JP3200027B2 - Method for producing cyclic oligo (thioarylene) compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a cyclic oligo (thioarylene) compound. More specifically, the invention of this application relates to a method for producing a cyclic oligo (thioarylene) compound useful as a ring-opening polymerization monomer or the like for obtaining a linear high molecular weight poly (thioarylene) compound.

[0002]

BACKGROUND OF THE INVENTION Aromatic cyclic oligomers are known to be effective monomers for the synthesis of high molecular weight linear polymers by ring opening polymerization. There have already been many reports on such aromatic cyclic oligomers,
For example, cyclic carbonates (Macromolecules, 1991, 24,
3035), amides (Macromolecules, 1993, 26, 3476), ethers (Macromolecules, 1993, 26, 2408), ether ether ketones (Macromolecules, 1996, 29, 5502), thioethers (Macromolecules, 1996, 29, 4811) and the like. Aromatic cyclic oligomers have been synthesized. For cyclic oligo (thioarylene) compounds as monomers of poly (thioarylene), one of the excellent engineering plastics, polycondensation of dihaloaromatic compounds and alkali metal sulfides should be carried out under dilute conditions. Is synthesized.

However, the above-mentioned reaction method for synthesizing this cyclic oligo (thioarylene) compound useful as a ring-opening polymerization monomer is a high-temperature reaction based on aromatic nucleophilic substitution, so that it is generally difficult to control the reaction. There is a problem that the yield of the cyclic polymer remains low. Further, problems such as mixing of by-produced alkali metal salts have been pointed out.
For these reasons, there are no reports on cyclic oligo (thioarylene) compounds under mild conditions of normal temperature and normal pressure.

Accordingly, the invention of this application has been made in view of the above circumstances, and is intended to produce a cyclic oligo (thioarylene) compound in a high yield by a reaction that proceeds under mild conditions of normal temperature and normal pressure. It is an object of the present invention to provide a new manufacturing method that can be used.

[0005]

Means for Solving the Problems The inventors have made intensive studies to solve the above problems. As a result, it has been found that cyclic oligo (thioarylene) compounds are selectively produced by performing oxidative polymerization of a diaryl disulfide compound or oxidative polymerization of an aromatic compound and a sulfur compound under dilute conditions. It was completed.

The invention of the present application solves the above-mentioned problems by providing the following formula [1]

[0007]

Embedded image

(Ar represents an aromatic compound group which may have a substituent and may be bonded to a carbon ring via a hetero atom, and n is an integer of 2 or more and represents a degree of polymerization. The method for producing a cyclic oligo (thioarylene) compound represented by the following formula [2]:

[0009]

Embedded image

[0010] The cyclic oligo (A) is obtained by oxidatively polymerizing a diaryl disulfide compound represented by the formula (Ar represents the same as described above) at 0.01 M to 0.1 M in the presence of a sulfur compound. Thioarylene) compounds. And also, the invention of this application
The method for producing a cyclic oligo (thioarylene) compound as described above, wherein an aromatic compound which may have a substituent and may have a carbon ring bonded through a hetero atom is present in the coexistence of a sulfur compound. Below, in the coexistence of sulfur compounds 0.01M ~
Also provided is a method for producing a cyclic oligo (thioarylene) compound, which is characterized by oxidative polymerization at 0.1 M.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The invention of this application provides a method for producing a cyclic oligo (thioarylene) compound as described above. According to this method, the reaction is carried out under mild conditions of normal temperature and normal pressure. As the process proceeds, the desired cyclic oligo (thioarylene) compound can be obtained in high yield.

