JP3145324B2 - Method for producing poly (thioarylene) compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a poly (thioarylene) compound. More specifically, the invention of this application relates to a method for producing a high molecular weight poly (thioarylene) compound using a solvent-soluble poly (arylene sulfonium salt) compound as a precursor.

[0002]

2. Description of the Related Art Methods for producing poly (thioarylene) compounds such as poly (thiophenylene) have been proposed. In this method, a dihalo aromatic compound and an alkali metal sulfide are polycondensed in an aprotic polar organic solvent such as N-methylpyrrolidone. However, this conventional method is an aromatic nucleophilic substitution reaction, which is (1) a reaction under severe conditions of a high temperature of 200 ° C. or more and a high pressure of 10 atm or more. Problems have been pointed out, such as (2) a high molecular weight compound cannot be obtained, and (3) mixing of by-produced alkali metal salts cannot be avoided. further,
It is known that when an aromatic compound having a fluorine atom is used as a monomer, a branched or cross-linked structure is obtained.
It has been difficult to synthesize a fluorine-substituted poly (thioarylene) compound having a linear structure, particularly poly (thioperfluorophenylene).

Accordingly, the invention of this application has been made in view of the above circumstances, and solves the drawbacks of the conventional method. Under mild conditions of normal temperature and normal pressure, a high-molecular-weight poly ( It is an object of the present invention to provide a new method capable of producing poly (thioarylene) compounds including thioperfluorophenylene).

[0004]

Means for Solving the Problems The invention of this application is based on the following formula [1] to solve the above problems.

[0005]

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[0006] (Each of from R ₁ R ₈ is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, it may be different kinds be the same as each other, small
One even without Although halogen atom, X represents an oxygen atom or a sulfur atom indicates, n is showing the degree of polymerization of 2 or more integer)
A method for producing a poly (thioarylene) compound represented by the formula:

[0007]

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[0008] (R ₁ to each of R _8, the X and n indicates that the, R ₉ is an alkyl group or an aryl group,, Y ^- represents an anion) poly (arylene sulfonium represented by A method for producing a poly (thioarylene) compound, which comprises subjecting a salt) compound to a dealkylation or dearylation reaction.

Further, the invention of this application relates to a method for preparing a poly (arylene sulfonium salt) compound represented by the above formula [2] by the following formula [3]

[0010]

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(R ₁ to R ₈ each represent a hydrogen atom, a halo
Gen atom, alkyl group, or alkoxy group.
They may be the same or different types,
At least one is a halogen atom, R ₉ is an alkyl group,
Or an aryl group, X represents an oxygen atom or a sulfur atom
Aryl sulfoxide compound represented by shown), acids,
Or by polymerization using an acid anhydride, or by the following formula [4]

[0012]

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(R ₁ to R ₈ are each a hydrogen atom,
Represents a halogen atom, an alkyl group, or an alkoxy group
And may be the same or different types
Has at least one halogen atom and R ₉ is an alkyl
X represents an oxygen atom or a sulfur group;
The present invention also provides a method for producing an arylsulfide compound represented by a yellow atom) by oxidative polymerization. That is, the inventors of the present invention have intensively studied to solve the above problems. As a result, they found that a high molecular weight poly (thioarylene) compound having a linear structure was formed via a poly (arylene sulfonium salt) compound obtained by condensation polymerization of an aryl sulfoxide compound or oxidative polymerization of an aryl sulfide compound. Thus, the present invention has been completed.

In the production method of the present invention using the poly (arylene sulfonium salt) compound as described above, the reaction proceeds under mild conditions of normal temperature and normal pressure, and the desired poly (thioarylene) is obtained in high yield. ) The compound can be obtained.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the technical structure of the present invention will be described in detail. First, the formulas [1], [2],
Specific examples of each of R ₁ to R _{8 in} [3] and [4] include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydrogen atom: a methyl group, an ethyl group, Alkyl groups such as propyl group, 1-methylethyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, pentyl group, hexyl group, heptyl group and octyl group; methoxy Group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-
Examples thereof include alkoxy groups such as a butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group. The alkyl group and the alkoxy group may have any substituent as long as the reaction is not inhibited. Further, a compound in which one or more, particularly all of R ₁ to R ₈ are fluorine atoms is exemplified. Fluorine atom-substituted poly (thioarylene) compounds are attracting attention in various properties such as water repellency, heat resistance, low friction, oxygen affinity, and high refractive index.

