JP3256171B2 - Cyclic oligo (sulfonioarylene salt) compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The invention of this application relates to a cyclic oligo (sulfonioarylene salt) compound and a method for producing the same. More specifically, the invention of this application is an ion exchange resin excellent in heat resistance and chemical stability, can be effectively used as a surfactant, can include an anion inside the ring, and has a high ion Show conductivity,
In addition, protons are efficiently generated by irradiation with ultraviolet light, and can be used as a photopolymerization initiator such as an epoxy or vinyl compound. Further, poly (sulfonioarylene salts)
Cyclic oligo (sulfonioarylene salt) compounds, which are electrolytes in which arylene groups and sulfonio groups are alternately connected, and are also useful as ring-opening polymerization monomers for engineering plastics such as compounds and poly (thioarylene) compounds Things.

[0002]

2. Description of the Related Art Polymer electrolytes are used in a wide range of fields such as ion exchange materials, surfactants and ion conductive materials. Regarding polyanions, many polymers having functional groups such as sulfonic acid groups, carboxylic acid groups, and hydroxyl groups have been reported, but most of the polycations have an ammonio group as a functional group.

[0003] In recent years, the development of polymers having sulfonio groups has been actively pursued. For example, sulfonium ionene (Polymer J., 1983, 15, 401),
Poly (styryldimethylsulfonium salt (USPatent
3401152, 1968), poly (dimethylsulfonioethynylenephenylene salt) (J. Polym, Sci. A-1,
1968, 6, 1058). Poly (methylsulfoniophenylene salt) consisting only of methylsulfonio and phenylene groups has also been synthesized (Angew.
Chem. Int. Ed. Engl., 1996, 35, 2843).

[0004] However, there has been no example in which a cyclic oligomer having a sulfonio group has been synthesized so far, and it has been considered to be difficult by a conventional method for synthesizing a sulfonium salt compound. Therefore, it has not been known until now that the compound has excellent properties as an ion exchange material, a surfactant, and an ion conductive material.

The invention of this application has been made in view of the above circumstances, and an object of the invention is to provide a novel cyclic oligo (sulfonioarylene salt) compound which is a polymer electrolyte having a sulfonio group as a functional group, and a compound thereof. It is to provide a manufacturing method.

[0006]

Means for Solving the Problems The present invention solves the above-mentioned problems, and the first invention uses a general formula [1]

[0007]

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[0008] (wherein, Ar represents an aromatic group which may have a substituent, location of binding to ring members or ring
The substituent may include a hetero atom , and S is a ring structure of Ar.
Indicates a sulfur atom directly bonded to the atom . R is a methyl group;
Tyl, propyl, butyl, phenyl, and
It represents a substituent selected from the group consisting of a toluyl group . X
^- is an anion. n indicates the degree of polymerization as an integer of 2 or more. The present invention provides a cyclic oligo (sulfonioarylene salt) compound represented by the formula:

According to a second aspect of the present invention, there is provided the first invention.
In the following, Ar isPhenylene group, diphenylene
Ter groupOr a ring that is a diphenylene sulfide group
Oligo (sulfonioarylene salt) compound
For clarity, in the first or second invention,X
^- Is trifluoromethanesulfonic acid anion, methane
Sulfonate anion, sulfate anion, hydrogen sulfate anion
, Tetrafluoroborate anion, perchlorate anion
, Hexafluoroantimonate anion, or
Cyclic oligos that are hexafluorophosphate anions
(Sulfonioarylene salt) compound is provided.

Furthermore, the invention of this application relates to a method for producing a compound as described above, and in the fourth invention, a compound represented by the general formula [2]

[0011]

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[0012] (wherein, Ar represents an aromatic group which may have a substituent, location of binding to ring members or ring
The substituent may include a hetero atom , and S is a ring structure of Ar.
Indicates a sulfur atom directly bonded to the atom. n indicates the degree of polymerization as an integer of 2 or more. In the fifth invention, a method for producing a cyclic oligo (sulfonioarylene salt) compound comprising sulfonating a cyclic oligo (thioarylene) compound represented by

[0013]

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[0014] (wherein, Ar represents an aromatic group which may have a substituent, location of binding to ring members or ring
The substituent may include a hetero atom , and S is a ring structure of Ar.
Indicates a sulfur atom directly bonded to the atom. R is a methyl group;
Tyl, propyl, butyl, phenyl, and
It represents a substituent selected from the group consisting of a toluyl group. ) Cyclic characterized by polycondensation of aryl sulfoxide compound represented by the oligo (sulfo niobium arylene salt)
Methods for producing compounds are provided.