The general formula [1], which represents a cyclic oligo (thioarylene) compound as an object of the present invention, will be described in more detail. In the formula, Ar may have a substituent, and Represents an aromatic compound group which may be bonded via a hetero atom, and in the formula [1],
It can be referred to as an arylene group. This arylene group is not limited, but as a carbon number,
For example, it is preferably exemplified up to about 5 to 36. The arylene group has a suitable substituent, for example, a hydrocarbon group such as an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group, an alkoxy group, an aryloxy group, a hydroxy group, a sulfide group, a thioether group, a halogen atom, Carbonyl group, carbonyloxy group, oxycarbonyl group, carbonate group, nitro group,
It can have a substituent such as an amino group, a cyano group, a carbamate group, and a urea group.
It may have a carbon ring bonded through a sulfur atom. The carbocycle may be a single ring, a condensed ring, a heterocyclic ring, a biphenyl group directly bonded, or a carbon ring bonded through a carbon chain such as alkylene.

Illustrative examples of these are 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2-methyl-1,4-phenylene group, 2-ethyl-1,3 -Phenylene group, 3-methyl-1,4-phenylene group, 3-methyl-1,2-phenylene group, 3-methyl-1,5-phenylene group, 2-ethyl-1,4-phenylene group, 3- Ethyl-1,4-phenylene group, 2-propyl-1,4-phenylene group, 3-propyl-1,4
-Phenylene group, 2-methoxy-1,4-phenylene group, 3-methoxy-1,4-phenylene group, 2-ethoxy-1,4-phenylene group, 3-ethoxy-1,4-phenylene group, 2- Phenyl-1,4-phenylene group, 3
-Phenyl-1,4-phenylene group, 2-phenoxy-
1,4-phenylene group, 3-phenoxy-1,4-phenylene group, 2,3-dimethyl-1,4-phenylene group,
2,5-dimethyl-1,4-phenylene group, 2,6-dimethyl-1,4-phenylene group, 2,3-dimethyl-
1,5-phenylene group, 2,3-dimethyl-1,6-phenylene group, 2,5-diethyl-1,4-phenylene group, 2,6-diethyl-1,4-phenylene group, 2,5
-Dipropyl-1,4-phenylene group, 2,6-dipropyl-1,4-phenylene group, 2,5-dimethoxy-
1,4-phenylene group, 2,6-dimethoxy-1,4-
Phenylene group, 2,5-ethoxy-1,4-phenylene group, 2,6-diethoxy-1,4-phenylene group, 2,
5-diphenyl-1,4-phenylene group, 2,6-diphenyl-1,4-phenylene group, 2,5-diphenoxy-1,4-phenylene group, 2,6-diphenoxy-1,
4-phenylene group, 2,3,5-trimethyl-1,4-
Phenylene group, 2,3,6-trimethyl-1,4-phenylene group, 2-methyl-3,5-diethyl-1,4-phenylene group, 2,3,6-triethyl-1,4-phenylene group, 2,3,4,5-tetramethyl-1,6-phenylene group, 2,3,4,6-tetramethyl-1,5-phenylene group, 2,3,5,6-tetramethyl-1,4 −
Phenylene group, 2,3,4,6-tetraethyl-1,5
-Phenylene group, 2,3,5,6-tetraethyl-1,
4-phenylene group, 4,4'-biphenylene group, 2-methyl-4,4'-biphenylene group, 3-methyl-4,
4'-biphenylene group, 2-ethyl-4,4'-biphenylene group, 3-ethyl-4,4'-biphenylene group, 2
-Methoxy-4,4'-biphenylene group, 3-methoxy-4,4'-biphenylene group, 2-phenyl-4,4 '
-Biphenylene group, 3-phenyl-4,4'-biphenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group,
1,8-naphthylene group, 2-methyl-1,4-naphthylene group, 2-methyl-1,5-naphthylene group, 2-methyl-1,6-naphthylene group, 2-methyl-1,7-naphthylene group , 2-methyl-1,8-naphthylene group, 2-hydroxy-1,4-naphthylene group, 2-hydroxy-1,
