JPH0542458B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing arylene sulfide polymers. Arylene sulfide polymers, typified by polyphenylene sulfide, are produced by the method disclosed in Japanese Patent Publication No. 45-3368. That is,
The resin liquid obtained by reacting p-dichlorobenzene and sodium sulfide in an organic solvent such as N-methylpyrrolidone is taken out from the reaction vessel, and then the solvent is removed. The polyphenylene sulfide obtained by this method has an extremely low degree of polymerization and is unsuitable for use as it is.Industrially, this low degree of polymerization is heated in air and oxidatively crosslinked, and three-dimensional crosslinking is performed to increase the molecular weight. It is used for practical purposes such as injection molding. However, even this high-molecular-weight product had poor extrusion moldability and could not be used for applications such as fibers, films, pipes, and sheets. Furthermore, a method for obtaining an arylene sulfide polymer having a relatively high molecular weight through a polymerization reaction is already known. That is, JP-A-53-136100, JP-A-51-
As shown in JP-A No. 144495, JP-A-51-144497, and JP-A-56-28217, relatively high molecular weight polymers can be obtained by carrying out the polymerization reaction in the presence of various polymerization aids. However, many applications require relatively high molecular weight arylene sulfide polymers having a narrower molecular weight distribution than conventional ones, especially arylene sulfide polymers that do not contain low molecular weight components. Patents for this purpose have already been disclosed. In other words, Japanese Patent Publication No. 16078/1989 discloses a method for obtaining higher molecular weight polyphenylene sulfide by extracting and recovering low molecular weight polyphenylene sulfide polymer with an appropriate solvent and using it together with monomers during polymerization. ing. However, this method has several problems. First, a solvent extraction step is required after the polymerization step. That is, the product produced by the polymerization process is a mixture of low molecular weight polymers and high molecular weight polymers, and a separate solvent extraction process is required to separate this. This extraction step is carried out with N-methylpyrrolidone at a temperature range of 135-148.9°C or with benzene at a temperature range of 79.4-148.9°C and with toluene and its analogs at a temperature range of 110-148.9°C. Of course, if the extraction solvent is different from the polymerization solvent, but even if they are the same, the extraction temperature is different from the polymerization temperature. Second, as is clear from the examples of this patent, only extremely low molecular weight arylene sulfide polymers can be separated, and the remaining resin liquid contains a large amount of relatively low molecular weight polymers, resulting in a change in molecular weight distribution. It is difficult to obtain narrow relatively high molecular weight polymers. As a result of extensive studies, the present inventors have found that when obtaining a relatively high molecular weight arylene sulfide polymer through a polymerization reaction, a specific solvent is used and a specific combination of polymer/solvent ratio, temperature, and pressure is used. It was discovered that a liquid phase containing a relatively high molecular weight polymer and a liquid phase containing a low molecular weight polymer exist separately and can be separated, and the present invention has been achieved. That is, the present invention involves reacting a polyhaloaromatic compound with a sulfidizing agent in the presence of a polymerization aid in an amide-based polar solvent, and then forming a thick layer () of a relatively high molecular weight polymer and a thick layer (2) of a relatively low molecular weight polymer. Provided is a method for producing a polyarylene sulfide polymer, which comprises separating the thick layer () or the layer () from a produced resin liquid consisting of the thick layer (). In order to carry out the present invention, it is a prerequisite that a relatively high molecular weight polymer be produced by a polymerization reaction. For this purpose, it is necessary to carry out a polymerization reaction between the polyhaloaromatic compound