JPH0232297B2 - - Google Patents

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an aromatic sulfide polymer by dehalogenation/sulfurization reaction of a dihaloaromatic compound with a metal sulfide. More specifically, the present invention has a key feature in carrying out this reaction in a particular manner,
The present invention relates to a method for producing aromatic sulfide polymers of extremely high molecular weight with extremely high reproducibility. In recent years, there has been an increasing demand for thermoplastic resins with higher heat resistance for use in electronic equipment parts, automobile equipment parts, and the like. Aromatic sulfide polymers also have properties as resins that can meet these demands, but because these resins are highly crystalline and difficult to obtain with sufficiently high molecular weights, they are not suitable for use in films and sheets. However, there were major problems in that it was extremely difficult to mold into fibers and the molded product was extremely fragile. In order to solve these problems, the present invention provides a method for producing a linear aromatic sulfide polymer having a significantly high molecular weight. Prior art As a method for producing aromatic sulfide polymers,
Conventionally, the following are known. (1) A method of melting and reacting elemental sulfur, dichlorobenzene, and a base (for example, Na ₂ CO ₃ ) without a solvent (U.S. Pat. Nos. 2,513,188 and 2,538,941, etc.). (2) A method in which an alkali metal sulfide, especially hydrated Na ₂ S, is heated in a polar solvent to remove the water contained in the hydrated Na ₂ S, and dichlorobenzene is added thereto and polymerized by heating (US Patent No. 3354129) number specification, etc.). (3) In method (2) above, a method in which a carboxylic acid salt is coexisted in a polar solvent and heated to remove the water containing hydrated Na ₂ S, and then dichlorobenzene is added thereto and polymerized by heating (U.S. patent No. 3919177, same No.
4089847, etc.). However, to the best of the inventors' knowledge, these methods cannot be said to be fully satisfactory.
That is, in the method (1) above, the molecular weight of the resulting polymer is too low, making it difficult to obtain a practical linear aromatic sulfide polymer. Although method (2) yields a polymer with a molecular weight slightly higher than that of method (1), it is still difficult to obtain a polymer with a molecular weight sufficient for practical linear aromatic sulfide polymers. (3)
The method (2) was proposed to improve the disadvantage of the low molecular weight of the produced polymer in method (2), and it resulted in a considerable improvement in the molecular weight of the produced polymer. However, even with this method, as far as the inventors know, it is quite difficult to reproducibly and economically produce a polymer having a molecular weight sufficient for producing strong films, sheets, fibers, etc. Reproducibility is a particularly important issue in industrial production. The main reason why it is difficult to obtain high molecular weight polymers with good reproducibility using methods (2) or (3) above is that one of the raw materials, hydrated Na ₂ S (a reaction product of hydrated NaHS and NaOH) Since the method of physically heating and distilling water in the polymerization solvent is used to remove water (including (b) During water distillation, the sulfur content in the metal sulfide is entrained in the form of H ₂ S, etc., resulting in a loss, which causes the amount of sulfur content in the reaction system to fluctuate, and (c) a considerable amount of water remains. It is speculated that under such conditions, metal sulfides corrode the reaction vessel, and the eluted heavy metal ions inhibit the increase in molecular weight of the produced polymer. Furthermore, the problem with method (3) is that many water-soluble organic acid salts, especially acetates, are coexisting in the polymerization system during polymerization, resulting in a large amount of organic acids being mixed into the treated wastewater after polymerization. There is a risk of causing pollution problems, and a large amount of cost is required to eliminate the pollution. SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks of the conventional manufacturing method, and
A method for reproducibly and economically producing linear aromatic sulfide polymers with dramatically high molecular weights suitable for processing into molded products such as strong films, sheets, and fibers, and which eliminates the real problem of pollution. It provides an unconventional method. The inventors have conducted intensive studies on methods for economically obtaining high-molecular-weight linear aromatic sulfide polymers with good reproducibility ^. Alkaline earth metal hydroxides, which were thought to inhibit polymerization by forming and consuming sparingly soluble sulfides, were removed in large amounts from metal sulfides and dihaloaromatics in an aprotic solvent. When reacted in the presence of other compounds, it was unexpectedly found that extremely high molecular weight aromatic sulfide polymers could be produced with good reproducibility. The present invention was constructed based on this knowledge. Summary of the Invention The method for producing an aromatic sulfide polymer according to the present invention comprises combining a sulfide (A) of a metal selected from the group consisting of alkali metals and alkaline earth metals and an effective amount of an alkaline earth metal hydroxide (B). ) and a dihaloaromatic compound (C);
and 1 g of the sulfide (A) used in an approach solvent.
