JP3108891B2 - Method for producing polyarylene thioether derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyarylene thioether, and more particularly, to a method for producing a polyarylene thioether through a polymer precursor soluble in a solvent under mild polymerization conditions. The present invention relates to a method for producing a polyarylene thioether, which can easily provide the polymer of (1) at a low cost.

[0002]

2. Description of the Related Art Hitherto, polyarylene thioethers such as polyphenylene thioether have been produced by polycondensation reaction of a dihalogen aromatic compound with an alkali metal sulfide in a polar solvent at high temperature and pressure. Was. However, in this method, the thioether bond is decomposed by the alkali sulfide during the polymerization, and the molecular weight remains low. Alkali metal salts are present in the polyarylene thioether and deteriorate its electrical properties. Since it is necessary to carry out the polymerization under high temperature and high pressure, there are problems such as high energy consumption and high cost. A method using sulfuric acid as a catalyst is also known, but has disadvantages such as many by-products and a large amount of crosslinked polymer. Furthermore, although there is a report that applied the Friedel-Crafts reaction, the reaction can be performed under mild conditions, but the product formed due to termination of the polymerization reaction by precipitation in a solvent was a low molecular weight product.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyarylene thioether having excellent electrical properties, mechanical properties, chemical properties, and the like, particularly a cross-linked polymer having substantially no by-products. By providing a highly linear polyarylene thioether via a solvent-soluble precursor, an industrially remarkably advantageous production method can be obtained at low cost under mild conditions as a high molecular weight product. It is in.

[0004]

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that an aromatic compound having an electron-donating substituent and a sulfoxd group in the same molecule as a starting material. It was found that a water-soluble polymer precursor was formed in the presence of an acid, and high-molecular-weight polyarylene thioethers were formed by a demethylation reaction.

That is, the present invention provides a compound represented by the general formula [I]: (In the formula [I], R ^{1 to} R ⁸ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a lower alkyl group having 5 or less carbon atoms, or an alkoxy group.) the R ¹ -R ⁸ are aromatic compounds good .R ⁹ even different kinds may be the same type to each other represented by the alkyl group.), by reacting in the presence of acid, polyarylene sulfonium A method for producing a polyarylene thioether, comprising obtaining a target polymer by a dealkylation reaction using a nucleophile or a reducing agent after obtaining a salt.

The acid is hydrochloric acid, bromic acid, sulfuric acid, nitric acid, formic acid, acetic acid, perchloric acid, methanesulfonic acid, trifluorosulfonic acid, trifluoroacetic acid, antimony pentachloride, phosphorus oxychloride, antimony pentachloride or the like. The method according to claim 1.

The nucleophile or reducing agent is a pyridine derivative,
The method according to claim 1, wherein the quinoline derivative, aniline derivative, trialkylamine derivative, hydrazine derivative, ammonia, dialkyl sulfoxide, alkali salt, alkaline earth salt and the like are used.

The R ¹ -R ⁹ in the general formula [I] will be described in more detail as follows. That is, to illustrate each specific example of the above R ¹ -R ⁸ ,
For example, a hydrogen atom; a methyl group, an ethyl group, a propyl group,
Lower alkyl groups such as 1-methylethyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, pentyl group, hexyl group, heptyl group and octyl group; fluorine atom, chlorine Atom, bromine atom, iodine atom, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group,
Examples include an alkoxy group such as a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group. Among these, a hydrogen atom, a lower alkyl group such as a methyl group and an ethyl group, and a lower alkoxy group such as a methoxy group and an ethoxy group are preferable, and a hydrogen atom, a methyl group, an ethyl group, and a methoxy group are particularly preferable. R ⁹ is an alkyl group such as a methyl, ethyl, or propyl group, and is preferably a methyl group, an ethyl group, or the like.

In the method of the present invention, one or more of the aromatic compounds represented by the general formula [I] are homopolymerized or copolymerized to obtain various kinds and structures of various kinds. Polyarylene thioether (homopolymer / copolymer or a mixture or composition thereof) can be obtained.

