JPH0657748B2 - Method for producing polyary lentithioether - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polyarylene thioether, more specifically, a polyarylene thioether which can be efficiently obtained under mild polymerization conditions. It relates to the manufacturing method.

[Prior Art and its Problems] Conventionally, polyphenylene thioether (hereinafter referred to as PP
It may be abbreviated as T. ) And other polyarylene thioethers (hereinafter sometimes abbreviated as PAT) are produced by subjecting a dihalogenated aromatic compound and an alkali metal sulfide to polycondensation reaction in a polar solvent under high temperature and pressure. There is.

However, in this method, the alkali metal salt remains in the PAT and deteriorates the electrical characteristics of the PAT. There are problems such as large energy consumption and high cost.

On the other hand, as a method for polymerizing thiophenol to obtain PAT, Soviet Patent No. 698,988 is known, but this method uses an extremely expensive catalyst such as Mo Cl ₅ / CF ₃ COOH. It is industrially disadvantageous. Although a method using sulfuric acid as a catalyst is also known, it has drawbacks that many by-products and a large amount of crosslinked polymer are produced.

[Object of the Invention] The present invention has been made based on the above circumstances, and an object thereof is to solve the above problems and to provide a polyphenylene thioether having excellent electrical properties, mechanical properties, chemical properties, and the like. A polyarylene thioether, particularly a polyarylene thioether such as a substantially linear polyphenylene thioether having less by-products of a crosslinked polymer, can be simply
Another object of the present invention is to provide a method for producing a polyarylene thioether, which is industrially remarkably advantageous and can be obtained at low cost under mild polymerization conditions.

[Means for Solving Problems] The inventors of the present invention have conducted extensive studies to solve the problems, and as a result, use thiophenol as a raw material monomer,
It was found that a method of polymerizing this using a Lewis catalyst in the presence of an oxidizing agent is extremely effective for achieving the object of the present invention, and based on this finding, the present invention was completed.

That is, the present invention has the general formula [I] (In the formula [I], R ^{1 to} R ⁴ each represent a substituent selected from the group consisting of a hydrogen atom, a lower alkyl group, a halogen atom and a lower alkoxy group.

Note that R ^{1 to} R ⁴ may be the same type or different types. ) The thiophenol represented by the formula (3) is polymerized in the presence of an oxidizing agent using a Lewis acid catalyst.

The details of R ^{1 to} R ⁴ in the general formula [I] are as follows.

That is, specific examples of each of R ^{1 to} R ⁴ include, for example, hydrogen atom; methyl group, ethyl group, propyl group, 1-methylethyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group. , Lower alkyl groups such as 1,1-dimethylethyl group, pentyl group, hexyl group, heptyl group, octyl group; fluorine atom, chlorine atom, bromine atom, iodine atom; methoxy group, ethoxy group, propoxy group, isopropoxy group And lower alkoxy groups such as butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group and hexyloxy group.

Among these, a hydrogen atom; a lower alkyl group such as a methyl group and an ethyl group; a lower alkoxy group such as a fluorine atom, a chlorine atom and a methoxy group are preferable, and a hydrogen atom, a methyl group, an ethyl group and a chlorine atom are particularly preferable. Are preferred.

The thiophenols represented by the general formula [I] may be used alone or in combination of two or more.

