JP2560273B2 - Polymer manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of making an arylene sulfide polymer using a sodium sulfide composition.

The arylene sulfide polymer represented by polyphenylene sulfide is produced by the method disclosed in JP-B-45-3368. That is, it is produced by a method of reacting p-dichlorobenzene with sodium sulfide in an organic amide solvent such as N-methylpyrrolidone.
The polyphenylene sulfide obtained by this method has an extremely low degree of polymerization and is not suitable for use as it is, and industrially, this low degree of polymerization polymer is heated in air, oxidatively crosslinked, and increased in molecular weight by three-dimensional crosslinking and injected. It is used for practical purposes such as molding. However, even those having a high molecular weight are inferior in extrusion moldability and cannot be used for applications such as fibers, films, pipes and sheets.

Further, a method of obtaining a high molecular weight arylene sulfide polymer by a polymerization reaction is already known. That is, for example, as shown in JP-B-52-12240, a high molecular weight polymer can be obtained by carrying out a polymerization reaction in the presence of various polymerization aids. This high molecular weight polymer is melt-molded into engineering plastics, pipes, films or fibers by a method such as extrusion molding,
It is used for molded products that take advantage of heat resistance and chemical resistance.

By the way, in the above manufacturing method, sodium sulfide hydrate has been conventionally used industrially as a starting material. It is generally known that this sodium sulfide hydrate can be obtained by relatively high crystallization water such as Na ₂ S ・ 2.7H ₂ O (Na ₂ S purity 60%) by a method of concentrating at high temperature. . However, in order to produce a relatively high molecular weight arylene sulfide polymer, it is necessary to remove a part of the water of crystallization, and therefore a dehydration step must be performed before the polymerization reaction.

Conventionally, as a method for dehydrating sodium sulfide hydrate, Japanese Patent Publication No.
No. 3368, in an organic amide solvent such as N-methylpyrrolidone which is a polymerization solvent, or in JP-B-52-12.
As shown in No. 240, there is a method of distilling at least a part of water out of the system by heating sodium sulfide hydrate in an organic amide solvent in the presence of an alkali metal carboxylate.

However, in these methods, high temperature conditions such as about 200 ° C. are required for dehydration, and it takes a long time to sufficiently dehydrate, so that the decomposition of the solvent occurs or the reaction vessel such as sodium sulfide is used. There was a drawback that rust was generated along with the corrosion. Therefore, it is industrially disadvantageous in terms of production cost and maintenance of polymers such as raw materials, equipment and energy.

As a result of intensive investigations by the present inventors in view of such drawbacks, in the presence of a polyhaloaromatic compound, by contacting a specific metal salt with sodium sulfide hydrate, it is possible to efficiently dehydrate at a relatively low temperature. The inventors have found that a sodium sulfide composition with good corrosion resistance in a reaction kettle can be obtained, and have reached the present invention.

That is, the present invention, in the presence of a polyhalo aromatic compound,
Contact at least one metal salt selected from sodium sulfide hydrate and organic sulfonic acid metal salt, lithium halide, organic carboxylic acid metal salt, alkali metal phosphate salt to remove at least a part of water A method for producing an arylene sulfide polymer, which comprises reacting the sodium sulfide composition formed by the reaction in the presence of an organic amide polar solvent, comprising: a polyhaloaromatic compound in the presence of an organic amide polar solvent; At least one metal salt selected from sodium sulfide hydrate and organic sulfonic acid metal salt, lithium halide, organic carboxylic acid metal salt, alkali metal phosphate is brought into contact with at least a part of water content. Or in the presence of a polyhaloaromatic compound and an organic amide polar solvent. Machine sulfonic acid metal salt,
A sodium sulfide composition formed by contacting at least one metal salt selected from lithium halides and removing at least a part of water, and reacting the composition in the presence of an organic amide polar solvent. A method for producing an arylene sulfide polymer is provided.

The sodium sulfide hydrate used in the method of the present invention contains 1 mol or more of water of crystallization for 1 mol of sodium sulfide and has a Na ₂ S purity of 81%.
% Sodium sulfide hydrate. Specifically, sodium sulfide 9-hydrate (Na ₂ S purity 32%), sodium sulfide 6-hydrate (Na ₂ S purity 42%), sodium sulfide 5-hydrate (Na ₂ S purity 46%), Na as crystal water Na ₂ S purity 61 to ₂ S1 moles containing 2.7 moles of water
% Sodium sulfide hydrate and the like, and mixtures thereof. The shapes of these hydrates are crystals, flakes,
Either solid or solid is acceptable. Usually industrially pure
61% sodium sulphide 2.7 hydrate is used.