In the present invention, a polymerization reaction occurs in the presence of the aromatic compound represented by the general formula [I] and an acid,
Usually the general formula [II]

Embedded image (However, R ^{10 to} R ¹⁷ in the formula [II] each have the same meaning as R ^{1 to} R ⁸ in the general formula [I].
⁽¹⁸ has the same meaning as R ⁹ ) can be obtained as a linear polyarylene sulfonium salt having a main chain structure represented by the following formula:
Here, when the purpose is to obtain a so-called homopolymer, one kind of the aromatic compound represented by the general formula [I] may be used alone as a reaction raw material.

The aromatic hydrocarbon compound represented by the general formula [I] includes, for example, 2-methyl-4-
Methylsulfinylthiophenoxybenzene, 3-methyl-4-methylsulfinylthiophenoxybenzene,
2,3-dimethyl-4-methylsulfinylthiophenoxybenzene, 2,5 dimethyl-4-methylsulfinylthiophenoxybenzene, 2,6-dimethyl-4-methylsulfinylthiophenoxybenzene, 3,5-dimethyl-4-methyl Sulfinylthiophenoxybenzene, 2,2′-dimethyl-4-methylsulfinylthiophenoxybenzene, 2,3′-dimethyl-4-methylsulfinylthiophenoxybenzene 3,3′-dimethyl-4-methylsulfinylthiophenoxybenzene,
2,3,5-trimethyl-4-methylsulfinylthiophenoxybenzene, 2,3,6-trimethyl-4-methylsulfinylthiophenoxybenzene 2,2 ′, 3
-Trimethyl-4-methylsulfinylthiophenoxybenzene, 2,2 ', 5-trimethyl-4-methylsulfinylthiophenoxybenzene, 2,2', 6-trimethyl-4-methylsulfinylthiophenoxybenzene, 2,3 ', 3-trimethyl-4-methylsulfinylthiophenoxybenzene, 2,3 ′, 5-trimethyl-4-methylsulfinylthiophenoxybenzene,
2,3 ', 6-trimethyl-4-methylsulfinylthiophenoxybenzene, 3,3', 5-trimethyl-4
-Methylsulfinylthiophenoxybenzene, 2,
3,5,6-tetramethyl-4-methylsulfinylthiophenoxybenzene, 2,2 ', 3,3'-tetramethyl-4-methylsulfinylthiophenoxybenzene, 2,2', 3,5'-tetramethyl -4-methylsulfinylthiophenoxybenzene, 2,3,3 ',
5'-tetramethyl-4-methylsulfinylthiophenoxybenzene, 2,2'5,5'-tetramethyl-4
-Methylsulfinylthiophenoxybenzene, 2,
2 ', 5,6'-tetramethyl-4-methylsulfinylthiophenoxybenzene, 2,3', 5,5'-tetramethyl-4-methylsulfinylthiophenoxybenzene, 2,3 ', 5', 6- Tetramethyl-4-methylsulfinylthiophenoxybenzene, 2,2 ′, 3
5-tetramethyl-4-methylsulfinylthiophenoxybenzene, 2,3,3 ', 5-tetramethyl-4-
Methylsulfinylthiophenoxybenzene, 2,
2 ', 3'6-tetramethyl-4-methylsulfinylthiophenoxybenzene, 2,3,3', 6-tetramethyl-4-methylsulfinylthiophenoxybenzene, 2,2 ', 3,3'5-pentamethyl -4-methylsulfinylthiophenoxybenzene, 2,2 ', 3
5,5′-pentamethyl-4-methylsulfinylthiophenoxybenzene, 2,2 ′, 3,5,6′-pentamethyl-4-methylsulfinylthiophenoxybenzene, 2,3,3 ′, 5,5 ′ -Pentamethyl-4-methylsulfinylthiophenoxybenzene, 2,2 ′,
3,3 ′, 6-pentamethyl-4-methylsulfinylthiophenoxybenzene, 2,2 ′, 3,5 ′, 6-pentamethyl-4-methylsulfinylthiophenoxybenzene, 2,2 ′, 3,6,6 ′ , -Pentamethyl-4
-Methylsulfinylthiophenoxybenzene, 2,
3,3 ′, 5 ′, 6-pentamethyl-4-methylsulfinylthiophenoxybenzene, 2,2′3,3 ′,
5,5′-hexamethyl-4-methylsulfinylthiophenoxybenzene, 2,2 ′, 3,3 ′, 5,6′-
Hexamethyl-4-methylsulfinylthiophenoxybenzene, 2,2′3,3 ′, 5,5 ′, 6-heptamethyl-4-methylsulfinylthiophenoxybenzene, 2,2 ′, 3,3 ′, 5,6 6'-heptamethyl-4-methylsulfinylthiophenoxybenzene,
2,2 ′, 3,3 ′, 5,5′6,6′-octamethyl-4-methylsulfinylthiophenoxybenzene,
2,2′-diethyl-4-methylsulfinylthiophenoxybenzene, 3,3′-diethyl-4-methylsulfinylthiophenoxybenzene, 2,2 ′, 5,5 ′
-Tetraethyl-4-methylsulfinylthiophenoxybenzene, 3,3 ', 5,5'-tetraethyl-4-
Methylsulfinylthiophenoxybenzene, 2,2 ′
-Difluoro-4-methylsulfinylthiophenoxybenzene, 2,2'-dichloro-4-methylsulfinylthiophenoxybenzene, 2,2'-dibromo-4-
Methylsulfinylthiophenoxybenzene, 2,2 ′
-Diiodo-4-methylsulfinylthiophenoxybenzene, 2,2 ', 5,5'-tetrafluoro-4-methylsulfinylthiophenoxybenzene, 2,2',
5,5′-tetrachloro-4-methylsulfinylthiophenoxybenzene, 2,2 ′, 5,5′-tetrabromo-4-methylsulfinylthiophenoxybenzene,
3,3′-dimethoxy-4-methylsulfinylthiophenoxybenzene, 2,2 ′, 5,5′-tetramethoxy-4-methylsulfinylthiophenoxybenzene,
3,3 ′, 5,5′-tetramethoxy-4-methylsulfinylthiophenoxybenzene, 3,3′-diethoxy-4-methylsulfinylthiophenoxybenzene,
2,2 ′, 5,5′-tetraethoxy-4-methylsulfinylthiophenoxybenzene, 3,3 ′, 5,5 ′
-Tetraethoxy-4-methylsulfinylthiophenoxybenzene, 3,3'-dipropoxy-4-methylsulfinylthiophenoxybenzene, 2,2 ', 5
5′-tetrapropoxy-4-methylsulfinylthiophenoxybenzene, 3,3 ′, 5,5′-tetrapropoxy-4-methylsulfinylthiophenoxybenzene, 3,3′-dipoxy-4-methylsulfinylthiophenoxy Diphenyl sulfides such as benzene are preferred for producing a high molecular weight target polymer.