Examples of the thiophenols represented by the general formula [I] include thiophenol, 2-methylthiophenol, 2-ethylthiophenol 2-propylthiophenol, 2- (1-methylethyl) thiophenol, and 2
-Butylthiophenol, 2- (1-methylpropyl)
Thiophenol, 2- (2-methylbutyl) thiophenol, 2- (1,1-dimethylethyl) thiophenol, supentylthiophenol, 2-hexylthiophenol, 2-octylthiophenol, 2-fluorothiophenol, 2 -Chlorothiophenol, 2-glomothiophenol, 2-iodothiophenol, 2-methoxythiophenol, 2-ethoxythiophenol,
2-propoxythiophenol, 2-isopropoxythiophenol, 2-butoxythiophenol, 2-sec
-Butoxythiophenol, 2-isobutoxythiophenol, 2-tert-butoxythiophenol, 2-pentyloxythiophenol, 2-hexyloxothiophenol, 2,6-dimethylthiophenol, 2,6-
Diethylthiophenol, 2-methyl-6-ethylthiophenol, 2,6-difluorothiophenol, 2-
Methyl-6-fluorothiophenol, 2-ethyl-6
-Fluorothiophenol, 2,6-dichlorothiophenol, 2,6-dibromothiophenol, 2-methyl-6-chlorothiophenol, 2,6-dimethoxythiophenol, 2-methyl-6-methoxythiophenol, 2 , 3-Dimethylthiophenol, 2,3-diethylthiophenol, 2,3-difluorothiophenol, 2-methyl-3-fluorothiophenol, 2-bromo-3-methylthiophenol, 2,3-dimethoxythiophenol, 2-methyl-3-methoxythiophenol, 2,3-dichlorothiophenol, 2-methyl-3-chlorothiophenol, 3-chloro-2-methylthiophenol, 2,5-dimethylthiophenol,
2,5-difluorothiophenol, 2,5-diethylthiophenol, 2-methyl-5-fluorothiophenol, 2-methyl-5-ethylthiophenol, 2-fluoro-5-methylthiophenol, 2,5-dichloro Thiophenol, 2,5-dimethoxythiophenol,
2-methyl-5-chlorothiophenol, 2-methyl-
5-methoxythiophenol, 2-chloro-5-methylthiophenol, 2-methoxy-5-methylthiophenol, 2-chloro-5-fluorothiophenol, 2-
Ethyl-5-chlorothiophenol, 2-chloro-5-
Ethylthiophenol, 3,5-dimethylthiophenol, 3,5-difluorothiophenol, 3,5-dimethoxythiophenol, 3,5-diethylthiophenol, 3,5-dichlorothiophenol, 3-methyl-5
-Fluorothiophenol, 3-methyl-5-chlorothiophenol, 3-methyl-5-methoxythiophenol, 2,3,5-trimethylthiophenol, 2,3,3
5-trifluorothiophenol, 2,3,5-triethylthiophenol, 2,3,5-trichlorothiophenol, 2-methyl-3,5-difluorothiophenol, 2,3,5,6-tetramethylthiophenol ,
2,3,5,6-tetrafluorothiophenol, 2,
3,5,6-tetrachlorothiophenol, 2,3,
5,6-tetramethoxythiophenol, 2,3,5
6-tetraethylthiophenol, 2,6-dimethyl-
3,5-tetrafluorothiophenol, 2,6-diethyl-3,5-difluorothiophenol, 2,6-diethyl-3,5-dichlorothiophenol, 2,6-diethyl-3,5-dimethylthiophenol 2,6-diethyl-3,5-dimethoxythiophenol, 2,6-
Examples thereof include dimethyl-3,5-dichlorothiophenol and 2-ethyl-6-ethyl-3,5-difluorothiophenol.

Among these, thiophenol, 2-methylthiophenol, 2-ethylthiophenol, 2-fluorothiophenol, 2-chlorothiophenol, 2-methoxythiophenol, 2,6-dimethylthiophenol, 2,6-diethyl, among others. Thiophenol, 2,6-difluorothiophenol, 2,6-dichlorothiophenol, 2,6-dimethoxythiophenol, 2,3,5
6-Tetrachlorothiophenol, 2,3,5,6-tetramethylthiophenol thiophenol and the like are preferable.

These compounds may be used alone or in combination of two or more.

In the method of the present invention, the thiophenol represented by the general formula [I] is used as a reaction raw material to polymerize the compound to give a compound of the general formula [II]. (However, in the formula [II], R ^{5 to} R ⁸ have the same meanings as R ^{1 to} R ⁴ in the general formula [I], and n represents an integer of 2 or more.). A polyarylene thioether having a main chain structure, particularly a linear or substantially linear polyarylene thioether having a remarkably low degree of crosslinking can be efficiently obtained with a high selectivity.