100 in the presence of 0.01 to 2 mol of added water per equivalent
It is characterized by heating to a temperature of ~250°C. In the present invention, the terms "metal sulfide,""dihaloaromaticcompound,""alkaline earth metal hydroxide," and "approtic solvent" are used within the scope of each of the mentioned compounds or substances. It must be understood that this includes cases where the term is a mixture. Therefore, for example,
One specific example of the present invention includes a case where the "dihaloaromatic compound" is composed of multiple types, particularly two types of compounds, and the resulting aromatic sulfide polymer is a copolymer. Effects of the Invention As described above, the present invention uses alkaline earth metal hydroxides, which were conventionally considered to be avoided, and also maintains the water content in the reaction system at a specific value by adding water to the reaction system. In particular, they succeeded in reproducibly producing aromatic polysulfide polymers with extremely high molecular weights, but it was unexpected that such an effect could be obtained under such specific conditions. It should be said that there was no such thing. DETAILED DESCRIPTION OF THE INVENTION Production of Polymers The method for producing aromatic sulfide polymers according to the present invention is based on the dehalogenation/sulfurization reaction of dihaloaromatic compounds with metal sulfides. Metal Sulfide (A) As the sulfide that functions as a sulfur source and a dehalogenating agent in the polymerization reaction of the present invention, a sulfide of a metal selected from alkali metals and alkaline earth metals is used. Sulfides of alkali metals such as Na and K or alkaline earth metals such as Ca, Mg, Na, and Sr are preferred. Among these, Na sulfide is particularly preferred from the viewpoint of ease of handling and stability. It is desirable that the metal sulfide is as anhydrous as possible. Some of the metal sulfides used in the present invention are incubated in the polymerization reactor before adding the alkaline earth metal hydroxide.
Those synthesized in situ (e.g. H ₂ S + 2NaOH→
Na ₂ S, 2H ₂ O, etc.) are also included. Alkaline earth metal hydroxide (B) The most important point of the present invention is the use of a specific metal hydroxide, which was determined as an appropriate additive that satisfies the following requirements. It was obtained from. Must be basic. The solubility in water and approach solvents should not be too high. It must be easy to remove in the post-treatment step after polymerization. Desirably low cost. For this reason, alkaline earth metal hydroxides are used, preferably Ca or Mg hydroxides. On the other hand, alkali metal hydroxides (such as LiOH) have too high a solubility and are therefore undesirable, and aluminum group metal hydroxides (such as Al(OH) ₃ ) are difficult to remove in post-treatment steps after the polymerization reaction. So I don't like it. The amount of alkaline earth metal hydroxide (B) used in the present invention must be an amount effective to achieve the intended purpose. This amount is per 1g equivalent of metal sulfide.
