JPH0542461B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing high molecular weight 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. Namely, JP-A-53-136100, JP-A-51
−144495, JP-A-51-144497, JP-A-56-
As shown in No. 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. 16078/1986 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. has been done. However, this method has several problems. First, the amount of relatively high molecular weight polymer in the produced resin liquid is small compared to the amount of relatively low molecular weight polymer, resulting in poor yield. Second
Second, 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 uses N-methylpyrrolidone at a temperature range of 135-148.9°C.
Alternatively, benzene in the temperature range of 79.4 to 148.9°C or toluene and its analogs in the temperature range of 110 to 148.9°C may be used, of course, if the extraction solvent is different from the polymerization solvent, but even if the extraction temperature is the same. 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 determined that a resin liquid consisting of a relatively high molecular weight arylene sulfide polymer layer and a relatively low molecular weight arylene sulfide polymer layer produced by a polymerization reaction can be used to obtain a polymer with a relatively low molecular weight. It has been found that the above-mentioned drawbacks can be improved by separating the layers, then adding a polymer raw material thereto and carrying out a polymerization reaction, and the present invention has been achieved based on this discovery. 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. The layer () is separated from the produced resin liquid consisting of the thick layer (), and then a polyhaloaromatic compound and a sulfiding agent, and if necessary, an amide polar solvent and a polymerization aid are added thereto and reacted. A method for producing a high molecular weight arylene sulfide polymer is provided. In the present invention, it is first necessary to produce a resin liquid consisting of a relatively high molecular weight arylene sulfide polymer layer and a relatively low molecular weight arylene sulfide polymer layer. For this purpose, for example, in an organic amide polar solvent in the presence of a polymerization aid,
A polymerization reaction between the polyhaloaromatic compound and the sulfidizing agent is carried out at a high temperature of at least 200°C or higher.
At that time, 200℃ of arylene sulfide polymer
By considering the insolubility at temperatures below, the solubility at temperatures above 200°C, especially its temperature dependence, the influence on the solubility of polymerization solvents and polymerization aids, and the specific gravity of the system, This causes separation of the relatively high molecular weight and relatively low molecular weight arylene sulfide polymer layers. 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 disulfide, 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. 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. When dehydrating an alkali metal hydrosulfide compound, it is preferable to coexist an alkali metal hydroxide compound or sodium N-methyl-4-aminobutyrate. 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. The organic amide polar solvent used in the method of the present invention includes N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl- It is selected from ε-caprolactam, hexamethylphosphoramide, etc., or a mixture thereof. Among these solvents, N-methyl-2-pyrrolidone (NMP) is particularly preferred. 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 carboxylic 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-tolylate, 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, dipotassium decanedicarboxylate, dilithium phthalate, disodium phthalate, dipotassium phthalate, dilithium isophthalate, disodium isophthalate, dipotassium isophthalate, terephthalic acid dilithium,
Disodium terephthalate, dipotassium terephthalate, trilithium trimellitate, trisodium trimellitate, tripotassium trimellitate, tetralithium pyromellitate, tetrasodium pyromellitate, tetrapotassium pyromellitate, dilithium toluenedicarboxylate, ditoluenedicarboxylate Sodium, dipotassium toluene dicarboxylate,
Mention may be made of dilithium naphthalene dicarboxylate, disodium naphthalene dicarboxylate, dipotassium naphthalene dicarboxylate, magnesium acetate, calcium acetate, calcium benzoate, and other similar salts and mixtures thereof. The alkali phosphate salt is selected from the group represented by the following general formulas. : : In the formula, R ₄ is hydrogen, C ₁ to C ₂₀ alkyl, C ₅ to
_C20 cycloalkyl, _C6 ~ _C24 aryl, C7 _~
C24 alkaryl, _C7 ~ _C24 aralkyl, C2 _~
C24 alkenyl, _C2 - _C20 alkynyl or _C5-
C ₂₀ 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. Methane-1-phosphonic 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
Phosphonic acid, vinyl-1-phosphonic acid,
propene-2-phosphonic acid, butene-2-phosphonic acid, indene-2-phosphonic acid,
Phenylmethanephosphonic 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 ratio of each raw material used when producing a resin liquid consisting of a relatively high molecular weight arylene sulfide polymer layer and a relatively low molecular weight arylene sulfide polymer layer using each of the raw materials described above is as follows. It is. The amount of the sulfidizing agent used is selected such that the amount of sulfur element is 0.8 to 1.2 mol, preferably 0.9 to 1.1 mol, per mol of the polyhaloaromatic compound.
The amount of the amide polar solvent to be used is in a molar ratio of 2.5 to 20, preferably 3 to 10, relative to the dihaloaromatic compound. Further, 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 the polymerization aid that can be used in the method of the present invention varies depending on the type of compound used, but is usually in the range of 0.01 to 300% by weight, preferably 0.5 to 200% by weight, based on the polyhaloaromatic compound. 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, creating dense layers of relatively high molecular weight polymer and relatively low molecular weight polymer. By increasing the concentration of the active end of the polymer in a relatively high-molecular-weight polymer-rich layer, the reaction rate increases, and the two synergistically produce a layer rich in high-molecular-weight polymer. Infer. 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. It is also preferable to blow carbon dioxide during or at the end of the polymerization reaction, which not only prevents the decomposition of the arylene sulfide polymer and contributes to increasing the molecular weight of the resulting polymer, but also prevents the decomposition of N-methylpyrrolidone. effective. In the above resin liquid, there is a thick layer of relatively high molecular weight arylene sulfide polymer (hereinafter referred to as high molecular weight polymer) and a relatively low molecular weight arylene sulfide polymer (hereinafter referred to as low molecular weight polymer). In order to easily cause layer separation from the dense layer, 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 ratio of the amide polar solvent/produced polymer is in the range of 20/1 to 1/2 by weight. This ratio