X in the formulas [1], [2], [3] and [4] is an oxygen atom or a sulfur atom, and the presence of X in the para-position of the benzene ring bonded during the polymerization reaction. The reactivity with the electrophilic reagent increases, resulting in the formation of a high molecular weight product. In the formulas [2], [3] and [4],
R ₉ is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; a phenyl group, a toluyl group,
An aryl group such as a xylyl group is exemplified. Preferable examples are lower alkyl groups, especially methyl groups.

[0017] Y in formula (2) ^- To illustrate specific examples of the anion, for example, fluorine anion, chlorine anion, bromine anion, halogen anion of iodine anion, etc.; acetate anion, trifluoroacetate anion,
Examples thereof include a sulfate anion, a hydrogen sulfate anion, a methane sulfate anion, a trifluoromethane sulfate anion, a perchlorate anion, a tetrafluoroborate anion, a hexafluorophosphate anion, and a hexachloroantimonate anion. From the viewpoint of the synthesis and stability of the poly (arylene sulfonium salt) compound, a sulfate anion, a hydrogen sulfate anion, a methane sulfate anion, a trifluoromethane sulfate anion, a perchlorate anion, a tetrafluoroborate anion and the like are preferred, and a trifluoromethane sulfate anion is particularly preferred. Is most preferred.

Then, the poly (arylene sulfonium salt) compound represented by the formula [2], which is a precursor for the production of the poly (thioarylene) compound represented by the formula [1] of the present invention, is described next. The manufacturing method will be described. The poly (arylene sulfonium salt) compound represented by the formula [2] is produced by condensation polymerization of the aryl sulfoxide compound represented by the formula [3]. This polycondensation proceeds by reaction with an acid or acid anhydride. Known acids can be used as the acid in this case. It is for suppressing the deactivation of the polymerization active species, and serves as a counter ion for the poly (arylene sulfonium) compound which is a polymerization product. A substance which is partially changed to a protonic acid by the coexistence of a protonic acid or a proton-donating substance, and a known organic acid, inorganic acid, or a mixture or complex thereof is used. Specifically, for example, hydrochloric acid,
Non-oxygen acids such as hydrobromic acid and hydrocyanic acid, sulfuric acid, phosphoric acid, chloric acid, bromic acid, nitric acid, carbonic acid, boric acid, molybdic acid, inorganic oxoacids such as impolic acid and heteropolyacid, sodium hydrogen sulfate, phosphoric acid Sodium dihydrogen, proton residual heteropolyacid, monomethyl sulfate, trifluoromethane sulfate,
Acetic acid, propionic acid, butanoic acid, succinic acid, benzoic acid,
Monovalent or polyvalent carboxylic acids such as phthalic acid, halogen-substituted carboxylic acids such as monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monofluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, methanesulfonic acid, ethanesulfonic acid, and propanesulfonic acid Monovalent or polyvalent sulfonic acids such as acid, toluenesulfonic acid, trifluoromethanesulfonic acid, benzenedisulfonic acid, etc., antimony pentachloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, zinc chloride, copper chloride And Lewis acids such as iron chloride.

The corresponding acid anhydrides mentioned above are also shown. Among them, highly stable strongly acidic protonic acids are preferred, and trifluoromethanesulfonic acid, perchloric acid,
Tetrafluoroboric acid and the like are preferably used. In addition,
These acids or acid anhydrides may be used alone or in a combination of two or more.
Further, the reaction may be performed by diluting with an organic solvent.

