JPH02212520A - Production of polyarylene thioether - Google Patents

Abstract

PURPOSE:To produce a polyarylene thioether lowered in the contents of residual chloride ion, etc., and improved in electrical properties, anticorrosiveness, melt flow properties, etc., by oxidatively polymerizing a specified thiophenol and/or a diphenyl disulfide in the presence of a proton acid. CONSTITUTION:A thiophenol (A) of formula I (wherein R<1-4> are each a substituent selected from among H, a lower alkyl, a halogen atom and a lower alkoxy) and/or a diphenyl disulfide (B) of formula II (wherein R<5-12> are each R<1>) is polymerized at -30 to 220 deg.C for 0.1-100hr in the presence of a proton acid (e.g. sulfuric acid) and 0.2-50mol, per mol of (A), of an oxidizing agent (B) (e.g. dicyanodichlorobenzoquinone) in a solvent (e.g. nitromethane) to obtain a linear polyarylene thioether having a main chain structure of formula III (wherein R<13-16> are each R<1>, and n>=2).

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a method for producing polyarylene thioether, and more specifically, the present invention relates to a method for producing polyarylene thioether, and more specifically, the present invention relates to a method for producing polyarylene thioether, which has good electrical properties with little residual elementary ions, etc. This invention relates to a method for producing polyarylene thioether that can be efficiently obtained under mild polymerization conditions.

[Prior art and the problem to be solved by the invention] Conventionally,
Polyphenylene lentioether (hereinafter sometimes abbreviated as PPT) and other polyarylene lentioethers (hereinafter sometimes abbreviated as PAT) are
The dihalogen aromatic compound and the alkali metal sulfide are produced by polycondensation reaction at high temperature and pressure in a polar solvent.

However, in this method, (1) the alkali metal salt remains in the FAT, deteriorating the electrical characteristics of the FAT; ■There were problems such as high energy consumption and high costs.

On the other hand, there is a known method of polymerizing thiophenol to obtain PAT, as disclosed in Soviet Patent No. 698,988. Industrially disadvantageous.

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

Therefore, based on such circumstances, the present inventors proposed a method for producing polyarylene thioether using a Lewis acid catalyst in the presence of an oxidizing agent (Japanese Patent Application Laid-Open Nos. 63-213526 and 63-21:1527). reference).

However, FAT obtained by this method still has room for improvement in its electrical properties due to residual chlorine ions from aluminum chloride, titanium tetrachloride, antimony pentachloride, etc. used as Lewis acid catalysts.

The present invention has been made based on the above circumstances.

The purpose of Undeveloped 1j is to solve the above-mentioned problems and to produce polyarylene thioethers such as polyphenylene thioethers with improved electrical properties 1 mechanical properties, chemical properties, etc., especially polyarylene thioethers with less cross-linked polymer by-products and substantially linear chains. It is an object of the present invention to provide a method for producing polyarylene thioethers, which is industrially extremely advantageous and allows polyarylene thioethers such as polyphenylene thioethers to be obtained easily and at low cost under mild polymerization conditions.

[Means for Solving the Problems] In order to solve the problems described in item 1rj, the present inventors have made extensive studies and found that thiophenols and/or diphenyl disulfides are used as raw material monomers, and they are mixed in the presence of a protonic acid. Below, polymerization using an oxidizing agent improves electrical properties 1 mechanical properties, chemical properties, etc. In particular, polymerization of substantially linear polyphenylene thioether with less by-products of cross-linked polymers. Polyarylene lentioether can be easily polymerized under mild conditions.

The present invention was achieved by discovering that it can be obtained at low cost.

The structure of the present invention is represented by the general formula [I]: (In formula [I], R1 to R4 are each a substituent selected from the group consisting of a hydrogen atom, a lower alkyl group, a halogen atom, and a lower alkoxy group. In addition, R1-R4 may be the same type or different types.) thiophenols represented by - and/or general formula [+1]; [In 111, S represents a sulfur atom, R
8-R12 is a hydrogen atom, a lower alkyl group,
Represents a substituent selected from the group consisting of a halogen atom and a lower alkoxy group, and R5 to R'' may be of the same type or different types,
) This is a method for producing polyarylene thioether, which is characterized in that diphenyl disulfides represented by the following are polymerized using an oxidizing agent in the presence of a protonic acid.