Examples of the Lewis acid catalyst used in the method of the present invention include halogen compounds such as metals, halogen compounds such as oxyhalogen compounds, sulfates, nitrates, phosphates, chlorates, bromates, and silicates. Examples include known so-called Lewis acids (formal aprotic acids) such as oxo acid salts such as metallosilicates and hetero acid salts, fluorosilicates, acidic oxides or Lewis acid compositions containing them. .

Incidentally, these Lewis acids or Lewis acid compositions are partly classified by the coexistence of proton donating substances such as those which are formally classified as aprotic acids, and trace amounts of water of crystallization, water of structure, water of adsorption and the like. Is known to change into a protic acid, and even when these aprotic Lewis acid catalysts are used in a general acid-catalyzed reaction, protons may possibly be involved in the acid catalysis. It is pointed out that there is.

Also in the method of the present invention, the Lewis acid or the Lewis acid catalyst composition can be used in a state of containing water or a proton donating substance in an amount such that the catalytic activity is not substantially lost, or in the presence thereof. .

When using hydrates such as the various metal salts,
If necessary, activation treatment such as heat treatment may be performed to use the Lewis acid catalyst in the method of the present invention.

In the method of the present invention, substances which can be usually suitably used as the Lewis acid catalyst include, for example, Periodic Tables IIa to VI.
A halide of at least one element selected from the group Ia, VIII, IIb to VIb elements, an oxyhalide,
Examples thereof include a halogen compound such as a halogen complex, and among them, a halide is preferable.