When water is generated as the polymerization proceeds,
It is desirable to carry out the polymerization in the presence of a dehydrating agent. Usually, dehydrating agents that can be suitably used include phosphorus pentoxide, inorganic acids such as acetic anhydride, trifluoroacetic anhydride, and trifluoromethanesulfonic anhydride. In addition, there is no problem as long as it does not affect the polymerization reaction, and anhydrous sodium sulfate, potassium chloride or the like may be used. Of these, phosphorus pentoxide is most preferred.

With respect to the use ratio of the above-mentioned acid or acid anhydride and the dehydrating agent, the ratio of the acid or acid anhydride to the aryl sulfoxide compound (molar ratio) is usually 0 relative to the above-mentioned aryl sulfoxide compound. It may be about 0.1 to 50, and more preferably about 0.15 to 10.
The same applies to the dehydrating agent / arylsulfoxide compound (molar ratio).

The poly (arylene sulfonium salt) compound represented by the formula [2] is obtained by oxidizing the aryl sulfide compound represented by the formula [4] and subjecting it to polycondensation as the above formula [3], or The compound can be produced by oxidatively polymerizing the arylsulfide compound represented by 4). For the oxidative polymerization reaction, an oxidizing agent may be used, a catalyst may be used, or electrolytic oxidation may be used. The oxidizing agent is not particularly limited as long as it has a capability of oxidizing the aryl sulfide compound and does not hinder the progress of the polymerization reaction.

Specific examples of the oxidizing agent applicable to the reaction include 2,3-dichloro-5,6-dicyano-p-benzoquinone, chloranil, bromanyl, 1,4-diphenoquinone, tetramethyldiphenoquinone, tetracyanoquinone Organic oxidants such as quinodimethane, tetracyanoethylene and thionyl chloride; organic peroxides such as perbenzoic acid, m-chloroperbenzoic acid and benzoyl peroxide; lead tetraacetate, thallium triacetate, and cerium (IV) , Acetylacetonato, vanadium pentoxide and the like. Above all, 2,3-
Dichloro-5,6-dicyano-p-benzoquinone, chloranil, promanyl, vanadium pentoxide are preferred.

These oxidizing agents may be used alone or in combination of two or more. The amount of the oxidizing agent can not be uniformly defined because it varies depending on the reaction raw material used, the type of the solvent, the type of the oxidizing agent, etc.
The molar ratio is about 0.1 to 50, preferably 0.5 to
It is about 5.

When this value is less than 0.5, the polymerization rate becomes slow, and a decrease in the polymer yield is also observed. 5
If it exceeds 0, the effect corresponding to it will not be seen. Further, the aryl sulfide compound represented by the above formula [4] generates the poly (arylene sulfonium salt) compound by oxygen oxidative polymerization by adding an oxygen oxidizing catalyst and stirring.

The oxidative polymerization catalyst has the ability to oxidize the aryl sulfide compound, and
There is no particular limitation as long as it does not inhibit the progress of the polymerization reaction. It may be an organometallic compound, a metal complex, or the like. In this case, the ligand and the counter ion are not limited, and among them, salts such as cerium (IV), acetylacetone, and porphyrin are preferable.

Examples of these metal compounds include cerium compounds such as cerium ammonium nitrate;
Vanadium compounds such as vanadyl acetylacenate, vanadyl tetraphenylporphyrin, and vanadium acetylacenate; and molybdenum oxide compounds such as molybdenum acetylacenate and molybdenum oxide. Among them, cerium ammonium nitrate, vanadyl acetylacenate, vanadium acetylacenate, vanadium tetraphenylporphyrin and the like are preferably used.

These oxidation polymerization catalysts may be used alone or in a combination of two or more. When this oxidation polymerization catalyst is used, it does not proceed in a system having no oxygen at all, such as in a nitrogen atmosphere, and the presence of oxygen is required. Therefore,
Normally, the higher the oxygen partial pressure, the better, but it is sufficient to be in the atmosphere, and the reaction proceeds even under reduced pressure if oxygen is present to some extent.