The invention of this application having the above-mentioned features is based on the fact that a cyclic oligo (sulfonioarylene salt) compound in which an arylene group and a sulfonio group are alternately linked, which has been obtained as a result of an intensive study by the inventors, has been obtained. It can be synthesized by sulfonylation of an oligo (thioarylene) compound or by polycondensation of an arylsulfoxide compound, and a cyclic oligo (sulfonioarylene salt) compound is
It has low viscosity, excellent heat resistance and chemical stability, and has been completed based on the finding that it is effective as a monomer for ion conductors, ion exchange resins, and engineering plastics.

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. First, with respect to the compound represented by the general formula [1], Ar in the formula represents an aromatic group which may have a substituent as described above, and represents a ring-constituting atom or a substituent bonded to a ring. _May contain a heteroatom, and a typical example thereof represents an aromatic compound group consisting of C ₅ -C ₃₆ , and N,
It may contain a hetero atom such as O or S. That is, when a specific example is illustrated for the Ar,
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-dimethyl-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'-diphenylene 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'-di Phenylene ether group, 2-methyl-4,4'-diphenylene sulfide group, 3-methyl-4,4'-diphenylene 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, '- diphenylene sulfide group, 3-phenyl-4,4'-diphenylene sulfide group, 4,4'-diphenylene sulfone group, 4,4'-benzo-phenylene group, 4,4' Tafueniren 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-pyrrolylene group, 3,4-dimethyl-
2,5-pyrrolylene group, 3,4-diethyl-2,5-pyrrolylene group, 3,4-dipropyl-2,5-pyrolylene group, 3,4-dibutyl-2,5-pyrrolylene 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-furanylene group, 3,4
-Dipropyl-2,5-furanylene group, 3,4-dibutyl-2,5-furanylene group, and the like.
Among them, 1,4-phenylene group and 2,5-dimethyl-1,4 are preferred in terms of stability and synthesis yield of the compound.
-Xylylene group, 4,4'-biphenylene group, 4,4 '
-Diphenylene ether group, 4,4'-diphenylene sulfide group and the like are preferable. S is a sulfur atom
Yes, it suffices if it can be directly bonded to the ring constituting atom of Ar.

R in the general formula [1] is
In terms of ease of synthesis, ion exchange capacity, and ion conductivity,
Methyl, ethyl, propyl, butyl, phenyl
Group and a substituent selected from the group consisting of a toluyl group are preferably used.

[0018] X in the general formula (1) ^- is the is a anion, specific examples, for example, fluorine anion,
Halogen anions such as chloride anion, bromine anion and iodine anion; acetate anion, trifluoroacetate anion, sulfate anion, hydrogen sulfate anion, methane sulfonate anion, trifluoromethane sulfate anion, perchlorate anion, tetrafluoroborate anion, hexa Examples thereof include a fluorophosphate anion, a hexachloroantimonate anion, and a hexafluoroantimonate anion. Among these,
From the viewpoint of the synthesis yield and stability of the compound, trifluoromethanesulfonic acid anion, methanesulfonic acid anion, sulfate anion, hydrogensulfate anion, tetrafluoroborate anion, perchlorate anion, hexafluoroantimonate anion, and hexafluoroanion Phosphate anions and the like are preferred.