The acid used in the method of the present invention is a known citrate, inorganic acid or a mixture or complex thereof.

Specifically, for example, hydrochloric acid, hydrobromic acid,
Non-oxygen acids such as hydrocyanic acid and tetrafluoroboric acid, sulfuric acid, phosphoric acid, perchloric acid, bromine formic acid, nitric acid, carbonic acid, boric acid, molybdic acid, isopoly acids, inorganic polyoxo acids such as heteropoly acids, sodium hydrogen sulfate, phosphoric acid Partial salts or esters of sulfuric acid such as sodium dihydrogen, proton residual heteropolyacid salts, monomethyl sulfate, trifluoromethane sulfate, etc .; formic acid, acetic acid, propionic acid, butanoic acid, succinic acid,
Monovalent or polyvalent carboxylic acids such as benzoic acid and phthalic acid, halogen-substituted carboxylic acids such as monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monofluoroacetic acid, difluoroacetic acid and trifluoroacetic acid, methanesulfonic acid, ethanesulfonic acid Monovalent or polyvalent sulfonic acids such as propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid and benzenedisulfonic acid; partial metal salts of polyvalent sulfonic acids such as sodium benzenedisulfonate; Examples thereof include Lewis acids such as antimony chloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, zinc chloride, copper chloride, and iron chloride.

