JPS61111329A - Production of arylene sulfide polymer - Google Patents

Abstract

PURPOSE:To obtain a polymer substantially free of any oligomer component effectively and economically, by adding a specified compound to a resin solution containing a low-MW arylene sulfide polymer or oligomer, obtained by a polymerization reaction. CONSTITUTION:A polyhaloaromatic compound is reacted with a sulfiding agent in an amide polar solvent, and to this reaction solution at least one selected from among organic metal sulfonates, organic metal carboxylates, polyalcohols, lithium halides and alkali phosphates, is added. From the formed resin solution comprising a low-MW polymer-rich layer (I) and an oligomer-rich layer (II), layer (I) or (II) is separated. As the polyhaloaromatic compound used, a dihaloaromatic compound is usually used, and p-dichlorobenzene is preferably used. As the amide polar solvent, N-methyl-2-pyrrolidone is particularly preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing arylene sulfitopo+3-2-.

[Conventional technology and its problems]

Arylene sulfide polymers, typified by polyphenylene sulfide, are produced by the method disclosed in Japanese Patent Publication No. 45-3368.

Arylene sulfide polymers having a relatively low molecular weight, such as polyphenylene sulfide, are heated in air and subjected to oxidative three-dimensional crosslinking to increase their molecular weight, and are used in practical applications such as injection molding. Such low molecular weight arylene sulfide polymers can be produced by, for example, removing the resin liquid obtained by reacting p-dichlorobenzene and sodium sulfide in an organic solvent such as N-methylpyro IJ pn from a reaction vessel, and then removing the solvent. (Special Publication No. 45-3368)
. However, in the conventional production method of low molecular weight arylene sulfide polymer, since the low molecular weight polymer obtained first has a wide molecular weight distribution, corrosion of the reactor inner wall during the three-dimensional crosslinking reaction and corrosion during melt molding occur. It contains a relatively large amount of Orico 9mer components, which cause foaming, tar generation, thermal deterioration, corrosion of molds, and deterioration of thermal stability and mechanical properties of products. is JP-A-57
-205425, a polymerization reaction step,
After the solvent recovery process and washing process, the polymer is further treated with a solvent such as acetone, benzene, tetrahydrofuran, etc. to extract and remove the oligomer component. There are problems with processing, etc. In addition, in conventional production methods, the system is a homogeneous solution or slurry when the reaction mixture is taken out, so it is not possible to physically separate the low molecular weight polymer from the oligomer. The polymerization solvent must be removed from the entire reaction mixture prior to solvent extraction of the oligomer. This is because a large amount of polymerization solvent is used, so the post-processing process is complicated and takes a long time, and equipment investment and energy costs are large.The amount of polymer obtained is small compared to the amount of polymerization solvent processed. There are problems such as the need to carry out the wastewater treatment process strictly in order to prevent a large amount of polymerization solvent from being mixed into the wastewater.

[Means for solving problems]

1. As a result of intensive studies in view of these drawbacks, the present inventors have developed a resin liquid (reaction mixture) containing a low molecular weight arysine sulfide polymer and oligomer obtained by a polymerization reaction.
By adding at least one selected from organic sulfonic acid metal salts, organic caldic acid metal salts, polyhydric alcohols, etc., the content of the organic amide polar solvent is small and the low molecular weight polymer is present in a relatively large amount. It is possible to separate and fractionate a liquid layer from a liquid layer containing a large amount of organic amide polar solvent and a relatively large amount of oligomer components, and the amount of polymerization solvent to be processed is small, and The inventors have discovered that a polymer containing almost no oligomer components can be obtained efficiently and economically, leading to the present invention.

That is, in the present invention, after reacting a polyno-aromatic compound and a nulphitizing agent in an amide-based polar solvent, organic sulfonic acid metal salts, organic carboxylic acid metal salts, polyhydric alcohols, lithium chloride, and At least one selected from alkali phosphate salts is added, and then layer (I) or layer (II) is formed from the resulting resin liquid consisting of a dense layer (I) of a low molecular weight polymer and a concentrated layer (II) of an oligomer.
Provided is a method for producing a polyarylene sulfide polymer characterized by tt fractionation.