The synthesis of the cyclic oligo (sulfonioarylene salt) compound represented by the general formula [1] as described above can be achieved by several methods. For example, it can be synthesized by subjecting the cyclic oligo (thioarylene) compound represented by the above general formula [2] to a sulfonylation reaction. Examples of sulfoniolating agents applicable to this reaction include, for example, methyl iodide, ethyl iodide, propyl iodide,
Alkyl iodides such as butyl iodide and pentyl iodide; iodonium salt compounds such as diphenyliodonium salt, ditolyliodonium salt, and phenyltolyliodonium salt; trimethyloxonium salt, triethyloxonium salt, tripropyloxonium salt, tributyl Oxonium salts, tripentyl oxonium salts,
Oxonium salt compounds such as trihexyloxonium salt, triphenyloxonium salt, tritolyloxonium salt, etc .; methyl formate, ethyl formate, propyl formate,
Butyl formate, pentyl formate, hexyl formate, phenyl formate, toluate formate, benzyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, phenyl acetate, toluyl acetate, benzyl acetate, methyl benzoate, benzoate Ethyl acetate, propyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, phenyl benzoate, toluyl benzoate, benzyl benzoate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, butyl trifluoroacetate , Pentyl trifluoroacetate, hexyl trifluoroacetate, phenyl trifluoroacetate, toluyl trifluoroacetate, benzyl trifluoroacetate, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, methane Butyl sulfonate, pentyl methanesulfonate, hexyl methanesulfonate, phenyl methanesulfonate, toluyl methanesulfonate, benzyl methanesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, propyl trifluoromethanesulfonate, trifluoromethanesulfone Butyl phosphate, pentyl trifluoromethanesulfonate, hexyl trifluoromethanesulfonate, phenyl trifluoromethanesulfonate, toluyl trifluoromethanesulfonate, benzyl trifluoromethanesulfonate, methyl sulfate, ethyl sulfate, propyl sulfate, dimethyl sulfate, diethyl sulfate, dipropyl sulfate And ester compounds such as methanol, ethanol, propanol, butanol, pentanol, hexanol, Phenol,
Alcohol compounds such as cresol, catechol, xylenol and the like can be mentioned. Of these, methyl trifluoromethanesulfonate is preferred from the viewpoint of synthesis yield.

Alternatively, the cyclic oligo (sulfonioarylene salt) compound represented by the general formula [1] can also be synthesized by polycondensation of the arylsulfoxide compound represented by the general formula [3]. . The reaction can be carried out in the presence of a known acid compound. It is for suppressing the deactivation of the sulfonium cation as a reactive species, and is a known organic acid, 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,
Inorganic oxo acids such as chloric acid, bromic acid, nitric acid, carbonic acid, boric acid, molybdic acid, impolyic acid, heteropoly acid, etc .; sodium hydrogen sulfate, sodium dihydrogen phosphate, proton residual heteropoly acid, monomethyl sulfuric acid, trifluoromethane sulfuric acid, acetic acid Mono- or polyvalent carboxylic acids such as, propionic acid, butanoic acid, succinic acid, benzoic acid, phthalic acid;
Halogen-substituted carboxylic acids such as monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monofluoroacetic acid, difluoroacetic acid, and trifluoroacetic acid; methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, and benzenedisulfonic acid Monovalent or polyvalent sulfonic acids; Lewis acids such as antimony pentachloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, zinc chloride, copper chloride, and iron chloride; . Among these, highly stable and strongly acidic protonic acids are preferred, and trifluoromethanesulfonic acid, sulfuric acid, methanesulfonic acid, tetrafluoroboric acid and the like are particularly preferably used.

These acids may be used alone or in a combination of two or more. Further, the reaction may be carried out after dilution with a known organic solvent. With respect to the above reaction, the anion X ^- is usually a reaction substrate at the time of completion of the reaction, or a counter anion of the acid compound used, but using a known anion exchange reaction,
Anion X ^- reaction substrate other cyclic oligo (sulfo niobium arylene salt) or other than counter anions of an acid compound, can be synthesized compound.

When water is generated with the progress of the reaction,
It is desirable to carry out the reaction in the presence of a dehydrating agent. Usually, preferred dehydrating agents include, for example, acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, trifluoromethanesulfonic anhydride, diphosphorus pentoxide, and inorganic acids. In addition, anhydrous sodium sulfate, potassium chloride and the like may be used without any problem as long as they do not affect the reaction. Among these, trifluoromethanesulfonic anhydride and diphosphorus pentoxide are most preferred.