Examples of these halogen compounds include beryllium halides such as BeF ₂ , BeCl ₂ and BeBr ₂ , magnesium halides such as MgF ₂ , MgCl ₂ and MgBr ₂ , lanthanum halides such as LaF ₃ and LaCl ₃ , CeF. Cerium halides such as ₃ , CeCl ₃ , CeF ₄ , CeCl ₄ , and CeBr ₃ , titanium halides such as TiCl ₂ , TiCl ₃ , TiF ₄ , TiCl ₄ , TiBr ₄ , TiI ₄ , and TiCl ₂ Br ₂ , ZrF ₄ , ZrCl _4, ZrBr zirconium halides such as _4, hafnium halide such as _{HfCl 4, VCl 2, VCl 3} , VF 3, VCl 4, vanadium halides such as _{VBr 4, NbCl 3, NbBr 3} , NbF 5, NbCl _5, a halogenated niobium such _{NbBr 5, TaF 5, TaCl 3} , TaCl 5, TaBr 3, tantalum halide such as _{TBr 5, CrF 3, CrCl 2} , CrCl 3, CrBr 2, CrBr 3, CrI 2, CrI 3 Chromium halide, such as MoF ₃ , MoF ₄ , MoF ₅ , MoF ₆ , MoCl ₂ , MoCl ₃ , MoCl ₄ , MoCl ₅ , MoBr ₃ ,
Molybdenum halides such as MoBr ₄ , MoBr ₅ , MoI ₅ , tungsten halides such as WF ₄ , WF ₆ , WCl ₂ , WCl ₄ , WCl ₅ , WCl ₆ , WBr ₆ , and WI ₆ , MnF ₂ , MnCl ₂ , MnBr ₂ , manganese halides such as MnI ₂ , rhenium halides such as ReF ₆ , ReCl ₃ , ReCl ₅ , iron halides such as FeF ₂ , FeCl ₂ , FeBr ₂ , FeI ₂ , FeCl ₃ , FeBr ₃ , FeI ₃ , CoF ₂ , CoCl ₂ , CoBr ₂ , CoI ₂ , CoCl ₃ , CoBr ₃ , CoI ₃ and other cobalt halides, RuCl ₃ , RuBr ₃ , RuI ₃ and other ruthenium halides, NiF ₂ , NiCl ₂ , NiBr ₂ , NiI nickel halide such as _{2, PdF 2, PdCl 2,} PaBr 2, palladium halides such as _{PdI 2, RhCl 3, RhBr 3} , halogenated rhodium such as _{RhI 3, PtF 2, PtCl 2} , PtBr 2, PtI 2, PtCl _4, platinum halides, such as _{PtBr 4, CuCl, CuF 2,} CuCl 2, copper halides such as _{CuBr 4, CuI 2, AgF,} AgCl, AgBr, halogen such as AgI Silver halide, zinc halide such as ZnF ₂ , ZnCl ₂ , ZnBr ₂ , ZnI ₂ , cadmium halide such as CdF ₂ , CdCl ₂ , CdBr ₂ , CdI ₂ , mercury halide such as Hg ₂ Cl ₂ , HgCl ₂ halogenated such as BF _3, BCl _3, boron halide such as _{BBr 3, BI 3, AlF 3} , AlCl 3, AlBr 3, Haroken aluminum such as _{AlI 3, GaF 3, GaCl 3} , GaBr 3, GaI 3 Indium halides such as potassium, InF ₃ , InCl ₃ and InBr ₃ , thallium halides such as TlF ₃ , TlCl ₃ , TlCl and Tl ₂ Br ₄ , silicon halides such as SiF ₄ and SiCl ₄ , GeF ₄ and GaCl ₄ , Germanium halide such as GeBr ₄ , tin halide such as SnF ₂ , SnF ₄ , SnCl ₂ , SnCl ₄ , SnBr ₂ , SnBr ₄ , SnI ₂ , SnI ₄ , PbF ₂ , PbF ₄ , PbCl ₂ , PbCl ₄ , PbCl ₄ , PbBr _2, PbI ₂ halogen such as lead iodide, PF _5, phosphorus halides such as PCl _5, AsF _5, AsCl ₅ halogenated, such as arsenic, SbF _5, SbCl ₅ , Antimony halides such as SbBr ₅ , bismuth halides such as BiF ₃ and BiCl ₃ , various halides such as tellurium halides such as TeCl ₂ and TeCl ₄ , ZiCOl ₂ , Ti (OH) Cl ₃ , MoOCl, MoO Oxyhalides such as ₂ Cl ₂ , WOCl ₄ , WO ₂ Cl ₂ , GrOCl ₄ , GrO ₂ Cl ₂ , VOCl ₃ , POCl ₃ and SO ₂ Cl ₂ can be mentioned.

Of these, among elements selected from helium, magnesium, zinc, boron, aluminum, gallium, tin, antimony, bismuth, tellurium, titanium, zirconium, niobium, tantalum, chromium, molybdenum, tungsten, iron, cobalt, and copper. Halides and the like are preferable, and aluminum chloride, titanium tetrachloride, antimony pentachloride, tungsten hexachloride and the like are particularly preferable.

In addition, these compounds are substantially anhydrous, as a complex having a ligand that easily dissociates in a reaction form such as an ether complex, an alcohol complex, a carboxylic acid complex, or a nitrile complex, or have substantially catalytic activity. Can be used in a state of containing water or other proton donating substance in an amount that does not destroy the.

The Lewis acids or Lewis acid compositions such as these compounds may be used alone or in combination by mixing or combining two or more kinds.

Furthermore, these Lewis acids or Lewis acid compositions,
Other compounds such as alkali metal compounds may be mixed or combined in an amount within a range that does not substantially destroy the catalytic activity.

The oxidizing agent is not particularly limited as long as it has an oxidizing ability to oxidize thiophenol and produces diphenyl disulfide, and does not substantially deactivate the catalytic activity of the Lewis acid catalyst used. There is no.