and the sulfiding agent at a high temperature of at least 200° C. in the presence of a polymerization aid in, for example, an organic amide polar solvent. In the present invention, we investigate the dissolution and insolubility of arylene sulfide polymers at temperatures below 200°C, their solubility at temperatures above 200°C, especially their temperature dependence, the influence of polymerization solvents and polymerization aids on solubility, and the specific gravity of the system. Taking this into account, the produced resin liquid is separated into two layers, one containing an arylene sulfide polymer having a relatively high molecular weight and a relatively low molecular weight arylene sulfide polymer. The polyhaloaromatic compound used in the method of the present invention is a halogenated aromatic compound having two or more halogen atoms directly bonded to an aromatic nucleus, and specifically p-dichlorobenzene, m-dichlorobenzene, o -dichlorobenzene, trichlorobenzene, tetrachlorobenzene, dichloronaphthalene, trichloronaphthalene, dibromobenzene,
Tribromobenzene, dibromnaphthalene, diiodobenzene, triiodobenzene, dichlordiphenyl sulfone, dibromodiphenylsulfone, dichlorobenzophenone, dibrombenzophenone, dichlordiphenyl ether, dibromodiphenyl Examples include ether, dichlorodiphenyl sulfide, dibromodiphenyl sulfide, dichlorbiphenyl, dibrombiphenyl, and mixtures thereof. Usually dihaloaromatic compounds are used, preferably p-dichlorobenzene. Incidentally, in order to increase the viscosity of the polymer due to the branched structure, a polyhaloaromatic compound having three or more halogen substituents in one molecule may be used in combination with a small amount of a dihaloaromatic compound. The sulfidizing agent used in the present invention includes:
Alkali metal sulfide compound; combination use of a sulfur source and an alkali metal hydroxide compound, etc. Alkali metal sulfide compounds include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof. Such alkali metal sulfide compounds can be used as hydrates and/or aqueous mixtures or in anhydrous form. In addition, alkali metal bisulfide, which exists in trace amounts in alkali metal sulfide,
There is no problem in adding a small amount of alkali metal hydroxide to react with the alkali metal thiosulfate. As the alkali metal sulfide compound, mono- to dihydrate sodium sulfide is preferred. Examples of the sulfur source include alkali metal hydrosulfide compounds, hydrogen sulfide, thioamides, thioureas, thiocarbanates, thiocarboxylic acids, carbon dioxide, thiocarboxylates, sulfur, and phosphorous pentasulfide. Preferred sulfur sources are alkali metal hydrosulfides. In particular, the alkali metal hydrosulfide compounds include lithium hydrosulfide, sodium hydrosulfide,
Includes potassium bisulfide, rubidium bisulfide, cesium bisulfide and mixtures thereof. Such alkali metal hydrosulfide compounds can be used in hydrated and/or aqueous mixtures or in anhydrous form. As such an alkali metal hydrosulfide compound, sodium hydrosulfide is preferable and used in combination with an alkali metal hydroxide compound, but sodium N-methyl-4-aminobutyrate or an alkali metal carbonate compound may be used in place of the compound. Also good. Examples of the alkali metal hydroxide compound include potassium hydroxide, sodium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and mixtures thereof, with sodium hydroxide being preferred. The appropriate ratio of the sulfur source to the alkali metal hydroxide compound is 0.8 to 3.0 moles of the alkali metal hydroxide compound per mole of sulfur element. In particular, when an alkali metal hydroxide compound is used in combination, the amount used is 0.9 per 1.00 mol of an alkali metal hydrosulfide compound.
A range of 1.2 moles is suitable. In addition, when sodium N-methyl-4-aminobutyrate is used in combination, the amount used is per 1.00 mol of alkali metal hydrosulfide.
A range of 0.9 to 1.2 moles is suitable. When using each hydrate of the alkali metal sulfide compound or alkali metal hydrosulfide compound, it is necessary to dehydrate it in advance in a solvent before using it in the reaction. In addition, when dehydrating the alkali metal hydrosulfide compound, an alkali metal hydroxide compound or N-methyl-4