The amount of the oxidative polymerization catalyst is usually 0.0001 to 0.0001 as a molar ratio with the aryl sulfide compound.
It may be about 0.1. If this value is less than 0.0001, the polymerization rate will be slow. On the other hand, when it exceeds 5, the cost of the catalyst becomes high, which is economically disadvantageous. In both cases of the reaction using the oxidizing agent and the reaction using the oxidation catalyst, it is desirable to add an acid to the polymerization reaction system. Examples of the acid in this case include perchloric acid, tetrafluoroboric acid, phosphoric acid, hexafluorophosphoric acid, hydrochloric acid, sulfuric acid, hydrogen bromide, hydrogen iodide and the like.

The oxidative polymerization can also be performed by electrolytic oxidation. The supporting electrolyte may be a known organic acid, inorganic acid or a salt of a mixture or complex thereof. Specific examples include, for example, lithium perchlorate, sodium perchlorate, lithium tetrafluoroborate, tetrabutylammonium iodide, lithium bromide, tetraethylammonium hexachloroantimonate, hexafluorinate, etc. Lithium oxide, lithium tetrafluoroborate, tetrabutylammonium salt and the like are preferably used.

These supporting electrolytes may be used alone or in a combination of two or more. Further, any material may be used as long as it does not react with the above-mentioned poly (arylene sulfonium salt) compound which is soluble and formed in a solvent. The electrolysis method is not limited, and may be either constant potential or constant current, as long as the arylalkyl sulfide compound can be oxidized.

Also in this case, it is preferable to add the same acid as described above to the reaction system. The electrode to be used is not particularly limited, and may be any of platinum, gold, silver, carbon and the like, and platinum is particularly preferably used. The shape of the electrode is not particularly limited, such as a rod shape, a plate shape, and a net shape. Also,
The form of use of the electrodes is not particularly limited, and they may be used singly or may be used in layers. If necessary, a reinforcing agent may be used.

The reference electrode to be used is not particularly limited and may not be used, but an Ag / AgCl, saturated calomel electrode or the like may be used. In any of the above condensation polymerization reactions and oxidative polymerization reactions, a solvent can be appropriately used. For example, hydrocarbon solvents such as pentane, hexane, benzene, toluene, xylene, etc .: dichloromethane, chloroform, carbon tetrachloride,
Halogenated hydrocarbon solvents such as dichloroethane, tetrachloroethane, trichlorofluoromethane, 1,1,2-trichloro-1,2,2-trifluoroethane; and nitrogen-containing solvents such as nitromethane, nitroethane, nitropropane, nitrobenzene, etc. No. In addition, a solvent generally used for Friedel-Crafts reaction, cationic polymerization, or the like can be appropriately selected and suitably used.

These solvents may be used alone or as a mixture of two or more. If the monomer to be reacted is a liquid, it may be directly reacted without a solvent. The reaction time varies significantly depending on the type of reaction raw materials used, the proportion used, the reaction temperature, and the conditions of the solvent.
About 100 hours, preferably 1 to 50 hours.

The reaction method is not particularly limited, and the reaction is carried out using a continuous, semi-continuous or batch reaction layer. When using a batch system, it is desirable to carry out the reaction with stirring. In constituting the polymerization reaction system, especially the order and method of compounding the monomers such as the aryl sulfoxide compound of the formula [3] and the aryl sulfide compound of the formula [4], acid, oxidizing agent, catalyst and solvent, etc. There is no limitation, and they can be compounded simultaneously or stepwise in various orders and manners.

The reaction temperature is usually from -50 ° C to 150 ° C.
℃, preferably 0 ℃ ~ 50 ℃. The reaction pressure is not particularly limited, and may be increased or decreased as necessary. Usually, the reaction can be suitably performed 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.

In any case, the poly (arylene sulfonium salt) compound represented by the formula [2] can be produced, for example, in a polymerization degree of 2 to 10 by a polymerization method under extremely mild conditions.
00, manufactured with a viscosity of about 0.05 to 3.
The poly (arylene sulfonium salt) compound represented by the formula [2] of the present invention thus obtained is represented by R ₉
Is converted to a poly (thioarylene) compound of the present invention represented by the above formula [1] by elimination (dealkylation or dearylation reaction).

By reacting with a reducing agent or a dealkylating or dearylating reagent such as a nucleophile, R
₉ desorbs. Specific examples of the reducing agent in this case include ascorbic acid, sodium, sodium hydride, lithium aluminum hydride, sodium dithionite, hydrazine and the like. Examples of the nucleophilic reagent include alkali metal salts such as potassium chloride, sodium chloride and potassium bromide; ammonium salts such as ammonium chloride, ammonium bromide, tetraethylammonium chloride, tetrabutylammonium chloride and tetrabutylammonium bromide. Ammonia, trimethylamine, triethylamine, aniline, methylaniline,
Examples thereof include amine compounds such as dimethylaniline, pyridine, methylpyridine, and quinoline. Among them, pyridine and quinoline are most preferably used.

The reduction may be performed electrically. The reducing agent or nucleophilic reagent is required in an equimolar amount or more with respect to R ₉ to be eliminated. If it is less than equimolar, the elimination reaction will be incomplete. A solvent may be appropriately used for the dealkylation or dearylation reaction. Examples of the solvent include halogenated hydrocarbon solvents such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, and trichlorofluoromethane; and halogenated aromatic solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, and 1-chloronaphthalene. Is mentioned.

These solvents may be used alone or as a mixture of two or more. If the dealkylation and dearylation reagent is a liquid, it may be directly reacted without a solvent.
The reaction temperature is not uniform depending on the reagent used, but is usually 0 to 250 ° C, preferably 100 to 200 ° C.
It is. There are no particular restrictions on the reaction pressure, oxygen partial pressure, and the like, and the reaction can usually be suitably performed at normal pressure or the self-pressure of the reaction system.

The reaction time also varies significantly depending on conditions such as the type and concentration of the reagent, the reaction temperature, the pressure, the solvent and the like, but is usually about 0.5 to 100 hours, preferably 2 to 20 hours. In constructing the reaction, the order and method of compounding the poly (arylene sulfonium salt) compound, the dealkylating reagent and the solvent are not particularly limited, and they may be mixed simultaneously or stepwise in various orders and manners. Is also possible.

The reaction method is not particularly limited, and the reaction is carried out using a continuous, semi-continuous or batch reaction layer. When using a batch system, it is desirable to carry out the reaction with stirring. By the above-described dealkylation and dearylation reaction, the desired poly (thioarylene) compound can be obtained in a solution or as a precipitate. In this case, the degree of polymerization of the resulting poly (thioarylene) compound is the same as the degree of polymerization of the poly (arylene sulfonium salt) compound as a starting material. For example, a high-molecular-weight linear poly (thioarylene) compound having a degree of polymerization of 1000 is used. Obtainable.

The post-treatment is the formation of poly (thioarylene)
Although slightly different depending on the compound, it can be carried out according to a known method. An example of this post-processing is as follows. That is, when the dealkylation or dearylation reaction has proceeded to the required degree, the reaction mixture is added to a large excess of 10% hydrochloric acid-methanol solution to precipitate the desired poly (thioarylene) compound. The precipitated polymer is separated from the liquid by a conventional separation operation such as filtration. The separated polymer is subjected to operations such as dissolution / precipitation / separation / washing using an appropriate solvent, if necessary, and then dried, and is recovered as a produced polymer.

As a solvent for dissolving the polymer,
For example, trichloroethane, 1-chloronaphthalene,
N-methylpyrrolidone and the like are preferably used. Also,
As the precipitation liquid and the washing liquid, water, methanol, acetone, dichloromethane, chloroform, diethyl ether, and a mixture thereof are usually used, and methanol is most preferably used.

The poly (thioarylene) compound of the present invention, in particular, the fluorine atom-substituted poly (thioarylene) compound obtained by the above-described method has heat resistance, chemical resistance,
Excellent rigidity, strength, impact resistance, and friction resistance. Compared with the conventional method, there is no crosslinked structure or branched structure, and since it is a high molecular weight substance, it is excellent in processability. Further, since there is no mixing of impurities such as alkali metal salts, the film has high insulating properties. These characteristics can be suitably used for electric / electronic parts and axles of automobiles. The film can be formed by a solvent casting method, and can be used as an oxygen-enriched film.