The polyhaloaromatic compound is a halogenated aromatic compound having two or more halogen atoms directly bonded to an aromatic nucleus, and specific examples thereof include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene and trichloro. benzene,
Tetrachlorobenzene, dichloronaphthalene, trichlornaphthalene, dibromobenzene, tribromobenzene, dibromonaphthalene, jodobenzene, triiodobenzene, dichlorodiphenylsulfone, dibromodiphenylsulfone, dichlorobenzophenone, dibromobenzophenone, dichloro Examples thereof include diphenyl ether, dibromodiphenyl ether, dichlorodiphenyl sulfide, dibromodiphenyl sulfide, dichlorobiphenyl, dibromobiphenyl and the like, 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 3 or more halogen substituents in one molecule may be used in combination with a small amount of dihaloaromatic compound.

The amount of the polyhaloaromatic compound used in producing the sodium sulfide composition is usually 0.2 mol or more, preferably 0.2 to 5 mol, based on 1 mol of the sodium sulfide in the sodium sulfide hydrate. When an arylene sulfide polymer is produced using a sodium sulfide composition, the amount of polyhaloaromatic compound used is usually 0.8 to 1.2 with respect to 1 mol of sodium sulfide.
The amount is preferably 0.9 to 1.1 mol, and when the amount of the compound in the sodium sulfide composition is small, it is added during the production of the polymer, and when it is large, it is distilled off. still,
The polyhaloaromatic compound used during the production of the sodium sulfide composition and the polyhaloaromatic compound added during the production of the polymer may be the same or different, or may be a mixture of two or more polyhaloaromatic compounds.

In the present invention, at least one metal salt selected from organic sulfonic acid metal salts, lithium halides, organic carboxylic acid metal salts and alkali metal phosphate salts is used when producing a sodium sulfide composition.

The organic sulfonic acid metal salt is selected from the group represented by the following general formulas I to IV.

(In the formula, R ¹ represents hydrogen or an alkyl group having 1 to 30 carbon atoms, n represents an integer of 0, 1 or 2, M represents an alkali metal selected from sodium, potassium, rubidium and cesium, and X represents direct bond, -CH ₂ -,
_{-C (CH 3) 2 -,} - O -, - S-, It is selected from the group consisting of. ) Specific examples of the acid group component constituting these metal sulfonates include benzenesulfonic acid, p-toluenesulfonic acid, 2,4-dimethylsulfonic acid, 2,5-dimethylbenzenesulfonic acid, p
-Ethylbenzene sulfonic acid, dodecyl benzene sulfonic acid, α-naphthalene sulfonic acid, biphenyl sulfonic acid, alkylnaphthalene sulfonic acid, lauryl benzene sulfonic acid and alkyl diphenyl ether disulfonic acid. The salt of these sulfonic acids may be either an anhydrous salt or a hydrated salt, or may be an aqueous solution, but needless to say, the anhydrous salt is preferable for the purpose of the present invention.

Examples of lithium halides include lithium chloride, lithium bromide, lithium iodide, and mixtures thereof.