5-naphthylene group, 2-hydroxy-1,6-naphthylene group, 2-hydroxy-1,7-naphthylene group, 2-hydroxy-1,8-naphthylene group, 4,4'-diphenylene ether group, 2- Methyl-4,4'-diphenylene ether group, 3-methyl-4,4'-diphenylene ether group, 2-ethyl-4,4'-diphenylene ether group, 3-ethyl-4,4'-di Phenylene ether group,
2-methoxy-4,4'-diphenylene ether group, 3
-Methoxy-4,4'-diphenylene ether group, 2-
Phenyl-4,4'-diphenylene ether group, 3-phenyl-4,4'-diphenylene ether group, 2-methyl-4,4'-diphenylene sulfide group, 3-methyl-4,4'-di Phenylene sulfide group, 2-ethyl-
4,4'-diphenylene sulfide group, 3-ethyl-
4,4'-diphenylene sulfide group, 2-methoxy-
4,4'-diphenylene sulfide group, 3-methoxy-
4,4'-diphenylene sulfide group, 2-phenyl-
4,4'-diphenylene sulfide group, 3-phenyl-
4,4'-diphenylene sulfide group, 4,4'-diphenylene sulfone group, 4,4'-benzophenylene group,
4,4'-tert-phenylene group, 2,5-pyrrolylene group,
3-methyl-2,5-pyrrolylene group, 3-ethyl-2,
5-pyrrolylene group, 3-propyl-2,5-pyrrolylene group, 3-butyl-2,5-pyrrolylene group, 3-octyl-2,5-pyrrolylene group, 3-dodecyl-2,5-pyrroleline group, 3 , 4-dimethyl-2,5-pyrroleline group,
3,4-diethyl-2,5-pyrroleline group, 3,4-dipropyl-2,5-pyrroleline group, 3,4-dibutyl-
2,5-pyrroleline group, 2-fluoro-1,4-phenylene group, 2,6-dichloro-1,4-phenylene group,
2,2'-difluoro-4,4'-biphenylene group, 3
-Nitro-1,4-phenylene group, 3-cyano-1,4
-Phenylene group, 2,3-dibromo-1,6-naphthylene group, 2-methoxy-5-carbonylmethyl-1,6-
Naphthylene group, 2,2'-dichloro-4,4'-diphenylene ether group, 2,5-thiophenylene group, 3-methyl-2,5-thiophenylene group, 3-ethyl-2,5
-Thiophenylene group, 3-propyl-2,5-thiophenylene group, 3-butyl-2,5-thiophenylene group, 3
-Octyl-2,5-thiophenylene group, 3-dodecyl-2,5-thiophenylene group, 3,4-dimethyl-2,
5-thiophenylene group, 3,4-diethyl-2,5-thiophenylene group, 3,4-dipropyl-2,5-thiophenylene group, 3,4-dibutyl-2,5-thiophenylene group, 2, 5-furan group, 3-methyl-2,5-furanylene group, 3-ethyl-2,5-furanylene group, 3-propyl-2,5-furanylene group, 3-butyl-2,5-furanylene group, 3 -Octyl-2,5-furanylene group, 3
-Dodecyl-2,5-furanylene group, 3,4-dimethyl-2,5-furanylene group, 3,4-diethyl-2,5-
And a furanylene group, a 3,4-dipropyl-2,5-furanylene group, a 3,4-dibutyl-2,5-furanylene group, and the like. Among them, 1,4-phenylene group, 4,4'-
A biphenylene group and a 4,4'-diphenylene ether group are preferred.

In the formula (1), n represents the degree of polymerization.
Is an integer of 2 or more, but there is no particular upper limit. In general, n may be considered to be up to about 200. As described above, the method for producing the cyclic oligo (thioarylene) compound of the present invention represented by the general formula [1] includes <I> the diaryl disulfide compound represented by the above formula [2], and <II>> A in the above formulas [1] and [2]
Either the aromatic compound corresponding to r or the sulfur compound undergoes oxidative polymerization. Examples of the sulfur compound in the case of the above <II> include sulfur halides such as sulfur dichloride, disulfur dichloride, sulfur dibromide, disulfur dibromide, sulfur diiodide, thionyl chloride, sulfuryl chloride, and the like. Sulfur and the like can be mentioned, and in particular, disulfur dichloride is exemplified as the most desirable in view of high reactivity, high stability, and solubility.