Hereinafter, the present invention will be described in more detail with reference to examples. Of course, this invention is not limited at all by the following Examples.

[0047]

EXAMPLE 1 Synthesis of poly (thio-2,3,5,6-tetrafluoro-1,4-phenylene) 4-methylsulfinyl-2,3,5 in 10 ml of trifluoromethanesulfuric acid under air. , 6,2 ', 3',
5 ', 6'-octafluorodiphenyl sulfide
008 mol and 0.004 mol of phosphorus pentoxide,
The mixture was stirred at room temperature for 2 days. The reaction solution was dropped into ether, and a white precipitate was obtained. The precipitate was filtered for purification, washed with ether and dried to give poly (methylsulfonio-2,3,5,6-tetrafluoro-1,
4-phenylenethio-2,3,5,6-tetrafluoro-1,4-phenylenetrifluoromethane sulfate) was obtained at a yield of 100%.

This precursor polymer was dissolved in 50 ml of pyridine, stirred at room temperature for 30 minutes, and reacted at 120 ° C. overnight. When the reaction solution was dropped into 500 ml of 10% hydrochloric acid-methanol, a white powder precipitate was obtained. The precipitate was filtered for purification, washed with methanol and dried to give poly (thio-2,3,5,6-tetrafluoro-
1,4-phenylene) was obtained with a yield of 100%.

The reaction formula is as follows.

[0050]

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The analysis results are shown below.

[0052]

[Table 1]

Example 2 Synthesis of poly (thio-2,6-fluoro-1,4-phenylene) 4-methylsulfinyl-3,5,2 ', 6' - tetrane in 10 ml of trifluoromethanesulfuric acid under air. Dissolve 0.01 mol of fluorophenyl sulfide and add 10 mol
Stirred at C for 24 hours. When the reaction solution was dropped into ether, a white precipitate was obtained. After filtration the precipitate for purification by washing with ether drying, poly (methylsulfonyl niobium-2,6-fluoro-1,4-Fenirenchio 2,6-difluoro-1,4-phenylene Rent trifluoromethane Sulfate) was obtained in a yield of 100%.

This precursor polymer was dissolved in 50 ml of quinoline, stirred at room temperature for 30 minutes, and reacted at 180 ° C. for 20 hours. When the reaction solution was dropped into 500 ml of 10% hydrochloric acid-methanol, a white powder precipitate was obtained. The precipitate was filtered for purification, washed with methanol and dried to obtain poly (thio-2,6-difluoro-1,4-phenylene) represented by the following formula in a yield of 100%.

[0055]

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The analysis results are shown below.

[0057]

[Table 2]

Example 3 Poly (thio-2,3,5,6-
Tetrafluoro-1,4-phenyleneoxy-1,4-
Synthesis of phenylene) In air, 4-methylsulfinyl-2,3,5,6-tetrafluorodiphenyl ether (0.007 mol) was dissolved in 10 ml of methanesulfuric acid, and the mixture was stirred at room temperature for 10 hours. The reaction solution was dropped into ether, and a white precipitate was obtained. The precipitate was filtered for purification, washed with ether and dried to give poly (methylsulfonio-2,2).
3,5,6-tetrafluoro-1,4-phenyleneoxy-1,4-phenylene methane sulfate) in a yield of 100
%.

This precursor polymer was dissolved in 50 ml of pyridine, stirred at room temperature for 30 minutes, and reacted at 120 ° C. for 20 hours. When the reaction solution was dropped into 500 ml of 10% hydrochloric acid-methanol, a white powder precipitate was obtained. The precipitate was filtered for purification, washed with methanol and dried to obtain poly (thio-2,3,5,6) represented by the following formula.
-Tetrafluoro-1,4-phenyleneoxy-1,4
-Phenylene) in a yield of 100%.

[0060]

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The results of the analysis are shown below.