In the present invention, the term "oligomer" refers to an arylene sulfide polymer with an intrinsic viscosity of less than 0.05, as well as an oligomer that has a low molecular weight and contains a nitrogen atom in the molecule (this nitrogen atom is formed during polymerization during the polymerization reaction). It is presumed that primary to quaternary amino groups are formed by partial decomposition of the solvent.)
This is a general term that also includes low molecular weight impurities that are produced as by-products during the reaction.

Furthermore, the low molecular weight polymer referred to in the present invention refers to an intrinsic viscosity [0,0
5 to 0.20 arylene sulfide polymer.

The polyno-orthoaromatic compounds used in the method of the present invention are halodanated aromatic compounds having two or more norodane atoms directly bonded to an aromatic nucleus, such as sb, specifically p-dichlorobenzene, m-dichlorobenzene. , 0-dichlorobenzene, trichlorobenzene, tetrachlorobenzene, dichloronaphthalene, trichloronaphthalene, dibromobenzene, trifluorobenzene, dibromnaphthalene, jodope/zene, triiodobenzene, dichlorodiphenylsulfo/, dibromciphere Examples thereof include sulfone, dichlorobenzophenone, dibrombenzophenone, dichlordiphenyl ether, dibromidiphenyl ether, dichlordiphenyl sulfide, dibromidiphenyl sulfide, dichlorbiphenyl, dibrombiale, and mixtures thereof. Usually dihaloaromatic compounds are used, preferably p-dichlorobenzene. In order to increase the viscosity of the polymer due to the branched structure, a polyhaloaromatic compound having three or more halogaff substituents in one molecule may be used in combination with a small amount of a dihaloaromatic compound.

Examples of the sulfidating agent used in the present invention include an alkali metal sulfide compound alone, or a combination of this compound or another sulfur source and an alkali metal hydroxide compound.

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. Note that there is no problem even if a small amount of alkali metal hydroxide is added to react with the electrified alkali metal and alkali metal thiosulfate present in the alkali metal sulfide.

As the alkali metal sulfide compound, mono- to dihydrate sodium sulfide is preferred.

Other sulfur sources include, for example, alkali metal hydrosulfides, hydrogen sulfide, thioamides, thioureas, thiocarbanates, thiocaldic acids, carbon disulfide, thiocal? These include xylate, sulfur, and phosphorus pentasulfide. Preferred sulfur sources are alkali metal hydrosulfides. In particular, the alkali metal hydrosulfide compounds include lithium bisulfide, sodium bisulfide, potassium bisulfide, rubidium bisulfide, cesium bisulfide, and mixtures thereof. Such alkali metal hydrosulfide compounds can be used in hydrated and/or monoaqueous 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. It's okay.

Further, examples of the alkali metal hydroxide compound include potassium hydroxide, sodium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and mixtures thereof, and IJium hydroxide is preferred.

The ratio of the sulfur source to the alkali metal hydroxide compound is 0.00 to 1 mole of sulfur element to the alkali metal hydroxide compound.
8 to 3.0 mol is suitable. In particular, when used in combination with an alkali metal hydroxide compound, the appropriate amount is in the range of 0.9 to 1.2 mol per 1.00 mol of the alkali metal hydroxide compound. When an alkali metal carbonate compound is used in combination, it is appropriate that the alkali metal hydroxide compound be used in a high proportion. In addition, when sodium N-methyl-4-aminobutyrate is used in combination, the amount used is alkali metal hydrosulfide i,
A suitable range is 0.9 to 1.2 mol per oo' mol.

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. Incidentally, when dehydrating the alkali metal hydrosulfide compound, it is preferable to coexist an alkali metal hydroxide compound or sodium N-methyl-4-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-epsilon-caglolactam, hexamethylphosphoramide, etc. or mixtures thereof.

