JP2000143671A - Purification of tetrakis(fluorinated aryl)borate compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for purifying a tetrakis(fluorinated aryl)borate compound, capable of efficiently and simply separating and removing coloring components contained in the tetrakis(fluorinated aryl)borate compound and capable of efficiently providing the tetrakis(fluorinated aryl)borate compound in a high purity at a low cost. SOLUTION: This method for purifying a tetrakis(fluorinated aryl)borate compound of the formula [R1-R10 are independently each H, F, a hydrocarbon groups or an alkoxy group, provided that at least one of R1-R5 is F and provided that at least one of R6-R10 is F; M is H, an alkyl metal, an alkaline earth metal or an alkaline earth metal halide; (n) is 3 or 4; (m) is 2, when M is an alkaline earth metal, or 1 in other cases] comprises mixing a solution containing an organic solvent and a compound of the formula containing impurities with water. The purified compound is reacted with a compound generating a monovalent cation species to produce a derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for purifying a tetrakis (fluoroaryl) borate compound containing impurities. Further, the present invention provides a method for producing a tetrakis (fluoroaryl) borate derivative useful as, for example, a co-catalyst of a metallocene catalyst (polymerization catalyst) to be subjected to a cationic complex polymerization reaction or a catalyst for photopolymerization of silicone. It is about.

[0002]

2. Description of the Related Art Tetrakis (fluoroaryl) borate derivatives are useful as, for example, cocatalysts for increasing the activity of metallocene catalysts (polymerization catalysts) to be subjected to a cationic complex polymerization reaction and catalysts for photopolymerization of silicone. It is.
The tetrakis (fluoroaryl) borate compound is a compound useful as an intermediate for producing the above tetrakis (fluoroaryl) borate derivative.
Incidentally, metallocene catalysts have been particularly noted in recent years as polyolefin polymerization catalysts.

[0003] For example, J. Organometal. Chem., 2 (196
4) For 245-250, pentafluorobenzene bromide was reacted with butyllithium (organic lithium compound) at -78 ° C using dry pentane as a solvent to obtain pentafluorophenyllithium. A method for synthesizing tris (pentafluorophenyl) boron by reacting with boron chloride (boron halide) and then reacting this compound with pentafluorophenyllithium to synthesize a tetrakis (pentafluorophenyl) borate derivative is disclosed. ing. Also, JP-A-6-24798
No. 1 discloses a method for synthesizing lithium tetrakis (pentafluorophenyl) borate, a kind of tetrakis (fluoroaryl) borate compound, from pentafluorobenzene using an organolithium compound and a boron halide. Have been.

However, in these methods, 1) special equipment is required because the temperature of the reaction system must be maintained at -65 ° C. or lower because the organolithium compound is unstable to heat. In addition, the cost required for cooling increases; 2) an expensive organolithium compound must be used, and the compound may be ignited by reaction with water or the like; Must be used, and moreover,
The compound is gaseous and corrosive, so that its handling is difficult.
Therefore, the method described in this publication is difficult to implement industrially.

On the other hand, for example, US Pat.
No. 3,036 discloses that after reacting pentafluorobenzene bromide with magnesium to obtain pentafluorophenylmagnesium bromide, the compound, which is a Grignard reagent, is reacted with a boron trifluoride diethyl ether complex to form tetrakis ( A method is disclosed for synthesizing (pentafluorophenyl) borate magnesium bromide and then reacting this compound with triethylammonium chloride to produce triethylammonium tetrakis (pentafluorophenyl) borate. JP-A-6-247980 discloses a method for synthesizing a tetrakis (fluoroaryl) borate compound by utilizing a Grignard reaction, specifically, a) a pentafluorophenylmagnesium halide and a boron halide. To produce tetrakis (pentafluorophenyl) borate / magnesium halide by reacting the compound; b) reacting pentafluorophenylmagnesium halide with tris (pentafluorophenyl) boron to produce tetrakis (pentafluorophenyl)
A method for producing borate magnesium halide is disclosed.