A range of 0.5 to 20 g equivalents is preferred. In the present invention, the "effective amount" of alkaline earth metal hydroxide (B) means the amount used within this range. A particularly preferred amount used is in the range of 1 to 5 g equivalent. If the amount is less than 0.5 g equivalent, the effect of increasing the molecular weight by addition will be insufficient, and if the amount exceeds 20 g equivalent, the proportion of monomer components (metal sulfide (A) and dihalo aromatic compound (C)) per weight of the polymerization raw material will be greatly reduced. In the polymerization method of the present invention, the alkaline earth metal hydroxide (B) is a substantially anhydrous chemical mixture with the metal sulfide (A) or Used as a physical mixture. In particular, chemical mixtures are most preferred as they give good results. Here, a "chemical mixture" is one in which, for example, a sulfide is combined with an alkali metal salt. In this case, if (A) is represented by (M ⁺ ) ₂ (S ^2- ) and (B) is represented by (N ²⁺ ) (OH ^- ) ₂ (M: alkali metal, N: alkaline earth metal ), their 1:2 (g equivalent ratio) chemical mixture is (M ⁺ ) ₂
It refers to a glassy ionic complex in which two types of cation components and two types of anion components represented by (N ²⁺ ) ₂ (S ^2- )(OH ^- ) ₄ are randomly bonded together. Such a glassy ion complex is
It can be formed by heating (A) and (B) in the presence of water to melt and mix them, followed by rapid removal of the water. In order to make it substantially anhydrous, a method such as heating at a temperature of 100° C. to 900° C. under reduced pressure or normal pressure may be used. Here, the term "substantially anhydrous" means that the glassy ion complex has been sufficiently dried, and even if the residual water content is large, it does not exceed 1 mole per 1 g equivalent. On the other hand, a substantially anhydrous physical mixture of (A) and (B) refers to a substantially anhydrous powder of (A) and a substantially anhydrous powder of (B) that are uniformly mixed mechanically. It can be obtained by If such a mixture is mixed before the polymerization charge, it can be made using an ordinary mixer, or if it is mixed after the polymerization charge, the solvent can be made in the coexistence of the solvent using a stirring device in the polymerization vessel before heating to the polymerization temperature. It can be made by stirring both at the same time. In the case of this physical mixture, it is desirable that (A) and (B) be in powder form, and in particular, the alkaline earth metal oxide (B) preferably has a particle size of 2 mm or less. Regarding this physical mixture, a substantially anhydrous substance is one in which (A) and (B) have been sufficiently dried, and even if the total residual water content of both is greater than 1 mol per gram of metal sulfide equivalent. This means that it cannot be exceeded. Dihaloaromatic compound (C) A dihaloaromatic compound corresponding to a monomer that should form the skeleton of an aromatic sulfide polymer has an aromatic nucleus and two halo substituents on the nucleus. Any material can be used as long as it can be polymerized through a dehalogenation/sulfurization reaction with an alkali or alkaline earth metal sulfide. Therefore, the aromatic nucleus may not only consist of aromatic hydrocarbons, but may also have various substituents that do not inhibit this dehalogenation/sulfurization reaction. Specifically, examples of dihaloaromatic compounds that can be used in the present invention include compounds represented by the following formula. Here, each substituent has the following meaning. X: Cl, Br, I or Fo, especially a halogen selected from the group consisting of Cl and Br. Y: selected from the group consisting of -R, -OR and -COOH (R is selected from the group consisting of H, alkyl, cycloalkyl, aryl and aralkyl). Here, the alkyl or alkyl moiety usually has about 1 to 18 carbon atoms, and the aryl or aryl moiety usually has about 6 to 18 carbon atoms. V:-O-,

[Formula] -S-, -SO-, - SO ₂ - and

[Formula] (R' and R'' are selected from the group consisting of H, alkyl, cycloalkyl, aryl and aralkyl), where alkyl or an alkyl moiety and an aryl or aryl moiety is defined in the same way as above. In formula (A), m and n are m=2, 0≦n, respectively.
≦4 integer. In formula (B), a and b are a=2 and 0≦b, respectively.