- It is better to coexist with sodium aminobutyrate. The organic amide polar solvents used in the method of the present invention include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-ε - selected from caprolactam, hexamethylphosphoramide, etc. or mixtures thereof. Among these solvents, N-methyl-2-pyrrolidone (NMP) is particularly preferred. The amount of the sulfidizing agent used in the present invention is sulfur element per mole of dihaloaromatic compound.
The amount is selected to be 0.8 to 1.2 mol, preferably 0.9 to 1.1 mol. In addition, the amount of organic polar solvent used is 2.5 to 20 molar ratio to the dihalo aromatic compound.
, preferably from 3 to 10. Examples of polymerization aids include organic sulfonic acid metal salts, lithium halides, carboxylic acid metal salts, and alkali phosphate salts. The organic sulfonic acid metal salt is selected from the group represented by the following general formulas. : : : : (In the formula, R ³ is hydrogen or has 1 to 30 carbon atoms.
an alkyl group, n represents an integer of 0, 1 or 2, M represents an alkali metal selected from sodium, potassium, rubidium and cesium, X is a direct bond, -CH ₂ -, -C(CH ₃ ) ₂ −, −
O-, -S-, Indicates that it is selected from the group consisting of. ) Specific examples of acid group components constituting these metal sulfonates include benzenesulfonic acid, p-toluenesulfonic acid, 2,4-dimethylsulfonic acid, 2,5-dimethylbenzenesulfonic acid, and p-ethylbenzenesulfonic acid. , dodecylbenzenesulfonic acid, α-
naphthalenesulfonic acid, biphenylsulfonic acid,
Examples include alkylnaphthalene sulfonic acid, laurylbenzenesulfonic acid, and alkyl diphenyl ether disulfonic acid. The salts of these sulfonic acids may be either anhydrous salts or hydrated salts, or may be an aqueous solution, but it goes without saying that anhydrous salts are preferred from the purpose of the present invention. The lithium halide is selected from lithium chloride, lithium bromide, lithium iodide, and mixtures thereof. The organic group other than the carboxyl group of the organic carbonic acid metal salt usually has 1 to 50 carbon atoms,
It may also contain nitrogen, oxygen, halogen, silicon, and sulfur, and is preferably an alkyl group, a cycloalkyl group, an aryl group, or an alkylaryl group. Further, the metal atom of the organic carboxylic acid metal salt is selected from lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, zinc, strontium, cadmium, and barium, and alkali metals are particularly preferred. Specific examples of organic carboxylic acid metal salts include lithium acetate,
Sodium acetate, potassium acetate, lithium propionate, sodium propionate, lithium 2-methylpropionate, rubidium butyrate, lithium valerate, sodium valerate, cesium hexanoate, lithium heptanoate, lithium 2-methyloctoate, potassium dodecanoate , rubidium 4-ethyl ettradecanoate, sodium octadecanoate, sodium heneicosanoate, lithium cyclohexanecarboxylate, cesium cyclododecanecarboxylate, sodium 3-methylcyclopentanecarboxylate, potassium cyclohexylacetate, potassium benzoate, lithium benzoate, benzoic acid. sodium acid, potassium m-tolyl acetate, lithium phenyl acetate, sodium 4-phenylcyclohexanecarboxylate, potassium p-tolyl acetate, 4-
Lithium ethylcyclohexyl acetate, dilithium succinate, disodium succinate, dipotassium succinate, dilithium adipate, disodium adipate, dipotassium adipate, dilithium sebacate, disodium sebacate, dipotassium sebacate, Dilithium decanedicarboxylate, disodium decanedicarboxylate, disodium decanedicarboxylate, dipotassium decanedicarboxylate, dilithium phthalate, disodium phthalate, dipotassium phthalate, dilithium isophthalate, disodium isophthalate, isophthalate dipotassium terephthalate, dilithium terephthalate, disodium terephthalate, dipotassium terephthalate, trilithium trimellitate, trisodium trimellitate, tripotassium trimellitate, tetralithium pyromellitate, tetrasodium pyromellitate, tetrapotassium pyromellitate, toluene Dilithium dicarboxylate, disodium toluene dicarboxylate, dipotassium toluene dicarboxylate, dilithium naphthalene dicarboxylate, disodium naphthalene dicarboxylate, dipotassium naphthalene dicarboxylate, magnesium acetate, calcium acetate, calcium benzoate, and other similar types Mention may be made of salts and mixtures thereof. The alkali phosphate salt is selected from the group represented by the following general formula. : : In the formula, _R4 is hydrogen, _C1 to _C20 alkyl, _C5 to _C20
cycloalkyl, _C6 - _C24 aryl, _C7 - _C24
