JPS63213527A - Production of polyarylene thioether - Google Patents

Abstract

PURPOSE:To industrially and advantageously obtain the titled polymer under a mild reaction condition simply by using an inexpensive raw material and an inexpensive catalyst, by polymerizing a specific thiophenol in the presence of an oxidizing agent by the use of the Lewis acid catalyst. CONSTITUTION:A thiophenol (preferably thiophenol, 2-methylthiophenol, etc.) shown by formula (R<1>-R<4> are H, lower alkyl, halogen or lower alkoxy) is polymerized in the presence of an oxidizing agent [preferably iodine, antimony pentachloride, oxygen, copper oxide (II) or iron oxide (III)] by the use of Lewis acid catalyst (preferably aluminum chloride, titanium tetrachloride or antimony pentachloride) preferably at 0-50 deg.C for 8-72hr to give the aimed polymer shown by formula II (R<5>-R<8> are as shown for R<1>-R<4>).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing polyarylene thioether, and more specifically, to a method for producing polyarylene thioether, which can be efficiently obtained under mild polymerization conditions. It concerns the manufacturing method.

[Prior art and its problems] Conventionally, polyphenylene thioether (hereinafter referred to as PP)
It is sometimes abbreviated as T. ) and other polyarylene thioethers (hereinafter sometimes abbreviated as FAT).

) is produced by subjecting a dihalogen aromatic compound and an alkali metal sulfide to a polycondensation reaction in a polar solvent under high temperature and pressure.

However, in this method, (1) Al and potassium metal salts remain in the FAT, deteriorating the electrical properties of the FAT. ■There were problems such as high energy consumption and high costs.

On the other hand, as a method for obtaining FAT by polymerizing thiophenol, Soviet Patent No. 898.988 is known, but this method uses a very expensive catalyst such as No C15/CF3COOH, which makes it difficult to produce industrially. This is disadvantageous.

A method using sulfuric acid as a catalyst is also known, but it has the drawbacks of producing many by-products and producing a large crosslinked polymer.

[Objective of the invention] This invention has been made based on the above-mentioned circumstances, and its purpose is to solve the above-mentioned problems and to provide polyphenylene thioether etc. that have excellent electrical properties, mechanical properties, chemical properties, etc. Polyarylene thioethers, especially polyarylene thioethers such as substantially linear polyphenylene thioethers with less cross-linked polymer by-products,
The object of the present invention is to provide an extremely industrially advantageous method for producing polyarylene thioether, which can be obtained at low cost under mild polymerization conditions.

[Means for Solving the Problems] As a result of intensive research to solve the above problems, the inventors used thiophenol as an IX ingredient, and in the presence of an oxidizing agent, It has been discovered that a method of polymerization using a Lewis catalyst is extremely effective in achieving the object of the present invention, and based on this knowledge, the present invention has been completed.

(1) In the general formula [Il, lit, R4 are each,
Represents 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, R1-R4 may be the same type or different types.) The thiophenols represented by ) can be polymerized using a Lewis ugly catalyst in the presence of an oxidizing agent. This is a method for producing polyarylene thioether characterized by the following.

A more detailed explanation of R4 in the general formula [Il] is as follows.

That is, as specific examples of each of the above 1it, , 1 (4), for example, hydrogen atom: methyl group, ethyl group,
Propyl group, l-methylethyl group, butylno^, l-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, pentyl group, hexyl group, heptyl group,
Lower alkyl groups such as octyl groups: fluorine atom, chlorine atom, bromine atom.

Iodine atom; methoxy group, ethoxy group, propoxy group,
Impropoxy group, butoxy group, imbutoxy group, 5
Examples include lower alkoxy groups such as ee-butoxy group, terk-butoxy group, pentyloxy group, and hexyloxy group.