When the ratio exceeds 20/1, 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. Preferably, such a ratio is between 20/1 and 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 2/1 to 1/30 by weight, preferably 1/1 to 1/20.
It is. 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 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. There is no particular restriction on the method for separating the low molecular weight polymer layer from the resin liquid consisting of the high molecular weight polymer layer and the low molecular weight polymer layer obtained as described above. For example, it is possible to take out the high molecular weight polymer layer using a sample tube using a straw method while stirring is stopped or under laminar flow stirring, leaving the low molecular weight polymer layer as a residue, or it is also possible to selectively take out the low molecular weight polymer layer. Alternatively, it is also possible to selectively separate and take out both layers from the bottom of the pot.
However, the production of arylene sulfide polymers is generally carried out at high temperatures and under pressure if necessary.
Moreover, since the extraction is carried out at a high temperature, a reaction vessel such as an autoclave must be used in which the reaction state and the state of the produced resin liquid cannot be seen from the outside. 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, generally the resin liquid taken out from the bottom of the pot (mainly the high molecular weight polymer layer formed in the lower layer of the produced resin liquid) The difference in logarithmic viscosity of the polymer (including the molecular weight polymer layer) is 0.1 or more, preferably 0.15 or more, compared to the logarithmic viscosity of the polymer of the low molecular weight polymer layer forming the upper layer of the produced resin liquid. is preferable. That is, it is preferable that the low molecular weight polymer layer remains inside the reaction vessel. In practice, it is industrially advantageous for the weight percentage of the resin liquid containing the high molecular weight polymer to be taken out from 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, and in this 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. This is the above, and it is preferable to carry out the extraction so that the weight ratio taken out is 30 to 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. The separation method used in the present invention is not particularly limited to the methods described above, as long as it is a method that allows for separate collection. In the present invention, the reaction is carried out by adding the above-mentioned polyhaloaromatic compound and sulfidizing agent, and optionally the above-mentioned amide polar solvent and polymerization aid to the resin liquid mainly containing the low molecular weight polymer separated above. At this time, it is appropriate that the resin liquid has a polymer logarithmic viscosity of preferably 0.05 to 0.20, more preferably 0.07 to 0.19. The amount of the polyhaloaromatic compound added is preferably 20 to 100 parts by weight of the polymer in the resin liquid.
The amount is 3000 parts by weight, more preferably 50 to 2000 parts by weight. Further, the amount of the sulfidizing agent may be an amount corresponding to the proportion of the polyhaloaromatic compound used in producing the resin liquid. Further, the amount of the amide polar solvent added is preferably determined so that the resin concentration of the finally obtained resin liquid is 2 to 50% by weight. Furthermore, the amount of the polymerization aid added is preferably such that the weight ratio of the total weight of the amount of the polymerization aid remaining in the resin liquid to the total amount of the amide polar solvent is preferably 2/1.
It is from 1/30 to 1/30, more preferably from 1/1 to 1/20. Incidentally, the reaction conditions during polymerization, such as temperature and pressure, may be the same as those for producing the resin liquid described above. In the present invention, in particular, the logarithmic viscosity of the polymer is from 0.05 to
By manufacturing a high molecular weight polymer using a resin solution containing a low molecular weight polymer of 0.20, a high molecular weight polymer with a logarithmic viscosity of 0.24 or more is produced.
A resin liquid containing at least % by weight can be obtained. The resin liquid at this time is separated into a high molecular weight polymer layer and a low molecular weight polymer layer in the reaction vessel, and the low molecular weight polymer layer is usually the upper layer. The polymer layer and the low molecular weight polymer layer can be separated. Any conventional method may be used to collect the polymer from the resin liquid containing the high molecular weight polymer taken out. 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. [Example] Next, the present invention will be further explained with reference to Examples. Note that parts and percentages in the examples are based on weight. Synthesis Examples 1 to 4 43.20 kg (436 mol) of N-methylpyrrolidone was placed in a 15 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 0.18. 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 found to be 0.310. Next, set the extraction container at the bottom of the extraction port,
30 seconds after stopping stirring, adjust the opening cross-sectional area of the outlet to 5 mm ² and start taking out at 260°C, until the resin liquid (high molecular weight polymer content) reaches 40.1% (taken out amount) of the produced resin shown in Table 1. was collected. The low-molecular-weight polymer was used as the residue. amount of polymer and logarithmic viscosity for each,
The amount of polymerization aid and solvent was investigated. This was designated as Synthesis Example 1. Next, polymerization was carried out in the same manner as in Synthesis Example 1, and low molecular weight polymers were fractionated as shown in Table 1 (Synthesis Examples 2 to 4). The results are shown in Table 1.