alkaryl, _C7 ~ _C24 aralkyl, _C2 ~ _C24
alkenyl, _C2 - _C20 alkynyl or _C5 - _C20
cycloalkenyl, M is an alkali metal, preferably sodium. Alkaline phosphate salts suitable for the present invention include trisodium phosphate and the disodium salts of the following acids. Methanephosphonic acid, ethane-1-phosphonic acid, propane-1-phosphonic acid, butane-1-phosphonic acid, butane-2-phosphonic acid, pentane-
1-phosphonic acid, cyclohexane-1-phosphonic acid, vinyl-1-phosphonic acid, propene-2-phosphonic acid, butene-2-phosphonic acid, indene-2-phosphonic acid, phenylmethane-phosphonic acid, (4- Methyl-phenyl)-methane-phosphonic acid, β-naphthyl-methane-phosphonic acid, 2-phenyl-ethane-1-phosphonic acid, 2,2-diphenyl-ethane-1-phosphonic acid, 4-phenyl-butane-1 -Phosphonic acid, 2-phenyl-ethylene-1-phosphonic acid, 2,2-diphenylethylene-phosphonic acid, phenyl-acetylene-phosphonic acid, 4-phenyl-butadiene-
Phosphonic acid, benzene-phosphonic acid, 4
-Methyl-benzene-phosphonic acid and 2-phenoxy-ethane-1-phosphonic acid. It is necessary to use at least one kind of these polymerization aids. As for the types thereof, organic sulfonic acid alkali salts and organic carboxylic acid salts are preferable. In particular, it is most preferable to use an organic sulfonic acid alkali salt and an organic carboxylic acid salt together. The amount of the polymerization aid to be used is preferably within a range that allows it to be dissolved in the amide polar solvent during polymerization. Even if it is used above the solubility limit, it will not promote separation and is unnecessary. The amount of polymerization aid that can be used in the method of the present invention varies depending on the type of compound used, but
Usually from 0.01 to polyhaloaromatic compounds
300% by weight, preferably in the range from 0.5 to 200%. The effect of such a polymerization auxiliary agent is not only to simply improve the polymerization reaction activity, but also to change the solubility of the polymer in the polymerization system, thereby creating dense layers of a relatively high molecular weight polymer and a relatively low molecular weight polymer.
In addition, the reaction rate increases due to the high concentration of the active end of the polymer in the relatively high-molecular-weight polymer-rich layer, and the two synergistically produce a layer rich in high-molecular-weight polymer. I guess. The reaction temperature at which polymerization is carried out in the present invention is generally
The temperature is 200°C to 330°C, preferably 210°C to 300°C.
The pressure should be in a range that maintains the polymerization solvent and the polymerization monomer, the haloaromatic compound, substantially in the liquid phase, generally between 1.1 Kg/cm ² and 200 Kg/cm 2 .
^cm2 , preferably selected from the range of 1.1Kg/ ^cm2 to 20Kg/ ^cm2 . The reaction time varies depending on temperature and pressure, but generally ranges from 10 minutes to about 72 hours, preferably from 1 hour to 48 hours. The polymerization reaction is carried out under an inert atmosphere, such as nitrogen gas,
The reaction is preferably carried out in carbon dioxide, and there is no particular restriction on the order in which the reaction components are mixed, and the above-mentioned components may be added in small portions or all at once during the polymerization step. In addition, it is preferable to blow carbon dioxide during or at the end of the polymerization reaction, which not only prevents the decomposition of polyarylene sulfide and contributes to increasing the molecular weight of the resulting polymer, but also has the effect of preventing the decomposition of N-methylpyrrolidone. be. In the present invention, layer separation between a dense layer of relatively high molecular weight polymer (hereinafter referred to as high molecular weight polymer) and a concentrated layer of relatively low molecular weight polymer (hereinafter referred to as low molecular weight polymer) is facilitated. In order to cause this to occur, it is preferable to select the conditions as shown below. Of course, conditions other than those shown below can be used as long as they cause layer separation. The weight ratio of the amide polar solvent-generated polymer is in the range of 20/1 to 1/2. This ratio is 20/