Among these, hydrogen atoms: methyl group, ethyl group, lower alkyl groups: fluorine atom, chlorine atom,
A lower alkoxy group such as a methoxy group is preferred, and a hydrogen atom, methyl group, ethyl group, chlorine atom, etc. are particularly 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-ethylthiophenol.
-Butylthiophenol, 2-(1-methylpropyl)thiophenol, 2-(2-methylbutyl)thiophenol, 2-(1,1-dimethylethyl)thiophenol, supentylthiophenol, 2-hexylthiophenol , 2-octylthiophenol, 2-fluorothiophenol, 2-chlorothiophenol, 2-bromothiophenol, ? -iodothiophenol, 2-
Methoxythiophenol? -Ethoxythiophenol, 2-propoxythiophenol, 2-impropoxythiophenol, 2-butoxythiophenol, 2-5
ec-butoxythiophenol, 2-imbutoxythiophenol, 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-butoxythiophenol, 2,3-dimethylthiophenol, 2.3
-diethylthiophenol, 2,3-difluorothiophenol, 2-methyl-3-fluorothiophenol,
2-Blue 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-dichlorothiophenol, 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,
3.5-trifluorothiophenol, 2,3.5-triethylthiophenol, 2,3.5-1-lichlorothiophenol, 2-methyl-3,5-difluorothiophenol, 2,3,5.6 -Titramethylthiophenol, 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-danityl-3,5-dimethylthiophenol,
Examples include 2,6-diethyl-3,5-dimethoxythiophenol, 2,6-dimethyl-3,5-dichlorothiophenol, and 2-methyl-6-ethyl-3,5-difluorothiophenol.

Among these, thiophenol, 2-methylthiophenol, 2-ethylthiophenol, 2-fluorothiophenol, 2-chlorothiophenol, 2-methoxythiophenol, 2,6-dimethylthiophenol, 2,6-dimethylthiophenol, Nitylthiophenol, 2,6-cyfluorothiophenol, 2,6-dichlorothiophenol,
2゜6-Simethoxythiophenol, 2,3,5.6-
Tetrachlorothiophenol, 2,3,5.6-titramethylthiophenol thiophenol, and the like are preferred.

Note that these compounds may be used alone.

You may use two or more types in combination.

In the method of the present invention, thiophenols represented by the general formula [I] are polymerized using as a reaction raw material.

(1) In the general formula [I[], R5-R8 are represented by the general formula [I].
Polyarylene thioether having the main chain structure represented by R1-R4 in R1-R4, where n represents an integer of 2 or more; 4. A linear or substantially linear polyarylene thioether having an extremely low degree of crosslinking in ν can be obtained efficiently with high selectivity.

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

Note that some of these Lewis acids or Lewis acid compositions are formally classified as aprotic acids, and some of them are due to the coexistence of proton-donating substances such as trace amounts of water such as crystal water, structured water, and adsorbed water. is known to change into a protic acid, and even when these aprotic Lewis acid catalysts are used in general acid-catalyzed reactions, there is a possibility that protons may be involved in the acid-catalyzed reaction. One thing has been pointed out.

Also in the method of this invention, the Lewis acid or Lewis acid catalyst composition can be used in a state containing or in the coexistence of water or a proton-donating substance in an amount that does not substantially eliminate the catalytic activity. .

In addition, when using hydrates of the various metal salts, etc.,
If necessary, it can be used as a Lewis acid catalyst in the method of the present invention after being subjected to an activation treatment such as heating.

In the method of the present invention, substances that can be normally suitably used as the Lewis acid catalyst include, for example, those in the periodic table IIa to
■A halide or oxyhalide of at least one element selected from the elements of group A, group II, and group nb to vtb,
Examples include halogen compounds such as halogen complexes, among which halides are preferred.

Examples of these halogen compounds include beryllium halides such as BeF2, BaCuz, and BeBr2.

MgF2, HgC12, MgBr2, etc. 17) Magnesium halides.

Lanthanum halides such as LaF3 and LaCJ13.