Among these, strongly acidic protonic acids having high stability are preferred, and perchloric acid, tetrafluoroboric acid, trifluoromethanesulfonic acid and the like are particularly preferred.

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

The solvent of the invention (1) can be used as long as it does not substantially lose the polymerization activity, but it is usually desirable to dissolve the reaction raw materials and acids used. It is a polar solvent such as phosphorus oxychloride, formic acid, nitrobenzene and nitromethane, and phosphorus oxychloride is particularly preferred.

These solvents may be used alone or as a mixture of two or more kinds, or may be used by being appropriately mixed with an inert solvent if necessary.

Since this reaction is a dehydration reaction,
A dehydrating agent may be present. The use ratio of the acid and the dehydrating agent varies depending on the type of the acid, the type of the dehydrating agent, the composition, the type of the reaction raw material and the solvent, the concentration of impurities such as water in the system, and the reaction temperature. Although not specified, the concentration may be a concentration at which a polymerization reaction is initiated and a concentration at which side reactions other than the intended polymerization reaction such as a decomposition reaction are suppressed.

The reaction temperature during the polymerization is not uniform depending on the type of acid used and the type of the reaction raw material.
It is 25-250 ° C, preferably 0-150 ° C.

The reaction pressure and the oxygen partial pressure are not particularly limited, and the reaction can usually be suitably carried out under normal pressure or the self-pressure of the reaction system. However, if necessary, the reaction can be carried out under pressure using a mixed gas with a diluent gas or the like which does not hinder the polymerization reaction.

The reaction time varies significantly depending on conditions such as the acid used, the type of the reaction raw materials and the proportion used, the reaction temperature, the oxygen partial pressure, the solvent and the like, but is usually 0.5 to 100 hours, preferably 2 to 100 hours. 50 hours.

In constituting the polymerization reaction system, the order of mixing the aromatic compound, the acid and the solvent is as follows.
There is no particular limitation on the method, and they can be compounded simultaneously or stepwise in various orders and manners.

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 a batch system, it is desirable to carry out the reaction with stirring.

By the above-mentioned method, after the reaction, the desired polymer precursor of polyarylene thioether can be obtained in a solution.

It is necessary to remove the alkyl group constituting the sulfonium cation, which is a solvent-soluble portion of the produced polymer precursor, by using a nucleophilic compound or a reducing agent. The general formula [I]
II] is obtained.

Embedded image (However, R ^{19 to} R ²⁶ in the formula [II] each have the same meaning as R ^{1 to} R ⁸ in the general formula [I].
²⁷ has the same meaning as R ⁹ )

Examples of the nucleophilic reagent used in the dealkylation reaction include nitrogen-containing aromatic compounds such as pyridine, quinoline, and aniline, trialkylamine, and ammonia, and pyridine and quinoline are particularly preferable. The reducing agent is potassium chloride, sodium chloride, hydrazine, or the like, or may be electrically reduced.

The solvent for the dealkylation reaction is not limited as long as it does not inhibit the desired reaction, and halogen-containing aromatic compounds such as chlorobenzene and α-chloronaphthalene are preferred. If the nucleophile is liquid at the reaction temperature, there is no problem without using a solvent.

The reaction temperature for the dealkylation reaction is as follows:
Although it is not uniform depending on the base used, it is usually 0-20.
It is 0 ° C, preferably 0-150 ° C.

The reaction pressure and the oxygen partial pressure are not particularly limited, and the reaction can be preferably carried out usually at normal pressure or at the pressure of the reaction system.

The reaction time varies significantly depending on conditions such as the kind of base used, its use ratio, reaction temperature, oxygen partial pressure, diluting solvent and the like, but it is usually 0.5-100 hours, preferably 0.5-100 hours. 50 hours.

In constructing the dealkylation reaction, the order and method of blending the polymer precursor, the nucleophilic reagent and the solvent are not particularly limited, and they may be simultaneously or stepwise in various orders and manners. It is also possible to mix.