When it exceeds 1, both the high molecular weight polymer and the low molecular weight polymer exist in a single layer, and the two layers are not separated. Further, when the ratio is less than 1/2, the high molecular weight polymer is not sufficiently dissolved, which is beyond the purpose of the present invention. This ratio is
The ratio is preferably 20/1 to 1/1. Further, the temperature range during polymerization is from 210°C to 300°C. At a temperature lower than 210°C, the high molecular weight polymer component does not dissolve in the solvent, which is beyond the purpose of the present invention, and at a temperature higher than 300°C, both the high molecular weight polymer component and the low molecular weight polymer component exist in a single layer and are not separated. A preferred temperature range is 220°C to 290°C. The polymerization aid/amide polar solvent ratio varies depending on the type of solvent and polymerization aid, but is generally from 2/1 to 1/30 by weight. If this ratio exceeds 2/1, a phenomenon occurs in which the polymerization aid is not dissolved in the solvent or the polymer component, particularly the high molecular weight polymer component, is not dissolved. Further, when the ratio is less than 1/30, the separation effect is insufficient and the high molecular weight polymer component and the low molecular weight component exist in a single layer, which deviates from the object of the present invention. The pressure during polymerization may be any pressure at which the amide polar solvent and the polymerization aid substantially form a liquid phase.
Specifically, it is 1.5Kg/cm ² to 100Kg/cm ² . Preferably it is 1.5Kg/cm ² to 30Kg/cm ² . The various conditions such as the solvent/polymer ratio, polymerization aid/solvent ratio, temperature, and pressure at the time of fractional extraction are within the range of suitable polymerization conditions, and once the polymerization reaction has progressed to a certain degree or more, the conditions are as follows. They are separated and taken out. However, there is no problem even if the conditions at the time of polymerization and at the time of fractional extraction are different as long as the conditions described above are met. For example, the solvent/polymer ratio can be suitably varied by adding additional material into the system or removing it from the system by distillation before fractional extraction. There are no particular restrictions on the method of separate collection. For example, it is possible to selectively take out the high molecular weight polymer layer or the low molecular weight polymer layer using a sample tube using a straw method while stirring is stopped or under laminar flow stirring, or alternatively, both layers can be selectively separated one after another from the bottom of the pot. It is also possible to take it out. However, in general, the production of arylene sulfide polymers is carried out at high temperatures and under pressure if necessary, and the removal is carried out at high temperatures, so the reaction state and the state of the produced resin liquid cannot be seen from the outside in a reaction vessel, such as an autoclave. etc. must be used.
Therefore, in the present invention, from the viewpoint of efficiently separating a high molecular weight polymer layer and a low molecular weight polymer layer from the produced resin liquid, it is generally necessary to It is preferable that the fractionation be performed such that the difference in logarithmic viscosity is 0.1 or more, preferably 0.15 or more, compared to the logarithmic viscosity of the polymer in the low molecular weight polymer layer forming the upper layer of the produced resin liquid. In practice, it is industrially advantageous for the weight ratio taken out to be 30 to 70% by weight. Of course, it is also possible to take out the low molecular weight polymer layer from the upper part of the reaction vessel, in which case the difference in logarithmic viscosity between the polymer in the resin liquid taken out and the polymer in the resin liquid remaining in the reaction vessel is 0.1 or more, preferably 0.15. or more, and the extraction weight ratio is 30~