Among these solvents, N-methyl-2-pyrrolidone (
NMP) is particularly preferred.

The amount of the sulfidating agent used in the present invention is 0.8 to 1.2 sulfur per mole of the dihaloaromatic compound.
mol, preferably 0.9 to 1.1 mol. Further, the amount of the organic polar solvent used is in the range of 2.5 to 20, preferably in the range of 3 to 10, in terms of molar ratio to the dihaloaromatic compound.

The reaction temperature at which polymerization is carried out in the present invention is generally 200℃~
The temperature is 330°C, preferably 210°C to 300°C. The pressure should be in a range to maintain the polymerization solvent and the polymerization monomer, the haloaromatic compound, substantially in the liquid phase, generally from 1.1' to 9/cm2 to 200 to 9/m2,
Preferably 1.1 kg/cm2 to 20 kg/cm'
f) The range is selected. Reaction times vary depending on temperature and pressure, but generally range from 10 minutes to about 72 hours, preferably from 1 hour to 48 hours.

Arylene sulfide polymers are prepared by mixing a polyhaloaromatic compound, a sulfidating agent and a polymerization aid, and heating preferably under an inert atmosphere.

can be manufactured. There is no particular restriction on the order in which the components are mixed, and the above components may be added in small portions or all at once during the polymerization step. Furthermore, it is preferable to blow carbon dioxide during or at the end of the polymerization reaction, which not only contributes to preventing the decomposition of the produced sita polyphenylene sulfide but also has an effect on preventing the decomposition of N-methylpyrrolidone.

The organic sulfonic acid metal salt as a dispersant used in the present invention is selected from the group represented by the following general formulas 1 to 2.

5(J, M5Iyl (wherein, R3 is hydrogen or an alkyl group having 1 to 30 carbon atoms, n is an integer of 0.1 to 12, and M
is an alkali metal selected from sodium, potassium, rubidium and cesium, X is a direct bond,
-C) I2-1-C(CH3)2-1-〇-1l -5-1-8-. )
Specific examples of acid group components constituting these metal sulfonates include toshiteha, benzenesulfonic acid, p-)luenesulfone [
, 2,4-dimethylsulfonic acid, 2,5-dimethylbenzenesulfonic acid, p-ethylbenzenesulfonic acid, dodecylbenzenesulfonic acid, α-naphthalenesulfonic acid,
Examples include biphenylsulfo/acids, alkylnaphthalenesulfonic acids, two-norbenzenesulfonic acids, and alkyldiphenyl ether disulfonic acids. These sulfonic acid salts are either anhydrous or hydrated.
It goes without saying that anhydrous salts are preferred for the purposes of the present invention.