≦6 integer. In formula (C), c, d, e and f each satisfy 0≦c
≦2, 0≦d≦2, c+d=2, 0≦e, f≦4
an integer of In formula (D), g, h, i and j are each 0≦g
≦2, 0≦h≦2, g+h=2, 0≦i, j≦4
an integer of Examples of the dihalogen-substituted aromatic compound having the above general formula include the following. p-dichlorobenzene, m-dichlorobenzene, 2,5-dichlorotoluene, p-dibromobenzene, 1,4-dichloronaphthalene, 1-methoxy-2,5-dichlorobenzene, 4,4' -dichlorbiphenyl, 3,5-dichlorobenzoic acid,
p,p'-dichlorodiphenyl ether, 3,3'-
Dichlordiphenyl sulfone, 3,3'-dichlordiphenyl sulfoxide, 3,3'-dichlordiphenyl sulfide, etc. Among them, p-dichlorobenzene, m-dichlorobenzene and 3,
3'-dichlorodiphenylsulfone is particularly preferably used. As mentioned above, a branched polymer or a copolymer containing two or more different reactive units can be obtained by appropriately selecting and combining dihaloaromatic compounds. If p-dichlorobenzene and m-dichlorobenzene or p,p'-dichlorodiphenyl sulfone are used in combination,

[Formula] Unit and

[Formula] or

A copolymer containing the unit [Formula] can be obtained. The amount of the dihaloaromatic compound (C) used in the present invention is preferably in the range of 0.8 to 1.1 g equivalent per 1 g equivalent of metal sulfide, and particularly preferably in the range of 0.9 to 1.05 equivalent to obtain a high molecular weight polymer. If the amount is less than 0.8 g equivalent or more than 1.1 g equivalent, it is difficult to obtain a polymer with a sufficiently high molecular weight, which is not preferred. The sulfide polymer according to the present invention is a polymer of the above-mentioned dihaloaromatic compound, but a monohalo compound (not necessarily an aromatic compound) may be used to form the terminal end of the resulting polymer or to control the polymerization reaction or molecular weight. It is also possible to use a trihalo or higher polyhalo compound (not necessarily an aromatic compound) in combination to form a branched or crosslinked polymer.
Specific examples when these monohalo or polyhalo compounds are aromatic compounds will be obvious to those skilled in the art as monohalo or polyhalo derivatives of the above specific examples. Specifically, for example, if dichlorobenzene is used in combination with a small amount of trichlorobenzene, a branched phenylene sulfide polymer can be obtained. Solvent and Water The solvent used in the polymerization reaction of the present invention is an organic solvent without active hydrogen, that is, an aprotic solvent. Solvents containing active hydrogen are undesirable because they themselves may inhibit the polymerization reaction or the products produced by reactions involving active hydrogen may cause secondary harmful reactions. This solvent must be stable under the temperature and alkaline conditions encountered in the polymerization reaction of the present invention, and must not unduly inhibit the polymerization reaction of the present invention. This solvent should have at least a dissolving power capable of dissolving the metal sulfide to a concentration necessary for the reaction to provide the starting dihaloaromatic compound and S ^2- . Therefore, the solvent is usually one containing nitrogen, oxygen and/or sulfur atoms, ie a polar solvent. This solvent is desirably not capable of participating in the same dehalogenation/sulfidation reaction as the raw material dihaloaromatic compound, and is therefore desirably not a haloaromatic hydrocarbon, for example. However, if desired, an excess amount of the starting dihaloaromatic compound may function as a solvent. Therefore,
In the present invention, the phrase "in an approximate solvent" includes a case in which the raw material dihaloaromatic compound itself is used as a solvent and is apparently solvent-free. Since the solvent used in the present invention is intended to provide a controlled, minute amount of water to the polymerization reaction, it is desirable that this water as a solute can be solvated. However, in the present invention, it is not practical to confirm that the aprotic solvent and water are actually solvated, and therefore, the water provided for the polymerization reaction in the present invention is water solvated with the aprotic solvent. It is sufficient that the amount corresponds to the amount of (details will be described later). Specific examples of such approach solvents include (1) amides, such as hexamethylphosphoric acid triamide (HMPA), N-methylpyrrolidone (NMP), tetramethylurea (TMU), dimethylformamide (DMF), dimethyl Acetamide (DMA), others, (2) Etherified polyethylene glycol, such as polyethylene glycol dialkyl ether (polymerization degree is up to about 2000, alkyl group is about C ₁ to C ₂₀ ), (3) Sulfoxide, such as tetramethylene sulfoxide, dimethyl There are sulfoxides (DMSO) and others. Among these, HMPA and NMP are particularly preferred because they have high chemical stability. The amount of approach solvent used is preferably within the range of 0.1 to 10 liters per mole of sulfide used in the polymerization. If the amount of solvent is less than this, the viscosity of the reaction system becomes too high, which prevents a uniform polymerization reaction, which is not preferable. On the other hand, if the amount of solvent is too large, the amount of solvent used will be enormous compared to the amount of polymer obtained, which is not preferred from an economic standpoint. In accordance with the present invention, water is present in the polymerization reaction in an added and dissolved form in the approach solvent.