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 a batch system, it is desirable to carry out the reaction with stirring.

After the reaction, the desired polymer of polyarylene thioether can be obtained in a solution by the above method.

This post-treatment can be carried out according to a known method. An example of this post-processing is as follows.

That is, when the dealkylation reaction is completed or proceeds to a necessary extent, the reaction mixture is poured into an acidic aqueous solution, filtered, and brought into contact with a lower alcohol such as methanol or a mixture thereof. To precipitate the desired polymer. As an acidic aqueous solution,
For example, inorganic acids such as hydrochloric acid, hydrobromic acid, hydrocyanic acid, sulfuric acid,
Organic acids such as formic acid and acetic acid, with hydrochloric acid being particularly preferred. The concentration of the acid is not particularly limited as long as it is a concentration sufficient to deactivate the unreacted nucleophilic compound, and usually 1 to 20%
Use

The time of introduction into the acid solution varies greatly depending on the type of acid used, its dilution ratio and the conditions of the reaction temperature, but is usually 0.1 to 200 hours, preferably 0.1 to 200 hours.
-10 hours.

The polymer precipitated by the above operation is separated from the liquid by a conventional separation operation such as filtration. The separated polymer was subjected to operations such as dissolution, reprecipitation, separation, and washing using an appropriate solvent and a reprecipitation solution as necessary, and then dried and purified to various purities. It can be recovered as a polymer.

As the solvent used for the dissolution and reprecipitation, for example, N-methylpyrrolidone, hot α-chloronaphthalene and the like are preferable from the viewpoint of dissolving the polymer efficiently.

The reprecipitating solution and the washing solution are usually, for example, water, methanol, acetone, chloroform, dichloromethane, a mixture thereof, etc., and methanol is particularly preferably used.

On the other hand, unreacted raw materials, by-product low-molecular compounds, solvents and the like in the mixed solution separated from the polymer are purified and recovered by a usual distillation operation, and are repeatedly used in a reaction system, a post-treatment step, or other processes. Can be effectively used for various applications.

The polyarylene thioethers such as the polyphenylene thioethers obtained according to the present invention are excellent in heat resistance, chemical resistance, various mechanical properties such as rigidity, strength, impact resistance and abrasion resistance. Further, since it does not contain a salt which deteriorates insulation properties such as a salt which has been a problem in the past, it has remarkably excellent electrical properties such as insulation resistance.
Furthermore, due to the fact that the polymer structure is substantially linear, it is an engineering plastic with excellent processability.
Equipment parts in various fields and related fields, such as automobiles and chemicals,
It can be suitably used as a material or the like.

[0042]

According to the present invention, the reaction conditions are extremely mild, and the production method is simple. The starting sulfoxide monomer can be easily obtained from diphenyl sulfide and methylbis (methylthio) sulfonium cation. This is industrially advantageous such that extremely inexpensive raw materials and catalysts can be used, and is particularly advantageous for providing a substantially linear polyarylene thioether having an extremely low degree of crosslinking.

[0043]

【Example】

Example 1 7 g of 4-methylsulfinylthiophenoxybenzene was dissolved in 16 ml of phosphorus oxychloride at 0 ° C., and 25 ml of perchloric acid (70%) was further added. Stir for 2 days.
When the reaction solution was slowly poured into 1 liter of water, a white precipitate was obtained. The precipitate was filtered, separated from unreacted substances, washed with water and dried to obtain 9.3 g of a white powder (yield: 100).
%).

[0044] IR spectrum ^{_{ν c = c = 1392,1475,1568cm -1 ν}} c104 = 1120,625cm -1 δ C-H = 814cm -1

H-NMR CH3: 3.8 ppm
(3H) Phenyl; 7.65, 8.05 ppm (8H)

Tm (decomposition) 227.7 ° C.

Thus, poly (methyl-4-thiophenoxyphenylsulfonium salt) was confirmed.