In the organic caldate metal salt, the organic group except the xyl group usually has 1 to 50 carbon atoms, and may also contain nitrogen, oxygen, hydrogen, silicon, sulfur, etc.
Preferred are alkyl groups, cycloalkyl groups, aryl groups and alkylaryl groups. In addition, the metal atoms of organic carboxylic acid metal salts include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium,
It is selected from zinc, strontium, cadmium, and barium, with alkali metals being particularly preferred. Specific examples of organic carbonate metal salts include lithium acetate, sodium acetate,
Potassium acetate, lithium propionate,! Sodium ropionate, lithium 2-methylpropionate, rubidium butyrate, lithium valerate A, sodium valerate, cesium hexanoate, lithium heptanoate, lithium 2-methyloctoate, potassium dodecanoate, rubidium 4-ethyletradecanoate , sodium octadecanoate, sodium heneicosanoate, lithium cyclohexanecarboxylate, cesium cyclododecanoate, sodium 3-methylcyclopentanecaldate, potassium cyclohexyl acetate, potassium benzoate, lithium benzoate,
Sodium benzoate, potassium m-toluate, lithium phenylacetate, 4-phenylcyclohexanecal? Sodium phosphate, potassium p-tolyl acetate, lithium 4-ethylcyclohexyl acetate, dilithium cono-1 phosphate, disodium succinate, dipotassium cono-1 phosphate, dilithium adipate, disodium adipate, dipotassium adipate , dilithium cepacate, disodium cepacate, dipotassium cepacate, dilithium decanedicaldate, disodium decanedicarmenate, decanedical? dipotassium phthalate, dilithium phthalate, disodium phthalate, dipotassium phthalate, dilithium isophthalate, disodium isophthalate, dipotassium isophthalate, dilithium terephthalate, disodium terephthalate, dipotassium terephthalate, Trilithium trimellitate, trisodium trimellitate, tripotassium trimellitate, tetrasticum pyromellitate, tetrasodium pyromellitate, tetrapotassium pyromellitate, dilithium toluene dicarboxylate, disodium toluene dicarboxylate, toluene Mention may be made of dipotassium dicarboxylate, dilithium naphthalene dicarboxylate, disodium naphthalene dicarboxylate, dilithium naphthalene dicarboxylate, magnesium acetate, calcium acetate, calcium benzoate, and other similar salts and mixtures thereof.

Polyhydric alcohols usually have two or more hydroxyl groups in one molecule, have 2 to 6 carbon atoms, and are suitably liquid under the treatment conditions of the present invention.

Specific examples of such solvents include ethylene glycol, fluoropylene gellicol, trimethylene glycol,
1.3-butanediol, 2-butene-1,4-diol, glycerin, neopentyl glycol, diethylene glycol, triethylene glycol, trimethylolprono-diol, trimethylolethanecyclohexanediol, etc.-1) 16; 4゜These may be used in the form of a mixture of two or more types. Among these, particularly preferred are ethylene glycol and glycerin.

Lithium halides include lithium chloride, lithium bromide, lithium iodide, and mixtures thereof.

The alkali phosphate salt is selected from the group represented by the following general formulas V to (2).

In the formula, R4 is hydrogen, C1-C2o alkyl, C5-C2
0 cycloalkyl, 06-7 reel of C24, 07-
C24 alkaryl, 07-C24 aralkyl, C
2-C24 alkenyl, C2-C2G fulkynyl 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. Methane-7m7oic acid, Ethane-1-7m7oic acid, Furopane-1-7m7oic acid, Butane-1-7m7oic acid, Butane-2-7m7oic acid, Pentane-1-phos7oic acid acid, cyclohexane-1-7-osulfonic acid, vinyl-1-7-osulfonic acid, floben-2-7-osulfonic acid, butene-2-
7 male 7 acid, indene-2-phosphonic acid, phenylmethanephosphonic acid, (4-methyl-phenyl)
-methane-phosphonic acid, β-naphthyl-methanephosphonic acid, 2-7enyl-ethane-1-phosphonic acid, 2,2-diphenyl-ethane-1-7-osphonic acid, 4-7-enyl-butane-1-7-osphonic acid, 2-7
Enyl-ethylene-1-phosphonic acid, 2,2-diphenylethylene-phosphonic acid, phenyl-acetylene-phosphonic acid, 4-phenyl-butadiene-7-osphonic acid, benzene-phosphonic acid, 4-methyl-
Benzene-7 male heptaonic acid and 2-phenoxy-ethane-1-phosphonic acid.

It is necessary to use at least one type of these separating agents. Moreover, as for the kind thereof, organic sulfonic acid alkali salts and organic carboxylic acid salts are preferable.

It is preferable that the amount of the separation agent added is within a range that allows it to be dissolved in the solvent in the reaction system at the end of the polymerization reaction, and separation will not be promoted even if it is used in an amount exceeding the solubility limit. The amount of separation agent added varies depending on the type of separation agent used, but it is 1 to 300% by weight based on the polyhalogenated aromatic compound of the electro-conductor.
, preferably in the range of 5 to 200 weight.