The organic carboxylic acid metal salt generally has an organic group other than the carboxyl group having 1 to 50 carbon atoms, and may contain nitrogen, oxygen, halogen, silicon, and sulfur, preferably an alkyl group and a cycloalkyl group. A group, an aryl group and an alkylaryl group. 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 metal is particularly preferable. Specific examples of the organic carboxylic acid metal salt include lithium acetate, sodium acetate, potassium acetate, lithium propionate, sodium propionate, lithium 2-methylpropionate, rubidium butyrate, lithium valerate, sodium valerate, and cesium hexanoate. Lithium heptanoate, lithium 2-methyloctanoate, potassium dodecanoate, rubidium 4-ethylethoradecanoate, sodium octadecanoate, sodium heneicosanate, lithium cyclohexanecarboxylate, cesium cyclododecanecarboxylate, sodium 3-methylcyclopentanecarboxylate , Potassium cyclohexyl acetate, potassium benzoate, lithium benzoate, sodium benzoate, potassium m-toluate, lithium phenylacetate, 4-phenylcyclohexanecarbo Sodium acid, p- tolyl potassium acetate, 4-ethyl cyclohexyl acetate lithium, succinate dilithium,
Disodium succinate, dipotassium succinate, dilithium adipate, sodium adipate, dipotassium adipate, dilithium sebacate, disodium sebacate, dipotassium sebacate, dilithium decanedicarboxylate, disodium decanedicarboxylate , Decane dicarboxylate, dilithium phthalate, disodium phthalate, dipotassium phthalate, dilithium isophthalate, disodium isophthalate, dipotassium isophthalate, dilithium terephthalate, disodium terephthalate, diterephthalate Potassium, trilithium trimellitic acid, trisodium trimellitic acid, tripotassium trimellitic acid, tetralithium pyromellitic acid, tetrasodium pyromellitic acid, tetrapotassium pyromellitic acid, dilithium toluenedicarboxylic acid , Disodium toluenedicarboxylate, dipotassium toluenedicarboxylate, dilithium naphthalene dicarboxylate, disodium naphthalene dicarboxylate, dipotassium naphthalene dicarboxylate, magnesium acetate, calcium acetate, calcium benzoate and other salts of the same kind and their A mixture may be mentioned.

The alkaline phosphate is selected from the group represented by the following general formulas V and VI.

In the formula, R ² is hydrogen, C ₁ -C ₂₀ alkyl, C ₅ -C ₂₀ cycloalkyl, C ₆ -C ₂₄ aryl, C ₇ -C ₂₄ alkylaryl, C ₇ -C ₂₄ alkyl, alkenyl of C ₂ ~C _24, C ₂
To C ₂₀ alkynyl or C _{5 to} C ₂₀ cycloalkenyl, and M is an alkali metal such as sodium, lithium or potassium, preferably sodium. Specific sodium phosphate used in the present invention is trisodium phosphate; 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, phenylmethanephosphonic acid Acid, (4-methylphenyl) -methanephosphonic acid,
β-naphthyl-methanephosphonic acid, 2-phenyl-
Mention may be made of disodium salts such as ethane-1-phosphonic acid, 2-phenyl-ethylene-1-phosphonic acid, 4-phenyl-butadiene-phosphonic acid and 2-phenoxy-ethane-1-phosphonic acid.

The addition amount of the above various metal salts varies depending on the kind of the compound used, but is usually 1 part by weight of the sodium sulfide hydrate.
It is in the range of 0.01 to 6 parts by weight, preferably 0.1 to 4 parts by weight.

The production of the sodium sulfide composition of the present invention is usually carried out without adding an organic amide-based polar solvent, but the dehydration efficiency of sodium sulfide hydrate is improved, stirring during dehydration and transfer of the composition after dehydration are easy. Therefore, the organic amide-based polar solvent may be added during the production of the sodium sulfide composition. The temperature at that time should be a temperature at which sodium sulfide and a polyhaloaromatic compound are hardly polymerized, and moreover, sodium sulfide hydrate can be dehydrated, usually 60 to 170 ° C, preferably 80 to 160 ° C. is there. Moreover, the pressure is not particularly limited.

The temperature for distilling off the water of the sodium sulfide hydrate without adding the organic amide polar solvent is at least the melting point of the hydrate, generally 60 ° C to 200 ° C, preferably 100 ° C to 185.
° C. The time required for the dehydration step varies depending on the temperature, the pressure and the water content of the hydrate, but is generally in the range of 15 minutes to 5 hours, preferably 30 minutes to 2 hours.
Under the above conditions, if the sodium sulfide hydrate and the metal salt are heated in the hydrocarbon solvent while stirring, most of the water in the system is efficiently distilled off by distillation, and the solvent in the system. In this, sodium sulfide particles are uniformly and finely dispersed together with the metal salt particles, so that a highly dispersible sodium sulfide composition is formed.

As the organic amide polar solvent, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-
2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-ε-caprolactam, hexamethylphosphoramide and the like can be mentioned, and these may be used in a mixture of two or more kinds. Of these, N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) is particularly preferable. The amount of polar organic amide solvent used is usually 2.
It is in the range of 5 to 20, preferably in the range of 3 to 10.