CeFx, CeC13, CeFa, CeC1a
, cerium halides such as CeBr3, Tici 2. TiCjL z, Tih, T
ick i, TiBr5. Ti1a, TrClzBr
2. Titanium halides such as.

ZrF4. Zirconium halides such as ZrCfL 4 and ZrBr1, hafnium halides such as HfCdLs /Z.

VClt, VCJ13, VF3, VCla
, VBr4 (1) Vanadium halide.

NbCnz, NbBrz, NbF3, NbC1s
, Niobium halides such as NbBr5, TaF5, TaCl3, TaCjLs, TaB
r3. ↑Tantalum halides such as Brs, CrF3, CrCn2. CrCn3. CrBr2
．． Chromium halides such as CrBr3, Orb, Crh, MoF3, MoFa, MoFs,
MOF6, No(j17, MoCfL:+, NoCu
4. How15, MoBr+, Mo
Molybdenum halides such as Bra, MoBr5, Mo1s, WFa, WF6. 'dc12.
'dC intersection 4, wC sentence 5. vCC60WBr6, W16
Tungsten halides such as MnF2, HnCn
2, manganese halides such as NnBr2, Nn12, rhenium halides such as ReF6, ReCl3, Re05, FeF2, FeCfL2, FeBr2,
Fe12, FeCl3°FeBr3. Fe1
Iron halides such as 3, GaF2, Ca1l2
, CoBr2, Co I2, CaCO2, CoB
r3, (cobalt halide such as OH3.

Ruthenium halides such as RuC13, RuBr3, Ru1x, NiF2, NiCl2. Nickel halides such as old Br2, Ni12, PdF2. PdC12, PaBr2, Pd12
Palladium halides such as RhC13, RhBrz, Rhl3, PtF2, PtC12, PtBr2,
Platinum halides such as PtI2, PtC15, PtBrA, CuC1, CuF2, CuC12, CuBr2, Cu
Copper halides such as El, silver halides such as AgF, AgC1, AgBr, Agl, ZnF2, ZnCfJ, 2, ZnBr2
, halogenated salivary lead such as ZnI2, CdF2. CtiCl2, CdBr2, G
Cadmium halides such as dI2, mercury halides such as Hg2Cfly, NiCl2,
Boron halides such as BF3, BCl3, BBr3, BI3.

Aluminum helokenide such as A-F3, An-C13, A-Br3, and A-I3.

GaF3, GaCJl3, GaBr3, Ga
(7) Indium halides such as potassium halides, IJIF3, InC13, and InBr3.

Tlh, thallium halides such as CfB, TI C1, TJlzBrs, silicon halides such as SiF4.5iC1a, GeF
4, Ge (fL4. Germanium halides such as GeBr4, SnF2, '; nFa, 5nCfL2, SnC;
fLs, SnBr2゜SnBrs, 5n12.5
Tin halides such as n14.

PbF2. PbF4, PbCl2, pbc sentence 4
, lead halides such as PbBr2, Pb12, phosphorus halides such as PFs, PCfLs, As
F5. Arsenic halides such as AsCl5.

Antimony halides such as SbF5, SbC, and 5bBrs.

BiF3. Bismuth halides such as B1C13,
Various halides such as tellurium halides such as TeC12, TeC1a, ZrC0fL2, Ti(OH)(J13, Mo0
GJ1, MOO2C12, WOCl, WO2C1
2, Cr0C1a, Gra2C12, VOCJ13,
Oxy/'i such as POCJ13, SO2CfLz
Examples include rogens.

Among these, beryllium, magnesium.

Preferred are halides of elements selected from zinc, boron, aluminum, gallium, tin, antimony, bismuth, tellurium, titanium, zirconium, niobium, tantalum, chromium, molybdenum, tungsten, iron, cobalt, and copper, and particularly, Preferred are aluminum chloride, titanium tetrachloride, antimony pentachloride, tungsten hexachloride, and the like.