Generally, the water that should be present in the polymerization reaction of the present invention is
It is better to have as few as possible. On the other hand, even if the polymerization reaction is completely anhydrous, there is a risk that side reactions such as decomposition of the solvent by the substantially anhydrous alkaline earth metal hydroxide or sulfide may occur.
Therefore, the amount of water to be added as solvation water in the polymerization reaction of the present invention is preferably in the range of 0.01 to 2 moles per 1 g equivalent of metal sulfide. A water amount of 0.01 to 1 mol/g equivalent metal sulfide is particularly preferred. Other salts In the method for producing an aromatic sulfide polymer of the present invention, a third salt may coexist in the polymerization system in addition to the metal sulfide (A) and alkaline earth metal hydroxide (B) described above. is not preferred because it generally leads to a decrease in the molecular weight of the resulting polymer. But the following salt
In the case of (D), coexistence in the polymerization system is acceptable because the actual damage is not too great unless it coexists in large amounts. That is, carbonates, sulfates of metals selected from the group consisting of alkali metals and alkaline earth metals;
One or more tertiary salts selected from the group of sulfites, halides, phosphates, borates, hydroxides (excluding alkaline earth metal hydroxides), carboxylates and sulfonates. It is permissible for salts such as (D) to coexist in the polymerization system. It is desirable that these salts be sufficiently dehydrated. Polymerization The polymerization according to the present invention proceeds by heating the reaction mixture consisting of the above-mentioned components to a temperature in the range of 100 to 250°C. If the temperature is lower than 100°C, the reaction rate is extremely low, which is not preferable from an economic standpoint. On the other hand, if the temperature is higher than 250°C, the hydroxide (B) will not act as a catalyst but as a dehalogenating agent, which may cause an abnormal reaction and activate the decomposition of the polymer or solvent, which is not preferable.