The polyhaloaromatic compound that is distilled out of the system together with the water content of the sodium sulfide hydrate in the production of the sodium sulfide composition of the present invention (dehydration step) is divided with water using a decanter or the like,
The dehydration may be continued by returning to the dehydration system, or the separated polhaloaromatic compound may be used in the next polymer production (polymerization step). The means for separating the distilled water and the polyhaloaromatic compound is not particularly limited, and any means can be used as long as they can be well separated. The time required for the dehydration step varies depending on the temperature, the pressure and the water content of sodium sulfide hydrate, but is generally in the range of 15 minutes to 5 hours, preferably 30 minutes to 2 hours.

The method for producing the sodium sulfide composition of the present invention is a polyhaloaromatic compound sodium sulfide hydrate, preferably the metal salt is stirred in the presence of an organic amide-based polar solvent, and heat-treated to efficiently remove water in the system. It can be removed and can be almost removed, and the corrosion to the reaction kettle can be made extremely small as compared with the conventional dehydration method. still,
The reason why corrosion to the reaction kettle can be suppressed is that dehydration can be carried out at a relatively low temperature and for a short time, so that the corrosion conditions are alleviated, and at least part of highly corrosive sodium sulfide is dehydrated with the polyhaloaromatic compound. It is presumed that the cause is that it reacts with time and changes into a substituted compound such as Ar-SNa, Ar-S-Ar, NaS-Ar-SNa (Ar is a polyhaloaromatic residue), which is less corrosive.

Then, in the step of reacting the composition obtained under the above conditions with a polyhaloaromatic compound in the presence of the organic amide polar solvent (hereinafter referred to as a polymerization step), the polymerization reaction temperature is generally 170 ° C to 330 ° C, preferably Is 210 ° C to 300 ° C. The pressure should be in a range such that the polymerization solvent and the polyhaloaromatic compound which is a polymerization monomer are substantially kept in a liquid phase, and generally 1.1 kg / cm ^{2 to} 200 kg / cm ² preferably
It is selected from 1.1kg / cm ² ~20kg / cm ² range. The reaction time varies depending on temperature and pressure, but it is generally in the range of 10 minutes to about 72 hours, preferably 1 hour to 48 hours. The relatively high molecular weight arylene sulfide polymer can be produced by mixing the above-mentioned sodium sulfide composition, polyhaloaromatic compound and organic amide polar solvent, and preferably heating under an inert gas atmosphere. The order of mixing each component is not particularly limited, and it is carried out by adding the above components partially in small portions or at one time during the polymerization step.

At the time of producing the arylene sulfide polymer, it is preferable to carry out polymerization by adding an alkali hydroxide. Examples of alkali hydroxides that can be used include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and mixtures thereof. The amount of alkali hydroxide used is generally 1 mol of sodium sulfide.
It is in the range of 0.008 to 1.8 mol, preferably 0.015 to 0.6 mol.

In addition, an alkali carbonate salt can be used as a substitute compound for the above alkali hydroxide. The amount of alkali carbonate used is generally in the range of 0.004 to 0.9 mol, preferably 0.010 to 0.4 mol, per mol of sodium sulfide. Also,
It is also preferable to add carbon dioxide during the polymerization reaction or at the end of the polymerization, which not only prevents the decomposition of the polymer and contributes to increasing the molecular weight of the produced polymer, but also prevents the decomposition of the polymerization solvent such as N-methylpyrrolidone. Is also effective.

Further, for the purpose of further improving the dispersibility of sodium sulfide during the dehydration step in the method of the present invention, it is possible to perform dehydration and polymerization in the presence of a low molecular weight arylene sulfide polymer. A typical example of a low molecular weight polymer that can be used is polyphenylene sulfide having an intrinsic viscosity [η] of 0.2 or less, and the amount thereof is 0.01 to 3 parts by weight, preferably 1 to 3 parts by weight of the sodium sulfide hydrate. 0.
The range is from 05 to 2 parts by weight.

The arylene sulfide polymer obtained by the method of the present invention may be subjected to a conventional method, for example, by passing the reaction mixture after the completion of the polymerization reaction, followed by washing with water, or by diluting the reaction mixture with water, followed by passing and washing with water, or a solvent. It can be separated from the reaction mixture by recovering by distillation under normal pressure or reduced pressure, and then washing with water and passing.

As a specific example of the arylene sulfide polymer produced by the method of the present invention, polyphenylene sulfide is typically mentioned. An arylene sulfide polymer having a repeating unit such as These arylene sulfide polymers can be used for injection molding, compression molding, extrusion molding of films, fibers, sheets, tubes, tubes and the like, and blow molding. It is also preferable to add a filler, a pigment, a flame retardant, a stabilizer and other polymers to this polymer if necessary. For example, glass fibers may be added to improve mechanical strength and heat resistance.

