5420 g of N-methylpyrrolidone (hereinafter abbreviated as NMP), 2084.6 g (16.0 mol) of sodium sulfide 2.9 and 4 were placed in a 16-liter autoclave.
26.7 g of 8.0% aqueous sodium hydroxide solution (0.02 mol with respect to 1 mol of sodium sulfide) was charged, and the temperature was raised to 204 ° C. under a nitrogen atmosphere to obtain water-NM.
The P mixture was distilled off. The composition in the distillate is NMP180
g, 466 g of water, and 48 mmol of ionic sulfur.
Then p-dichlorobenzene 2297.6 g was added to this system.
(15.63 mol) (sodium sulfide 1 m in the reaction solution)
sol (0.98 mol) in NMP1380g was added and the mixture was further heated at 220 ° C for 3 hours at 250 ° C.
At room temperature for 2 hours under a nitrogen atmosphere. After cooling the reaction vessel, the contents were taken out and a part thereof was sampled to obtain a sample for quantitative determination of terminal thiol, and the above-mentioned treatment was performed. Further, the remaining slurry was divided into the following four and treated by the methods described below.

Treatment method 1: Desolvation → Washing (5 times) → Drying Treatment method 2: Hydrochloric acid addition + desolvation → Washing (5 times) → Drying treatment method 3: Desolvation → Washing (3 times) → Acetone washing ( Two
→ Drying Treatment method 4: Washing with water (5 times) → Drying treatment method 5: Washing with water (2 times) → Pickling (dilute hydrochloric acid) → Washing with water (3 times) → Drying Treatment methods 4 and 5 are Treatment method 1, 2,
Filtration took significantly longer than that of No. 3.

Desolvation was carried out at a reduced pressure of 20 mmHg to 1
The drying was performed at 30 ° C., and the drying was performed at 80 ° C. under reduced pressure. The amount of water or acetone used for washing is 500 g based on 100 g of the polymer obtained by the treatment. Each of the obtained polymers was molded according to the method described above, and the adhesiveness was evaluated. The results are shown in Table 1.

In the following examples and comparative examples, the slurry after the reaction was treated according to the treatment method 1.

Example 2 Reaction time and reaction temperature were 220 ° C. for 6 hours, and 250
The same procedure as in Example 1 was carried out except that the temperature was 2 hours. The yield of the obtained polymer was 1610 g. Other results are shown in Table 1.

Example 3 Example 3 was repeated except that 53.4 g of 48.0% aqueous sodium hydroxide solution (0.04 mol per 1 mol of sodium sulfide) was used. The yield of the obtained polymer was 1600 g. Other results are shown in Table 1.

Example 4 2250.6 g (15.31 m) of p-dichlorobenzene
ol) (0.96 mol with respect to 1 mol of sodium sulfide in the reaction solution) was used, and the same procedure as in Example 1 was performed. The yield of the obtained polymer was 1570 g.
Other results are shown in Table 1.

Example 5 Instead of using sodium sulfide 2.9 hydrate in Example 1, anhydrous sodium sulfide (S purity 98.0%) 12
74.3 g (16.0 mol), 48.0% sodium hydroxide aqueous solution 26.7 g (0.02 mol per 1 mol of sodium sulfide), 320 g of water and NMP553.
0 g was placed in a 16 l autoclave and, after nitrogen substitution was sufficiently performed at room temperature, the system was closed and the temperature was raised to 220 ° C., and 2305.0 g (15.68 mol) of p-dichlorobenzene (0 mol per 1 mol of sodium sulfide in the reaction solution). .98mo
1) dissolved in 1240 g of NMP was added, and
The reaction was carried out at 0 ° C. for 3 hours and further at 250 ° C. for 2 hours under a nitrogen atmosphere. Thereafter, the same treatment as in Example 1 was performed. The yield of the obtained polymer was 1610 g. Other results are shown in Table 1.

Example 6 NMP 5420 g and sodium hydrosulfide 1.3 hydrate 1271, instead of sodium sulfide 2.9 hydrate.
4 g (16.0 mol) and 14.0 g (16.32 mol) of 48.0% sodium hydroxide aqueous solution were charged into a 16-liter autoclave, and the water-NMP mixture was distilled off by raising the temperature to 204 ° C. under a nitrogen atmosphere. The composition of the distillate was 440 g of NMP, 1092 g of water and 60 mmol of ionic sulfur. Then, 2296.3 g (15.62 mol) of p-dichlorobenzene (0.98 mol per 1 mol of the sulfur source in the reaction solution) was added to this system by NMP.
A solution dissolved in 1890 g was added, and the mixture was reacted at 220 ° C. for 3 hours and further at 250 ° C. for 2 hours under a nitrogen atmosphere. Thereafter, the same treatment as in Example 1 was performed. The yield of the obtained polymer was 1610 g. Other results are shown in Table 1.

Comparative Example 1 The amount of p-dichlorobenzene used was 2391.7 g (1
6.27 mol) (1.02 mol is used with respect to 1 mol of sodium sulfide). The yield of the obtained polymer was 1630 g. Other results are shown in Table 1.

