JPS62190228A - Production of polyarylene sulfide - Google Patents

Abstract

PURPOSE:To produce the titled compound with remarkably reduced degree of corrosion of a vessel material and impurities, e.g. ash or oligomer in the polymer, etc., by polymerizing components in the presence of water in a specific amount based on an alkali metal sulfide. CONSTITUTION:(A) A polyhalo aromatic compound, preferably p-dichlorobenzene is brought into contact with (B) an alkali metal sulfide, (C) at least one polymerization assistant selected from metal salts of organic sulfonic acids, organic carboxylic acids, lithium halides and metal salts of phosphoric acid and (D) 2.4-10mol water including water of hydration based on the alkali metal sulfide in the presence of at least one organic amide polar solvent and polymerized at 170-330 deg.C under 1.1-200kg/cm<2> pressure to afford the aimed polyarylane sulfide. The amount of the component (B) to be used is preferably within the range of 0.9-1.1mol based on 1mol component (A). An alkali hydroxide is preferably added in polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Industrial Field of Application The present invention relates to a method for producing boria leylene sulfide.

More specifically, fibers, films, fibers, etc., characterized in that the polymerization reaction is carried out in the presence of 2.4 to about 10 moles of water including water of hydration per mole of alkali metal sulfide;
This is a method for producing polyarylene sulfide used in sheets, engineering plastics, etc.

Special Publication No. 52-12240, No. 56-20031, U
As disclosed in SP 4,038,262, etc.
In the presence of various polymerization aids, an alkali metal sulfide and an aromatic compound are brought into contact with each other in an organic amide polar solvent such as N-methylpyrrolidone (hereinafter abbreviated as NMP), and polymerization is carried out. The polyarylene sulfide obtained by the reaction is cured in advance.
), it is known to have melt fluidity that allows it to be melt-spun without any process, and it can be melt-formed to make use of its excellent heat resistance, chemical resistance, electrical properties, etc., to create fibers, films, etc. It is becoming widely used in applications such as sheets and various engineering plastics.

By the way, in the production of polyarylene sulfide,
Prior to the polymerization reaction, an operation (hereinafter referred to as a dehydration step) is performed to remove a portion of water, etc., which is produced as a by-product during the preparation of water and alkali metal sulfides contained in the raw materials, from the system. However, in this dehydration process, highly corrosive raw materials are treated at high temperatures of about 100°C or higher for a long period of time, so the material of the reaction vessel, i.e., the material of the pot, is corroded and eluted ash and solvent are decomposed. It has been found that impurities such as acetone-soluble oligomers produced by side reactions remain in the polymer and adversely affect the performance of the polymer. Furthermore, it was necessary to incorporate a separate dehydration step during the continuous production of polymers, which caused problems in terms of the process.

As a result of intensive studies in view of such problems, the present inventors omitted the conventional dehydration step and found that the presence of water including hydration water in an amount of 2.4 to about 10 moles per mole of alkali metal sulfide. The inventors have discovered that the degree of corrosion of the pot material and the amount of impurities such as ash and oligomer components in the polymer can be reduced by carrying out the polymerization reaction below, leading to the present invention.

That is, in the production of polyarylene sulfide, the present invention provides the following methods: (1) at least one polyhaloaromatic compound (2)
) at least one alkali metal sulfide, (3) at least one polymerization aid selected from organic metal sulfonates, organic cargenate metal salts, lithium halides, and metal phosphates, and (4) alkali metal sulfides 1 2.4 to about 10 moles of water including water of hydration per mole are brought into contact with each other in the presence of (5) at least one organic amide polar solvent, and the composition is maintained under polymerization conditions. Provided is a method for producing polyarylene sulfide.

The polyhaloaromatic compound used in the production of the arylene sulfide polymer in the present invention is a halodanated aromatic compound having two or more halogen atoms directly bonded to an aromatic nucleus, specifically p-cyclopenze/, m -dichlorobenzene, 0-dichlorobenzene, trichlorobenzene, tetrachlorobenzene, dichloronaphthalene,
Trichlornaphthalene, dibromobenzene, tribromobenzene, dibromonaphthalene, dichlorobenzene, triiodobenzene, dichlordiphenyl sulfone, dibromodiphenyl sulfone, dichlorobenzophenone, dibromobenzophenone, dichlordiphenyl ether,
Examples include dibromidiphenyl ether, dichlordiphenyl sulfide, dibromidiphenyl 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.

As the polymerization aid used in the present invention, at least one metal salt selected from organic sulfonic acid metal salts, lithium halides, organic carbonic acid metal salts, and alkali metal phosphates is used.

The organic sulfonic acid metal salt is selected from the group represented by the following general formulas 1 to 2.

(In the formula, R1 is hydrogen or an alkyl group having 1 to 3 carbon atoms, n is an integer of 0, 1 or 2, M is an alkali metal selected from sodium, potassium, rubidium and cesium, and X is a direct bond, -C
Indicates that it is selected from the group consisting of H-1-〇(CH3)2-1-〇-1-5-5-8-. ) Specific examples of acid group components constituting these metal sulfonates include benzenesulfonic acid% p-toluenesulfonic acid, 2,4-dimethylsulfone e, 2,5-dimethylbenzenesulfonic acid,
Examples include p-ethylbenzenesulfonic acid, dodecylbenzenesulfonic acid, α-naphthalenesulfonic acid, biphenylsulfonic acid, alkylnaphthalenesulfonic acid, laurylbenzenesulfonic acid, and alkyldiphenyl ether disulfonic acid. These sulfonic acid salts may be either anhydrous salts or hydrated salts, and may be in a water bath or liquid form.

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

The organic carboxylic acid metal salt usually has 1 to 50 carbon atoms in its M tail excluding the xyl group, and may contain nitrogen, oxygen, halogeno, silicon, or sulfur. They are an alkyl group, a cycloalkyl 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, with alkali metals being particularly preferred. Specific examples of organic cargenate 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-ethyletradecanoate, sodium octadecanoate, sodium heneicoate, lithium cyclohexanecarboxylate, cesium cyclododecanecarboxylate, sodium 3-methylcyclopentanecarboxylate , potassium cyclohexyl acetate, potassium benzoate, lithium benzoate, sodium benzoate, m-)potassium tolyate, lithium phenylacetate, sodium 4-phenylcyclohexane carboxylate, potassium p-tolyl acetate, lithium 4-ethylcyclohexyl acetate , dilithium succinate, disodium succinate, dipotassium succinate, dilithium adipate, disodium adipate, dipotassium adipate, dilithium sepacate, disodium sepacate,
Dipotassium sepacate, tecandical? dilithium phthalate, disodium decanedicarboxylate, dipotassium decanedicarboxylate, dilithium phthalate, disodium phthalate, dipotassium phthalate, dilithium isophthalate,
Disodium isophthalate, dipotassium isophthalate,
Dilithium terephthalate, disodium terephthalate,
Dipotassium terephthalate, trilithium trimellitate,
Trisodium trimellitate, tripotassium trimellitate, tetralithium pyromellitate, tetrasodium pyromellitate, tetrapotassium pyromellitate, dilithium toluene dicarboxylate, dilithium toluene dicarboxylate, dilithium toluene dicarboxylate, naphthalenedicarbone dilithium acid, disodium naphthalene dicarboxylate, dipotassium naphthalene dicarboxylate, magnesium acetate,
Mention may be made of calcium acetate, calcium benzoate, other similar salts and mixtures thereof.

The alkali phosphate salt is selected from the group represented by the following general formulas V and WK.

V: R2-P-OM 0M Vl: MO-P-OM 0M In the formula, R2 is hydrogen, C4-C2o alkyl, C5-C
2o cycloalkyl, C6-C24 aryl, C7
-C24 alkylaryl, 07-c24 aralkyl, C2-C24 alkenyl, C2-C2o alkynyl, or 05-C2o cycloalkenyl 1), M is an alkali metal such as sodium, lithium, potassium, etc.; It is sodium. Specific examples of the alkali phosphate salts used in the present invention include trisodium phosphate; methanephosphonic acid, ethane-1-phosphonic acid, furopane-1-phosphonic acid, butane-1-phosphonic acid, butane-2-phosphonic acid, Phosphonic acid, pentane-1-phosphonic acid, cyclohexane-1-phosphonic acid, vinyl-1-phosphonic acid, glono-2-phosphonic acid, butene-2-phosphonic acid, indene-2-phosphonic acid
Phosphonic acid, phenylmethanephosphonic acid, (4
-Methylphenyl)-methanephosphonic acid, β-naphthyl-methanephosphonic acid, 2-phenyl-ethane-
Disodium salts such as 1-phosphonic acid, 2-phenyl-ethylene-1-phosphonic acid, 4-phenyl-butadiene-phosphonic acid and 2-phenoxy-ethane-1-phosphonic acid are mentioned.

The amount of the above-mentioned various metal salts added varies depending on the type of compound used, but is usually 0 parts by weight per 1 part by weight of the alkali metal sulfide.
．． The amount ranges from 0.1 to 6 parts by weight, preferably from 0.1 to 4 parts by weight.

Examples of organic amide polar solvents used as polymerization solvents in the present invention include N,N-dimethylformamide, N,N-dimethylacetamide), N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N- Methyl-ε-caglolactam, hexamethylphosphoramide, etc. may be used, and two or more of these may be used in a mixed form.Among these, N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) is particularly preferred. Preferably.The amount of the organic amide polar solvent used is usually 1 to 20 parts by weight per 1 part by weight of the alkali metal sulfide when producing the alkali metal sulfide composition.
Preferably 2 to 10 parts by weight: When producing an arylene sulfide polymer, the molar ratio to the alkali metal sulfide is usually in the range of 2.5 to 20, preferably in the range of 3 to 10. The amount of the organic amide polar solvent used during production of the alkali metal sulfide composition and during production of the polymer may be the same or different. Further, such a solvent can be added or distilled off after producing the alkali metal sulfide composition.

The alkali metal sulfides mentioned in the present invention include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide,
Mention may be made of cesium sulfide and mixtures thereof. These alkali metal sulfides can be used regardless of whether they are anhydrous, hydrated, or an aqueous solution.

The amount of alkali metal sulfide used in the method of the present invention is 1
．． je IJ molar ratio to haloaromatic compound 0.8
-1.2, preferably 0.9-1.1.

Further, when producing polyarylene sulfide by the method of the present invention, it is preferable to carry out the polymerization while separating the 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
o, oos to 1.8 mol, preferably 0.0 mol
It is within the range of 15 to 0.6 mol.

Further, as substitute compounds for the alkali hydroxide, alkali carbonates and alkaline aminoalkanoates such as sodium N-methylaminobutyrate can be used. The amount of alkali carbonate and alkali aminoalkanoate to be used is generally 0.004 to 0.00% per mole of alkali metal sulfide.
9 mol, preferably within the range of 0.010 to 0.4 mol. It is also preferable to add carbon dioxide during or at the end of the polymerization reaction, which not only prevents the decomposition of the polymer and contributes to increasing the molecular weight of the resulting polymer, but also decomposes the polymerization solvent such as N-methylpyrrolidone. It is also effective in prevention.

In addition, the alkali metal sulfides in the present invention include alkali metal hydrosulfides such as lithium bisulfide, sodium bisulfide, and potassium bisulfide, and hydrogen sulfide, lithium hydroxide, and hydroxide in the organic amide polar solvent. Those obtained by contacting an alkali hydroxide such as sodium or potassium hydroxide with an alkali aminoalkanoate such as sodium N-methylaminobutyrate can be used. The amount of alkali hydroxide and alkali aminoalkanoate used in this case is 0.9 to 1 mole of alkali metal hydrosulfide.
1.1 mol, and 1.8 to 2.2 per mol of hydrogen sulfide
Moles are appropriate.

The water referred to in the present invention refers to irrigation water contained in the alkali metal sulfide and polymerization aid, free water contained in the alkali metal sulfide and polymerization aid if the alkali metal sulfide and the polymerization aid are in the form of an aqueous solution or aqueous dispersion, When preparing an alkali metal sulfide from the alkali metal hydrosulfide or hydrogen sulfide and alkali hydroxide or alkali aminoalkanoate, the alkali metal hydrosulfide, alkali hydroxide, and alkali aminoalkanoate contain If the alkali metal hydrosulfide, hydrogen sulfide, alkali hydroxide, and alkali aminoalkanoate are in the form of an aqueous solution or aqueous dispersion, free water, alkali metal water 6i-ide, or hydrogen sulfide and water contained therein. These include a stoichiometric amount of water produced as a by-product when alkali oxide or alkaline aminoalkanoate or I-) alkali metal sulfide is produced, and filtrate added to the system prior to the polymerization reaction.

In the polymerization reaction according to the method of the present invention, the amount of water in the system must be from 2.4 to about 10 moles per mole of alkali metal sulfide. If the amount of water in the system is less than 2.4 mol per 1 mol of alkali metal sulfide, the dispersibility or solubility of the alkali metal sulfide and polymerization aid will decrease, making it difficult to adhere to the inner wall of the pot. This leads to the formation of kimono and the formation of red particulate inert compositions that have poor reactivity with polyhaloaromatic compounds, making it impossible to expect the formation of polymers that will restore normal performance. If the amount exceeds 10 moles, dispersibility and solubility are good, but decomposition of the solvent during the polymerization reaction and inhibition of polymer ridge extension are likely to occur, which is not preferable.

Prior to the polymerization reaction according to the method of the present invention, if the amount of water in the system is less than 2.4 mol per mol of alkali metal sulfide, new water is added to make 2.4 mol of water per mol of alkali metal sulfide. The polymerization reaction is carried out after the amount is adjusted to a range of mol to about 10 mol. If the amount of water in the system exceeds 10 moles per mole of alkali metal sulfide, remove the excess water by distillation, for example, and adjust the amount to a range of 2.4 moles to about 10 moles. A polymerization reaction must be carried out. Of course, if the amount of water in the system is within the range of 2.4 mol to about 10 mol per mol of alkali metal sulfide, the polymerization reaction can be carried out without dehydration.

In the method of the present invention, the polymerization reaction temperature is generally 170°C.
-330°C, preferably 210°C - 300°C. The pressure should be in a range to maintain the polymerization solvent and the polymerization monomer, the polyhaloaromatic compound, substantially in the liquid phase, and generally ranges from 1.1 V-9/an'' to 200 kg.
/am”, preferably 1.1’f&/cm” to 1
Selected from two ranges: 00k<97. 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, and can be destroyed by heating, preferably under an inert gas atmosphere. 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.

The arylene sulfide polymer obtained by the method of the present invention can be obtained by a conventional method, for example, by filtration of 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 filtration and washing with water, or by removing a solvent. It can be separated from the reaction mixture by distillation recovery at normal pressure or reduced pressure, followed by washing with water and filtration.

Specific examples of the arylene sulfide polymer prepared by the method of the present invention include polyphenylene sulfide, and other arylene sulfide polymers having repeating units.

The arylene sulfide polymer can be used for injection molding, compression molding, extrusion molding and blow molding of films, fibers, sheets, pipes, tubes, etc.

It is also suitable to incorporate fillers, pigments, flame retardants, stabilizers and other polymers into this polymer if necessary. For example, glass fibers can be added to improve mechanical strength and heat resistance.

(4) Effects of the invention According to the present invention, since the dehydration step prior to the polymerization reaction step can be omitted, corrosion and corrosion of the pot material are reduced, and the amount of impurities such as ash and oligomer components that adversely affect the performance of the polymer is reduced. It is possible to reduce the amount of carbon dioxide and to obtain a high-purity polymer. Furthermore, the time required to produce the polymer is shortened, improving production efficiency and reducing production costs.

(5) Examples The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.

[Example 1] In a Sus 316LW 3 l autoclave equipped with a stirrer, 313.711 (2
, 4 mol, water content 37.83%), sodium hydroxide 1.0.1F (0,025 mol), sodium para-toluenesulfonate (hereinafter abbreviated as PTS) 465
．． 61! After adding (2.4 mol) and NMpxool, the mixture was sealed and the temperature was raised to 120° C. with stirring. Next No. 4
359.9 g (2,45 mol) of radichlorobenzene and 1.3 g (0,0 mol) of 1,2,4-trichlorobenzene
300 g of a solution of 0.072 mol) was injected into the system from the dropping tank under nitrogen pressure. At this time, the amount of water in the system including hydration water was 2.75 mol per 1 mol of sodium sulfide.

Thereafter, the temperature was raised to 240°C, held at 240°C for 30 minutes, and further held at 260°C for 2 hours, then cooled to room temperature and opened. After the reaction, the slurry of the mixture was taken out, and the condition of the inner wall of the pot, the stirring blades, and the stirring shaft was visually observed, but no black substance due to corrosion was observed, and no unreacted sulfide was formed.〇 Mixture slurry after the reaction was washed with warm water, filtered four times, and dried at 120°C according to a conventional method to obtain a slightly yellow granular polymer 252.2.9 (yield 97.3).
%) was obtained.

A portion of this polymer was weighed in a platinum dish, and the weight of the residue after baking in a Matsufuru door at 600° C. for 3 hours was measured to calculate the ash content in the polymer. Also, after extracting a portion of the polymer with a Soxhlet type extractor using acetone as an extraction solvent for about 5 hours, the extract was evaporated to dryness, and the weight of the extract was measured to determine the content of oligomer components in the polymer. Ta. The results are shown in Table 1.

[Comparative Example 1] In Comparative Example 1, a dehydration operation was performed prior to the polymerization reaction.

That is, 313.7 p of sodium sulfide 2.75 hydrate (2,4
mole, water content 37.83%), sodium hydroxide 1.0
．． 9 (0,025 mol), PTS 465.6 p (
After adding 2.4 mol) and NMPlooOg, the temperature was raised to 202°C over about 4 hours with stirring under a nitrogen stream, and the distillate was 93.6. ! I got i'. The water content of this distillate was measured by the Karl Fischer moisture measurement method and found to be 77.7%, and the amount of water in the system prior to the polymerization reaction was calculated to be 1.06 mol per 1 mol of sodium sulfide.

Then / motherboard dichlorobenzene 359.9i2.45
mol) and 1.2.4-) lychlorobenzene 1.3 g
After injecting a solution of 300 g of NMP (0,0072 mol) into the system from a dropping tank under nitrogen pressure, the temperature was raised to 240°C, held at 240°C for 30 minutes, and further heated to 260°C for 2 After being kept for an hour, it was cooled to room temperature and opened. After the reaction, the slurry of the mixture was dark green and contained red grains of unreacted sulfide, and a large amount of black material produced by corrosion was attached to the inner wall of the bowl, the stirring blade, and the stirring shaft.

The taken out post-reaction mixture slurry was post-treated in the same manner as in Example 1 to obtain 247.3 g (yield: 95.4%) of light brown granular polymer.

Table IK The polymerization results of Example 1 and Comparative Example 1 were set as 1. Compared to Comparative Example 1, in Example 1, the dehydration operation was omitted and the polymerization reaction was carried out in the presence of 2.75 mol of carbon dioxide per 1 mol of Na2S in the system, so there was no corrosion of the pot and the ash content in the polymer was reduced. It can be seen that the content of oligomer components was significantly reduced and a highly pure polymer was obtained. Furthermore, due to the uniform progress of the reaction, effects such as less generation of unreacted red particles and improvement in the color tone of the polymer were observed.

[Examples 2-4 and Comparative Example 2, Comparative Example 3] Examples 2-4
And in Comparative Examples 2 and 3, sodium hydrosulfide was used as the sulfur source,
Sodium benzoate was used as a polymerization aid. In addition, prior to the polymerization reaction, water was added to the system, and the amount of water in the system was measured as shown in Table 2.
A polymer was prepared by adjusting as shown in .

For example, in Example 2, Sum 316L M with a stirrer was used.
31 Sodium bisulfide 1608 hydrate 156.1.9 (2.0 mol, water content 24.88 h) in an autoclave
, Sodium hydroxide 80.9 (2.0 mol), Sodium benzoate 288F (2.0 mol), NMP 860
g and water 33.2! ! After adding (1.84 mol), the mixture was sealed, and the temperature was raised to 100°C with stirring. Soradichlorobenzene 294.9 (2.0 mol) and 1.2.4-
) Lichlorbenzene 1.09,! i+ (0,006
A solution of 230 g of NMP (mol) was injected into the system from the dropping tank under nitrogen pressure. At this time, the amount of water in the system, including water of hydration and a stoichiometric amount of water produced as a by-product with the production of sodium sulfide, was per mole of sodium sulfide. ! 73.0
0 mol. Then, the temperature was raised to 230°C, held at 230°C for 1 hour, and further held at 250°C for 2 hours, cooled to room temperature, and opened. After the reaction, the mixture slurry IJ- was taken out and the inner wall of the pot, stirring blades, and stirring shaft were observed, but no black material due to corrosion was observed.

The taken out post-reaction mixture slurry was treated in the same manner as in Example 1 to obtain pale yellow granular polymer 210.6. @(Yield 97.
5ch) was obtained.

As shown in Table 2, in Examples 2 to 4 by the method of the present invention, there was no generation of black matter due to corrosion and no generation of unreacted red particles, the content of ash and oligomer components was reduced, and the color tone of the polymer was improved. etc. was recognized.

In addition, in Comparative Examples 2 and 3, which were synthesized by adjusting the amount of water in the system during the polymerization reaction to a value outside the scope of the claims of the present invention, the oligomer content was particularly high and the polymers were of low purity. Nineteen.

Table 1

Claims (1)

[Claims] In the production of polyarylene sulfide, (1) at least one polyhaloaromatic compound, (2) at least one alkali metal sulfide, (3) an organic sulfonic acid metal salt,
At least one polymerization aid selected from organic carboxylic acid metal salts, lithium halides, and phosphate metal salts, and (4) 2.4 to about 10 mol of water including water of hydration per 1 mol of alkali metal sulfide. (5) A method for producing polyarylene sulfide, which comprises maintaining a composition obtained by contacting the following in the presence of at least one organic amide polar solvent under polymerization conditions.