Specific examples of such substances include oxidizing gases such as oxygen gas, ozone and chlorine, or oxidizing gas compositions such as air containing the same; copper (II) oxide, silver (II) oxide, iron (III) oxide. , Cobalt (III) oxide, nickel oxide (I
I), manganese (IV) oxide, ruthenium (III) oxide, rhodium (III) oxide, platinum (II) oxide, platinum oxide (I
V), palladium (II) oxide, rhenium (IV) oxide, chromium (VI) oxide, molybdenum (VI) oxide, vanadium (V) oxide, thallium (III) oxide, tin (IV) oxide, lead (IV) oxide , Sulfur oxide (VI), sulfur oxide (IV), tellurium oxide (IV), arsenic oxide (V), bismuth oxide (II
I), bismuth (V) oxide, heteropoly acid, perovskite, potassium permanganate, perrhenic acid, sodium nichrome, sulfuric acid, chloric acid, sodium chlorate, hypochlorous acid, sodium hypochlorite, etc. Compounds, oxidizing complex oxides, oxidizing oxo acids, oxidizing oxo acid salts; antimony subchloride, copper (II) chloride, ferric chloride, cobalt (II) chloride, tin (IV) chloride, tellurium chloride (IV ), Lead (IV) chloride, palladium (II) chloride, trethenium (III) chloride, platinum (II) chloride, platinum (IV) chloride, silver (I) chloride, chromium dichloride, molybdenum oxychloride, etc. Examples thereof include metal chlorides or oxidizable metal oxychlorides, oxidizable simple substances such as iodine and iodine.

Among these, particularly preferable examples include copper (II) oxide, iodine, oxygen gas or air, antimony pentachloride, sulfuric acid, and the like, and further preferable examples include iodine, antimony pentachloride, oxygen, or Air, etc. can be mentioned.

These oxidizing agents may be used alone or in combination of two or more.

Of these oxidizing agents, one that can be used as the Lewis acid catalyst can also serve as the Lewis acid catalyst by using one of them. Examples thereof include oxidizing metal halides such as antimony pentachloride and ferric chloride.

Among these oxidizing agents, one that can also be used as a solvent for the polymerization reaction can be used as a solvent and an oxidizing agent by one of them. Examples of such a material include sulfuric acid.

In the method of the present invention, at least one thiophenol represented by the general formula [I] is added to at least 1
The polyarylene thioether is prepared by polymerizing in the presence of the oxidizing agent or in the atmosphere using the seed Lewis acid catalyst.

This polymerization can be performed in the absence of a solvent, but it is usually desirable to perform it in the presence of a solvent.

As the solvent, any solvent can be used as long as it does not substantially eliminate the catalytic effect of the Lewis acid catalyst used, but a solvent that can dissolve a normally used monomer is preferable.

Usually, as a solvent which can be preferably used, for example, nitromethane, dichloromethane, dibroloethane, tetrachloroethane, nitrobenzene and the like can be mentioned. In addition to these, solvents generally used in Friedel-Crafts reaction, cationic polymerization and the like are also included. It can be suitably used by appropriately selecting.

These solvents may be used alone or in combination of two or more, or if necessary, for example, an inert solvent such as an aromatic hydrocarbon such as benzene or toluene may be appropriately used. You may mix and use it.

The ratio of the Lewis acid catalyst [A] and the thiophenol [B] used in the polymerization reaction depends on other conditions such as the catalyst used, the type of solvent or monomer, and the concentration of impurities such as water in the system. It cannot be uniformly defined because it is different, but the [A] / [B] (molar ratio) is usually 0.05 to 30, preferably 0.5 to 8.

If this value is less than 0.05, the polymerization rate becomes slow, and the yield of the polymer may decrease. On the other hand, when it exceeds 30, the cost of the catalyst becomes high, which is economically disadvantageous.

The use ratio of the oxidizer [C] depends on the kind of the oxidizer used,
It cannot be specified uniformly because it remarkably differs depending on other conditions such as reaction conditions, but [C] / [B] (molar ratio) is usually
It is sufficient if it is 0.5 or more, preferably about 1 to 10.

The reaction efficiency can be improved by appropriately adjusting the amount and concentration of the oxidizing agent depending on the type and the polymerization conditions.