In the production method of US Pat. No. 5,473,036, magnesium fluorobromide and magnesium chloride are co-produced together with triethylammonium tetrakis (pentafluorophenyl) borate. However, this publication does not disclose any separation and removal of these by-produced magnesium halides from the reaction system. Since triethylammonium tetrakis (pentafluorophenyl) borate produced by the above method is a crude product, in order to finally obtain a purified product, the compound is converted into chloroform or
It needs to be recrystallized using methylene chloride / butyl ether. Therefore, it cannot be said that the production method is industrially advantageous.

[0007] In the production method a) according to JP-A-6-247980, magnesium halide is produced as a by-product together with tetrakis (pentafluorophenyl) borate / magnesium halide. However, the publication does not disclose and disclose any suggestion as to separation and removal of by-product magnesium halide from the reaction system. Tetrakis (pentafluorophenyl) produced using tetrakis (pentafluorophenyl) borate / magnesium bromide containing magnesium halide as an impurity
When a borate derivative is used, for example, as a co-catalyst for a metallocene catalyst, the activity of the catalyst is significantly reduced. Therefore,
The tetrakis (pentafluorophenyl) borate magnesium bromide obtained by this method is not suitable as an intermediate for producing the tetrakis (pentafluorophenyl) borate derivative.

[0008]

The above-mentioned U.S. Pat.
Pentafluorophenyl magnesium halide as a Grignard reagent used in JP-A-73,036 and JP-A-6-247980, specifically,
For example, pentafluorophenyl magnesium bromide obtained from bromopentafluorobenzene and magnesium is colored black by a coloring component that is an impurity generated by a side reaction or the like. Therefore, the tetrakis (fluoroaryl) borate compound synthesized using the pentafluorophenylmagnesium halide is colored black by the coloring component unless the step of removing the coloring component is performed. Therefore, when a target tetrakis (fluoroaryl) borate derivative is produced using this tetrakis (fluoroaryl) borate compound, the color tone of the tetrakis (fluoroaryl) borate derivative deteriorates, and as a result, the product is commercialized. It is difficult.

That is, a tetrakis (fluoroaryl) borate compound containing a coloring component as an impurity is not suitable as an intermediate for producing a tetrakis (fluoroaryl) borate derivative. However, in the above publication, there is no disclosure about the removal of the coloring component, and no suggestion is given.

Therefore, tetrakis (aryl fluoride)
There is a long-felt need for a purification method capable of efficiently and easily separating and removing coloring components, which are impurities contained in borate compounds. In addition, tetrakis (aryl fluoride)
There is a long-felt need for a method that can efficiently and inexpensively produce borate derivatives with high purity.

The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to efficiently and easily separate and remove coloring components which are impurities contained in a tetrakis (fluoroaryl) borate compound. It is an object of the present invention to provide a purification method which can be performed. Another object of the present invention is to produce a tetrakis (fluoroaryl) borate derivative useful as a cocatalyst of a metallocene catalyst, a catalyst for photopolymerization of silicone, or the like, with high purity, efficiently and at low cost. It is to provide a method that can be performed.

[0012]

Means for Solving the Problems The inventors of the present application have conducted intensive studies on a method for purifying a tetrakis (fluoroaryl) borate compound and a method for producing a tetrakis (fluoroaryl) borate derivative. As a result, by mixing a solution containing a tetrakis (fluoroaryl) borate compound containing a coloring component as an impurity and an organic solvent with water, the coloring component can be efficiently and easily separated and removed. I found what I could do. Then, by reacting the tetrakis (fluoroaryl) borate compound obtained by the above-described purification method with a compound generating a monovalent cation species, the tetrakis (fluoroaryl) borate derivative can be converted into a highly pure, efficient compound. The present inventors have found that they can be manufactured properly and at low cost, and have completed the present invention.

That is, the method for purifying a tetrakis (fluoroaryl) borate compound according to the present invention, in order to solve the above-mentioned problems, comprises a solution containing a tetrakis (fluoroaryl) borate compound containing impurities and an organic solvent. Is mixed with water.