The reaction can be carried out in the absence of a solvent, but also in the presence of a solvent. Examples of the solvent include hydrocarbon solvents such as pentane, hexane, benzene, toluene, xylene, etc .; dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, trichlorofluoromethane, 1,1,
Halogenated hydrocarbon solvents such as 2-trichloro-1,2,2-trifluoroethane; and nitrogen-containing solvents such as nitromethane, nitroethane, nitropropane, and nitrobenzene. In addition, a solvent generally used for Friedel-Crafts reaction, cationic polymerization, or the like can be appropriately selected and suitably used. Particularly, from the viewpoint of the stability of the solvent and the reactive species, dichloromethane, 1,1,2,2-
Tetrachloroethane is preferably used. These solvents may be used alone or as a mixture of two or more. If the reaction substrate is a liquid, it may be directly reacted without a solvent.

The raw material concentrations for the sulfonylation reaction of the cyclic oligo (thioarylene) compound and the polycondensation reaction of the arylsulfoxide compound are not particularly limited. Normal,
0.01 mM to 20 M, preferably 0.01 M to
2M. The reaction time varies significantly depending on the type of reaction raw materials used, the proportion used, the reaction temperature and the conditions of the solvent, but is usually 0.1 to 2000 hours, preferably 1 to 2000 hours.
~ 100 hours.

The reaction method is not particularly limited, and the reaction is carried out using a continuous, semi-continuous or batch type electrolytic layer. In the case of using a batch system, it is desirable to stir the reaction system. In constituting the reaction system, there is no particular limitation on the order and method of compounding the reaction substrate, sulfonylating agent, acid, dehydrating agent, solvent, etc., and they are mixed simultaneously or stepwise in various orders and manners. It is also possible.

The reaction temperature is from -80 ° C to 150 ° C.
And preferably 0 ° C to 50 ° 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 be carried out under pressure using a mixed gas with a diluent gas or the like which does not hinder the reaction.

The cyclic oligo (sulfonioarylene salt) compound synthesized by the above mild reaction is dissolved or precipitated in a reaction solvent and is stably isolated by an appropriate treatment. Hereinafter, the present invention will be described in more detail with reference to Examples. It goes without saying that the present invention is not limited to the following embodiments.

[0028]

EXAMPLES Example 1 Cyclic hexakis (methylsulfonio-1,4
Synthesis of -phenylene trifluoromethanesulfonate) In air, 0.10 g of cyclic hexakis (thio-1,4-phenylene) was dissolved in 5 ml of trifluoromethanesulfonic acid, and 10 mmol of methyl trifluoromethanesulfonate was added while cooling with ice. It was added dropwise. After completion of the dropwise addition, the mixed solution was further stirred for 10 hours. When the reaction solution was added dropwise to 200 ml of diethyl ether, a white precipitate was obtained. The precipitate was filtered for purification, washed several times with petroleum ether and diethyl ether, and dried under reduced pressure to obtain cyclic hexakis (methylsulfonio-
1,4-phenylene trifluoromethanesulfonate) was obtained in a yield of 100%. The reaction formula and analysis results are shown below.

[0029]

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[0030]

[Table 1]

Example 2 Synthesis of cyclic octakis (ethylsulfonio-1,4-phenylene methanesulfonate) 0.18 g of cyclic octakis (thio-1,4-phenylene) was dissolved in 10 ml of methanesulfonic acid in the air. Then, 20 mmol of ethyl acetate was added dropwise while cooling with ice. After completion of the dropwise addition, the mixed solution was heated to 80 ° C.
Stirred for days. When the reaction solution was added dropwise to 200 ml of diethyl ether, a white precipitate was obtained. The precipitate was filtered for purification, washed several times with petroleum ether and diethyl ether, and dried under reduced pressure to give cyclic octakis (ethylsulfonio-1,4-phenylene methanesulfonate) of the following formula in yield. Obtained at 81%.

The analysis results are also shown below.

[0033]

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[0034]

[Table 2]

Example 3 Cyclic tetrakis (oxy-1,
Synthesis of 4-phenylenephenylsulfonio-1,4-phenylene trifluoromethanesulfonate) Under nitrogen, 5 ml of trifluoromethanesulfonic acid was added to cyclic tetrakis (oxy-1,4-phenylenethio-1,4).
-Phenylene) dissolved in 0.12 g and cooled with ice for 6 m
mol of phenyl trifluoromethanesulfonate was added dropwise. After completion of the dropwise addition, the mixed solution was further stirred at 70 ° C. for 5 hours. When the reaction solution was added dropwise to 200 ml of diethyl ether, a white precipitate was obtained. The precipitate was filtered for purification, washed several times with petroleum ether and diethyl ether, and dried under reduced pressure to give the following cyclic tetrakis (oxy-1,4-phenylenephenylsulfonio-1,4-phenylene trifluoro) Methanesulfonate) in a yield of 74%.