Note that these compounds can be used as substantially anhydrous compounds, as complexes having a ligand that can be easily separated in the reaction layer, such as ether complexes, alcohol complexes, carboxylic acid complexes, or nitrile complexes, or as substantially catalytically active compounds. It can be used in a state containing water or other proton-donating substances in an amount that does not destroy the proton-donating substance.

Further, the Lewis acids or Lewis acid compositions such as these compounds may be used alone or in combination by mixing or compounding two or more.

Furthermore, these Lewis acids or Lewis acid compositions are
Other compounds such as alkali metal compounds can also be mixed or used in combination in amounts that do not substantially destroy the catalytic activity.

The oxidizing agent is particularly limited as long as it has an oxidizing ability capable of oxidizing thiophenol to produce diphenyl disulfide and does not substantially deactivate the catalytic activity of the Lewis acid catalyst used. There isn't.

Specific examples of such things include oxidizing gases such as oxygen gas, ozone, and chlorine, or oxidizing gas compositions such as air containing the same: copper(II) oxide, [(I
I) Iron oxide (■), cobal oxide) (m), nickel oxide (■), manganese oxide (■), ruthenium oxide (m)
, rhodium oxide (■), platinum oxide (■), platinum oxide (■)
), palladium (II) oxide, rhenium oxide (■), chromium oxide (■), molybdenum oxide (■), vanadium (V) oxide, thallium oxide (■), tin oxide (■), lead oxide (■), Sulfur oxide (Vl), sulfur oxide (■),
Tellurium oxide (■), arsenic oxide (V), bismuth mide (m
), bismuth (V) oxide, heteropolyacid, perovskite, potassium permanganate, perrhenic acid, sodium dichrome, sulfuric acid, chloric acid, sodium chlorate, sodium hypochlorite, sodium hypochlorite, etc. substances, oxidizing complex oxides, oxidizing oxoacids, oxidizing oxoacid salts; subtype antimony, copper(II) chloride, ferric chloride, cobal chloride) (II), tin chloride (■), tellurium chloride (■
), lead chloride (■), palladium (II) chloride, trethenium (III) chloride, platinum (II) chloride, platinum chloride (■)
, ffi(I) chloride, oxidizing metal chlorides or oxidizing metal oxychlorides such as chromium dioxide dichloride, and molybdenum oxychloride, and oxidizing simple substances such as iodine and oxal.

Among these, particularly suitable ones include, for example, 1 m
Examples include copper (II) chloride, iodine, oxygen gas or air, antimony pentachloride, sulfuric acid, and more preferred examples include iodine, antimony pentachloride, oxygen, and air.

Note that these oxidizing agents may be used alone or in combination of two or more.

Moreover, among these oxidizing agents, it is possible to use one type of the oxidizing agent that can also be used as the Lewis acid catalyst and the Lewis acid catalyst can also serve as the oxidizing agent. Examples of such materials include oxidizing metal halides such as antimony pentachloride and ferric chloride.

Furthermore, among these oxidizing agents, one type that can be used as a solvent for the polymerization reaction can serve both as a solvent and as an oxidizing agent.

Examples of such substances include sulfuric acid.

In the method of the present invention, at least one thiophenol represented by the general formula [II] is
A polyarylene thioether is produced by polymerization using the aforementioned Lewis acid catalyst in the presence or atmosphere of the aforementioned oxidizing agent.

Although this polymerization can be carried out in the absence of a solvent, it is usually desirable to carry out 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 it is desirable to use a solvent that can dissolve the commonly used hexamer.

Usually, examples of solvents that can be suitably used include nitromethane and dichloromethane.

Dichloromethane, tetrachloroethane, nitrobenzene, etc. can be mentioned, and in addition, solvents generally used in Friedel-Krach reactions, cationic polymerizations, etc. can also be suitably selected by appropriately selecting them.

These solvents may be used alone or in combination of two or more, or if necessary, an inert solvent such as an aromatic hydrocarbon such as benzene or toluene may be used as appropriate. They may be used in combination.