5 g of the obtained poly (methyl-4-thiophenoxyphenylsulfonium salt of methyl perchlorate) was dissolved in 100 ml of pyridine, and refluxed at the boiling point for 5 hours. The reaction solution was cooled to around room temperature, and slowly poured into 1 L of 20% aqueous hydrochloric acid. The precipitate was filtered, washed with 5% aqueous hydrochloric acid, and then washed with methanol, acetone and chloroform in this order. After drying, 3.1 g of a white powder was obtained (yield: 95).
%).

Elemental analysis (calcd.) C: 66.6
(66.7%) H; 3.7 (3.7x%) S; 29.7 (29.7%)

[0050] IR spectrum ^{_{ν c = c = 1386,1471,1574cm -1 δ}} C-H = 814cm -1

CPMAS ¹³ C-NMR Phqnyl; 132.8, 134.4 ppm

Tc 127 ° C.

Tm 278 ° C.

Td _10% 520 ° C.

Thus, the formation of poly (p-phenylene sulfide) was confirmed.

Example 2 7 g of 4-methylsulfinylthiophenoxybenzene was dissolved in 20 ml of phosphorus oxychloride at room temperature, and 30 g of aluminum bromide was further added. After stirring overnight, the reaction solution was slowly poured into 1 liter of water to obtain a white precipitate. The precipitate is filtered, separated from unreacted substances, washed with water,
Dried. 5 g of the reaction product was dissolved in 100 ml of pyridine, and the mixture was refluxed at the boiling point for 5 hours. The reaction solution was cooled to around room temperature, and slowly poured into 1 L of 20% aqueous hydrochloric acid. The precipitate was filtered, washed with 5% aqueous hydrochloric acid, and then washed with methanol, acetone and chloroform in this order. Dry,
2.9 g of a white powder was obtained (yield: 83.3%).

Elemental analysis (calcd.) C: 65.7
(66.7%) H; 3.6 (3.7%) S; 30.7 (29.7%)

[0058] IR spectrum ^{_{ν c = c = 1386,1471,1574cm -1 δ}} C-H = 814cm -1

Tm 240 ° C.

Thus, the formation of poly (p-phenylene sulfide) was confirmed.

Example 3 10 g of 4-methylsulfinylthiophenoxybenzene
Was dissolved in 20 ml of phosphorus oxychloride at 0 ° C., and 25 ml of tetrafluoroboric acid was further added. Stir for 2 days. When the reaction solution was slowly poured into 1 liter of water, a white precipitate was obtained. The precipitate was filtered, separated from unreacted materials,
After washing with water and drying, a white powder was obtained. 5 g of poly (methyl tetrafluoroborate-4-thiophenoxyphenylsulfonium salt) was dissolved in 100 ml of quinoline and refluxed at the boiling point for 5 hours. The reaction solution was cooled to around room temperature and filtered. After washing the reaction product with 5% hydrochloric acid, methanol, acetone and chloroform were washed in this order. After drying, 3.2 g of a white powder was obtained (yield: 94.2).
%)

Elemental analysis (calcd.) C: 65.0
(66.7%) H; 3.7 (3.7%) S; 30.5 (29.7%)

[0063] IR spectrum ^{_{ν c = c = 1386,1471,1575cm -1 δ}} C-H = 814cm -1

Tm 278 ° C.

As described above, formation of poly (p-phenylene sulfide) was confirmed.

Example 4 10 g of 4-methylsulfinylthiophenoxybenzene
Was dissolved in 20 ml of phosphorus oxychloride at room temperature, and 5 ml of methanesulfonic acid was further added. 30 minutes later, 15 ml of perchloric acid (70%) was added, and the mixture was stirred for 2 days. When the reaction solution was slowly poured into 1 liter of water, a white precipitate was obtained. The precipitate was filtered, separated from unreacted substances, washed with water and dried. 5 g of the reaction product was placed in 100 m of 2,6 dimethylpyridine.
and stirred at 110 ° C. for 5 hours. The reaction solution was cooled to around room temperature, filtered, and washed with 5% aqueous hydrochloric acid, methanol, acetone and chloroform in this order. After drying, 2.8 g of a white powder was obtained (yield: 84.5).
%).

