JPH0598008A - Production of fluoropolyarylene thioether - Google Patents

Abstract

PURPOSE:To provide a substantially linear polyarylene thioether containing a fluorocarbon chain as the main chain and having a markedly low degree of crosslinking under very mild reaction conditions. CONSTITUTION:At least one compound of the general formula (wherein R<1> to R<8> which may be the same or different from each other are hydrogen, halogen, alkyl or alkoxy; X is oxygen or sulfur; A is hydrogen or a substituted or unsubstituted phenoxy or thiophenoxy; and n is an integer of 1 or greater) and at least one sulfur source are subjected to oxidative polymerization.

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 containing a fluorocarbon chain in its main chain, and more particularly to a main chain of poly (diphenoxyfluorocarbon) thioether, poly (dithiophenoxyfluorocarbon) thioether, etc. The present invention relates to a simple method for producing a polyarylene thioether containing a fluorocarbon chain, which can be obtained at low cost under mild polymerization conditions.

[0002]

2. Description of the Related Art Conventionally, polyphenylene thioether is
Known as a resin with excellent heat resistance, mechanical properties, etc., dihalogeno aromatic compound and alkali metal sulfide,
It is produced by a polycondensation reaction in a polar solvent at high temperature and high pressure. Further, the fluorine-containing polymer is known as a resin excellent in oil resistance, chemical resistance, electrical characteristics and the like, and is generally synthesized by radical polymerization of a fluorine-containing unsaturated compound. A polymer having both of these structures in the main chain is expected to be a polymer having both properties such as heat resistance, chemical resistance, mechanical properties, and electrical properties. However, it was difficult to obtain a desired polymer because both polymers have completely different synthetic methods.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to solve the above-mentioned problems and to have the advantages of polyfluorocarbon and polyarylene thioether in combination with oil resistance and plasticity. ,chemical resistance,
A polyarylene thioether containing a fluorocarbon chain in the main chain, which has high heat resistance and is excellent in electrical properties, mechanical properties, chemical properties, etc., and in particular, a substantially linear polyphenoxyphenylene sulfide containing few by-products of crosslinked polymers and To provide a polymer having a polyfluoromethylene structure, a polyphenylene ether, and a polymer having a polyfluoromethylene structure simply, under mild polymerization conditions, at low cost, and to provide an industrially remarkably advantageous production method. is there.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the inventors have found that starting compounds containing a fluorine compound having an aromatic ring such as diphenoxyperfluorocarbon and dithiophenoxyperfluorocarbon and sulfur. It has been found that a one-step polymerization method using a source is extremely effective in achieving this purpose.

The gist of the present invention is as follows. Formula [1] (wherein R ^{1 to} R ⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R ^{1 to} R ⁸ may be the same kind or different kinds). X is an oxygen atom or a sulfur atom, A is a hydrogen atom, a substituted or unsubstituted phenoxy group or a thiophenoxy group, and n is an integer of 1 or more. A method for producing a polyarylene thioether, which comprises oxidatively polymerizing at least one kind and a sulfur source.

[0006]

[Chemical 3]

Specifically, in the above method for producing a polyarylene thioether, (1) a method in which oxidative polymerization is carried out in the presence of an acid and an oxidizing agent, and (2) oxidative polymerization is carried out in the presence of an acid, oxygen and an oxidative polymerization catalyst. And (3) oxidative polymerization in the presence of a Friedel-Crafts catalyst.

The details of R ^{1 to} R ⁸ in the general formula [1] are as follows. That is, exemplifying each specific example of R ^{1 to} R ⁸ above,
For example, hydrogen atom; methyl group, ethyl group, propyl group,
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, octyl group; fluorine atom, chlorine atom , Bromine atom,
Halogen atom such as iodine atom; alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, etc. You can Among these, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group and an ethyl group, and an alkoxy group having 1 to 4 carbon atoms such as a methoxy group and an ethoxy group are preferable, and particularly a hydrogen atom, a methyl group, an ethyl group. , Methoxy group and the like are preferable.

The A in the general formula [1] will be described in detail. A is a hydrogen atom, a phenoxy group or a thiophenoxy group. For the phenoxy group or the thiophenoxy group, a lower alkyl group such as a methyl group or an ethyl group, or methoxy. It may have a substituent such as a lower alkoxy group such as a group. When the phenoxy group or thiophenoxy group has a substituent, it preferably has at least one unsubstituted hydrogen atom, and this hydrogen is preferably in the para position.

Explaining n in the general formula [1] in detail, n is not limited as long as it is an integer of 1 or more. However, when n is extremely large, the solubility in a solvent is lowered, and therefore, 1 is preferable. <N <100 is preferable.

The compound represented by the general formula [1] is a diiodide represented by the general formula [2] (where n is an integer of 1 or more) I (CF ₂ ) _n I [2] And the general formula [3] (where R ¹
To R ⁴ are the same groups as R ^{1 to} R ⁸ in the general formula [1].
R ^{1 to} R ⁴ may be the same kind or different kinds. X and A are also X in the general formula [1],
It is the same group as A. It can be easily synthesized by mixing and reacting with the compound represented by

[0012]

[Chemical 4]

In the method of the present invention, not only can one of the compounds represented by the general formula [1] be polymerized to obtain a homopolymer polyarylene thioether, but also the above general formula Polyarylene thioethers (copolymers or mixtures or compositions of homopolymers / copolymers) of various types and structures can be obtained by copolymerizing a plurality of compounds represented by [1]. ..

It is also possible to obtain a polymer having an arbitrary fluorine content by copolymerizing the diphenyl sulfide and / or diphenyl ether in an appropriate amount.

In the present invention, at least one compound represented by the general formula [1] and a sulfur source are oxidatively polymerized to give a compound represented by the general formula [4] (where B is
A residue obtained by removing one hydrogen on the aromatic nucleus from the structure of A. However, when A is a hydrogen atom, B is a single bond, that is, a phenyl group and a sulfur atom are directly bonded. m represents an integer of 1 or more. It is possible to obtain a polyarylene thioether having a main chain structure represented by), particularly a linear polyarylene thioether having a remarkably low degree of crosslinking.

[0016]

[Chemical 5]

When diphenyl ether or diphenyl sulfide is copolymerized with the compound represented by the above general formula [1], it is usually represented by the general formula [5] or [6] (where B is aromatic from the structure of A). Residue obtained by removing one hydrogen atom from the nucleus, provided that when A is a hydrogen atom, B is a single bond, that is, a phenyl group and a sulfur atom are directly bonded, p, q, r each represents an integer of 1 or more), and thus a polyarylene thioether can be obtained.

[0018]

[Chemical 6]

[0019]

[Chemical 7]

Here, in the case of obtaining a so-called homopolymer, one of the compounds represented by the above general formula [1] may be used alone as a reaction raw material.

After the polyarylene thioether is obtained by such oxidative polymerization, the polyarylene thioether having a higher degree of polymerization can be obtained by heating the polyarylene thioether.

The method for producing a polyarylene thioether according to the present invention comprises a first step for synthesizing a polyarylene thioether and a second heating reaction for increasing the degree of polymerization of the polyarylene thioether synthesized by the first step.
Although it can be divided into two stages, since the yield and purity in the first step of oxidative polymerization of the compound represented by the general formula [1] are high, and the efficiency of the reaction in the second step is also high, the Hawkins method is used. Compared with the above, the reaction time can be shortened, the reaction temperature can be lowered, and the polyarylene thioether can be obtained in high yield. That is, according to the present invention, from an inexpensive raw material,
It is possible to easily obtain a high polymerization degree polyarylene thioether with a high yield.

The reaction of the second step is usually carried out by heating the polyarylene thioether obtained in the first step. The presence of a solvent having a high boiling point is not limited, but the reaction without a solvent is preferable. This reaction proceeds if heated in air. The heating temperature cannot be specified because it depends on the type of polyarylene thioether, but it is not limited as long as there is a temperature at which radicals are generated. The reaction time is also influenced by the concentration of the polyarylene thioether copolymer and the reaction temperature, and can be appropriately selected according to the purpose and conditions.
Thereby, a high degree of polymerization and high purity polyarylene thioether can be obtained.

Examples of the compound represented by the above general formula [1] include diphenoxydifluoromethane and 1,2-
Diphenoxytetrafluoroethane, 1,3-diphenoxyperfluoropropane, 1,4-diphenoxyperfluorobutane, 1,5-diphenoxyperfluoropentane, 1,6-diphenoxyperfluorohexane,
1,7-Diphenoxyperfluoroheptane, 1,8-
Examples thereof include diphenoxyperfluorooctane, 1,9-diphenoxyperfluorononane, and 1,10-diphenoxyperfluorodecane.

As the compound represented by the general formula [1], dithiophenoxydifluoromethane, 1,2-
Dithiophenoxytetrafluoroethane, 1,3-dithiophenoxyperfluoropropane, 1,4-dithiophenoxyperfluorobutane, 1,5-dithiophenoxyperfluoropentane, 1,6-dithiophenoxyperfluorohexane, 1,7- Dithiophenoxyperfluoroheptane, 1,8-dithiophenoxyperfluorooctane, 1,9-dithiophenoxyperfluorononane, 1,10-dithiophenoxyperfluorodecane and the like are also exemplified.

Further, as the compound represented by the general formula [1], 1,2-bis (3,5-dimethylphenoxy) -1,1,2,2-tetrafluoroethane, 1,3
-Bis (3,5-dimethylphenoxy) -perfluoropropane, 1,4-bis (3,5-dimethylphenoxy) -perfluorobutane, 1,5-bis (3,5-dimethylphenoxy) -perfluoropentane , 1,6-
Bis (3,5-dimethylphenoxy) -perfluorohexane, 1,7-bis (3,5-dimethylphenoxy)
-Perfluoroheptane, 1,8-bis (3,5-dimethylphenoxy) -perfluorooctane, 1,9-bis (3,5-dimethylphenoxy) -perfluorononane, 1,10-bis (3,5 -Dimethylphenoxy)-
Perfluorodecane and the like are also exemplified.

Further, as the compound represented by the above general formula [1], 1,2-bis (3,5-dimethylthiophenoxy) -tetrafluoroethane, 1,3-bis (3,5)
-Dimethylthiophenoxy) -perfluoropropane,
1,4-bis (3,5-dimethylthiophenoxy) -perfluorobutane, 1,5-bis (3,5-dimethylthiophenoxy) -perfluoropentane, 1,6-bis (3,5-dimethylthio Phenoxy) -perfluorohexane, 1,7-bis (3,5-dimethylthiophenoxy) -perfluoroheptane, 1,8-bis (3,5-
Dimethylthiophenoxy) -perfluorooctane,
1,9-bis (3,5-dimethylthiophenoxy) -perfluorononane and 1,10-bis (3,5-dimethylthiophenoxy) -perfluorodecane are also exemplified.

Further, as the compound represented by the above general formula [1], 1,4-bis (2,5-dimethylphenoxy) -perfluorobutane and 1,4-bis (2,5-dimethylthiophenoxy) -Perfluorobutane, 1,6
-Bis (2,5-dimethoxyphenoxy) -perfluorohexane, 1,6-bis (2,5-dimethoxyphenoxy) -perfluorohexane, 1,6-bis (4-phenoxyphenoxy) -perfluorohexane, 1 , 6
-Bis (4-phenoxythiophenoxy) -perfluorohexane, 1,6-bis (4-thiophenoxyphenoxy) -perfluorohexane, 1,6-bis (4-thiophenoxythiophenoxy) -perfluorohexane, etc. It is illustrated.

As the sulfur source used in the method of the present invention, a compound capable of forming a sulfide bond between aromatic nuclei by electrophilic reaction with aromatic nuclei under oxidative polymerization conditions is adopted. Examples thereof include sulfur and halogenated sulfur, with dichlorodisulfide and sulfur being particularly preferable.

The oxidizing agent in the above method (1) is not particularly limited as long as it has the ability to oxidize the sulfur source and does not inhibit the progress of the polymerization reaction.

As a specific example of such a device, 2,3-
Dichloro-5,6-dicyano-p-benzoquinone, tetrachloro-p-benzoquinone, tetrabromo-p-benzoquinone, 1,4-diphenoquinone, tetramethyldiphenoquinone, tetracyanoquinodimethane, tetracyanoethylene, thionyl chloride, etc. Organic oxidizers of perbenzoic acid,
Examples thereof include organic peroxides such as m-chloroperbenzoic acid and benzoyl peroxide; lead tetraacetate, thallium triacetate, cerium (tetravalent) acetylacetonate, vanadium pentoxide and the like. Among these, especially 2,3-dichloro-5,6
Preferred are quinones such as -dicyano-p-benzoquinone, tetrachloro-p-benzoquinone, tetrabromo-p-benzoquinone or vanadium pentoxide.

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

The above-mentioned amount [A] of the oxidizing agent cannot be uniformly defined because it varies depending on the reaction raw material used, the type of solvent, the type of oxidizing agent, etc., but it is usually the above-mentioned general formula [1]. The ratio [A] of the amount of the compound represented [B] or the amount of the sulfur source [C] to the compound having a small number of moles.
/ [B] or [C] (molar ratio) 0.1 to 50,
It is preferably 0.5 to 5.

If this value is less than 0.1, the polymerization rate will be slow and the yield of the polymer will be reduced. Meanwhile, 5
When it exceeds 0, the effect corresponding to it cannot be seen.

As the oxidative polymerization catalyst of the above-mentioned method (2), a metal complex or salt of Group 5 (Group 5A) or Group 6 (Group 6A) of the Periodic Table is suitable, and it is limited to a ligand and a counter ion. Of these, complexes with acetylacetone, porphyrin and the like are preferred.

Examples of the complexes of the metals of Groups 5 and 6 include vanadium compounds such as vanadyl acetylacetonate, vanadyl tetraphenylporphyrin, vanadium acetylacetonate, molybdenum oxide acetylacetonate, molybdenum oxide (tetravalent). Such as molybdenum compounds. Among these, vanadyl acetylacetonate, vanadium acetylacetonate, and vanadyl tetraphenylporphyrin are particularly preferable.

The above-mentioned oxidative polymerization catalysts such as these compounds may be used alone or in combination such as mixing or compounding two or more kinds.

Method using the above-mentioned oxidative polymerization catalyst (2)
Polymerization does not proceed in a system in which oxygen does not exist at all, for example, under a nitrogen atmosphere, and the presence of oxygen is required. Therefore, usually, the higher the oxygen partial pressure is, the more preferable it is, but the atmospheric pressure is sufficient, and even if the pressure is reduced, the reaction proceeds if oxygen is present to some extent.

On the other hand, in the polymerization of the method (1) using an oxidizing agent, oxygen is unnecessary because the sulfur source is directly oxidized by the oxidizing agent. However, even in this case, oxygen is acceptable.

The amount [D] of the oxidative polymerization catalyst used in the above-mentioned polymerization reaction is smaller than the amount [B] of the compound represented by the general formula [1] or the amount [C] of the sulfur source. The ratio [D] / [B] or [C] (molar ratio) of the number to the compound is 0.00001 to 5, preferably 0.001 to 0.1.

If this value is less than 0.00001, the polymerization rate becomes slow. On the other hand, if it exceeds 5, the cost of the catalyst becomes high, which is economically disadvantageous.

The acid in the above method (1) or (2) is for suppressing the deactivation of the polymerization active species, and a part thereof is changed to a proton acid by the coexistence of a proton acid or a proton donating substance. A known organic acid,
It is an inorganic acid or a mixture or complex thereof.

Specifically, for example, hydrochloric acid, hydrobromic acid,
Non-oxygen acids such as hydrocyanic acid; sulfuric acid, phosphoric acid, chloric acid, bromic acid,
Inorganic oxo acids such as nitric acid, carbonic acid, boric acid, molybdic acid, isopoly acid, heteropoly acid; sodium hydrogen sulfate, sodium dihydrogen phosphate, proton residual heteropoly acid salt,
Partial salts or partial esters of sulfuric acid such as monomethylsulfuric acid and trifluoromethanesulfuric acid; compounds that can be dissolved in solvents such as ammonium chloride, ammonium phosphate, ammonium sulfate, and ammonium heteropolyate, or that act as protic acids by decomposition; acetic acid, propionic acid , Butanoic acid, succinic acid, benzoic acid, phthalic acid and other monovalent or polyvalent carboxylic acids; halogen-substituted carboxylic acids such as monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monofluoroacetic acid, difluoroacetic acid, trifluoroacetic acid;
Monovalent or polyvalent sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, benzenedisulfonic acid; polyvalent sulfones such as sodium benzenedisulfonate Examples thereof include partial metal salts of acids.

Among these, strong acidic protonic acids which are non-volatile and have high stability are preferable, and sulfuric acid, trifluoroacetic acid, trifluoromethanesulfonic acid and the like are particularly preferable.

These acids may be used alone or 2
You may mix or combine 2 or more types, and may combine them.

The proportion of the acid used depends on the type and composition of the acid,
Type of reaction raw material and solvent, concentration of impurities such as water in the system,
It cannot be defined uniformly because it depends on other conditions such as reaction temperature, but it may be a concentration at which the polymerization reaction is started and a concentration at which side reactions other than the intended polymerization reaction such as decomposition reaction are suppressed. ..

When the oxidative polymerization catalyst of the method (2) is used, unlike the case of the method (1), water is generated along with the progress of the polymerization. Therefore, it is desirable to carry out the polymerization in the presence of a dehydrating agent. Usually, dehydrating agents that can be suitably used include acid anhydrides such as acetic anhydride, trifluoroacetic anhydride, trifluoromethanesulfonic anhydride. In addition, there is no limitation as long as it does not affect the polymerization reaction, and anhydrous sodium sulfate, calcium chloride or the like may be used.

The ratio of the dehydrating agent used cannot be uniformly defined because it depends on other conditions such as the type and composition of acid, the types of reaction raw materials and solvents, the concentration of impurities such as water in the system, and the reaction temperature. The concentration may be such that the polymerization reaction is started and the side reaction other than the intended polymerization reaction such as the decomposition reaction is suppressed.

The Friedel-Crafts catalyst of the above method (3) is a catalyst that promotes the Friedel-Crafts reaction, and known catalysts can be used. In particular,
In particular, antimony pentachloride, aluminum chloride, titanium tetrachloride, iron, silica gel, alumina, diphosphorus pentoxide and the like can be mentioned. Among these, antimony pentachloride is particularly preferable.

Amount [F] of the above Friedel-Crafts catalyst
Cannot be uniformly defined because it varies depending on the reaction raw material used, the type of solvent, the type of Friedel-Crafts catalyst, etc., but is usually the amount [B] of the compound represented by the general formula [1] or Ratio [E] / [B] or [C] of the sulfur source amount [C] to a small number of moles of the compound
The (molar ratio) is 0.00001 to 50, preferably 0.001 to 5.

When this value is less than 0.00001, the polymerization rate becomes slow, and the yield of the polymer also decreases.
On the other hand, if it exceeds 50, the effect commensurate with it cannot be seen.

The polymerization in the present invention can be carried out in the absence of a solvent, but it is usually desirable to carry out in the presence of a solvent. As the solvent, any solvent that does not substantially lose the polymerization activity can be used, but normally, a solvent that can dissolve the reaction raw material and the acid used is desirable.

Usually, suitable solvents include, for example, nitromethane, dichloromethane, dibromoethane, tetrachloroethane, nitrobenzene, etc., and also solvents generally used for Friedel-Crafts reaction, cationic polymerization and the like. It can be appropriately selected and used suitably.

These solvents may be used alone or in admixture of two or more, or may be appropriately mixed and used with an inert solvent or the like, if necessary. Further, when the reaction raw material is liquid, it is not necessary to use a solvent.

The concentration of the reaction raw materials, that is, the total concentration of the compound represented by the general formula [1] and the sulfur source is not particularly limited. Usually, for example, 10 ⁻⁴ mol /
It is preferable that the range is 1 or more.

The presence of water increases the rate of polymerization and, on the other hand, decreases the polymerization activity and affects the polymerization in various ways. Since the activity may be significantly reduced, it is preferable to set the concentration so that it falls within the allowable range. The permissible concentration range of water cannot be uniformly defined because it varies depending on the type of acid and solvent used.

The reaction temperature in the above-mentioned polymerization is not uniform depending on the acid used and the kind of the reaction raw material, but it is usually −
25-250 degreeC, Preferably it is 0-150 degreeC.

The reaction pressure and oxygen partial pressure are not particularly limited, and usually, normal pressure or the reaction system's own pressure can be suitably used. However, if necessary, it can be carried out under pressure using a mixed gas with a diluting gas which does not hinder the polymerization reaction.

The reaction time includes the acid to be used, the kind of reaction raw material and its usage rate, the reaction temperature, the oxygen partial pressure, the usage rate of the catalyst,
Although it varies remarkably depending on conditions such as a solvent, it is usually 0.5 to
It is 100 hours, preferably 2 to 50 hours.

In constructing the polymerization reaction system, the order and method of mixing the oxidizing agent, the oxidation polymerization catalyst, or the Friedel-Crafts catalyst, the compound represented by the general formula [1], the sulfur source, and the solvent are described. Is not particularly limited, and it is also possible to mix each of them simultaneously or stepwise in various orders and manners.

The polymerization may be carried out in a homogeneous or heterogeneous multiphase system or a slurry system.

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 stir the reaction system.

By the method as described above, the desired polyarylene thioether can be obtained in the solution after the reaction.

The treatment after the polymerization can be carried out according to a known method. An example of the 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 contacted with a poor solvent such as water, a lower alcohol such as methanol or a mixed solution thereof to deactivate the catalyst, and Allow the product polymer to precipitate. At this time, if necessary, a polymerization terminator such as a basic substance may be used in combination.

In the post-treatment method, it is not always necessary to contact with a poor solvent or a basic substance, and if the polymer is precipitated in the polymerization solvent during the polymerization, the polymer can be separated and dried while continuing the polymerization.

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 dissolved / reprecipitated / separated / methanol using an appropriate solvent and a reprecipitation solution. After repeating operations such as washing as many times as necessary, the polymer can be dried and recovered as purified polymers having 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.

As the reprecipitation liquid and the cleaning liquid, usually, for example, water, methanol, carbon disulfide, a mixed liquid thereof, or the like, particularly methanol or the like can be preferably used.

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

The fluorine-containing polyphenylene thioether obtained by the present invention is excellent in oil resistance, plasticity, heat resistance and chemical resistance, and is excellent in various mechanical properties such as rigidity, strength, impact resistance and abrasion resistance. Also, by selecting the length of the fluorocarbon chain in the main chain, viscosity and elasticity can be exhibited. Furthermore, in the present polymerization method, since impurities such as metal salts are small, electrical characteristics such as insulation resistance are remarkably excellent. It is an engineering plastic with excellent processability due to the fact that the structure of the polymer is substantially linear, and it is used in various fields such as electronics, electricity, machinery, paints, automobiles, and chemicals. It can be suitably used as a device part, a material, etc.

[0072]

【Example】

Example 1 Under a nitrogen atmosphere, 10.36 g of 1,6-dithiophenoxyperfluorohexane and 1.35 g of dichloride disulfide.
Was dissolved in 100 ml of dichloromethane, 2.27 g of 2,3-dichloro-5,6-dicyano-p-benzoquinone,
The mixture was mixed with 0.15 g of trifluoromethanesulfonic acid and stirred at room temperature for 40 hours. When the reaction solution was added dropwise to hydrochloric acid-methanol, a white precipitate was obtained. The precipitate was filtered to separate from unreacted substances and catalyst, washed and dried to obtain a polymer 3.8.
4 g was obtained.

The analysis results of the obtained polymer are as follows. Elemental analysis (calculated value) C; 40.89 (39.43) (%) H; 1.35 (1.47) F; 39.13 (41.56) S; 18.63 (17.54) IR spectrum ^{_{ν C = C; 1400,1480,1580cm -1 ν}} CF; 1100cm -1 δ CH; 825cm -1 mp 265 ° C. The weight average molecular weight (polystyrene equivalent by GPC (solvent N- methylpyrrolidone); the same applies hereinafter) 4200

Example 2 5.18 g of 1,6-dithiophenoxyperfluorohexane and 1.86 of diphenyl sulfide in an oxygen atmosphere
g, 1.35 g of dichloride disulfide is dissolved in 100 ml of tetrachloroethane, 0.27 g of vanadyl acetylacetonate, 0.15 of trifluoromethanesulfonic acid
g and 10.5 g of trifluoroacetic anhydride were mixed and reacted at room temperature for 40 hours. Purification by a predetermined method gave 6.53 g of a polymer.

The analysis results of the obtained polymer are as follows. Elemental analysis (calculated value) C; 47.45 (47.12) (%) H; 1.98 (2.11) F; 29.36 (29.81) S; 21.21 (20.96) IR Spectrum ν _{C = C} ; 1390, 1480, 1580 cm ⁻¹ ν _CF ; 1090 cm ⁻¹ δ _CH ; 815 cm ⁻¹ melting point 190 ° C. weight average molecular weight 6400

Example 3 In the air, 5.58 g of 1,6-bis (phenyloxy-1,4-phenylenethio) -perfluorohexane, 1.70 g of diphenyl ether, and 1.3 disulfide dichloride were prepared.
5 g Dissolved in 100 ml dichloromethane, 2,3-dichloro-5,6-dicyano-p-benzoquinone 2.27
g and 0.15 g of trifluoromethanesulfonic acid were mixed and reacted at room temperature for 20 hours. Purification by a predetermined method gave 7.19 g of a polymer.

The analysis results of the obtained polymer are as follows. Elemental analysis (calculated value) C; 53.86 (54.08) (%) H; 2.66 (2.59) F; 24.25 (24.43) S; 13.89 (13.75) O 5.35 (5.15) IR spectrum ν _{C = C} ; 1480, 1580 cm ⁻¹ ν _CF ; 1100, 1140, 1170 cm ⁻¹ ν _CO ; 1240 cm ⁻¹ δ _CH ; 830,870 cm ⁻¹ melting point 120 ° C. weight average Molecular weight 15400

Example 4 Under a nitrogen atmosphere, 7.71 g of 1,4-diphenoxyperfluorobutane and 1.35 g of disulfide dichloride were dissolved in 100 ml of dichloromethane to give 2,3-dichloro-
5,6-Dicyano-p-benzoquinone (2.27 g) and trifluoromethanesulfonic acid (0.15 g) were mixed and reacted at room temperature for 20 hours. After predetermined purification, poly (1,4-phenylene-oxy-1,4-perfluorobutylene-oxy-1,4-phenylene sulfide) having a melting point of 170 ° C.
8.03 g was obtained. The polymer was reacted in air at 250 ° C. for 10 hours and purified as described above to obtain 7.94 g of a polymer having a melting point of 265 ° C.

Example 5 1,4-bis (phenyloxy-1,4) under a nitrogen atmosphere
-Phenylenethio) -perfluorobutane 12.05
g, 1.35 g of dichloride disulfide and 6 g of nitrobenzene
It was dissolved in 0 ml, and 40 ml of a nitrobenzene solution containing 2.99 g of antimony pentachloride was added dropwise. After reacting at room temperature for 40 hours, predetermined purification was performed to obtain 12.10 g of a polymer.

The analysis results of the obtained polymer are as follows. Elemental analysis (calculated value) C; 53.14 (53.17) (%) H; 2.47 (2.55) F; 23.94 (24.02) S; 15.38 (15.21) O 5.07 (5.05) IR spectrum ν _{C = C} ; 1480,1580 cm ⁻¹ ν _CF ; 1100,1120,1170 cm ⁻¹ ν _CO ; 1240 cm ⁻¹ δ _CH ; 830,870 cm ⁻¹ melting point 114 ° C. weight average Molecular weight 28400

[0081]

INDUSTRIAL APPLICABILITY In the present invention, the reaction conditions are extremely mild and the production method is simple. In particular, it is advantageous to provide a substantially straight-chain polyarylene thioether having a fluorocarbon chain in the main chain, which has a significantly low degree of crosslinking.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsutoshi Terakasa 5029-38 Kasahata, Kawagoe City, Saitama Prefecture (72) Inventor Junya Kato 2-16-6 Nishi-Ikebukuro, Toshima-ku, Tokyo

Claims (10)

[Claims] 1. General formula [1] (wherein R ^{1 to} R ⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R ^{1 to} R ⁸ are the same type as each other. X represents an oxygen atom or a sulfur atom, and A represents a hydrogen atom, a substituted or unsubstituted phenoxy group or a thiophenoxy group.
n represents an integer of 1 or more. ) Oxidative polymerization of at least one compound represented by the formula (4) and a sulfur source, and a method for producing a polyarylene thioether. [Chemical 1] 2. General formula [1] (wherein R ^{1 to} R ⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R ^{1 to} R ⁸ are the same type as each other. X represents an oxygen atom or a sulfur atom, and A represents a hydrogen atom, a substituted or unsubstituted phenoxy group or a thiophenoxy group.
n represents an integer of 1 or more. ) Oxidative polymerization of at least one compound represented by the formula (4) and diphenyl sulfide or / and diphenyl ether in the presence of a sulfur source. [Chemical 2] 3. The method for producing a polyarylene thioether according to claim 1, wherein the oxidative polymerization is carried out in the presence of an acid and an oxidizing agent. 4. The method for producing a polyarylene thioether according to claim 3, wherein the oxidizing agent is a quinone or vanadium pentoxide. 5. The method for producing a polyarylene thioether according to claim 1, wherein the oxidative polymerization is carried out in the presence of an acid, oxygen and an oxidative polymerization catalyst. 6. The method for producing a polyarylene thioether according to claim 5, wherein the oxidative polymerization catalyst is a complex of a metal of group 5 (group 5A) or group 6 (group 6A) of the periodic table. 7. The method for producing a polyarylene thioether according to claim 1, wherein the oxidative polymerization is carried out in the presence of a Friedel-Crafts catalyst. 8. The method for producing a polyarylene thioether according to claim 7, wherein the Friedel-Crafts catalyst is antimony pentachloride. 9. The method for producing a polyarylene thioether according to claim 1, wherein the sulfur source is a halogenated sulfur compound. 10. A method for obtaining a polyarylene thioether having a higher degree of polymerization by heating the polyarylene thioether obtained by the production method according to claim 1.