A temperature range of 180 to 230°C is preferable because a high molecular weight product can be obtained quickly. The polymerization reaction can be carried out at a constant temperature, but it can also be carried out while increasing the temperature stepwise or continuously. When using a chemical mixture of (A) and (B) in the polymerization method of the present invention, a polymerization vessel is charged with a solvent, water, and a dihaloaromatic compound (C), and then a substantially anhydrous Add ion complex,
It is desirable to further add a third salt if necessary, stir thoroughly in the can, and then raise the temperature to carry out polymerization at the polymerization temperature. When using a physical mixture, the solvent, water, and dihaloaromatic compound (C) are charged into a polymerization reactor, and then the metal sulfide powder (A) and the alkaline earth metal hydroxide powder (B) are uniformly mixed. It is desirable to add the mixture or individual powders thereof, further add a third salt if necessary, stir and mix thoroughly in a polymerization vessel, and then raise the temperature and polymerize at the polymerization temperature. For the polymerization, various conventional polymerization methods such as a batch method, a batch method, and a continuous method can be employed. The atmosphere during polymerization is preferably a non-oxidizing atmosphere, and it is preferable to purge the system with an inert gas such as N ₂ or argon at the start of the polymerization reaction. To recover the polymer, first, after the reaction is completed, the reaction mixture is heated under reduced pressure or normal pressure to distill off only the solvent, and then the solid matter remaining in the can is mixed with water, ketones, alcohols, aromatic hydrocarbons, and halogens. Washed once or twice or more with a solvent such as hydrogenated hydrocarbon or ether,
This can then be done by neutralizing, washing with water, separating and drying. Alternatively, water, ethers,
Solvents such as halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons (those that are soluble in the polymerization solvent used and are at least non-solvents for the produced polymer) are added as precipitants. Solid products such as polymers and inorganic salts are precipitated and separated.
This can also be done by washing and drying. "Washing" in these cases can be carried out in the form of an extraction. In either method, unless an organic acid salt is allowed to coexist as a third salt, the problem of contamination due to the organic acid that should be dissolved and released in the washing water will not occur. Produced Polymer The polymer obtained by the method of the present invention (usually obtained in powder form) has a significantly higher molecular weight than conventional aromatic sulfide polymer powders and is easily oxidized. Since it is a linear polymer, it can be used as a polymer powder as it is, or by slightly oxidizing it if necessary, to provide excellent spinnability even at high melt viscosity, making it strong and heat resistant. It can be extremely easily molded into plastic films, sheets, fibers, etc. Furthermore, it can be processed into various molded products by injection molding, extrusion molding, rotary molding, etc., but even if it is thick, it is difficult to crack. Since the polymer according to the present invention falls under the category of thermoplastic polymers, various modifications applicable to thermoplastic polymers are possible. Therefore, for example,
This polymer is carbon black, calcium carbonate powder,
Powdered fillers such as silica powder and titanium oxide powder,
Alternatively, it can be filled with a fibrous filler such as carbon fiber, glass fiber, asbestos, or polyaramid fiber. This polymer can also be used in combination with one or more synthetic resins such as polycarbonate, polyphenylene oxide, polysulfone, polyarylene, polyacetal, polyimide, polyamide, polyester, polystyrene, and ABS. Experimental Examples Examples 1 to 11 1 Raw materials (1) Sulfide (A) Na ₂ S・9H ₂ O, Na ₂ S・5H ₂ O, and NaHS・
2H ₂ O is a product of Nagao Soda Co., Ltd. For CaS, use Kanto Kagaku Co., Ltd.'s first-class reagent. (2) Hydroxide (B) Ca(OH) ₂ , Mg(OH) ₂ , NaOH and Al(OH) ₃
uses special grade reagents from Junsei Kagaku Co., Ltd. (3) Solvent N-methylpyrrolidone (NMP) and hexamethylphosphoric acid triamide (HMPA) were manufactured by Kanto Chemical Co., Ltd.