Elemental analysis (calcd.) C; 65.1
(66.7%) H; 3.7 (3.7%) S; 30.9 (29.7%)

[0068] IR spectrum ^{_{ν c = c = 1386,1471,1574cm -1 δ}} C-H = 813cm -1

The formation of poly (p-phenylene sulfide) was confirmed at Tm of 279 ° C. or higher.

Example 5 10 g of 4-methylsulfinylthiophenoxybenzene
Was dissolved in 30 ml of nitromethane at room temperature, 20 ml of perchloric acid (70%) was added, and the mixture was stirred for 2 days. The reaction solution was slowly poured into 1 l of a water / methanol (1: 1) mixture to obtain a white precipitate. The precipitate was filtered, separated from unreacted substances, washed with water and dried. 5 g of the obtained white powder was dissolved in 100 ml of pyridine, and the mixture was refluxed at the boiling point for 5 hours. The reaction solution was cooled to around room temperature, filtered, and washed with 5% aqueous hydrochloric acid, methanol, acetone, and chloroform in this order. Dried, white powder 3.0g
Was obtained (yield: 91.8%).

Elemental analysis (calcd.) C: 65.2
(66.7%) H; 3.6 (3.7%) S; 31.0 (29.7%)

[0073] IR spectrum ^{_{ν c = c = 1388,1472,1574cm -1 δ}} C-H = 814cm -1

Tm 260 ° C.

As described above, formation of poly (p-phenylene sulfide) was confirmed.

Example 6 10 g of 3,5,3 ′, 5′-tetramethyl-4-methylsulfinylthiophenoxybenzene was dissolved in 20 ml of phosphorus oxychloride at 0 ° C., and perchloric acid (70%) was dissolved in 20 ml of 20%.
The resulting mixture was stirred at 0 ° C. for 2 days. Water 1
Upon slow pouring in 1 l a white precipitate was obtained. The precipitate was filtered, separated from unreacted substances, washed with water and dried.
10 g of the obtained white powder was dissolved in 150 ml of pyridine, and refluxed at the boiling point for 4 hours. The reaction solution was cooled to around room temperature, filtered, and washed with 5% aqueous hydrochloric acid, methanol, acetone and chloroform in this order. Dry,
6.8 g of a white powder was obtained (yield: 96.8%).

Elemental analysis (calcd.) C; 71.1
(70.6%) H; 5.7 (5.9%) S; 23.0 (23.5%)

IR spectrum ν (CH; CH ₃ ) 2850, 2920, 2690c
_{^{m -1 ν c = c = 1388}} , 1472,1574cm -1 δ C-H = 812cm -1

Tg 189 ° C.

As described above, poly (3,5- {methyl-p-
(Phenylene sulfide) was confirmed.

Claims (3)

(57) [Claims] 1. A compound of the general formula [I] (In the formula [I], R ^{1 to} R ⁸ each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a lower alkyl group having 5 or less carbon atoms, or an alkoxy group.) the R ¹ -R ⁸ are aromatic compounds good .R ⁹ even different kinds may be the same type to each other represented by the alkyl group.), by reacting in the presence of acid, polyarylene sulfonium A method for producing a polyarylene thioether, comprising obtaining a target polymer by a dealkylation reaction using a nucleophile or a reducing agent after obtaining a salt. 2. The method according to claim 1, wherein the acid is hydrochloric acid, bromic acid, sulfuric acid, nitric acid,
Formic acid, acetic acid, perchloric acid, methanesulfonic acid, trifluorosulfonic acid, trifluoroacetic acid, antimony pentachloride,
The method for producing a polyarylene thioether according to claim 1, which is phosphorus oxychloride or the like. 3. The method according to claim 1, wherein the nucleophile or reducing agent is a pyridine derivative, a quinoline derivative, an aniline derivative, a trialkylamine derivative, a hydrazine derivative, ammonia, dialkylsulfoxide, an alkali salt, an alkaline earth salt, or the like. 2. The process for producing a polyarylene wrench ether according to 2.