The logarithmic viscosity value [η] of the arylene sulfide polymer is 0.4 g / 100 ml at a polymer concentration of a solution,
Measured at 206 ° C in α-chlornaphthalene, formula It is the value calculated according to.

The dehydration amount and dehydration rate in the following examples are as follows.

(Dehydration amount): The polyhaloaromatic compound was separated from the distillate at the time of dehydration by a decanter device, and then measured by the Karl Fischer moisture measurement method.

(Dehydration rate) Dehydration rate (%) is the formula It is a value calculated according to.

 Hereinafter, the method of the present invention will be described according to examples.

[Example 1] A thermometer, a decanter device, and a stirrer were installed, and JIS
Standard autoclave made of SUS304 stainless steel (reaction vessel weight 6382.5g), sodium sulfide 2.7 hydrate 103g
(0.8 mol, purity 61%), paradichlorobenzene 117.6 g
(0.8 mol) and p-toluenesulfonic acid soda 155 g
(0.8 mol) was charged, and the temperature was gradually raised to 170 ° C. under nitrogen atmosphere with stirring for 1 hour to distill water and paradichlorobenzene. At that time, paradichlorobenzene, which was distilled at the same time as water, was returned to the autoclave by using a decanter device. Finally, 37.0 g of water (dehydration rate 95.1%) was distilled off to obtain a sodium sulfide composition.

Next, 0.44 g (0.0024 mol) of 1,2,4-trichlorobenzene and 0.4 g of sodium hydroxide were added to the sodium sulfide composition.
(0.01 mol) and NMP432g were added, and the mixture was reacted at 240 ° C. for 2 hours and further at 260 ° C. for 2 hours. During this time, the internal pressure at the end of the polymerization reaction was 4.7 kg / cm ² .

After that, the autoclave was cooled to separate the contents, and the cake (solid content) was washed with hot water three times, further washed with acetone twice, and dried at 120 ° C.
4.7 g of light grayish-brown granular polyphenylene sulfide was obtained (yield = 98.0%). The inherent viscosity [η] of this polymer was 0.41.

Using the same one autoclave as above, after repeating dehydration and polymerization reaction 9 times under the same conditions as above, the weight of the reaction vessel was measured and found to be 6382.2 g (weight reduction rate 0.005%). Moreover, no rust was generated on the inner wall of the reaction vessel.

[Comparative Example 1] 1 autoclave made of JIS standard SUS304 stainless steel equipped with a thermometer and a stirrer (reaction vessel weight 6382.0 g), sodium sulfide 2.7 hydrate 103 g (0.8 mol, purity 61%), para-
Sodium toluene sulfonate 155g (0.8mol) and NMP346g
Was gradually heated to 203 ° C. in a nitrogen atmosphere for 3 hours with stirring.
The dehydration rate was only 59.4%.

Then, in the composition after dehydration in one autoclave, 117.6 g (0.8 mol) of paradichlorobenzene, 0.4 g (0.01 mol) of sodium hydroxide and 0.44 g of 1,2,4-trichlorobenzene.
(0.0024 mol) and NMP86g are added, and further 2 hours at 240 ℃ 2
The reaction was performed at 60 ° C. for 2 hours. Internal pressure at the end of the polymerization reaction is 9.6k
It was g / cm ² .

After that, the autoclave was cooled to separate the contents, and the cake (solid content) was washed with hot water three times, further washed with acetone twice, and dried at 120 ° C.
0.1 g of light grayish-brown granular polyphenylene sulfide was obtained (yield = 92.7%). The logarithmic viscosity [η] of this polymer was 0.36. Both the yield and [η] were lower than those in [Example 1].

After repeating the dehydration and polymerization reaction 9 times under the same conditions using the same 1 autoflavor as above,
When the weight of the reaction vessel was measured, it was 6342.5 g (weight reduction rate: 0.619%), and rust was generated on the inner wall of the reaction vessel.

[Example 2] 1 autoclave (reactor vessel weight) similar to Example 1
6425.7g) to sodium sulfide 9-hydrate 192g (0.8mol, purity 32.5
%), 86.4 g (0.6 mol) of sodium benzoate and 29.4 g (0.2 mol) of paradichlorobenzene, and under an N ₂ atmosphere.
The temperature was gradually raised to 175 ° over 1 hour with stirring to distill water and paradichlorobenzene. At that time, paradichlorobenzene, which was distilled at the same time as water, was repeatedly returned to the autoclave by using a decanter, and finally 120.7 g of water (dehydration rate 93.1%) was distilled.