[0062]

[Table 3]

Example 4 Poly (thio-2,3,5,6-
Synthesis of tetrafluoro-1,4-phenylene) Oxygen and 0.01 mol of methylsulfenyl-2,3,5,6,2 ′, 5 ′, 6′-octafluorodiphenylsulfide in 10 ml of trifluoromethane sulfate under oxygen. 0.02 mol of phosphorus pentoxide and 0.0004 mol of cerium ammonium nitrate were mixed and stirred at room temperature for 1 day. When the reaction solution was dropped into ether, a white precipitate was obtained. The precipitate was filtered for purification, washed with ether and dried to obtain poly (methylsulfonio-2,
3,5,6-tetrafluoro-1,4-phenylenethio-2,3,5,6-tetrafluoro-1,4-phenylene trifluoromethane sulfate) was obtained at a yield of 96%.
This precursor polymer was dissolved in 60 ml of pyridine, stirred at room temperature for 30 minutes, and reacted at 120 ° C. overnight. When the reaction solution was added dropwise to 600 ml of 10% hydrochloric acid-methanol, a white powder precipitate was obtained. The precipitate was filtered for purification, washed with methanol and dried to obtain poly (thio-2,3,5,6-tetrafluoro-1,4-phenylene) at a yield of 100%.

[0064]

As described in detail above, a high molecular weight poly (thioarylene) compound having a linear structure is produced by the method of the present invention using a poly (arylene sulfonium salt) compound as a precursor. In particular, fluorine-substituted poly (thioarylene) compounds have heat resistance, chemical resistance, friction resistance,
It shows excellent properties such as oxygen permeability and high refractive index.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 75/00-75/12

Claims (7)

(57) [Claims] [Claim 1] Formula [1] (However, each of from R ₁ R ₈ is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, may be different kinds be the same as each other, small
Both one but with a halogen atom, X is, indicates oxygen atom or a sulfur atom,, n to a method of manufacturing a poly (Chioariren) compound represented by indicating the degree of polymerization of 2 or more integer), Formula [2] (Each of R ₁ to R ₈ , X and n represent the same as described above.)
And, R ₉ is an alkyl group or an aryl group,, Y- is poly (Chioariren, wherein the poly (arylene sulfonium salt) compound represented by an anion) reacting dealkylation or de arylation A) a process for preparing the compound; 2. A halogen source in which all of R ₁ to R ₈ are the same.
2. Preparation of the poly (thioarylene) compound of claim 1 which is a
Construction method. 3. All of R ₁ to R ₈ are fluorine atoms
A method for producing the poly (thioarylene) compound according to claim 1. 4. A reducing agent or a nucleophilic reagent, or electrolysis.
Dealkylation or dearylation reaction by reduction
Poly (thioarylene) according to any one of claims 1 to 3
Manufacturing method of compound. 5. The method according to claim 1, wherein
Li (arylene sulfonium salt) compound has the formula (3) ## STR3 ## ( Each of R ₁ to R ₈ represents a hydrogen atom, a halogen atom,
Represents an alkyl group or an alkoxy group.
Or different types, but at least one
Is a halogen atom, and R ₉ is an alkyl group or an aryl
X represents an oxygen atom or a sulfur atom).
The aryl sulfoxide compound is an acid or an acid anhydride.
(Thiol) obtained by polymerizing
(Rylene) a method for producing a compound. 6. The method according to claim 1, wherein
The poly (arylene sulfonium salt) compound is represented by the following formula [4] : ( Each of R ₁ to R ₈ represents a hydrogen atom, a halogen atom
, An alkyl group and an alkoxy group.
Or different types, but at least one
Is a halogen atom, and R ₉ is an alkyl group or an aryl
X represents an oxygen atom or a sulfur atom)
Oxidative polymerization of the aryl sulfide compound
Preparation of the poly (thioarylene) compound obtained
Construction method. 7. The oxidative polymerization according to claim 6, wherein the oxidizing agent and the oxidizing agent
And / or oxidative polymerization in the presence of a catalyst or electrolysis
Poly (thioarylene) compound, which is oxidative polymerization by oxidation
Manufacturing method of goods.