The above separating agent is preferably added at the end of the polymerization reaction.

It is known that if the above-mentioned separating agent is added to the system before the end of the polymerization reaction, it has the effect of accelerating the polymerization reaction, and the polymerization does not stop at the low molecular weight polymer that is the raw material for injection molding, but also causes the polymerization to proceed further. , there is a risk that the molecular weight will increase. To determine the end point of the polymerization reaction, a portion of the reaction mixture in the system is sampled over time and subjected to the usual treatment, ie, washing with water.

− After filtering and drying, the intrinsic viscosity of the obtained polymer [
[eta]] and the point when [η] becomes constant can be taken as the end point, at which time a separating agent is added and fractionation is taken out.

The method of adding the separating agent is not particularly limited, but the separating agent may be added alone or after being dispersed or dissolved in a polymerization solvent.

It is assumed that the effect of the separating agent is due to a kind of "salting out phenomenon" caused by modification of the solubility of the polymer in the system at the end of the polymerization reaction.

In the present invention, in order to more effectively perform layer separation by adding the separation agent, it is preferable to set the conditions during separation as follows.

The amide polar solvent/produced polymer ratio is 20 by weight.
It is in the range of 71 to 1/2. Preferably, such a ratio is between 20/1 and 1/1. Incidentally, this ratio may be set at the time of polymerization.

Separating agent/amide polar solvent ratio (the above amide polar solvent/
Although the ratio of produced polymers is constant), the weight ratio is generally 271 to 1/20, although it varies depending on the type of solvent and separating agent. Incidentally, this ratio may be set at the time of polymerization.

The temperature during separation is 170 to 300°C. A particularly preferred temperature range is 190 to 290°C.

The pressure during separation may be any pressure that allows the polymerization solvent and separation agent to form a substantially liquid phase, specifically 1.2 to 9.
/an2 to 100 97cm2, preferably 1.5k
p/cm2 to 30 kg7cm2.

The polymer may be separated by adding a separating agent and separated and taken out once the polymerization reaction has progressed to a certain degree, and even if the conditions at the time of polymerization and the time of separation and removal are different, the above conditions are met. There is no problem if you do. For example, the solvent/polymer ratio can be 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 also possible to selectively take out one layer of low molecular weight polymer or one layer of oligomer from the sample tube using one type of straw with stirring stopped or under laminar flow stirring, or it is possible to selectively separate both layers from the bottom of the pot. It is also possible to take it out separately.

In the present invention, as a method for separating a single layer of low molecular weight polymer and a single layer of oligo9 polymer, a sensor capable of detecting both layers can also be used. These sensors are based on the differences in physical properties between the two layers, such as specific gravity, viscosity, dielectric constant, electrical conductivity,
These include refractive index, light transmittance, and two-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.

In the present invention, the separation between the low molecular weight polymer-rich layer and the oligomer-rich layer is usually performed mainly based on the oligomer content (% by weight of the polymer) in the separated liquid containing the low molecular weight polymer.
is 3% or less, and the polymer content is 97% of the total polymer.
It is preferable to carry out the weight including below.

Any conventional method may be used to collect the polymer from the resin liquid containing mainly low molecular weight polymers extracted according to the present invention. For example, the solvent is removed from the resin liquid by distillation or flashing, then water or acetone,
The purified 17-mer can be obtained by washing with a poor solvent such as methanol.

In addition, the fractionated liquid mainly containing oligomers contains, in addition to the oligomer components, most of the polymerization solvent and separation agent, and a small amount of low molecular weight polymer. It can be reused as a separating agent the next time the reactant is taken out.

Of course, it is also possible to add the /IJ haloaromatic compound, sulfidating agent, solvent, etc. to the fractionated liquid containing the oligomer and use it for the second reaction.