Comparative Example 2 330 g of water was used without using any aqueous sodium hydroxide solution.
The same procedure as in Example 5 was carried out except that it was used. The yield of the obtained polymer was 1620 g. Other results are shown in Table 1.
Shown in.

Comparative Example 3 The amount of p-dichlorobenzene used was 2352 g (16.0 g).
mol) (1 mol is used for 1 mol of sodium sulfide), and the same procedure as in Example 1 was carried out. The yield of the obtained polymer was 1630 g. Other results are shown in Table 1.
Shown in.

[0058]

[Table 1]

Examples 7, 8 and 9 The polymer obtained by the treatment method 1 of Example 1 and the polymer obtained in Comparative Example 1 were mixed in the proportions shown in Table 2 and molded,
The adhesiveness was evaluated.

[0060]

[Table 2] Composition in molded product: (polymer of Example 1 + polymer of Comparative Example 1) / GF /
CaCO ₃ = 40/35/25

Examples 10, 11, 12 and Comparative Examples 4, 5,
6 The polymer obtained by the treatment method 1 of Example 1 and the polymer obtained in Comparative Example 2 were respectively thermally crosslinked at 250 ° C. in a hot-air dryer until the viscosities shown in Table 3 were obtained, and then molded to obtain adhesiveness. evaluated.

[0062]

[Table 3] Composition in Molded Product: Example 10, Comparative Example 4 Polymer / GF / CaCO ₃ = 40/35/25 Examples 11, 12, Comparative Examples 5 and 6 Polymer / GF = 70/30

[0063]

INDUSTRIAL APPLICABILITY By the production method of the present invention, PAS having significantly improved reactivity can be easily obtained. Since the obtained PAS is highly reactive, various properties such as adhesiveness and adhesiveness with other resins and / or inorganic fillers, metals and adhesives are remarkably improved.

Claims (10)

[Claims] 1. When a polyarylene sulfide is obtained by reacting an alkali metal sulfide with a dihalogenoaromatic compound in a polar solvent, the first step: the alkali metal sulfide is added to the dihalogenoaromatic compound in a polar solvent. A step of reacting by using a molar ratio in excess and adding a base; a second step: a step of distilling a liquid component from the reaction solution after the reaction is completed; a third step: a step of washing the residual solid component with water; A method for producing a polyarylene sulfide, which comprises the steps of: 2. When a polyarylene sulfide is obtained by reacting an alkali metal sulfide with a dihalogenoaromatic compound in a polar solvent, the first step is to convert the alkali metal sulfide to the dihalogenoaromatic compound in a polar solvent. A step of reacting by adding a base in excess with a molar ratio and reacting, a second step: a step of adding an acid to the reaction solution and distilling off a liquid component after the reaction, a third step: a residual solid component A method for producing a polyarylene sulfide, which comprises three steps of washing with water. 3. When a polyarylene sulfide is obtained by reacting an alkali metal sulfide with a dihalogenoaromatic compound in a polar solvent, the first step is to convert the alkali metal sulfide to the dihalogenoaromatic compound in a polar solvent. A step of reacting by adding a base in excess with a molar ratio, a second step: a step of distilling a liquid component from the reaction solution after completion of the reaction, a third step: a step of washing residual solid components with water, a fourth step Step: a step of washing the residual solid component with an acid and / or an organic solvent, wherein the order of the third step and the fourth step may be replaced with each other. Production method. 4. When a polyarylene sulfide is obtained by reacting an alkali metal sulfide with a dihalogenoaromatic compound in a polar solvent, the first step is the step of adding the alkali metal sulfide to the dihalogenoaromatic compound in a polar solvent. A step of reacting by adding a base in excess with a molar ratio and reacting, a second step: a step of adding an acid to the reaction solution and distilling off a liquid component after the reaction, a third step: a residual solid component A step of washing with water, a fourth step: a step of washing a residual solid component with an organic solvent, (the order of the third step and the fourth step may be interchanged), and the polyarylene sulfide. Manufacturing method. 5. The dihalogeno aromatic compound is used in a molar ratio of 0.90 to 0.99 with respect to the alkali metal sulfide, and the base is added in a molar ratio of 0.02 or more with respect to the alkali metal sulfide. The manufacturing method according to claim 1. 6. The method for producing a polyarylene sulfide according to claim 1, wherein the alkali metal sulfide is produced by a reaction between an alkali metal hydrosulfide and an alkali metal hydroxide. 7. The production method according to claim 1, wherein the base is an alkali metal hydroxide. 8. The method for producing a polyarylene sulfide according to claim 1, wherein the liquid component (2) contained in the residual solid component after distilling off the liquid component.
A liquid state at 5 ° C.) is 5% by weight or less. 9. The production method according to claim 1, wherein the polyarylene sulfide is polyphenylene sulfide. 10. A resin composition comprising the polyarylene sulfide obtained by the production method according to claim 1.