Preferably, the amount is 70% by weight. In the present invention, as a method for separating a high molecular weight polymer layer and a low molecular weight polymer layer, it can also be used in a sensor capable of detecting both layers. These sensors include differences in the physical properties of both layers, such as specific gravity, viscosity, dielectric constant, electrical conductivity, refractive index, light transmittance, and color difference. It is also possible to perform separate extraction by predicting the weights of both layers in advance and measuring changes in the amount taken out or the amount remaining. There is no particular limitation to such a method as long as it allows for separate collection. Any conventional method may be used to collect the polymer from the resin liquid taken out according to the present invention. For example, a purified polymer can be obtained by removing the solvent from the resin liquid by distillation or flashing, and then washing with water or a poor solvent such as acetone or methanol. The production method of the present invention can produce a high molecular weight polymer containing almost no low molecular weight polymer. Of course, if a dense layer of low molecular weight polymer is removed, a low molecular weight polymer containing almost no high molecular weight polymer can be produced. The high molecular weight arylene sulfide polymer obtained by the present invention does not need to be heat-crosslinked in air, and can be used for fibers, sheets, film tubes, tubes, etc., which conventionally required particularly high molecular weight polymers. It can be used for extrusion molding and blow molding. Naturally, it can also be used for injection molding or compression molding, which are the main applications for conventional products. If necessary, it is also suitable to blend the arylene sulfide polymer obtained by the present invention with fillers, pigments, flame retardants, stabilizers and other polymers. For example, glass fibers can be added to improve mechanical strength and heat resistance. Hereinafter, the method of the present invention will be explained according to examples. The logarithmic viscosity value [η] of the arylene sulfide polymer was measured at 206°C in α-chlornaphthalene at a polymer concentration of 0.4 g/100 ml solution.
This is a value calculated according to the formula [η]= _lo (relative viscosity)/polymer concentration. Note that parts and percentages in the examples are based on weight. Example 1 43.20 kg (436 mol) of N-methylpyrrolidone was placed in a 150 liter autoclave having an outlet at the bottom of the container.
Sodium hydroxide 0.084Kg (2.1mol), 60% sodium sulfide flakes 8.86Kg (68.2mol) and sodium p-toluenesulfonate 16.29Kg (80mol)
The temperature was gradually raised from 160℃ to 205℃ over 2 hours while stirring under a nitrogen atmosphere, and the water was heated to 3.6℃.
kg, and a fraction consisting of 0.4 kg of N-methylpyrrolidone was removed from the system. Thereafter, 10.02 kg (68.2 mol) of p-dichlorobenzene, 0.018 kg (0.1 mol) of 1,2,4-trichlorobenzene, and 10.80 kg (109 mol) of N-methylpyrrolidone were added. then
The reaction was carried out at 220°C for 1 hour and then at 260°C and a pressure of 10 kg/cm ² for 3 hours. A portion of the surface layer of the produced resin liquid was taken from the upper part of the reaction vessel and the logarithmic viscosity of the polymer was measured and found to be 0.14. Further, when the resin liquid was sampled from the bottom of the reaction vessel and the logarithmic viscosity of the polymer was similarly measured, it was 0.310. Next, set the container K1 for taking out at the bottom of the taking out port, and after stopping stirring for 30 seconds, reduce the opening cross-sectional area of the taking out port to ^5mm2.
Adjust the temperature to 260°C and start taking out the resin liquid until it reaches 10.2% (takeout amount) of the resin liquid shown in Table 1. Next, set the taking out container K2 and collect the remaining amount of resin liquid. I took it out on K2. The amount of polymer, logarithmic viscosity, amount of polymerization aid, and amount of solvent were investigated for each of K1 and K2. This was designated as Experiment No. 1. Next, polymerization was carried out in the same manner as in Experiment No. 1, and experiments were conducted in which the polymers were taken out at various amounts as shown in Table 1 (Experiments No. 2 to 10). The results of each experiment are shown in Table 1. As can be seen from Table 1, it was possible to separate and extract high molecular weight polymers and low molecular weight polymers.