〔Effect of the invention〕

Since the low molecular weight polymer produced by the method of the present invention has oligomer components removed compared to those produced by conventional production methods, corrosion of the reactor inner wall during oxidative crosslinking reaction, foaming during melt molding, etc. The generation of tar, the corrosion of metal, the thermal stability of the product, the mechanical properties, etc. are significantly improved. In addition, the present invention simplifies the post-treatment process because the amount of polymerization solvent to be treated is small, making it possible to reduce equipment investment and energy costs.Also, the amount of polymerization solvent contained in wastewater can be reduced to a very small amount, which is environmentally friendly. This is also preferable from a conservation standpoint.

[Industrial application field]

Fillers, pigments, flame retardants, stabilizers, if necessary, for the arylene sulfide polymer produced by the method of the invention;
Bulking agents or other polymers can also be blended.

For example, lath fiber and aramid fiber to improve mechanical strength and heat resistance.

Carbon fiber etc. can also be blended. The polymer obtained according to the invention has a maximum of 4
8011: to cause cross-linking and/or chain elongation, thereby obtaining a cured product with excellent thermal stability and chemical resistance. These polymers can be used in applications such as paints and various molded articles.

1 [Example] Hereinafter, the method of the present invention will be explained according to examples.

The logarithmic viscosity value of arylene sulfide polymer is 0
．． Given the polymer concentration sum of 4Ji'/Zoo solution,
This value was measured in α-chlornaphthalene at 206°C and calculated according to the formula.

In addition, to quantify the oligomer components, extract the powdered polymer using a Soxhlet extractor using acetone as the extraction solvent for 92 hours or more until the extraction amount becomes constant, and then dry and solidify the acetone-soluble content. In the Examples, the content (%) of the oligomer component is expressed relative to the amount of /IJ mom before acetone extraction. Note that parts and parts in the examples are based on weight unless otherwise specified.

[Examples 1 to 6 and Comparative Example 1] 5200 g of N-methylpyrrolidone, 60% □ 1560 g of sodium sulfide flakes (12.0 mol as anhydrous Na 2 S) and water were placed in a 181 autoclave having an outlet at the bottom of the container. Sodium oxide l'(0,2
mol) and heated to 160°C while stirring under nitrogen atmosphere.
The temperature was gradually raised to 205° C. over 1.5 hours, and a fraction consisting of 3511 N-methylpyrrolidone and 19 g of water was removed from the system.

Next, 1852 g (I2.6 mol) of p-dichlorobenzene was dissolved in N-methylpyrrolid y6001, and after addition, the mixture was heated at 225°C and a maximum pressure of 3°C for 2 hours, and for an additional 26°C.
The reaction was carried out at 5° C. and a maximum pressure of 8.7 kg and 7 m for 3 hours. After 1.5 hours had passed at 265°C, a small amount of the reaction mixture was sampled every 30 minutes, washed with water, filtered, and dried according to a conventional method, and the intrinsic viscosity [η] of the obtained polymer was measured. As a result, it was confirmed that [η] remained constant at 0.13 after 2 hours. was added all at once into the reaction system through a dropping tank heated to 265°C.
After 1 minute, stirring was stopped, and after being left for another 1 minute, fractional extraction was started. The internal pressure at the start of extraction was 9.2 kU'6n, and the internal temperature was 265°C.

The extraction operation is as follows. That is, after preparing the preparation, place the container in the lower part of the outlet, and after stopping stirring for 1 minute, adjust the opening cross-sectional area of the outlet to 31 ML2, start taking out, and wait for the time ('r1) shown in Table IK. ) Stop ejecting in i minutes,
Next, to the container for taking out! was set and the entire amount of the remaining reaction mixture was taken out.

The content of N-methylpyrrolidone in the reaction mixture taken out in K□ and 8 was measured by gas chromatography. In addition, the reaction mixtures taken out in K1 and 2 were washed separately with water according to a conventional procedure.

After separating the p-filtered polymer, it was dried, and the weight and intrinsic viscosity of the polymer were measured.