The concentration of the diaryl disulfide compound or the aromatic compound and the sulfur chloride compound in the reaction is not particularly limited. Usually, it is 0.01 mM to 10M, preferably 0.01M to 0.1M. In a concentrated solution, the selectivity of cyclic oligo (thiophenylene) for producing a linear polymer decreases, and in a dilute solution, the reaction rate decreases.

The oxidizing agent used in the oxidative polymerization reaction has the ability to oxidize the diaryl disulfide compound of the formula [2] or the diaryl disulfide compound formed by the reaction between the aromatic compound and the sulfur compound, and The type is not particularly limited as long as it does not hinder the progress of the polymerization reaction. Specific examples of applicable oxidants include 2,3-dichloro-5,6-dicyano-p
Organic oxidizing agents such as benzoquinone, chloranil, bromanyl, 1,4-diphenoquinone, tetramethyldiphenoquinone, tetracyanoquinodimethane, tetracyanoethylene, thionyl chloride, perbenzoic acid, m-chloroperbenzoic acid, Organic peroxides such as benzoyl oxide, aluminum chloride, iron chloride, titanium tetrachloride, tin chloride, antimony pentachloride, tungsten hexachloride, boron trifluoride, aluminum bromide, iron bromide, lead tetraacetate, and thallium triacetate , Cerium (IV) acetylacetonate, vanadium pentoxide, chlorine, bromine, iodine, and the like. Among these, in particular, 2,3-dichloro-5,6-dicyano-
Preferred are p-benzoquinone, chloranil, bromanyl, vanadium pentoxide.

These oxidizing agents may be used alone or in combination of two or more. The amount of the oxidizing agent [A] is determined by the amount of
Since it differs depending on the type of the oxidizing agent and the like, it cannot be uniformly defined, but usually, the diaryl disulfide compound of the formula [2] or the sulfur compound [B]
[A] / [B] (molar ratio) is about 0.1 to 50, and preferably about 0.5 to 5.

If this value is less than 0.1, the polymerization rate becomes slow, and the yield of cyclic oligo (thioarylene) decreases. On the other hand, if it exceeds 50, the effect corresponding thereto cannot be seen. Further, the diaryl disulfide compound or the aromatic compound and the sulfur compound are mixed with an oxygen oxidation catalyst and stirred to form a target cyclic oligo (thioarylene) of the formula [1] by oxygen oxidation polymerization.
Can also be generated.

The oxidative polymerization catalyst has the ability to oxidize the diaryl disulfide compound or the diaryl disulfide compound formed by the reaction of the aromatic compound and the sulfur compound, and does not inhibit the progress of the polymerization reaction. There is no particular limitation. There are no restrictions on ligands and counter ions, among which cerium (IV),
Salts such as acetylacetone and porphyrin are preferred.

Illustrating these metal compounds, for example,
Cerium compounds such as cerium ammonium nitrate; vanadium compounds such as vanadyl acetylacenate, vanadyl tetraphenylporphyrin, and vanadium acetylacenate; molybdenum oxide compounds such as molybdenum oxide acetylacenate and molybdenum oxide. Among them, cerium ammonium nitrate, vanadyl acetylacenate, vanadium acetylacenate, vanadyl 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 necessary. Therefore, it is usually preferable that the oxygen partial pressure is higher, but it is sufficient if the pressure is in the atmosphere, and the reaction proceeds even under reduced pressure if oxygen exists to some extent.