A more detailed explanation of R1 to R4 in the general formula [I] is as follows.

That is, specific examples of each of R1 to R4 include, for example, a hydrogen atom; a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group; , l, 1-Dimethylethyl group, pentyl group, hexyl group, heptyl group, lower alkyl group such as octyl group; Fluorine atom, chlorine atom, bromine atom, iodine atom: methoxy group, ethoxy group, propoxy group, impropoxy group , butoxy group, imbutoxy group, 5ec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group and other lower alkoxy groups.

Among these, hydrogen atoms: lower alkyl groups such as methyl groups and ethyl groups: lower alkoxy groups such as fluorine atoms, chlorine atoms, and methoxy groups are preferred, particularly hydrogen atoms, methyl groups, ethyl groups, and chlorine atoms. etc. are preferable.

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

Examples of the thiophenols represented by the general formula [I] include thiophenol, 2-methylthiophenol, 2-ethylthiophenol, 2-propylthiophenol, 2-(l-methylethyl)thiophenol, and 2-ethylthiophenol.
-butylthiophenol, 2-(1-methylpropyl)
Thiophenol, 2-(2-methylbutyl)thiophenol, 2-(1,1-dimethylethyl)thiophenol, subentylthiophenol, 2-hexylthiophenol, 2-octylthiophenol, 2-fluorothiophenol, 2-chlorothiophenol, 2-bromothiophenol, 2-iodothiophenol, 2-methoxythiophenol, 2-ethoxythiophenol, 2
-Propoxythiophenol, 2-isopropoxythiophenol, 2-butoxythiophenol, 2-5ec
-butoxythiophenol, 2-isobutoxythiophenol, 2-tertoxythiophenol, 2-
Pentyloxythiophenol, 2-hexyloxothiophenol, 2.6-dimethylthiophenol, 2.
6-diethylthiophenol, 2-methyl-6-ethylthiophenol, 2,6-difluorothiophenol,
2-Methyl-6-fluorothiophenol, 2-ethyl-6-fluorothiophenol, 2,6-dichlorothiophenol, 2,6-dibromothiophenol, 2-methyl-6-chlorothiophenol, 2.6- Dimethoxythiophenol.

2-Methyl-6-methoxythiophenol.

2.3-dimethylthiophenol, 2,3-diethylthiophenol, 2.3-difluorothiophenol, 2
-Methyl-3-fluorothiophenol, 2-fluoro-3-methylthiophenol, 2,3-dimethoxythiophenol, 2-methyl-3-methoxythiophenol, 23-dichlorothiophenol, 2-methyl-3-chlorothiophenol , 3-chloro-2-methylthiophenol, 2.5-dimethylthiophenol, 2.5-difluorothiophenol, 2.5-diethylthiophenol, 2-methyl-5-fluorothiophenol, 2-
Methyl-5-ethylthiophenol, 2-fluoro-5
-Methylthiophenol, 2,5-dichlorothiophenol, 2゜5-dimethoxythiophenol, 2-methyl-5-chlorothiophenol, 2-methyl-5-methoxythiophenol, 2-chloro-5-methylthiophenol, 2 -methoxy-5-methylthiophenol, 2-
Chloro-5-fluorothiophenol, 2-ethyl-5
-chlorothiophenol, 2-chloro-5-ethylthiophenol, 3.5-diethylthiophenol, 3.5
-difluorothiophenol, 3,5-dimethoxythiophenol, 3.5-diethylthiophenol, 3.5
-dichlorothiophenol, 3-methyl-5-fluorothiophenol, 3-methyl-5-chlorothiophenol, 3-methyl-5-methoxythiophenol, 2,3
．． 5-)-Dimethylthiophenol, 2,3.5-)-
Lifluorothiophenol, 2,3.5-triethylthiophenol, 2,3.5-tosochlorothiophenol, 2-methyl-3,5-difluorothiophenol, 2
,3,5.6-titramethylthiophenol,2,3,
5.6-tetrafluid phenol, 2,3,5.
6-tetrachlorothiophenol, 2,3,5.6-tetramethoxythiophenol, 2,3,5.6-tetraethylthiophenol, 2.6-dimethyl-3.5-tetrafluorothiophenol, 2.6- Jinichiru 3.
5-difluorothiophenol, 2,6-diethyl-3
, 5-dichlorothiophenol, 2゜6-diethyl-3
, 5-dimethylthiophenol, 2,6-ethyl-3
．． Examples include 5-dimethoxythiophenol, 2,6-dimethyl-3,5-dichlorothiophenol, and 2-methyl-6-nityl-3,5-difluorothiophenol.

Among these, thiophenol, 2-methylthiophenol, 2-ethylthiophenol, 2-fluorothiophenol, 2-chlorothiophenol, 2-methoxythiophenol, 2,6-dimethylthiophenol, 2,6-dimethylthiophenol, Nithylthiophenol, 2,6-difluorothiophenol, 2,6-dichlorothiophenol,
2,6-dimethoxythiophenol, 2,3゜5.6-
Preferred are tetrachlorothiophenol, 2,3°5,6-titramethylthiophenol, and the like.

Note that these compounds are l! ! It can be used alone or
You may use two or more types in combination.

A more detailed explanation of R5 to R'' in the general formula [11] is as follows.

That is, as specific examples of each of R5 to R'', the same examples as those shown as specific examples of R1 to R4 in the general formula [I] can be mentioned. Preferred examples are also the same as the specific examples of R1 to R4 in the general formula [I]. These are the same as those preferable as R1 to R4 in [Katsuju CI].

Examples of the diphenyl disulfides represented by the general formula [II] include:

Diphenyl disulfide, 2.2'-dimethyldiphenyl disulfide, 3,3-diphenyldimethyl disulfide, 2.2', 3.3'-tetramethyldiphenyl disulfide, 3.3'5.5''-tetramethyldiphenyl disulfide, 2 .2', 3.3', 5.5'
-hexamethyldiphenyl disulfide, 2.2',
3゜3', 5.5', 6.8'-octamethyldiphenyl disulfide, 2.2'-diethyldiphenyl disulfite, 3.3'-diethyldiphenyl disulfite,
2.2', 6.6'-tetramethyldiphenyl disulfide, 2.2', 3°3', 5.5', 6.6'-
Octaethyldiphenyl disulfide, 2.2'-dibropyluciphenyl disulfite, 3.3'-diphenyl disulfide, 2.2', 5.5'-tetraprobyl diphenyl disulfite, 2.2' -(1-methylethyl)diphenyl disulfide, 2.2'-dimethyldiphenyl disulfide, 2.2'-cybentyldiphenyl disulfide, 2.2'-cyhexyldiphenyl disulfide, 2.2'-difluorodiphenyl disulfide , 2.2'-dichlorodiphenyl disulfide, 2.
2'-dibromodiphenyl disulfide, 2.2'-short triphenyl disulfide, 3.3'-difluorodiphenyl disulfide, 3.3'-dichlorodiphenyl disulfide, 3.3'-dibromodiphenyl disulfide, 3 .3'-short triphenyl disulfite,
2.2', 3.3'-tetrafluorodiphenyl disulfite, 2°2', 3.3'-tetrachlorodiphenyl disulfide, 2.2', 5.5'-tetrafluorodiphenyl disulfide, 2.2 ', 5.5'-tetrachlorodiphenyl disulfide, 2.2'6.6'-tetrafluorodiphenyl disulfide, 2.2', 6.
6'-tetrachlorodiphenyl disulfide, 2.2'
, 6.6'-tetrabromodiphenyl disulfide, 3
．． 3', 5゜5'-tetrafluorodiphenyl disulfide, 3.3', 5.5'-tetrachlorodiphenyl disulfide, 2.2', 3.3', 5.5' hexafluorodiphenyl disulfide, 2゜2', 3.3
', 5,5'-hexachlorodiphenyl disulfide,
2.2', 3.3', 6゜6'-hexafluorodiphenyl disulfide, 2.2', 3.3', 6.6'-
Hegisa chlorocyphenyl disulfite, 2.2', 3
．． 3'5.5', 6.6'-octafluorodiphenyl disulfite, 2.2', 3.3', 5.5'6.
6'-octachlorodiphenyl disulfide, 2.2'
-dimethoxydiphenyldisulfide, 2,2'-diethoxydiphenylcisulfide, 2.2'-diisobroboxycyphenyldisulfide, 2.2'-dibroboxycyphenylcisulfite, 2.2'-dibutoxycyphenylcisulfite , 2.2', 3.3'-tetramethoxydiphenyl disulfide, 2.2', 6°6'
-Tetramethoxydiphenyl disulfide.

2.2', 6.6'-tetraethoxydiphenyldisulfide, 3,3'-dimethoxydiphenyldisulfide, 2.2', 5.5'-tetramethoxydiphenylcisulfyl~, 2.2'-dimethyl-3 , 3'-diethyldiphenyl disulfide, 2,2'-dimethyl-6,
6'-difluorodiphenyl disulfide, 2.2'-
Dimethyl-6,6'-dichlorodiphenyl disulfide, 22',6.6'-tetramethyl-3,3'5.
5′-tel~rafluorodiphenyl disulfide):
．． 2'-difluoro-6,6'-dichlorodiphenyl disulfide, 2,2'-difluoro-6,6'-simethoxydiphenyl disulfite, 2,2'-difluoro-
3,3'-dichlorodiphenyl disulfide, 2,2'
-difluoro-3,3'-dichlorodiphenyl disulfide, 2,2'-difluoro-6,6'-ethyldiphenyl disulfite, 2,2',6゜6'-tetrafluoro-3,3',5 .5'-tetramethyldiphenyl disulfide, 2.2'6.6'-tetramethyl-3,3
' , 5.5' tetrachlorodiphenyl disulfite,
2゜2', 6.6'-tetraethyl-3,3', 4゜4
'-tetramethyldiphenyl disulfide, 2.2',
6. Symmetrical diphenyl disulfides such as 6'-tetraethyl-3,3'5.5'-tetrafluorodiphenyl disulfide, 2-methyldiphenyl disulfide, 2
-ethyldiphenyldisulfide, 2-propyldiphenyldisulfite, 2-butyldiphenyldisulfide 2-fluorodiphenyldisulfide, 2-chlorodiphenyldisulfide, 2-methoxydiphenyldisulfide, 2,6-dimethylsiphenyldisulfite, 2.
6-diethyldiphenyl disulfide, 2,6-difluorodiphenyl disulfide, 2,3,5.6-tetrafluorodiphenyl disulfide, 2,3,5.6-tetramethyldiphenyl disulfide, 2,3,6-trimethylsiphenyldis rufido, 2,6-cymethyl-2
'-Ethyldiphenyl disulfide, 26'-dimethyl-2', 3', 5', 6'-tetrafluorodiphenyl disulfide, 2,6-dimethyl-2'-methoxydiphenyl disulfide, 2,6-diethyl-2'-
Methyl diphenyl disulfide, 2,6-diethyl-2
'-Methyl diphenyl disulfide, 2,6-diethyl-2'-ethyl diphenyl disulfide, 2,6=diethyl-2,3,5,6-tetrafluorodiphenyl disulfide, 2,6-dimethyl-2 ',6'-ethiethylsiphenyl disulfite.

2.6-dimethyl-2',6'-diethyldiphenyl disulfide, 2.6-dimethyl-2'6'-difluorodiphenyl disulfide, 2゜3.5.6-titramethyl-2',3',5'6'-tetra Mention may be made of asymmetric diphenyl disulfides such as fluorodiphenyl disulfide.

In the method for unreleased shellfish, one or more compounds selected from thiophenols represented by the general formula [I] and diphenyl disulfides represented by the general formula [+11] are added to Polyarylene thioethers (homopolymers, copolymers, or mixtures or compositions thereof) of various types and structures can be obtained by polymerization or copolymerization. [In ml, R13 to RI6 are R1-R4 in the above-described [11] or R in the-determined [11]
It is the same as 8-R6 or R9 to R12. Also, n
is an integer greater than or equal to 2. ) It is possible to efficiently obtain a polyarylene thioether having a main chain structure represented by the following formula, particularly a linear or substantially linear polyarylene thioether having an extremely low degree of crosslinking, with high selectivity.

As the protonic acid to be used, known organic acids, inorganic acids, or mixtures or complexes thereof can be used. Specifically, for example, non-oxygen acids such as hydrochloric acid, hydrobromic acid, prussic acid, sulfuric acid, phosphoric acid, chloric acid, nitric acid,
Inorganic oxoacids such as carbonic acid, boric acid, molybdic acid, isopoly acid, heteropolyacid, sodium hydrogen sulfate, sodium dihydrogen phosphate, proton-retaining heteropolyacid salts, sulfuric acid such as monomethyl sulfate, fluorosulfate, trifluoromethyl sulfate, etc. Partial salts or partial esters: Compounds that dissolve in solvents such as ammonium chloride, ammonium phosphate, ammonium heteropolyacid, or act as protonic acids by decomposition: acetic acid, propionic acid, butanoic acid, succinic acid, benzoic acid , monovalent or polyvalent carboxylic acids such as phthalic acid, halogenated carboxylic acids such as monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monofluoroacetic acid, difluoroacetic acid, trifluoroacetic acid; methanesulfonic acid, ethanesulfonic acid, benzene Monovalent or polyvalent sulfonic acids such as sulfonic acid, propanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, and benzenedisulfonic acid: parts of polyvalent sulfonic acids such as sodium benzenedisulfonate Examples include metal salts.

Among these, strong acidic protonic acids that are easily soluble in liquid or solvents, nonvolatile, and highly stable, such as sulfuric acid, phosphoric acid, trifluoromethyl sulfuric acid, heteropolyacid, and sulfonic acid, are preferred, and in particular, sulfuric acid, trifluoroacetic acid,
Trifluoromethyl sulfate and the like are preferred.

In the method of the present invention, one type of the protonic acid may be used alone, or two or more types may be mixed or combined and used in combination.

Polymerization is carried out with an oxidizing agent in the presence of at least one compound or composition selected from the thiophenols represented by the above-mentioned -Kiraku [I] and the diphenyl disulfides represented by the -Kirkuri [Irl], Manufactures polyarylene lentioether.

Although the polymerization can be carried out in the absence of a solvent, it is usually desirable to carry out it in the presence of a solvent.

The above-mentioned solvent can be used as long as it does not substantially eliminate the polymerization activity, but it is usually preferable that the solvent is capable of dissolving the protonic acid and the protonic acid used. Preferably, it is stable against.

Usually, examples of solvents that can be suitably used include nitromethane, dichloromethane, dibromoethane,
Tetrachloroethane, nitrobenzene, etc. can be mentioned, and in addition, solvents generally used in Friedel-Crach reactions, cation synthesis, etc. can also be suitably used by appropriately selecting them.

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

Furthermore, if the protic acid has favorable properties as a solvent, it can also be used itself as a solvent for this polymerization.

The oxidizing agent has the ability to oxidize the thiophenols represented by the above-mentioned -Kiroku [I] and/or the diphenyl disulfides represented by the above-mentioned -Kiraku [11], and has the ability to inhibit the progress of the polymerization reaction. There is no particular restriction as long as it does not interfere.

Examples of such are dicyanodichlorobenzoquinone, chloranil, promanil l.

Organic oxidizing agents such as 4-diphenoquinone, tetramethyldiphenoquinone, tetracyanoquinodimethane, tetracyanoethylene, and thionyl chloride; Organic peroxides such as perbenzoic acid, metachloroperbenzoic acid, and benzoyl peroxide; Lead tetraacetate , thallium triacetate, cerium (IV) acetylacetonate, manganese (m) acetylacetonate, and the like.

Note that these oxidizing agents may be used alone or in combination.
You may use combinations of more than one species.

The oxidizing agent used in the polymerization reaction (hereinafter referred to as [A
] may be written. ), and the thiophenols represented by the above-mentioned -Kanbatsu [1] and/or the above-mentioned -Kanbatsu [■
Thiophenols represented by 1 (hereinafter both are referred to as [
It is sometimes written as B]. ) The ratio of [A]/
[B] (mole ratio) or 0.2 to 50, preferably 0
．． 5-5.

If this value is less than 0.1, the polymerization rate will be slow;
The yield of the polymer decreases significantly, and on the other hand, even if it exceeds 50, the corresponding effect may not be achieved.

In addition, the ratio of the protonic acid used cannot be specified as the acidity varies depending on the solvent used, the type of the protonic acid, and the concentration of impurities such as water. Since the purpose is to suppress side reactions, the amount of acid may be adjusted appropriately.

The reaction temperature during the polymerization varies depending on the catalyst used and the type of polymer, but it is usually -0~220
℃, preferably -10 to 200℃.

There is no particular restriction on the reaction pressure; normally, the reaction can be carried out suitably at normal pressure or the own pressure of the reaction system, or if necessary, it may be carried out under pressure using a diluent gas etc. that does not interfere with the polymerization reaction. can.

The reaction time may vary considerably depending on other conditions such as the catalyst used, the type and proportion of the 7-mer used, and the reaction temperature, but it may normally be appropriately set in the range of about 0.1 to 100 hours.

In constituting the polymerization reaction system, the oxidizing agent, the thiophenols represented by the above-described [I] and/or
There is no particular restriction on the order and method of blending the diphenyl disulfides represented by -Kakuro [11] and the solvent, and each may be blended simultaneously or in stages in various orders, or the solvent Some require protic acids. For example, it is possible to suitably employ a method in which the diphenyl disulfides and protonic acid are dissolved in a solvent and the oxidizing agent is added to this solution.

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

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

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

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

An example of this post-processing is as follows.

That is, once the polymerization reaction is completed or has proceeded to a necessary extent, the reaction mixture is brought into contact with water, a lower alcohol such as methanol, or a mixture thereof to precipitate the product polymer. At this time, if necessary,
A polymerization terminator such as a basic substance may be used in combination.

This precipitated polymer is separated from the liquid by conventional separation operations such as filtration. The separated polymer is washed or neutralized with a washing liquid such as an alkaline aqueous solution as necessary, and then dissolved, reprecipitated, separated, or dissolved in methanol using an appropriate solvent and reprecipitation liquid as necessary. After repeating washing as many times as necessary, it can be dried and recovered as polyarylene thioether purified to various purity levels.

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

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

On the other hand, unreacted upper particulate matter 1 by-product low-molecular compounds, solvents, methanol, etc. in the mixed solution separated from the polymer are purified and recovered by normal distillation operations, and are repeatedly added to the reaction system or post-treatment process, or It can be effectively used for various other purposes.

Polyarylene thioethers such as polyphenylene thioether obtained by the method of this invention have heat resistance,
It has excellent chemical resistance and various mechanical properties such as rigidity, strength, impact resistance, and abrasion resistance.In particular, the content of common salt, which has been a problem in the past, is extremely low at a few ppm or less. Since it does not contain the C1 terminal, it has particularly excellent electrical properties and can be used in electrical and electronic fields. Furthermore, due to the fact that the polymer structure is substantially linear, it is an engineering plastic with excellent processability, and is used in the electrical and electronic fields (K&E).

In addition to parts, sealing TiA, etc.), R machine field, paint-related,
Equipment parts for various fields such as automobiles and chemicals,
It can be suitably used as mechanical parts, materials, etc.

[Example] Next, Examples of the present invention will be shown and the present invention will be explained more specifically.

(Example 1) Dicyano dichlorobenzoquinone z, z8 gt
! : Mixed and stirred at room temperature for 20 hours.

Thereafter, this reaction solution was dropped into methanol to obtain a pale yellow precipitate.

The obtained precipitate was separated, washed with an alkaline aqueous solution, boiled with water, dissolved in N-methylpyrrolidone, and reprecipitated in methanol to obtain purified polymers Z and Og in the form of white powder.
I got g.

From the following measurement results, it was confirmed that the obtained polymer was polyphenylene thioether.

Elemental analysis (theoretical value) C66,4% (56, [i), H3,7% (3,7), 329.8% (29,1i) IR spectrum ν c-s ”: 1000. 3050 cm-'ν ,
,, = 1:180.1460.1560cmδc-
u = 820c Otori 1 x ML diffraction 0M9.5, 10.5' ”C-NMR δ (phenyl C) = 135ppm Melting point 17
5°C to 210°C (Example 2) 2.2 = 6.6'-tetraethyldiphenyl disulfide 4. 4 g of lead tetraacetate and 2.51 g of fluoro'li&acid dissolved in 100 ml of nitromethane.
．． 44 g were mixed and stirred for 10111f at 80°C.

Thereafter, in the same manner as in Example 1, 160 g of a purified polymer in the form of white powder was obtained.

From the following measurement results, the obtained Bommer is poly(2,6'
-Diethylphenylenethionidel).