Uses first class reagents. (4) Haloaromatic compound (C) para-dichlorobenzene (p-DCB) is a product of Kureha Chemical Co., Ltd. (additive-free product). Meta-dichlorobenzene (m-DCB), p,
p′-dichlorodiphenyl sulfone (DCDPS),
1,3,5-trichlorobenzene (TCB) is
Uses Tokyo Kasei Co., Ltd.'s first class reagent. (5) The third salts CaCO ₃ , Na ₂ CO ₃ , Li ₂ SO ₄ and Na ₂ HPO ₄ are
Uses special grade reagents from Kanto Kagaku Co., Ltd. 2. Preparation of chemical mixture (glassy ion complex) Add 400.0 g equivalent of Na ₂ S・9H ₂ O to 20 liters of hot water and dissolve it, and add 800.0 g equivalent of Ca(OH) ₂ or Mg(OH) ₂ to it. Equivalents of 800.0 g were each added and dissolved by heating, and the mixture was flash-evaporated using a rotary evaporator to rapidly solidify to obtain a water-containing solid. These solids are dried in a vacuum dryer at 200℃/
Each substantially anhydrous glassy ionic complex e ₁ (S ^2- /
Na ⁺ /Ca ²⁺ /OH ^- = 1:1:2:2 (g equivalent ratio))
and e ₂ (S ^2- /Na ⁺ /Mg ²⁺ /OH ^- = 1:1:2:
2 (g equivalent ratio)) was obtained. The residual water content is
They were 0.15 mol and 0.17 mol per 1 g equivalent of S ^2- . 3 Preparation of physical mixture Na ₂ S・5H ₂ O in a vacuum dryer at 200℃/2Torr
The mixture was dried under reduced pressure for 3 hours to collect plate-shaped Na ₂ S solids. It was ground in a mortar and sifted through a 9-mesh (Tyler) screen to obtain particles with a particle size of less than 2 mm. It was further dried under reduced pressure at 200° C./2 Torr for 3 hours to obtain substantially anhydrous Na ₂ Sa ₁ (water content was 0.10 mol/g equivalent of S ^2- ).
For CaS, crush the reagent in a mortar and make 9 meshes (Tyler).
Particles of 2 mm or less were collected by sifting through a screen, and dried in a vacuum dryer at 200°C/4 Torr for 6 hours to obtain substantially anhydrous CaS powder _a2 (residual water content was 0.04 mol/g equivalent). . Ca(OH) ₂ and Mg(OH) ₂ were each sifted through a 48 mesh (Tyler) screen to collect particles smaller than 0.3 mm. Then dry it in a vacuum dryer at 200℃/
Dry at 5 Torr for 6 hours to obtain virtually anhydrous Ca.
(OH) ₂ b ₁ and Mg(OH) ₂ b ₂ were obtained (residual water content is
(0.02 mol or less per 1 g equivalent). A physical mixture was prepared by mixing predetermined amounts of a ₁ and b ₁ or b ₂ using a V-type mixer, and the mixture was subjected to polymerization. 4. Preparation of the third salt CaCO ₃ , Na ₂ CO ₃ , Li ₂ SO ₄ and NaHPO ₄ were each ground in a ball mill to give 48 mesh (Tyler).
It sifters through a screen and collects particles smaller than 0.3mm.
Dry under reduced pressure at 230°C/2 Torr for 24 hours to obtain d ₁ , d ₂ ,
Obtained _d3 and _d4 . CH ₃ COONa was obtained by drying each powdered reagent under reduced pressure over P ₂ O ₅ in a desiccator to obtain d ₅ . 5 Polymerization 14 liters of solvent was charged into a 20 liter stainless steel autoclave equipped with a stirring blade, and then the measured amounts of water and dihaloaromatic compound were charged. It is charged with a measured amount of a substantially anhydrous chemical or physical mixture, optionally with the addition of a further measured amount of a third salt, melt-sealed, and after being replaced with _N2 , approximately 100
After stirring for 1 hour at °C to uniformly disperse the mixture, the temperature was raised to the polymerization temperature and polymerization was carried out for a predetermined period of time. After polymerization, the autoclave was cooled, the contents were taken out, and the contents were heated to 100℃ using a rotary evaporator.
Most of the solvent was removed by heating under reduced pressure.