Furthermore, a portion of each of the obtained polymers was extracted using a Soxhlet type extractor using acetone as an extraction solvent for about 5 hours, and then the extract was evaporated to dryness. The weight was measured, and the content of the 17th-f mer component (f) in the polymer was determined. This is shown in Table 1 as Example 1. Further, Examples 2 to 6 and Comparative Example 1 were conducted under the same conditions as Example 1 except that the take-out time T8 as shown in Table 1 was changed, and the results are also listed in Table 1.

In addition, FIG. 1 shows the ratio between the amount of N-methylpyrrolidone and the amount of polymer contained in the reaction mixture taken out in step 8 into the container in Example 3, and the oligomer component content in the polymer taken out into the container in step 1. The relationship with the take-out time T1 is shown.

In Example 3 and Comparative Example 1, which was taken out all at once, the polymer obtained in 1 was heated in a container at 300°C in vacuum.
The melt viscosity and the amount of H2S and S02 generated during the heat treatment were measured before and after heating at 300° C. and at a shear rate of 20 am, and are shown in Table 2. It is clear that Example 3, in which the oligomer components are separated, has better thermal stability than Comparative Example 1, in which the oligomer components are mixed, and corrosive gas is generated during heat treatment! (The total amount of 2S and SO□ (determined by gas chromatography) was also compared to Comparative Example 60770 p
It can be seen that compared to pm, it is very small at 11 ppm.

Table 2 [Comparative Example] This example shows p-)luenesulfonic acid in the present invention.
This is a control example to confirm the sewing effect of 7um.

21 At the end of the reaction, reaction and extraction operations were carried out under the same conditions as in Example 1, except that sodium p-)luenesulfonate was not added and only 71,000 g of N-methylpyrrolid was added. After the removal time of 3 minutes, the removal was stopped, and the resulting reaction mixture (taken amount: 4509.9, removal rate: 45.1%) was subjected to the same post-treatment. the result,
Solvent weight 123L9 to de 13ma weight 535
g, and the solvent weight//rimer ratio was 2.3.

Furthermore, the [η] of the obtained polymer was 0.13, and the oligomer component content (relative to the polymer) was 5.3%. Melt viscosity of this polymer (300°C, shear rate 2007
sec) was 69 poise, which decreased to 3 poise after heat treatment at 300° C. for 3 hours in vacuum. In addition, H2S and SO2 generated during heat treatment can be removed using gas chromatography.
When it was quantified using 5 RAF, it was found to be 3.785 ppm.

On the other hand, when the remaining portion taken out into the take-out container was similarly measured, similar data were obtained.

It was found that in a system in which p-) sodium luenesulfonate was not added at the end of the polymerization reaction, separation between the oligomer component-rich layer and the low-molecular-weight polymer-rich layer did not occur.

[Examples 7 and 8, Comparative Examples 3 and 4] In Examples 7 and 8, the polymerization reaction and extraction operation were performed under the same conditions as in Example 1 except that the type of polymerization solvent was changed. K,
The amount taken out (takeout time T8) was determined in advance so as to maximize the separation efficiency. The results are shown in Table 3.

Further, Comparative Examples 3 and 4 correspond to Examples 7 and 8, respectively, and are cases where the samples were taken out all at once without being separated as in Comparative Example 1, and the results are also listed in Table 3.

Table 3 [Examples 9 and 10] The same procedure as in Example 3 was carried out except that the temperature conditions at the time of extraction were changed. However, the extraction time T1 was determined so as to maximize the separation efficiency. The results are shown in Table 4.

Table 4 [Examples 11 to 13] In Example 11, N-methylpyrrolidone 5200.9,6 was placed in a 501 autoclave having an outlet at the bottom of the container.
0% Sodium Sulfide Flake 1560I (Anhydrous Na
2S (12.0 mol as S) and IJium 8# (0.2 mol) as hydroxide were charged, and the temperature was gradually raised from 160°C to 205°C over 2 hours while stirring in a nitrogen atmosphere. Warm, 333p of water, 2511p of N-methylpyrrolidone
The better fractions were removed from the system.