The analysis results are also shown below.

[0037]

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[0038]

[Table 3]

Example 4 Synthesis of cyclic oligo (methylsulfonio-2,5-dimethyl-1,4-phenylene trifluoromethanesulfonate) 4 m in 5 ml of trifluoromethanesulfonic acid under air
1 mol of 1-methylsulfinyl-2,5-dimethylbenzene and 4 mmol of diphenylamine were added and reacted with stirring at room temperature for 20 hours. 200 m of reaction solution
Upon dropwise addition of 1 l of diethyl ether, a white precipitate was obtained. The precipitate was filtered for purification, washed several times with petroleum ether and chloroform, and dried under reduced pressure to obtain cyclic oligo (methylsulfonio-2,5-dimethyl-1,4-phenylene trifluoromethanesulfonate). Was obtained in a yield of 98%. Cyclic oligo (methylsulfonio-
2,5-dimethyl-1,4-phenylene trifluoromethanesulfonate) was confirmed to be a mixture of 3,4,5,6,7,8-mers.

The reaction formula and analysis results are shown below.

[0041]

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[0042]

[Table 4]

[0043]

The cyclic oligo (sulfonioarylene salt) compound of the present invention is an ion exchange resin having excellent heat resistance and chemical stability, is effective as a surfactant, and has an anion inclusion inside the ring. Shows high ionic conductivity. Protons are efficiently generated by irradiation with ultraviolet light, and can be used as a photopolymerization initiator such as epoxy and vinyl compounds. Further, it is also effective as a ring-opening polymerization monomer for engineering plastics such as a poly (sulfonioarylene salt) compound and a poly (thioarylene) compound.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 341/00 C07D 327/00 C07D 339/00 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A compound of the general formula [1] (However, Ar represents an aromatic group which may have a substituent, the ring-constituting atom or the substituent bonded to the ring may contain a hetero atom , and S is directly bonded to the ring-constituting atom of Ar.
Shows a sulfur atom to be combined . R represents a methyl group, an ethyl group,
Pill, butyl, phenyl, and toluyl
A substituent selected from the group consisting of: X ^- is an anion. n indicates the degree of polymerization as an integer of 2 or more. A cyclic oligo (sulfonioarylene salt) compound represented by the formula: 2. Ar is a phenylene group, diphenylene
2. The cyclic oligo (sulfonioarylene salt) compound according to claim 1, which is a ether group or a diphenylene sulfide group. Wherein wherein X ^-, trifluoromethanesulfonic acid
Anion, methanesulfonic acid anion, sulfate anion,
Hydrogen sulfate anion, tetrafluoroborate anion,
Perchlorate anion, hexafluoroantimonate ani
On or with hexafluorophosphate anion
3. The cyclic oligo (sulfo) according to claim 1 or 2,
Nioarylene salt) compound . 4. A compound according to any one of claims 1 to 3,
A manufacturing method, the general formula (2) ## STR2 ## (However, Ar represents an aromatic group which may have a substituent.
And the substituents attached to the ring members or the ring
S may be directly bonded to a ring-constituting atom of Ar.
Shows a sulfur atom to be combined. n is an integer of 2 or more,
Show. ) To the cyclic oligo (thioarylene) compound
Cyclic oligo (sulfonio)
(Arylene salt) A method for producing a compound. 5. The compound of any one of claims 1 to 3,
A manufacturing method, the general formula [3] [of 3] (However, Ar represents an aromatic group which may have a substituent.
And the substituents attached to the ring members or the ring
S may be directly bonded to a ring-constituting atom of Ar.
Shows a sulfur atom to be combined. R represents a methyl group, an ethyl group,
Pill, butyl, phenyl, and toluyl
A substituent selected from the group consisting of: Aryl sulfoxide compound polycondensation child represented by)
And a cyclic oligo (sulfonioarylene salt)
Method for producing the compound.