What is the ratio of the Lewis acid catalyst [A] and the thiophenol [B] used in the polymerization reaction?

It cannot be specified uniformly because it varies depending on other conditions such as the type of catalyst, solvent, and monomer used, and the concentration of water molecule impurities in the system, but usually [A] / [B] (molar ratio) is 0. .05-30, preferably 0.5-8.

If this value is less than 0.05, the polymerization rate may become slow and the yield of the polymer may decrease. On the other hand, if it exceeds 30, the cost of the catalyst will increase, resulting in an economic disadvantage.

The usage ratio of the oxidizing agent [C] depends on the type of oxidizing agent used,
Although it cannot be specified uniformly because it varies significantly depending on other conditions such as reaction conditions, it is sufficient that [C]/[B] (molar ratio) is usually 0.5 or more, preferably about 1 to 10.

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

The reaction temperature during the polymerization varies depending on the catalyst used and the type of hexamer, but is usually between -5 and 150°C.
℃, preferably 0 to 50℃.

There is no particular restriction on the reaction pressure, and the reaction can usually be carried out suitably at normal pressure or the autogenous pressure of the reaction system. However,
If necessary, the reaction can also be carried out under pressure using a diluting gas that does not interfere with the polymerization reaction.

The reaction time varies considerably depending on other conditions such as the catalyst used, the type and proportion of monomers used, and the reaction temperature, but is usually 1 to 80 hours, preferably 8 to 80 hours.
It is 72 hours.

In constructing the polymerization reaction system, there is no particular restriction on the order and method of blending the Lewis acid catalyst, the thiophenol, the oxidizing agent, and the solvent, and each may be added simultaneously or stepwise in various orders and manners. It can be blended with.

There are no particular restrictions on the reaction method, and it is a continuous method.

Either a semi-continuous system or a batch system may be used. When a 0-batch system is used, it is desirable to stir one reaction system.

As the polymerization method, a suspension polymerization method, a bulk polymerization method, etc. are also possible, but a solution polymerization method is usually preferred.

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

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

That is, once the polymerization reaction has been completed or progressed to the required extent, the reaction mixture is brought into contact with water, a lower alcohol such as methanol, or a mixture thereof to deactivate the catalyst and deactivate the product polymer. Let it settle. At this time, a polymerization terminator such as a basic substance may be used in combination, if necessary.

This precipitated polymer is separated from the liquid by conventional separation operations such as filtration. The separated polymer is washed or neutralized with a washing solution such as an alkaline aqueous solution, if necessary, and then dissolved, reprecipitated, separated, or methanol using an appropriate solvent and reprecipitation solution. After repeating the cleaning process as many times as necessary, it is dried.

It can be recovered as polyarylene thioether purified to various purity levels.

In addition, the solvent used for the above-mentioned dissolution/reprecipitation is as follows.

For example, N-methylpyrrolidone is preferably used because it dissolves the polymer efficiently.

Further, as the reprecipitation liquid and the washing liquid, ice, methanol, or a mixture thereof, particularly methanol, can be preferably used.

On the other hand, unreacted monomers, by-product low-molecular compounds, solvents, methanol, etc. in the mixed liquid separated from the polymer are purified and recovered by normal distillation operations, and then added to the reaction system or post-treatment process, or It can be effectively used for various other purposes.

Polyarylene thioethers such as polyphenylene thioether obtained by the method of this invention have heat resistance,
It has excellent chemical resistance and various mechanical properties such as rigidity, strength, impact resistance, and abrasion resistance, and in particular, it does not contain salts that deteriorate insulation resistance, such as common salt, which has been reported in the past. It is an engineering plastic with outstanding electrical properties such as insulation resistance, and also has excellent processability due to the fact that the polymer structure is essentially linear. It can be suitably used as equipment parts, mechanical parts, materials, etc. in various fields and fields, such as coatings, automobiles, and chemicals.