Next, the solid matter was taken out, neutralized with diluted HCl, washed three times with hot water, extracted twice with acetone, and dried at about 80°C to obtain each polymer. 6 Evaluation of physical properties The melt viscosity of the obtained polymer was measured using a Koka type flow tester on a pores plate obtained by melt-pressing polymer powder without preheating (310℃,
100Kg load). These results are collectively shown in Table 1. Comparative Example 1 Raw Material Preparation NaHS.2H ₂ O was treated in the same manner as a ₁ to obtain a substantially anhydrous powder a ₃ (water content 0.15 mol/equivalent to 1 g of S ² ). For NaOH, the granular reagent was ground in a mortar to form a powder, and for Al(OH) ₃ , the powdered reagent was dried as it was in a desiccator over P ₂ O ₅ to obtain b ₃ and b ₄ , respectively. Comparative Example 1 Polymerization was carried out using the same recipe as in Example 1 or 4, except that Ca(OH) ₂ was not used. Comparative Example 2 Except for using a small amount of Ca(OH) ₂ ,
Polymerization was carried out using the same recipe as in Example 4. Comparative Example 3 Polymerization was carried out using the same recipe as in Example 9, except that Ca(OH) ₂ was not used. Comparative Example 4 Polymerization was carried out using the same recipe as in Example ₄ , except that _a3 was used instead of a1. Comparative Example 5 Polymerization was carried out using the same recipe as in Example 4, except that _b3 was used instead of _b1 . Comparative Example 6 Polymerization was carried out using the same recipe as in Example 4, except that _b4 was used instead of _b1 . These results are collectively shown in Table 2. Analysis of Results The melt viscosities of the polymers obtained in Comparative Examples 1 to 4 were significantly lower than those of Examples 1, 4, or 9. In the case of Comparative Example 5, decomposition occurred during polymerization and a normal polymer could not be obtained. In the case of Comparative Example 6, a large amount of Al ₂ O ₃ in the polymer
Otherwise, viscosity measurement was not performed because Al(OH) ₃ remained.

【table】

【table】

【table】

[Table] *1 Decomposed during polymerization *2 Viscosity was not measured because Al ₂ O ₃ etc. in the polymer could not be removed.

Claims (1)

[Claims] 1. Substantially anhydrous chemistry of a sulfide of a metal selected from the group consisting of alkali metals and alkaline earth metals (A) and an effective amount of an alkaline earth metal hydroxide (B) target or physical mixture and dihaloaromatic compound (C)
and 1 g of the sulfide (A) used in an approach solvent.
100 in the presence of 0.01 to 2 mol of added water per equivalent
A method for producing aromatic sulfide polymers, characterized by heating to a temperature of ~250°C. 2. The aromatic sulfide polymer according to claim 1, wherein the amount of alkaline earth metal hydroxide (B) used is in the range of 0.5 to 20 (g equivalent) per 1 g equivalent of sulfide (A) used. manufacturing method. 3. The method for producing an aromatic sulfide polymer according to claim 1 or 2, wherein the alkaline earth metal hydroxide (B) is Ca(OH) ₂ or Mg(OH) ₂ . 4. Any one of claims 1 to 3, wherein the amount of dihaloaromatic compound (C) used is within the range of 0.8 to 1.1 (g equivalent) per 1 g equivalent of metal sulfide (A) used. A method for producing an aromatic sulfide polymer as described in 2. 5 Alkaline earth metal hydroxide (B) and metal sulfide (A)
Any one of claims 1 to 4, wherein the mixture is a substantially anhydrous chemical mixture in which the cation components and anion components of (A) and (B) are randomly ionically bonded. A method for producing an aromatic sulfide polymer as described in 2. 6 Alkaline earth metal hydroxide (B) and metal sulfide (A)
Claim 1 wherein the mixture with the respective powders is a homogeneous substantially anhydrous physical mixture of the respective powders.
A method for producing an aromatic sulfide polymer according to any one of items 1 to 4. 7. The method for producing an aromatic sulfide polymer according to any one of claims 1 to 6, wherein the dihaloaromatic compound (C) is dichlorobenzene. 8. Production of an aromatic sulfide polymer according to any one of claims 1 to 7, wherein the dihaloaromatic compound (C) contains a small amount of a trihalo, tetrahalo or more haloaromatic compound. Law.