Elemental analysis (theoretical value) C72.8% (7:1.2) H7.6% (73) S 19.4% (19.5) IR, subexcl. -□= 2890.2945.2980cm-'ν
. , c = 1380.1465c■-1δ. −□ =
890c■-1 True H-NMR spectrum δ(-C1l:l) = 1.25pp■δ(-C
H2-) = 2.70ppmδ(phenyl)
= 7.00ppm"C-NMR δ(-CH3G)=I!ip+'■δ(-CIl
□−〇)=24pp謹δ (phenyl (:)
= 1:1 Opp Melting point 167°C to 185°C Molecular weight 4300 (Example 3) 2.2'-dimethyldiphenyl disulfide 2.46g
and trifluoromethyl sulfate (0.1 Otomi) in a mixed solvent of 100 si of nitrobenzene and 20 layers of dichloromethane, metachlorobenzene, U aromatic acid 1.7
2 g were mixed and stirred at room temperature for 50 hours.

Thereafter, the purified polymer was precipitated in the same manner as in Example 1 above.

From the following measurement results, it was confirmed that the obtained polymer was poly(2-methylphenylenethioether).

Elemental analysis (theoretical value) CIi 7.7% (68,9) H4, 98% (4,92) S 25°9% (26,2) IR spectrum ν. -□=2845.2910.2950c+i-'
l CsC=I core5. 1440. 1550cm
-'δc-1I=870c@-''H-NMR spectrum δ(-CH33H) = 215ppm+δ (phe
nyl 3H) = 7.15 ppm (Example 4) 1.08 g thiophenol and 0.5 methyl sulfate
3.3' to a solution of an in dichloroethane
, 5.5'-tetramethyldiphenoquinone (5 g) were mixed and stirred at 150°C for 3 hours.

Thereafter, in the same manner as in Example 1, a purified polymer in the form of white powder was obtained.

From the following measurement results, it was confirmed that the obtained polymer was polyphenylene thioether.

Elemental analysis (theoretical value) C56,1% (66,6), H3,8% (:1.7), S 29.4% (29,6) IR spectrum p c-, = :1000.105105O'νc =c
-1380, 1460, 1560cm-'δc-n
= 820 cm-' 1,000 sums shown in Table 1 - ■
With respect to polyphenylene sulfide obtained by oxidative polymerization of by the method of the present invention, the contained Na, CfL,
Cu, nitrogen components, etc. were investigated.

The results are shown in Table 1.

(Raiko, hereafter blank) δ (phenyl C) -1:15ppm, and various fillers, stabilizers, etc. in the form of male-shaped single grains are added, for example, as molded products, sealants, paints, etc. Industrially useful polyarylene thioethers have various advantages, such as being able to be suitably used in various fields including electrical and electronic fields, and greatly expanding the range of applications. Can you provide the manufacturing method?

[Effects of the Invention] According to the present invention, (1) Since a specific raw material, a specific acid (protonic acid), and a specific oxidizing agent are used, the reaction conditions are mild, and the production method is easy. It is easy to use, and the raw materials and catalysts are inexpensive, making it possible to efficiently obtain industrially advantageous polyarylene thioethers, particularly substantially linear polyarylene thioethers having an extremely low degree of crosslinking.

(2) Impurities such as metal salts such as sodium chloride, halogen ions such as chloride ions, heavy metals such as aluminum, and nitrogen contained in the obtained polyarylene thioether are extremely small, so that a highly pure polyarylene thioether can be obtained. It comes,

Claims (1)

[Claims] (1) General formula [I]; ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] (However, in formula [I], R^1 to R^4 are hydrogen atoms, lower alkyl groups, and halogens, respectively. Represents a substituent selected from the group consisting of atoms and lower alkoxy groups. R^1 to R^4 may be the same type or different types.) Phenols and/or general formula [
II]; ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] (However, in formula [II], S represents a sulfur atom, and R^
5 to R^1^2 each represent a substituent selected from the group consisting of a hydrogen atom, a lower alkyl group, a halogen atom, and a lower alkoxy group. In addition, R^5 ~ R^1^
2 may be of the same type or different types. 1. A method for producing a polyarylene thioether, which comprises polymerizing diphenyl disulfides represented by the following formula with an oxidizing agent in the presence of a protonic acid.