【table】

[Table] Examples 1 to 4 Raw materials as shown in Table 2 were added to the low molecular weight polymers obtained in each pot residue obtained in Synthesis Examples 1 to 4, and then reacted in the same manner as in Synthesis Example 1. A high molecular weight polymer was taken out at the extraction rate shown in 2. The results are shown in Table 2.

【table】

[Table] As can be seen from Table 2, it is possible to separate and extract high molecular weight polymers, and moreover, the molecular weight is higher than in each synthesis example, and the production rate is also high. Synthesis Examples 5 to 12 Table 3 shows the extraction temperature and extraction ratio in Synthesis Example 1.
The experiment was carried out under the conditions shown in . The results are shown in Table 3.

【table】

[Table] Examples 5 to 12 Raw materials as shown in Table 4 were added to the low molecular weight polymers obtained in each pot residue obtained in Synthesis Examples 5 to 12, and reacted in the same manner as in Synthesis Examples 5 to 12, respectively.
A high molecular weight polymer was extracted at the extraction ratio shown in Table 4. The results are shown in Table 4.

【table】

[Table] Synthesis Examples 13 to 15 Synthesis Example 1 was carried out by changing the raw materials as shown in Table 5. The results are shown in Table 5.

【table】

[Table] Examples 13 to 15 Raw materials as shown in Table 6 were added to the low molecular weight polymers obtained in each pot residue obtained in Synthesis Examples 13 to 15, and reacted in the same manner as in Synthesis Examples 13 to 15, respectively.
A high molecular weight polymer was extracted at the extraction ratio shown in Table 6. The results are shown in Table 6.

【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 relatively high molecular weight polymer () and a thick layer of relatively low molecular weight polymer () are formed.
A resin liquid containing mainly a relatively low molecular weight polymer is separated from the resin liquid produced, and then a polyhaloaromatic compound and a sulfiding agent, and if necessary, an amide polar solvent and a polymerization aid are added and reacted. A method for producing a high molecular weight arylene sulfide polymer characterized by: