JPS60200807A - Production of sodium sulfide composition for manufacturing arylene sulfide polymer and manufacture of said polymer - Google Patents

Abstract

PURPOSE:To attain improved dispersibility in a polymn. reaction and to improve the yield of an arylene sulfide polymer by dehydrating sodium sulfide hydrate with a prescribed metallic salt in the presence of a hydrocarbon solvent and by using the resulting composition as a starting material for the arylene sulfide polymer. CONSTITUTION:One or more kinds of metallic salts selected among metallic salts of org. sulfonic acid, lithium halides, metallic salts of org. carboxylic acid and alkali metallic salts of phosphoric acid are brought into contact with sodium sulfide hydrate in the presence of a hydrocarbon solvent to remove part of water in the hydrate. The resulting sodium sulfide composition is reacted with an aromatic polyhalo-compound in the presence of org. amide as a polar solvent to obtain an arylene sulfide polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of arylene sulfide polymers, a method for producing a sodium chloride composition, and a method for producing arylene sulfide polymers using the sodium chloride composition.

Arylene sulfide polymers, typified by polyphenylene sulfide, are produced by a method as disclosed in Japanese Patent Publication No. 3368/1983. That is, it is produced by a method in which p-dichlorobenzene and sanitized soda are reacted in an organic amide solvent such as N-methylpyrrolidone. The 7'L polyphenylene sulfide obtained by this method has an extremely low degree of polymerization and is not suitable for use in this 11. It has a high molecular weight and is used for practical purposes such as injection molding. However, even this high-molecular-weight product has poor extrusion moldability and cannot be used for applications such as fibers, films, pipes, and sheets.

Furthermore, a method for obtaining a high molecular weight arylene sulfide polymer by a polymerization reaction is already known. That is, as shown in Japanese Patent Publication No. 52-12240, for example, a polymer capping polymer can be obtained by carrying out a polymerization reaction in the presence of various polymerization aids. These high molecular weight polymers are melt-molded into engineering plastics, pipes, films, fibers, etc. using methods such as extrusion molding, and are used to make molded products that take advantage of their heat resistance and chemical resistance.

By the way, in the above production method, sodium sulfide hydrate has conventionally been used industrially as a starting material. This sodium sulfide hydrate is produced by concentrating it at high temperature.
It is generally known that it is possible to obtain products with low relative water of crystallization such as Na18@2.7H,0 (NIL!8 purity 60%). However, in order to produce the arylene sulfide polymer, which is a comparative polymer, it is necessary to further remove some of the water of crystallization, and therefore a dehydration step must be performed prior to the polymerization reaction.

Conventionally, as a dehydration method for sodium sulfide hydrate,
-3368, the polymerization solvent N-methylpyrrolidone in an organic amide general medium, or
As shown in No. 2-12240, there is a method in which at least part of the water is distilled out of the system by heat treating sodium sulfide hydrate in an organic amide bath medium in the presence of an alkali metal carboxylate. Ru.

However, these methods require high-temperature conditions such as about 200°C for dehydration, and it takes a long time to achieve sufficient dehydration, resulting in decomposition of the solvent or damage to the reactor using sodium sulfide, etc. There was a drawback that rust occurred due to corrosion. Therefore, it has been industrially disadvantageous in terms of polymer production costs such as raw materials, equipment, and energy. Furthermore, even if sufficient dehydration is achieved, the yield and molecular weight of the resulting polymer are unsatisfactory due to poor dispersibility of the sodium sulfide particles in the polymerization reaction after the dehydration step. Along with this, it is also disadvantageous in terms of the cost of recovering or disposing of unreacted sodium sulfide.

The inventors of the present invention have made extensive studies in view of these drawbacks, and have found that by bringing a specific metal salt into contact with sodium sulfide hydrate in the presence of a specific hydrocarbon solvent, it is possible to achieve efficient dehydration at a relatively low temperature. It was discovered that a sodium sulfide composition with good dispersibility could be obtained by a one-coat reaction of 1% to 50%, leading to the present invention.

That is, the present invention provides at least one selected from sodium sulfide hydrate, organic sulfone metal salts, lithium halides, organic carboxylic acid metal salts, and alkali metal phosphate salts in the presence of a hydrocarbon solvent. A method for producing a sodium sulfide composition for producing an arylene sulfide polymer, which comprises bringing a metal salt into contact with the polyhaloaromatic compound and removing at least a portion of the water, and the method for producing a sodium sulfide composition and a polyhaloaromatic compound in the presence of an organic amide polar solvent. Provided is a method for producing an arylene sulfide polymer, characterized in that the reaction is carried out under the following conditions.

The sodium sulfide hydrate used in the method of the present invention is sodium sulfide 1
It is a sodium hydride hydrate containing 1 mol or more of water of crystallization per mol and having a purity of 81 mol or less of Jph Na, 8. Specifically, sodium sulfide nonahydrate (Na!S purity 32%), sodium sulfide hexahydrate (Na1S purity 42%), and sodium sulfide pentahydrate (N
A2S purity 46%), sodium sulfide hydrate with Na2S purity 61% containing 2.7 mol of water per 1 mol of Na2S as crystallization water, etc., can be mentioned. The shape of these hydrates may be crystal, flake, or solid. Normally, industrial purity is about 61%.
Soda 2.7 hydrate is used.

The hydrocarbon solvent used in the method of the present invention has a boiling point of 65°C or higher under normal pressure or reduced pressure, and has a boiling point higher than the melting point of sodium chloride hydrate, and is in liquid form. Suitable. Specifically, benzene, toluene, xylene,
Aromatic hydrocarbons such as ethylbenzene, tetralin, diphenyl, triphenylnato, aliphatic hydrocarbons such as 11-hexane, n-hebutane, n-octane, and isooctane, and alicyclic hydrocarbons such as cyclohexane and decalin. t. Two or more of these may be used in a mixed form. Among these, xylene is particularly preferred.

The amount of this hydrocarbon solvent used is within a range of 0.1 to 20 parts by weight per 1 part by weight of the above-mentioned valorized soda hydrate.
Preferably it is in the range of 1 to 10 pieces.

In the present invention, when producing the sodium monoxide composition, at least one metal salt is used in t'L7 selected from organic sulfonic acid metal salts, lithium chlorides, organic carboxylic acid metal salts, and alkali metal phosphates. be done.

The organic sulfonic acid gold salts are 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 60 carbon atoms, n is an integer of 0.1 or 2, M is an alkali metal selected from sodium, potassium, rubidium, and cesium, and is a direct bond, -C
)l, -.

Show that you are chosen. ) Specific examples of acid group components constituting these metal sulfonates include benzenesulfone ff
1L p-toluenesulfonic acid, 2.4-dimethylsulfonic acid, 2゜5-dimethylbenzenesulfonic acid, p-ethylbenzenesulfonic acid, dodecylbenzenesulfonic acid, α-naphthalenesulfonic acid, biphenylsulfonic acid,
Examples include alkylnaphthalenesulfonic acid, laurylbenzenesulfonic acid, and alkyldiphenyl ether disulfonic acid. The salts of these sulfonic acids may be either anhydrous salts or hydrated salts, or may be a water bath solution, but it goes without saying that anhydrous salts are preferred for the purposes of the present invention.

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

In the organic carboxyl metal salt, the organic group excluding the carboxyl group usually has 1 to 50 carbon atoms and may contain a di-, 1-divalent element, oxygen, halogen, silicon, or sulfur, preferably an alkyl group, They are a cycloalkyl group, an aryl group and an alkylaryl group. Further, the metal atom of the organic carboxylic acid metal salt is selected from lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, zinc, strontium, cadmium, and barium, and alkali metals are particularly preferred. Specific examples of organic carboxylic acid metal salts include lithium acetate, sodium acetate, potassium acetate, lithium propionate, sodium propionate, lithium 2-methylpropionate, rubidium butyrate, lithium valerate, sodium valerate, cesium hexanoate, Lithium heptanoate, lithium 2-methyloctoate, potassium dodecanoate, rubidium 4-ethyletradecanoate, sodium octadecanoate, sodium heneicosanoate, lithium cyclohexanecarboxylate, cesium cyclododecanecarboxylate, sodium 6-methylcyclopentanecarboxylate , potassium cyclohexyl acetate, potassium benzoate, lithium benzoate, sodium benzoate, m-) potassium tolyate, lithium phenylacetate, sodium 4-phenylcyclohexanecarboxylate, potassium p-tolyl acetate, lithium 4-ethylcyclohexyl acetate, amber dilithium acid, disodium succinate, dipotassium succinate, dilithium adipate, disodium adipate, dipotassium adipate, dilithium sebacate, disodium sebacate, dipotassium sebacate, dilithium decanedicarboxylate, Disodium decanedicarboxylate, dipotassium decanedicarboxylate, dilithium phthalate, disodium phthalate, dipotassium phthalate, dilithium isophthalate, disodium isophthalate, dipotassium inphthalate, dilithium terephthalate, dipotassium terephthalate Sodium, dipotassium terephthalate, trilithium trimellitate, trisodium trimellitate, tripotassium trimellitate, tetralithium pyromellitate, tetrasodium pyromellitate, tetrapotassium pyromellitate, dilithium toluene dicarboxylate, toluene Disodium dicarboxylate, dipotassium toluene dicarboxylate, dilithium naphthalene dicarboxylate, disodium naphthalene dicarboxylate, dipotassium naphthalene dicarboxylate, magnesium acetate, calcium acetate, calcium benzoate, and other similar salts and the like. The mixture is washed out.

The alkali phosphate salt is selected from the group shown in the following general formula (V).

V: R2-P-OM 0M 1'%/l: MO-P-OM where R2H hydrogen, C, %C,. (D 7 JL'#
Le, C, ~C,. (7) ') Chloalkyl k C
Aryl of 6 to C24, alkylaryl of C7 to C24% Aralkyl of C7 to C24, alkenyl of c, to C24% Alkynyl of C6 to C7° or cycloalkenyl of C5 to C20, M is sodium, lithium, potassium, etc. an alkali metal, preferably sodium. Specific examples of the alkali phosphate salts used in the present invention include trisodium phosphate; methane-1-phosphonic acid, ethane-1-phosphonic acid, propane-1-phosphonic acid, butane-1-phosphonic acid, and butane-2-phosphonic acid. -Phosphonic acid, pentane-1-phosphonic acid, cyclohexane-1-7osphonic acid, vinyl-1-phosphonic acid, propene-2-phosphonic acid, butene-2-7os7onic acid, indene-2-phosphonic acid, Phenylmethanephos7one, (4-methylphenyl)-methanephosphonic acid, β-naphthyl-methanephos7one [
,2-phenyl-ethane-1-phosphonfit,2
-phenyl-ethylene-1-phosphonic acid, 4-phenyl-butadiene-phosphonic acid and disodium salts such as 2-phenoxy-ethane-1-phosphonic acid.

The amount of the above-mentioned various metal salts added varies depending on the type of compound used, but is usually 0.01 to 6 parts by weight, preferably 0.1 to 4 M parts by weight, per 11 parts of the sodium sulfide hydrate. This is the range.

The polyhalo aromatic compound used in the production of arylene sulfide polymers is a halogenated aromatic compound having two or more halogenated atoms directly bonded to an aromatic nucleus, specifically hap-')chloro Benzene, m-dichlorobenzene, 0-dichlorobenzene, trichlorobenzene, tetrachlorobenzene, dichloronaphthalene, trichloronaphthalene, dibromobenzene, tribromobenzene, dibromnaphthalene, shortbenzene, triiodobenzene, dichlorodiphenyl Sulfone, cyfuromodiphenyl sulfone, dichlorobenzophenone, cyfurombenzophenone, dichlordiphenyl needle, cyfuromidiphenyl ether, dichlordiphenyl sulfide, dibromodiphenyl sulfide, dichlorbiphenyl, dibrombiphenyl, etc., and mixtures thereof. I'm going to try everything. Usually dino-aromatic compounds are used, preferably p-dichlorobenzene.

In addition, in order to increase the viscosity of the polymer due to the branched structure,
A small amount of a borinoaromatic compound having six or more halogen substituents in one molecule may be used in combination with a dihaloaromatic compound.

In addition, N,N-dimethylformamide, N,N-dimethylformamide,
N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-ε
-caglolactam, hexamethylphosphoramide, etc., and these may be used in the form of a mixture of two or more types. Among them, N-methyl-2-pyrrolidone (hereinafter, N
MP) is particularly preferred.

Incidentally, the amount of the sodium sulfide composition used during the production of the arylene sulfide polymer is usually in the range of 0.8 to 1.2 in molar ratio to the Dino-Kuchi aromatic compound, preferably 0.
．． It is in the range of 9 to 1.1. ′! In addition, the amount of organic amide polar solvent used is 2.5 to 2 in molar ratio to sodium sulfide.
The range is 0, preferably 6 to 10.

In the method of the present invention, the temperature in the step of distilling off water from the sodium sulfide hydrate (hereinafter referred to as the dehydration step) is above the melting point of this hydrate, generally 60°C to 200°C, preferably 80°C.
℃~150℃. The time required for the dehydration process varies depending on the temperature, pressure and water content of the hydrate, but is generally 15
The time range is from 1 minute to 5 hours, preferably from 60 minutes to 2 hours. Under the above conditions, if the sodium sulfide hydrate and the metal salt are heated and stirred in the hydrocarbon solvent, most of the water in the system will be efficiently distilled off. A highly dispersible soda sulfide composition is formed in which sodium sulfide particles are uniformly and finely dispersed together with metal salt particles in a solvent.

Next, 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 the N-combination step), the polymerization reaction temperature is generally 170°C to 330°C. , preferably 210°C ~,
It is 1Soo℃. The pressure should be in a range such that the polymerization solvent and the polymerization monomer, the polyhaloaromatic compound, remain in the liquid phase, typically 1.1 b/cm
2-20 ke 12, preferably 1.1 ke 2-20 K
The reaction time varies depending on the temperature and pressure, but is generally in the range of 10 minutes to about 72 hours, preferably 1 hour to 4N hours. The sulfide polymer can be produced by mixing the above-mentioned sodium sulfide composition, polyhaloaromatic compound, and organic amide polar solvent, and heating the mixture preferably under an inert gas atmosphere.There are no particular restrictions on the order of mixing each component. Rather, the above-mentioned components are added in small portions or all at once during one polymerization step!

When producing the arylene sulfide polymer, it is preferable to add an alkali hydroxide to carry out the polymerization. Examples of the alkali hydroxides used include hydroxide≠rum, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and mixtures thereof. The use lid of alkali hydroxide is 0 for 1 mole of general sodium dichloride.
．． 008-1.8 mol, preferably 0.015-0.6
Within the molar range.

An alkali carbonate salt can be used as a substitute compound for the above-mentioned alkali hydroxide. The amount of alkali carbonate used is generally 0.04 to 0.9 per mole of sodium sulfide.
The mole percentage is preferably within the range of 0.010 to 0.4 mole. It is also preferable to add carbon dioxide during the polymerization reaction or at the end of the polymerization.This prevents the decomposition of the polymer and increases the molecular weight of the resulting polymer. It is also effective in preventing decomposition of polymerization solvents.