Next, sodium hydroxide 0.4 g (0.01 mol) 1,2,4-
0.44 g (0.0024 mol) of trichlorobenzene, 88.2 g (0.6 mol) of paradichlorobenzene and 432 g of NMP were added and a polymerization reaction was carried out in the same manner as in Example 1. The internal pressure at the end of the polymerization reaction was 5.0 kg / cm ² , and finally 84.1 g (yield 97.3%) of pale grey-brown granular polyphenylene sulfide polymer
I got The inherent viscosity [η] of this polymer was 0.39.

Using the same one autoclave as above, after repeating dehydration and polymerization reaction 9 times under the same conditions,
When the weight of the reaction vessel was measured, it was 6424.6 g (weight reduction rate
0.017%), and no rust was generated on the inner wall of the reaction vessel.

[Comparative Example 2] Example 2 except that 1 autoclave having a weight of 6417.7 g was used and 14.7 g (0.1 mol) of paradichlorobenzene was used.
In the same manner as above, water and paradichlorobenzene were distilled off by gradually raising the temperature to 195 ° C. under N ₂ atmosphere with stirring for 2 hours. At that time, as in Example 2, the operation of returning paradichlorobenzene to the autoclave was repeated using the decanter device. As a result, as compared with Example 2, 79.4 g of water (dehydration rate 6
(1.3%) was only distilled out.

Then, a polymerization reaction was carried out in the same manner as in Example 2 except that 102.9 g (0.7 mol) of paradichlorobenzene was used, and the internal pressure at the end of the polymerization reaction was 9.7 kg / cm ² , and finally a pale grayish brown color was obtained. 81.3 g of granular polymer (yield 94.1
%) Was obtained. The logarithmic viscosity [η] of this polymer was 0.36.

Using the same one autoclave as above, after repeating dehydration and polymerization reaction 9 times under the same conditions,
When the weight of the reaction vessel was measured, it was 6392.5g (weight reduction rate
0.393%), and rust was generated on a part of the inner wall of the reaction vessel.

Example 3 A single autoclave weighing 6380.6 g was used and charged in the same manner as in Example 2 except that 235.2 g (1.6 mol) of paradichlorobenzene was used, and the mixture was stirred under N ₂ atmosphere to 170 ° C. for 1 hour while stirring. The temperature was gradually raised to distill off water and paradichlorobenzene. At that time, as in Example 2, the operation of returning paradichlorobenzene to the autoclave by using a decanter was repeated. After the distilling of water has almost stopped, paradichlorobenzene is distilled out of the system without returning to the system, and finally 126.1 g of water (dehydration rate 97.3%) and 110.3 g of paradichlorobenzene (0.75 mol) Was distilled.

Then, a polymerization reaction was carried out in the same manner as in Example 2 except that paradichlorobenzene was not added, and the internal pressure at the end of the polymerization reaction was 5.5 kg / cm ² , and finally a pale grayish brown granular polymer 82.3 g (yield 95.3%) was obtained. The inherent viscosity [η] of this polymer was 0.38.

Using the same one autoclave as above, after repeating dehydration and polymerization reaction 9 times under the same conditions,
The weight of the reaction vessel was measured to be 6380.4 g (weight reduction rate
0.003%), and no rust was generated on the inner wall of the reaction vessel.

Example 4 Using one autoclave having a weight of 6295.8 g, paradichlorobenzene (58.8 g (0.4 mol)) and 4,4'-dichlorodiphenyl sulfone (114.8 g (0.4 mol)) were used as polyhaloaromatic compounds.
(Mole), except that the mixture was used in the same manner as in Example 1, and the temperature and the temperature were gradually raised to 180 ° C. over 1.5 hours with stirring under N ₂ atmosphere to distill water and a polyhaloaromatic compound. At that time, the polyhaloaromatic compound distilled at the same time as water was repeatedly returned to the autoclave by using a decanter, and finally 36.7 g of water (dehydration rate 94.3%) was distilled.