【table】

[Table] Example 2 Experiment No. 4 of Example 1 was repeated 5 times. The results are shown in Table 2. As can be seen from Table 2, the reproducibility was good.

【table】

[Table] Examples 3 and 4 Table 3 shows the extraction temperature and extraction ratio in Example 1.
The experiment was carried out under the conditions shown in . The results are shown in Table 3.

【table】

[Table] Examples 5 to 7 1728 g (17.5 mol) of N-methylpyrrolidone, 3.4 g (0.08 mol) of sodium hydroxide, 60%
520 g (4.0 mol) of sodium sulfide flakes and 576 g (4.0 mol) of sodium benzoate were charged, and the temperature was gradually raised from 160°C to 205°C over 2 hours while stirring under a nitrogen atmosphere, and 130 g of water and N- A fraction consisting of 18 g of methylpyrrolidone was removed from the system.
p-dichlorobenzene 588g (4.0mol), 1,2,
0.72 g (0.004 mol) of 4-trichlorobenzene and 432 g (4.4 mol) of N-methylpyrrolidone were added. Then at 220℃ for 1 hour and then at 260℃ under pressure.
The reaction was carried out at 8.0 Kg/cm ² for 3 hours. After the reaction was completed, the solvent/polymer weight ratio was changed as shown in Table 4 by adding a solvent or removing a portion of the solvent by distillation, and then the polymer was taken out at the takeout ratio shown in Table 4. The results are shown in Table 4. Example 8 The reaction and fractional extraction were carried out under the same conditions as in Example 6, except that 410 g (5 mol) of anhydrous sodium acetate was used instead of sodium benzoate and the solvent/polymer ratio was 8/1. . Note that the extraction ratio was determined in advance so as to maximize the separation efficiency. The results are also listed in Table 4.

【table】

[Table] Example 9 3456 g (25 moles) of N-methylpyrrolidone was placed in a 25 autoclave having an outlet at the bottom of the container.
6.8 g (0.16 mol) of sodium hydroxide, 1040 g (8 mol) of 60% sodium sulfide flakes, and the polymerization aid shown in Table 5 were added, and while stirring under a nitrogen atmosphere,
The temperature was gradually raised from 160°C to 205°C over a period of 2 hours, and a fraction consisting of water and N-methylpyrrolidone was distilled out of the system. The composition of the fraction is also listed in Table 4.
p-dichlorobenzene 1176g (8 mol), 1,2,
1.44 g (0.008 mol) of 4-trichlorobenzene and 864 g (8.8 mol) of N-methylpyrrolidone were added. Next, at 220℃ for 1 hour, and then at 260℃ with a pressure of 8.2
The reaction was carried out at Kg/cm ² for 3 hours. After completion of the reaction, 2592g of solvent N-methylpyrrolidone
was added, and fractional extraction was performed at the extraction ratio shown in Table 5. The results are also listed in Table 5.

【table】

[Table] Example 10 Experiment No. 33 of Example 9 was carried out by changing the amount of polymerization aid as shown in Table 6. Table 6 shows the results.
Shown below.

【table】

[Table] Example 11 Experiment No. 36 of Example 10 was carried out by changing the type, amount used, and amount taken out of the polymerization aid as shown in Table 7. The results are shown in Table 7.

【table】

[Table] Comparative Example Experiment No. 1 of Example 1 was conducted without using a polymerization aid. When the obtained resin liquid was taken out at the takeout ratio shown in Table 8, the logarithmic viscosity of the taken out polymer and the residual polymer in the reaction vessel were almost the same. In this example, the resin liquid produced was not separated into two layers. Note that the extraction temperature was 260°C.

【table】

【table】

Claims (1)

[Claims] 1 After reacting a polyhaloaromatic compound and a sulfiding agent in the presence of a polymerization aid in an amide polar solvent, a thick layer of a relatively high molecular weight polymer () and a thick layer of a relatively low molecular weight polymer () are formed.
A method for producing a polyarylene sulfide polymer, which comprises separating the layer () or the layer () from a produced resin liquid consisting of.