The amount of the oxidative polymerization catalyst [C] varies significantly depending on the type of the diaryl disulfide compound or the aromatic compound and the sulfur compound to be used, but usually, the ratio of the diaryl disulfide compound or the sulfur compound [B], [C] ] / [B], 0.0001 to 5, more preferably 0.001 to 0.1.

When this value is less than 0.0001, the polymerization rate becomes low. On the other hand, when it exceeds 5, the cost of the catalyst becomes high, which is economically disadvantageous. Furthermore, the oxidative polymerization of the diaryl disulfide compound or the aromatic compound and the sulfur compound can also be performed by electrolytic oxidation. The supporting electrolyte is a known organic acid, inorganic acid, or a mixture or composite 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 compound may be used as long as it does not react with the cyclic oligo (thioarylene) compound which is soluble and formed in the solvent. The electrolysis method is not limited, and may be either a constant potential or a constant current, as long as the diaryl disulfide compound or the diaryl disulfide compound generated by the reaction between the aromatic compound and the sulfur compound can be oxidized.

There are no particular restrictions on the electrodes used.
It is performed with platinum, gold, silver, carbon, and the like, and platinum is particularly preferably used. Regarding the shape of the electrode, rod shape, plate shape,
There is no particular limitation such as a net shape. 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.

The oxidative polymerization of the diaryl disulfide compound or the aromatic compound and the sulfur compound can be carried out in the presence of a known acid compound. This is for suppressing the deactivation of the sulfonium cation, which is a polymerization active species, and is a known organic acid, inorganic acid, or a mixture or complex thereof. Specifically, for example,
Non-oxygen acids such as hydrochloric acid, hydrobromic acid, tetrafluoroboric acid, hydrocyanic acid, sulfuric acid, phosphoric acid, chloric acid, bromic acid, nitric acid, carbonic acid,
Inorganic oxo acids such as boric acid, molybdic acid, impolyic acid, heteropoly acid, etc., sodium hydrogen sulfate, sodium dihydrogen phosphate, proton residual heteropoly acid, monomethyl sulfate, trifluoromethyl sulfate, acetic acid, propionic acid, butanoic acid, succinic acid , Benzoic acid, monovalent or polyvalent carboxylic acids such as phthalic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monofluoroacetic acid, difluoroacetic acid, halogen-substituted carboxylic acid such as trifluoroacetic acid,
Monovalent or polyvalent sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, benzenedisulfonic acid, antimony pentachloride, aluminum chloride,
Examples thereof include Lewis acids such as aluminum bromide, titanium tetrachloride, tin tetrachloride, zinc chloride, copper chloride, and iron chloride. Among these, highly stable strongly acidic protonic acids are preferable, and in particular, trifluoromethanesulfonic acid,
Trifluoroacetic acid, tetrafluoroboric acid and the like are preferably used.

These acids may be used alone or in a combination of two or more. The reaction may be carried out by diluting with a known organic solvent. When the generation of water accompanies the progress of the polymerization, it is desirable to carry out the polymerization in the presence of a dehydrating agent. Normal,
Preferred examples of the dehydrating agent include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, trifluoromethanesulfonic anhydride, diphosphorus pentoxide, and inorganic acids. In addition, there is no problem as long as it does not affect the polymerization reaction.
Potassium chloride or the like may be used. Among these, trifluoroacetic anhydride and trifluoromethanesulfonic anhydride are most preferred.