Furthermore, in order to further improve the dispersibility of the starvation soda during the dehydration step in the method of the present invention, it is also possible to carry out the dehydration and polymerization in the presence of a low molecular weight arylene sulfide polymer. A typical example of the low molecular weight polymer used is polyphenylene sulfide with an intrinsic viscosity [η] of 0.2 or less, and the amount used is 0.01 to 3 M per part by weight of the sodium sulfide hydrate. parts, preferably 0.05 to 2 parts by weight.

The present inventors speculated as follows regarding the effect of the metal salt used in the dehydration step. First, due to the metal salts dispersed in the hydrocarbon solvent during the dehydration process, the soda sulfide particles, which generally have poor dispersibility in the system as water removal progresses, are dispersed appropriately, resulting in efficient dehydration. Not only
A dispersed mixture of high surface area soda sulfide particles is formed. In its dispersed state, the sodium sulfide component not only has a high 1-polymer reaction activity, but also the metal salt is effective as a polymerization aid for increasing the molecular weight in this polymerization reaction, and the effects of both are synergistic to increase the polymerization rate. The intrinsic viscosity value of the one that produces high molecular weight polymer in high yield and the one that produces a polymer with a high molecular weight is 0. dl//100 at a polymer concentration of a vertical bath liquid, measured in α-chlornaphthalene at 206°C, and calculated according to the formula.

The arylene sulfide polymer obtained by the method of the present invention can be prepared by a conventional method, for example, by passing the reaction mixture through one sieve after the completion of the polymerization reaction, followed by washing with water, or by diluting the reaction mixture with water, followed by one sieve and washing with water. Alternatively, the solvent can be separated from the reaction mixture by distilling and recovering the solvent at normal pressure or reduced pressure, followed by washing with water and filtering.

Specific examples of arylene sulfide polymers produced by the method of the present invention include polyphenylene sulfide arylene sulfide polymers. These arylene sulfide polymers can be used for injection molding, compression molding, extrusion molding, blow molding of films, fibers, sheets, φ pipes, tubes, etc. It is also suitable to incorporate fillers, pigments, flame retardants, stabilizers and other polymers into the polymer, if necessary. For example, in order to improve mechanical strength and heat resistance, glass fibers are placed in an autoclave equipped with a stirrer and sulfurized sorter'2,7 hydrate 103.9 (0.8 mol, purity 6
1%), xylene 606I and p-) sodium sulfonate (155.10.8 mol), and gradually raised the temperature to 140°C in a nitrogen atmosphere for 40 minutes while stirring to combine water and xylene. was distilled out. At that time, the xylene distilled out at the same time as the water was returned to the autoclave using a decanter R. Next, 2609 xylene was distilled off under reduced pressure, and finally 55.0 I of water was added! was distilled out.

As a result, a composition in which the reddish-brown soda sulfide fine particles were uniformly mixed with the p-)luenesulfone cough sorter particles and had good dispersibility in the intoxicant was obtained. Benzene 118.9 (0
, 8 mol) and 1,2,4-trichlorobenzene 0.44
#(0,0024 molha sodium hydroxide 0.41!
(0.01 mol) and N-methylpyrrolidone 4321
In addition to 9, it was heated at 260°C for 2 hours, and further heated at 260°C. “6 in C
Allowed time to react. During the polymerization, the internal pressure at the end of the polymerization reaction was 4,
It was 5~/-2.

Thereafter, the autoclave was cooled and the contents were separated, and the cake (solid content) was washed six times with hot water, further washed twice with acetone, and then dried at 120°C.
84.0 g of pale gray-brown granular polyphenylene sulfide was obtained (yield = 912%). The intrinsic viscosity [η] of this polymer was 0.40. In addition, after the reaction is completed, J
There was no black rust in the autoclave (hereinafter referred to as reaction vessel) made of IS standard 5 US304 stainless steel.