The reaction temperature in the polymerization is not uniform depending on the type of catalyst and monomer used, but is usually -5 to 150 ° C, preferably 0 to 50 ° C.

The reaction pressure is not particularly limited, and usually normal pressure or the self-pressure of the reaction system can be suitably used. However,
If necessary, it can be carried out under pressure using a diluting gas or the like that does not hinder the polymerization reaction.

The reaction time is usually 1 to 80 hours, preferably 8 to 72 hours, though it varies remarkably depending on other conditions such as the catalyst to be used, the kind of the monomer and its use ratio, and the reaction temperature.

In constructing the polymerization reaction system, there is no particular limitation on the order / method of blending the Lewis acid catalyst, the thiophenol, the oxidant, and the solvent, and each of them may be simultaneously or stepwise in various orders / modes. Can be blended with.

The reaction system is not particularly limited, and any of a continuous system, a semi-continuous system and a batch system may be used. When using the batch system, it is desirable to stir the reaction system.

The polymerization method may be a suspension polymerization method or a bulk polymerization method, but a solution polymerization method is usually preferable.

This post-treatment can be performed according to various known methods.

An example of this post-treatment when the polymerization is carried out by solution polymerization is as follows.

That is, when the polymerization reaction is completed or progressed to a required degree, the reaction mixture is brought into contact with water, a lower alcohol such as methanol or a mixed solution thereof to deactivate the catalyst, and at the same time, the product polymer is removed. Allow it to settle. At this time, if necessary, a polymerization terminator such as a basic substance may be used in combination.

The precipitated polymer is separated from the liquid by a separation operation such as ordinary filtration. The separated polymer is washed or neutralized / washed with a washing solution such as an alkaline aqueous solution, if necessary, and further, if necessary,
After washing, such as dissolution / reprecipitation / separation / methanol washing, using an appropriate solvent and reprecipitation liquid, as many times as necessary, it can be dried and recovered as polyarylene thioether purified to various purities. .

As the solvent used for the dissolution / reprecipitation, for example, N-methylpyrrolidone is preferably used from the viewpoint of efficiently dissolving the polymer.

Further, as the reprecipitation liquid and the cleaning liquid, for example, water, methanol, a mixed liquid thereof, and the like, particularly methanol can be preferably used.

On the other hand, unreacted monomers, by-produced low molecular weight compounds, solvents, methanol, etc. in the mixed liquid separated from the polymer are purified and recovered by a normal distillation operation, and repeatedly, in a reaction system or a post-treatment step, or other Can be effectively used for various purposes.

The polyarylene thioether such as polyphenylene thioether obtained by the method of the present invention has heat resistance,
It has excellent chemical resistance and various mechanical properties such as rigidity, strength, impact resistance, and abrasion resistance, and in particular, since it does not contain salt, which has been a problem in the past, that deteriorates insulation resistance, It is an engineering plastic that has excellent electrical properties such as insulation resistance, and also has excellent processability due to the fact that the structure of the polymer is substantially linear. It can be suitably used as equipment parts, machine parts, materials and the like in various fields / related fields such as paints, automobiles, and chemicals.

A reaction mixture containing the desired polymer can be obtained by the method described above.

The desired polymer can be recovered in various purities by subjecting the reaction mixture to various post-treatments.

[Advantages of the Invention] According to the present invention, since a specific raw material monomer and a specific catalyst are used, the reaction conditions are mild, the manufacturing method is simple, and the raw material and the catalyst are inexpensive. Advantageous polyarylene thioethers can be provided, in particular a process for preparing substantially linear polyarylene thioethers with a significantly lower degree of crosslinking.

[Example] (Example 1) 2.18 g of thiophenol was dissolved in 100 ml of nitromethane, 4 g of iodine was mixed, and after 1 hour, aluminum chloride 10 was added.
After mixing g and reacting for 24 hours, the reaction solution was dropped into methanol to obtain a poly (p-phenylene thioether) precipitate. The obtained precipitate was washed with an alkaline aqueous solution, dissolved in N-methylpyrrolidone, and reprecipitated in methanol to obtain a purified polymer. The g yield of the purified polymer was 85%, and the melting point was 160 to 180 ° C.