The oxidative polymerization reaction can be carried out in the absence of a solvent, but can also be carried out in the presence of a solvent. Examples of the solvent include hydrocarbon solvents such as pentane, hexane, benzene, toluene, and xylene; dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, trichlorofluoromethane,
Halogenated hydrocarbon solvents such as 1,1,2-trichloro-1,2,2-trifluoroethane; nitromethane;
Nitrogen-containing solvents such as nitroethane, nitropropane, and nitrobenzene are included. In addition, a solvent generally used for Friedel-Crafts reaction, cationic polymerization, or the like can be appropriately selected and suitably used. In particular, from the viewpoint of the stability of the solvent and the polymerization active species, dichloromethane, 1,1,
2,2-tetrachloroethane is preferably used. These solvents may be used alone or in combination 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 depending on the type of the reaction raw materials used, the proportion used, the reaction temperature and the conditions of the solvent, but is usually 0.5 to 2000 hours, preferably 8 to 10 hours.
0 hours. In order to efficiently obtain a cyclic oligo (thioarylene) compound, the reaction is preferably performed under a dilution condition. That is, it is desirable to carry out the reaction by adding the reaction raw materials dropwise. The dripping time of the reaction raw material varies depending on the type of the reaction raw material and its use ratio, the reaction temperature and the conditions of the solvent, but is usually 0.5 to 1000 hours, preferably,
8-100 hours. If the dropping time is 0.5 hour or less, the yield of the cyclic polymer decreases, and if it exceeds 1000 hours, the dropping effect commensurate with the yield cannot be seen.

The reaction method is not particularly limited, and the reaction is carried out using a continuous, semi-continuous or batch type electrolytic layer. When using a batch system, it is desirable to carry out the reaction with stirring. In constituting the polymerization reaction system, diaryl disulfide compounds, monomers such as aromatic compounds and sulfur compounds, oxidizing agents, catalysts and oxygen, acids, dehydrating agents, solvents, the order of compounding, such as, there is no particular limitation. Can be compounded simultaneously or stepwise in various orders and manners.

The reaction temperature is usually -50 ° C to 15 ° C.
About 0 ° C. can be used as a guide, and preferably 0 ° C. to 5 ° C.
0 ° C. The reaction pressure is not particularly limited, and may be increased or decreased as necessary. Usually, the reaction can be suitably performed at normal pressure or the self-pressure of the reaction system. However, if necessary,
The reaction can also be performed under pressure using a mixed gas with a diluent gas or the like which does not hinder the polymerization reaction.

The cyclic oligo (thioarylene) compound synthesized by the extremely mild polymerization method as described above dissolves or precipitates in a reaction solvent. For example, the degree of polymerization, that is, n in the above formula [1] is 2 Approximately 100 are manufactured.

[0033]

The present invention will be described below in more detail with reference to examples. Needless to say, the present invention is not limited by the following embodiments. Example 1 Synthesis of cyclic hexa (thio-1,4-phenylene) 0.03 mol of trifluoroacetic acid and 1.5 mmol of 2,3-dichloro-5,6-dicyano-p-benzoquinone in 10 ml of dichloromethane under air. To dissolve
2 dissolved 1.5 mmol of diphenyl disulfide
0 ml of dichloromethane solution was added dropwise over 20 hours. After completion of the dropwise addition, the reaction solution was further stirred for one day. The reaction solution was added dropwise to 200 ml of a 10% hydrochloric acid-methanol solution to give a white precipitate. The precipitate was filtered for purification, washed several times with a 5% aqueous potassium hydroxide solution and methanol, and dried to obtain cyclic hexa (thio-thio) as synthesized according to the following reaction formula.
1,4-phenylene) was obtained with a yield of 100%.

[0034]

Embedded image

The analysis results are shown below.

[0036]

[Table 1]

Example 2 Synthesis of cyclic oligo (thio-1,4-phenylene) 0.04 mmol of trifluoromethanesulfonic acid and 4 mmol of trifluoroacetic anhydride in 10 ml of 1,1,2,2-tetrachloroethane in air , And 2mm
ol of 2,3-dichloro-5,6-dicyano-p-benzoquinone, and 30 ml of 1,1,2,2-tetrachloroethane solution containing 4 mmol of diphenyl disulfide and 2 mmol of disulfur dichloride were dissolved in 12 ml. It was added dropwise over time. After completion of the dropwise addition, the reaction solution was further stirred for 2 days. The reaction solution was added dropwise to 200 ml of a 10% hydrochloric acid-methanol solution to give a white precipitate. After filtering the precipitate for purification, the precipitate was washed several times with a 5% aqueous potassium hydroxide solution and methanol. The obtained polymer was extracted with 300 ml of hot chloroform, and the soluble portion was removed by solvent and dried to obtain a cyclic oligo (thio-1,1).
4-phenylene) in 91% yield. The reaction scheme is shown as follows: MALDI-TOF-MS
From the spectrum, the generated cyclic oligo (thio-1,4-
(Phenylene) was confirmed to be a mixture of 6,8,10-mers.