Then, 0.4 g (0.01 mol) of sodium hydroxide and 390 g of NMP were added to the composition after dehydration in one autoclave,
The reaction was carried out at 3 ° C for 3 hours and further at 265 ° C for 2.5 hours. The internal pressure at the end of the polymerization reaction was 5.7 kg / cm ² .

After cooling the autoclave, the contents were treated as in Example 1 to give 137.4 g of a gray, granular polymer (yield 9
6.5%). The logarithmic viscosity [η] of this polymer is 0.38
Met.

Using the same one autoclave as above, after repeating dehydration and polymerization reaction 9 times under the same conditions,
When the weight of the reaction vessel was measured, it was 6295.4 g (weight reduction rate 0.006%), and rust did not occur at all on the inner wall of the reaction vessel.

Comparative Example 3 Using 1 autoclave having a weight of 6315.5 g, 7.4 g (0.05 mol) of paradichlorobenzene as a polyhaloaromatic compound and 14.4 g (0.05 mol of 4,4'-dichlorodiphenyl sulfone) were used.
(Mole) except that the mixture was used in the same manner as in Example 4, and the temperature was gradually raised to 200 ° C. under stirring in an N ₂ atmosphere for 2.5 hours to distill the water and the polyhaloaromatic compound. At that time, the operation of returning the polyhaloaromatic compound into the autoclave was repeated by using the decanter apparatus as in Example 4. As a result, 23.3 g of water (dehydration rate of 59.9
%) Was only distilled out.

Next, 51.4 g (0.35 mol) of paradichlorobenzene and
A polymerization reaction was carried out in the same manner as in Example 4, except that 100.4 g (0.35 mol) of 4,4'-dichlorodiphenyl sulfone was added, and the internal pressure at the end of the polymerization reaction was 10.2.
Granular polymer 135, which is kg / cm ² and finally has a gray colour.
6 g (yield 95.2%) was obtained. The logarithmic viscosity [η] of this polymer was 0.35.

Using the same one autoclave as above, after repeating dehydration and polymerization reaction 9 times under the same conditions,
When the weight of the reaction vessel was measured, it was 6283.0 g (weight reduction rate 0.515%), and rust was generated on the inner wall of the reaction vessel.

[Example 5] JIS standard SUS31 with thermometer, decanter and stirrer
2 autoclaves made of 6 stainless steel (reaction vessel weight 9603.2g), sodium sulfide 9-hydrate 480g (2.0mol), paradichlorobenzene 308.7g (2.1mol), sodium p-toluenesulfonate 388g (2.0mol) and NMP432g. After charging, the temperature was gradually raised to 165 ° C. over 2 hours with stirring under a nitrogen atmosphere to distill off water, paradichlorobenzene and a part of NMP. At that time, paradichlorobenzene that distilled out together with water and a part of NMP was repeatedly returned to the 2 autoclave using a decanter device, and finally 314.3 g of water (dehydration rate 97.0%) was distilled out.

Then, after dehydration in 2 autoclaves, 1.0 g (0.025 mol) of sodium hydroxide, 1.1 g (0.006 mol) of 1,2,4-tortorolbenzene and 432 g of NMP were added to the composition, and the mixture was further heated at 230 ° C. for 1 hour at 260 ° C. The reaction was carried out for 3 hours. The internal pressure at the end of the polymerization reaction was 5.0 kg / cm ² , and finally 210.6 g (yield 97.5%) of pale gray-brown granular polyphenylene sulfide was obtained. The inherent viscosity [η] of this polymer was 0.39.

Using the same 2 autoclaves as above, dehydration and polymerization reactions were repeated 9 more times under the same conditions, and the weight of the reaction vessel was measured to be 9602.5 g (weight reduction rate 0.007
%), And no rust was generated on the inner wall of the reaction vessel.

[Comparative Example 4] A 2 autoclave having a weight of 9602.0 g was used and charged in the same manner as in Example 5 except that paradichlorobenzene was removed. Under a nitrogen atmosphere, the temperature was gradually raised to 202 ° C over 3.5 hours with stirring, and water was added. Some NMP was distilled. As a result, compared to Example 5, although the temperature was high and the time was long,
Only 171.7 g of water (dehydration rate 53.0%) was distilled off.

Then, a polymerization reaction was carried out in the same manner as in Example 5 except that 308.7 g (2.1 mol) of paradichlorobenzene was added, and the internal pressure during the polymerization reaction was 11.5 kg / cm ² , and finally a grayish brown color was obtained. 200.1 g of granular polymer (yield 92.6%) was obtained. The logarithmic viscosity [η] of this polymer was 0.33, and both the yield and [η] were lower than those in Example 5.