A reaction mixture containing a 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.

[Effects of the Invention] According to the present invention, since a specific raw material, a catalyst, and a specific catalyst are used, the reaction conditions are mild, the manufacturing method is simple, and the raw materials and catalyst are inexpensive. It is possible to provide an industrially advantageous method for producing polyarylene thioethers, particularly substantially linear polyarylenchioethers with a significantly low degree of crosslinking.

[Example] (Example 1) 2.18 g of thiophenol was added to 100 ml of nitromethane.
After 1 hour, 10 g of aluminum chloride was mixed and reacted for 24 hours.

The reaction solution was dropped into methanol to obtain a precipitate of poly(p-phenylenethioether). The obtained precipitate was washed with an aqueous alkaline solution, dissolved in N-methylpyrrolidone, and reprecipitated in methanol to obtain a purified polymer. The purified polymer had a g yield of 85% and a melting point of 113G-180°C.

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

Original 'X Analysis (RiiJMti) CB8.1% (88,8
), H3,79! (3,7), S29.4 IR spectrum )l,-,=3000.3050
cm-1, νc=c 1380.14130.1580
cm-'δc-H-820cm-' X-ray diffraction θ bow, 5.10.5°13C-NM
Rδ (phenyl G) - 135 ppm spectrum (Example 2) 4.15 g of 2.6-dinitylthiophenol was dissolved in nitrobenzene, mixed with antimony pentachloride, and the mixture was heated at 0°C for 30 minutes.
The reaction was allowed to proceed for several days to obtain a powdery precipitate of poly(2,6-diethyl-1,4-phenylenethioether). 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% and the melting point is 187-1
The temperature was 82°C, and the number average molecular weight determined by the VPO method was 48.
It was 00.

Polymer structure is determined by IR spectrum and elemental analysis.

Confirmed by lH-NMR.

IR spectrum C-H-2890, 2945
,2980cm-1νc-〇-1380,1485cm
-1, δc-H=890cm-' I H-NIP δ(-GHz
11)=1.25ppm.

δC-CH2-4H)-2,70pp ■δ (phen
yl 2H) = 7.00ppm elemental analysis (theoretical value)
C71,5% (73,2), H7,91% (7,3)
, S 19.44 (19,5) (Example 3) 2-Methyl-thiophenol (12,4 g) was dissolved in 25 g of dichloromethane, TiC1a (30 g) and thionyl chloride (15 mjL) were added, The reaction mixture was reacted for 1 day at 20° C. in the presence of oxygen. Then, 8.49 g of purified powdered poly(2-methylphenylenethioether) was obtained in the same manner as in Example 1. The polymer structure was confirmed by the following data.

IR spectrum c-n=2845. 291
0. 2950cm-'shi,,c-1375.1440
．． 1550cm-1δ Dew 870c+s-1 -H

Claims (5)

[Claims] (1) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] (However, in formula [I], R^1 to R^4 are hydrogen atoms, lower alkyl groups, and halogen atoms, respectively. and a lower alkoxy group. Note that R^1 to R^4 may be the same type or different types.) 1. A method for producing polyarylene thioether, which comprises polymerizing phenols using a Lewis acid catalyst in the presence of an oxidizing agent. (2) The method for producing polyarylene thioether according to claim 1, wherein the polyarylene thioether is a linear or substantially linear polyarylene thioether. (3) The Lewis acid catalyst is selected from groups IIa to VIIa of the periodic table, and group VIIa of the periodic table.
The method for producing polyarylene thioether according to claim 1 or 2, which is a Lewis acid consisting of a halogen compound of at least one element selected from Group II and Groups Ib to VIb. (4) The method for producing polyarylene thioether according to any one of claims 1 to 3, wherein the Lewis acid catalyst is aluminum chloride, titanium tetrachloride, or antimony pentachloride. (5) 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 polyarylene thioether according to any one of Items 1 to 5.