[0038]

Embedded image

The analysis results are shown below.

[0040]

[Table 2]

Example 3 Cyclic oligo (oxy-1,4-
Synthesis of phenylenethio-1,4-phenylene) In air, at 5 ° C., 0.5 mmol of aluminum chloride was added to 10 ml of 1,2-dichloroethane, and 0.4 mm
ol of diphenyl ether and 0.2 mmol of disulfur dichloride in 10 ml of dichloromethane were added dropwise over 8 hours. After completion of the dropwise addition, the reaction solution was further stirred at 10 ° C. for 5 hours. 200 ml of reaction solution
Was added dropwise to a 10% hydrochloric acid-methanol solution to give a white precipitate. After filtering the precipitate for purification, the precipitate was washed several times with a 5% aqueous potassium hydroxide solution and methanol. The obtained polymer was extracted with 300 ml of hot chloroform,
By removing the solvent from the soluble portion and drying the solvent, the cyclic oligo (oxy-1,4-phenylenethio-) represented by the following formula was obtained.
1,4-phenylene) was obtained in a yield of 77%. MALDI
From the -TOF-MS spectrum, it was confirmed that the generated cyclic oligo (oxy-1,4-phenylenethio-1,4-phenylene) was a mixture of 3, 4, and pentamers.

[0042]

Embedded image

The analysis results are shown below.

[0044]

[Table 3]

[0045]

[0046]

[0047]

[0048]

[0049]

As described in detail above, in the invention of this application, cyclic oligo (thio) is obtained in high yield by oxidative polymerization under mild conditions starting from a diaryl disulfide compound or an aromatic compound and a sulfur compound. Arylene) compounds can be obtained. This cyclic oligo (thioarylene) compound is an effective monomer that gives a high molecular weight linear poly (thioarylene) compound by ring-opening polymerization.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-88828 (JP, A) JP-A-7-3021 (JP, A) JP-A-2-169626 (JP, A) JP-A-2- 212520 (JP, A) JP-A-4-153225 (JP, A) JP-A-4-91132 (JP, A) JP-A-3-221528 (JP, A) (58) Fields investigated (Int. ⁷ , DB name) C08G 75/00-75/02

Claims (2)

(57) [Claims] [Claim 1] The following formula [1] (Ar represents an aromatic compound group which may have a substituent and may be bonded to a carbon ring via a hetero atom, and n represents an integer of 2 or more to indicate the degree of polymerization.) A method for producing a cyclic oligo (thioarylene) compound represented by the following formula [2]: Wherein the diaryl disulfide compound represented by the formula (Ar represents the same as above) is subjected to acid polymerization at 0.01 M to 0.1 M, wherein the cyclic oligo ( thioarylene ) compound is Manufacturing method. 2. The following formula [1] (Ar represents an aromatic compound group which may have a substituent and may be bonded to a carbon ring via a hetero atom, and n represents an integer of 2 or more to indicate the degree of polymerization.) A method for producing a cyclic oligo (thioarylene) compound represented by the formula: wherein an aromatic compound which may have a substituent and may have a carbon ring bonded through a hetero atom is a sulfur compound. The method for producing a cyclic oligo ( thioarylene ) compound as described above, wherein the polymerization is carried out by oxidative polymerization at 0.01 M to 0.1 M in the presence of