Next, p-dichlorobenzene 1764!1 (I2.0 mol) was dissolved in N-methylpyrrolidone 600.9, and after adding, 2
The reaction was continued for 2 hours at 270° C. and a maximum pressure of 10.0 kl, 17 cm. After reaching 270°C, a small amount of the reaction mixture was sampled every 30 minutes from the first hour, washed with water, filtered, and dried according to a conventional method, and the logarithmic viscosity [l] of the obtained polymer was measured. As a result, it was confirmed that the shi[η] remained constant at 0.14 from the 1st and 5th hours, and the temperature was lowered to 230°C at the 2.5th hour, and sodium benzoate 129
6. l1F (9.0 mol) and N-methylpyrrolidone 70
0 g of the solution was added all at once into the reaction system from a dropping tank heated to 230°C, and 1 minute after the addition was completed, stirring was stopped and further K.
After leaving it for 1 minute, separate extraction was started. The internal pressure at the start of extraction is 4.7 kg/? 112, and the internal temperature was 230°C.

In Examples 12 and 13, the amount of N-methylpyrrolidone used when adding +7 um was increased, a portion of it was removed from the distillation trap, and the solvent/polymer ratio at the start of extraction was changed. Then, fractional extraction was performed in the same manner as in Example 3. Note that the extraction time T1 was determined in advance so as to maximize the separation efficiency. Table 5 shows the results.
Shown below.

/″' Table 5 [Example 14] In this example, the solvent/polymer ratio was set to 57, which is the same as in Example 12.
The weight ratio was fixed at 1 and the separating agent/solvent ratio was varied. Other conditions were the same as in Example 11. However, the extraction time T1 was determined in advance in order to obtain the best separation efficiency. The results are shown in Table 6.

Table 6 [Example 15] N of p-) sodium luenesulfonate of Run 9113
- Ethylene glycol 2480. as separating agent instead of methylpyrrolidone solution. ! Reaction and extraction were carried out in the same manner as in Example 3 except that i+ (40.0 mol) was used. As a result, the extraction time was 2.5 minutes (the extraction amount was 4630
The separation efficiency was the best at JF, extraction rate 36.3%),
At that time, the ratio of solvent weight/remer of the reaction mixture taken out to the takeout container was 1.2. Further, the logarithmic viscosity [η] of the obtained polymer was 0.14, and the oligo9mer content was O, ? , %Met.

The melt viscosity of this polymer (300°C, shear rate 200
7 seconds), it was 73 poise, and it was measured at 300°C in vacuum.
After heat treatment for 3 hours, the amount decreased only slightly to 69 poise, and the total amount of H2S and S02 generated during the heat treatment was also very small at 15 ppm.

[Examples 16 to 18] Reaction and extraction were carried out in the same manner as in Example 1, except that the compound shown in Tatsumi 7 was used as a separating agent in place of p-) sodium luenesulfonate in Example 3. . Note that the extraction time is the time at which the separation efficiency was the best.

[Brief explanation of drawings]

FIG. 1 shows the relationship between the time taken for discharging into the dispensing container 1, the ratio of N-methylpyrrolidone/polymer amount in the resin liquid taken out in the dispensing container 1, and the oligomer component content (relative to polymer) in Example 3. It is a graph.

Claims (1)

[Claims] After reacting a polyhaloaromatic compound and a sulfidating agent in an amide polar solvent, an organic sulfonic acid metal salt,
At least one selected from organic carboxylic acid metal salts, polyhydric alcohols, lithium halides, and alkali phosphate salts is added, and then a concentrated layer of low molecular weight polymer (I
) and a dense layer (II) of oligomers. A method for producing a polyarylene sulfide polymer, which comprises separating said layer (I) or said layer (II) from a produced resin liquid consisting of said layer (I) or said layer (II).