[Comparative Example 1] Dehydration and polymerization reactions were carried out in the same manner as in Example 1 except that p-) sodium luenesulfonate was not used, and 31.9.9 of water was distilled out, but the water was reddish brown. Sodium sulfide was not obtained in the form of large, fine particles in the form of small agglomerates, and only a composition with poor dispersibility in the solvent was obtained. Furthermore, the yield of the polymer obtained after the polymerization reaction was 64.1 (yield 75.0%), and the intrinsic viscosity [η] was 0.14, indicating that both the yield and the molecular weight were low.

[Comparative Example 2] NMP306 instead of xylene. r'(f- The same preparation method as in Example 1 was used except that
Water and N were gradually heated while stirring for 3 hours until
A part of MP was distilled off. In the end, 22.61 g of water was distilled out, but even though the temperature was higher and the time was longer than in Example 1, less wood was distilled out. As a result, black rust developed in the reaction vessel.

Next, a polymerization reaction was carried out in the same manner as in Example 1, and finally a granular polymer of SO and OG in a pale grayish brown color was obtained (yield: 92.6%). The intrinsic viscosity [η] of this polymer was 0.27, and both the p1 yield and the molecular lid were Example 1.
The results were lower than those of

[Example 2] Sodium sulfide 9-hydrate 19 instead of 2.7-hydrate sodium sulfide
21 (0.86, purity 32%) and Nidiclohexane 306y instead of xylene. The temperature was raised to distill water and cyclohexane.

Finally, 111.9% of water and 290.9% of cyclohexane were distilled. As a result, a soda sulfide composition with good dispersibility similar to that of Example 1 was obtained. At that time, there was no black rust in the reaction vessel.

Next, a polymerization reaction was carried out in the same manner as in Example 1, and finally 5 grains of light grayish brown polymer of 83.4mm were obtained (yield: 96.5%). The intrinsic viscosity of this polymer [
η] was 0.67.

[Example 3] K'/vn306. ? 'r103F, p-toluenesulfonic acid sodium 0.5 hydrate' + 229 (0.6 mol, purity 95
．． 5%) was used in the same manner as in Example 1.
．． 2 g and 21 g of xylene were completely distilled out. As a result, a soda sulfide composition with good dispersibility similar to that of Example 1 was obtained. Further, there was no black rust in the first reaction pot at that time.

Next, 118 g of p-dichlorobenzene (0,
8 mol), sodium hydroxide 0.4'il (0,0
1 mol), and NMP 432. In addition to V', t%23
The reaction was carried out at 0° C.-C2 hours +1 U and then at VC260° C. for 6 hours. The internal pressure at the end of the polymerization reaction is 5.7 h/crt? Met. Finally, a pale gray-brown, granular polymer of 8661 was obtained (yield: 96.8%). The intrinsic viscosity of this polymer [η
] is 0.62 and nine.

[Examples 4 to 11] Dehydration and polymerization reactions were carried out in the same manner as in Example 1, except that all the hydrocarbon solvents and metal salts shown in Table 1 were used.

The results are shown in Table 1.

Claims (2)

[Claims] (1) Soda sulfide hydrate and at least one metal salt selected from organic sulfonic acid metal salts, lithium halides, organic carboxylic acid metal salts, and alkali metal phosphates in the presence of a hydrocarbon bath medium. 1. A method for producing a sanitizing soda composition, which comprises contacting the composition and removing at least a portion of water. (2) In the presence of a hydrocarbon bath medium, at least one kind of f'Lfc selected from among sodium sulfide, metal salts of organic sulfonic acids, lithium halides, organic carboxyl salts, and alkali metal salts of phosphates is added. nfc formed by contacting metal salts and removing at least some of the water
1. A method for producing a polyethylene sulfide polymer, which comprises reacting a fM soda composition, a polynoroaromatic compound, and an organic amide polar solvent in the presence of an organic amide polar solvent.