Using the same 2 autoclaves as above, dehydration and polymerization reaction were repeated 9 more times under the same conditions,
When the weight of the reaction container was measured, it was 9547.4 g (weight reduction rate 0.569%), and rust was generated on the inner wall of the reaction container.

Example 6 Sodium sulfide 2.7 was added to a 1 L autoclave similar to Example 1.
103 g (0.8 mol, 61% purity) of water salt, 117.6 g (0.8 mol) of paradichlorobenzene and 155 g (0.8 mol) of sodium p-toluenesulfonate were charged and stirred under nitrogen atmosphere to 170 ° C for 1 hour while stirring. The temperature was gradually raised to distill off water and paradichlorobenzene.

At that time, paradichlorobenzene, which was distilled at the same time as water, was returned to the autoclave by using a decanter device. Finally, 37.2 g of water (dehydration rate 95.3%) was distilled off to obtain a sodium sulfide composition.

Next, 432 g of NMP was added to this sodium sulfide composition, and the mixture was reacted at 240 ° C. for 2 hours and at 255 ° C. for 3.5 hours. During this time, the internal pressure at the end of the polymerization reaction was 4.6 Kg / cm ² .

The autoclave is then cooled to separate the contents, then the cake (solids) is washed 3 times with hot water, then twice with acetone and dried at 120 ° C. 84.
8 g of granular porphenylene sulfide was obtained. (Yield 98
%). The logarithmic viscosity of this polymer was 0.23.

Using the same 1 L autoclave as above, dehydration and weight reaction were further repeated 9 times under the same conditions as above, and the weight of the reaction vessel was measured.
It was 005% and no rust was generated on the inner wall of the reaction vessel.

Comparative Example 5 Sodium sulfide 2.7 was added to a 1 L autoclave similar to that of Example 1.
Although 103 g (0.8 mol, 61% purity) of water salt, 155 g (0.8 mol) of sodium P-toluenesulfonate and NMP346G were charged, the temperature was gradually raised to 203 ° C. under nitrogen atmosphere over 2.9 hours with stirring. The dehydration amount was 23.2 g and the dehydration rate was 5 in spite of being carried out at a high temperature and for a long time as compared with the additional example 1.
It was only 9.6%.

Then 117.6 g (0.8 mol) of paradichlorobenzene and 86 g of NMP were added to the dehydrated composition in a 1 L autoclave, and 2
The reaction was carried out at 40 ° C for 2 hours and further at 255 ° C for 3.5 hours. During this period, the internal pressure at the end of the polymerization reaction was 9.8 Kg / cm ² .

After that, the autoclave is cooled to separate the contents, and then the cake (solid content) is washed 3 times with hot water, further washed twice with acetone, and then dried at 120 ° C. 80.
1 g of granular polyphenylene sulfide was obtained. (Yield 92
%). The inherent viscosity of this polymer was 0.17. yield,
It is clear that both logarithmic viscosities are lower than those of the examples.

Using the same 1 L autoclave as above, dehydration and polymerization reaction were repeated 9 more times under the same conditions as above, and the weight of the reaction vessel was measured.
615%, and rust was generated on the inner wall of the reaction vessel.

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Claims (1)

(57) [Claims] 1. At least one metal selected from sodium sulfide hydrate and organic sulfonic acid metal salt, lithium halide, organic carboxylic acid metal salt, and phosphoric acid alkali metal salt in the presence of a polyhaloaromatic compound. Bring the salt into contact,
A method for producing an arylene sulfide polymer, which comprises reacting a sodium sulfide composition formed by removing at least a part of water in the presence of an organic amide polar solvent, in the presence of a polyhaloaromatic compound, And in the absence of an organic amide polar solvent, at least one metal salt selected from sodium sulfide hydrate and organic sulfonic acid metal salt, lithium halide, organic carboxylic acid metal salt, phosphoric acid alkali metal salt At least a part selected from among sodium sulfide hydrate and organic sulfonic acid metal salt, and lithium halide in the presence of a polyhaloaromatic compound and an organic amide polar solvent by contacting to remove at least a part of water. Sodium sulfide composition formed by contacting a metal salt and removing at least part of the water Preparation of arylene sulfide polymers characterized by reacting in the presence of an organic amide polar solvent.