The structure of the polymer was determined by the following measurement results.

Elemental analysis (theoretical value) C66.1% (66.6), H3.79% (3.7), S29.
4 IR spectrum ν _CH = 3000, 3050 cm ^-1 , ν _{C = C} 1380, 1460, 1560 cm ^1- δ _CH = 820 cm ^-1 X-ray diffraction θ = 9.5, 10.5 ° ¹³ C-NMR δ (phenyl C) = 135 ppm spectrum (Example 2) 4.15 g of 2,6-diethylthiophenol was dissolved in nitrobenzene, mixed with antimony pentachloride and reacted at 0 ° C for 3 days to give poly (2,6-diethyl-1,4-phenylenethioether). A powdery precipitate was obtained. This precipitate was purified in the same manner as in Example 1 to obtain 2.9 g of purified polymer. The g yield of this polymer is 70%, the melting point is 167-182 ° C,
The number average molecular weight determined by the VPO method was 4,800.

The polymer structure was confirmed by IR spectrum, elemental analysis and ¹ H-NMR.

IR spectrum ν _CH = 2890, 2945, 2980cm ^-1 ν _CC = 1380, 1465cm ^-1 , δ _CH = 890cm ^{-1 1} H-NMR δ (-CH ₃ 1H) = 1.25ppm, δ (-CH ₂ -4H) ＝ 2.70ppm δ (phenyl 2H) ＝ 7.00ppm Elemental decomposition (theoretical value) C71.5% (73.2), H7.91% (7.3), S19.4
4 (19.5) (Example 3) 2-Methyl - thiophenol (12.4 g) was dissolved in dichloromethane 25M1, TiCl ₄ (30M1) and thionyl chloride (15 m
1) was added and reacted at 20 ° C. in the presence of oxygen for 1 day. Then, 6.49 g of powdered poly (2-methylphenylene thioether) purified by the same procedure as in Example 1 was obtained.
The polymer structure was confirmed by the following data.

IR spectrum ν _CH = 2845, 2910, 2950cm ^-1 ν _CC = 1375, 1440, 1550cm ^-1 δ _CH = 870cm ^{-1 1} H-NMR δ (-CH ₃ 3H) = 2.35ppm, spectrum δ (phenyl 3H) = 7.15ppm Elemental analysis (theoretical value) C67.7% (68.9), H4.98% (4.92), S25.9% (26.2)

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Claims (5)

[Claims] 1. A general formula [I] (In the formula [I], R ^{1 to} R ⁴ each represent a substituent selected from the group consisting of a hydrogen atom, a lower alkyl group, a halogen atom and a lower alkoxy group. In addition, R ^{1 to} R ⁴ May be of the same kind or of different kinds.) The thiophenols represented by the formula (1) are polymerized in the presence of an oxidizing agent using a Lewis acid catalyst. Method for producing arylene thioether. 2. The method for producing a polyarylene thioether according to claim 1, wherein the polyarylene thioether is a linear or substantially linear polyarylene thioether. 3. The Lewis acid catalyst is a periodic table IIa to VIIa.
A process for producing a polyarylene thioether according to claim 1 or 2, which is a Lewis acid comprising a halogen compound of at least one element selected from Group I, Group VIII, and Groups Ib to VIb. . 4. The Lewis acid catalyst is aluminum chloride,
The method for producing a polyarylene thioether according to any one of claims 1 to 3, which is titanium tetrachloride or antimony pentachloride. 5. The method according to claim 1, wherein the oxidizing agent is one or more selected from the group consisting of iodine, antimony pentachloride, oxygen, copper (II) oxide and iron (III) chloride. A method for producing the polyarylene thioether according to any one of the items 1 to 5.