According to the method for purifying a tetrakis (fluoroaryl) borate compound according to the present invention, in order to solve the above-mentioned problems, the tetrakis (fluoroaryl) borate compound has the general formula (1)

[0015]

Embedded image

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ , R ₇ , R ₈ , R ₉ , and R ₁₀ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of R _{1 to} R ₅ is fluorine. An atom, at least one of R _{6 to} R ₁₀ is a fluorine atom, M represents a hydrogen atom, an alkali metal, an alkaline earth metal or an alkaline earth metal halide;
n is 3 or 4, and m is 1 when M is a hydrogen atom, an alkali metal or an alkaline earth metal halide, and 2 when M is an alkaline earth metal. Features.

The method of purifying a tetrakis (fluoroaryl) borate compound according to the present invention is characterized in that, in order to solve the above-mentioned problems, the above solution is mixed with water, and then the organic solvent is distilled off from the mixture. And

The method for purifying a tetrakis (fluoroaryl) borate compound according to the present invention is obtained by mixing the above solution with water and distilling an organic solvent from the mixture in order to solve the above problems. The aqueous solution is further mixed with an aromatic hydrocarbon.

According to the method of purifying a tetrakis (fluoroaryl) borate compound of the present invention, in order to solve the above-mentioned problems, an aqueous solution of the tetrakis (fluoroaryl) borate compound obtained by mixing the above solution with water is used. And isolating the tetrakis (fluoroaryl) borate compound as a solid.

Further, in order to solve the above-mentioned problems, a method for producing a tetrakis (fluoroaryl) borate derivative according to the present invention comprises: a tetrakis (fluoroaryl) borate compound obtained by the above-mentioned purification method; Characterized by reacting with a compound that generates a cationic species of

According to the method for producing a tetrakis (fluoroaryl) borate derivative according to the present invention, in order to solve the above-mentioned problems, the tetrakis (fluoroaryl) borate derivative is represented by the general formula (2):

[0022]

Embedded image

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ , R ₇ , R ₈ , R ₉ , and R ₁₀ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of R _{1 to} R ₅ is fluorine. At least one of R _{6 to} R ₁₀ is a fluorine atom; Z ⁺ represents a monovalent cation species;
Is 3 or 4).

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The method for purifying a tetrakis (fluoroaryl) borate compound according to the present invention is a method of mixing a solution containing an impurity-containing tetrakis (fluoroaryl) borate compound and an organic solvent with water. It is. The water may be distilled water, ion-exchanged water, or pure water. The tetrakis (fluoroaryl) borate compound is tetrakis (fluoroaryl)
It is suitable as an intermediate of a borate derivative. Further, the method for producing a tetrakis (fluoroaryl) borate derivative according to the present invention is a method of reacting a tetrakis (fluoroaryl) borate compound obtained by the above-mentioned purification method with a compound generating a monovalent cation species. It is.

The tetrakis (fluoroaryl) borate compound to be purified in the present invention is a borate having at least three fluorinated aryl groups in which at least one of the hydrogen atoms in the aryl group is replaced by a fluorine atom. Any compound may be used, and there is no particular limitation. Specifically, the tetrakis (fluoroaryl) borate compound to be purified in the present invention is represented by the general formula (3)

[0026]

Embedded image

(Wherein R represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms;
R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of R _{1 to} R ₅ is fluorine. Is an atom, M represents a hydrogen atom, an alkali metal, an alkaline earth metal or an alkaline earth metal halide, n is 3 or 4, and m is a hydrogen atom, an alkali metal or an alkaline earth metal halide. 1 when the compound is an alkaline earth metal, and 2 when the compound is an alkaline earth metal). In the formula, the alkyl group in the substituent represented by R specifically refers to a linear or branched alkyl group.

Among these compounds, a tetrakis (fluoroaryl) borate compound represented by the general formula (1) is more preferable. Hereinafter, the present invention will be described using the tetrakis (fluoroaryl) borate compound represented by the general formula (1) as an example.

In the tetrakis (fluoroaryl) borate compound represented by the general formula (1) to be purified in the present invention, the substituents represented by R _{1 to} R ₁₀ are each independently hydrogen. Atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of the substituents represented by R _{1 to} R ₅ is a fluorine atom, and the substituent represented by R _{6 to} R ₁₀ At least one of which is a fluorine atom, the substituent represented by M is a hydrogen atom, an alkali metal, an alkaline earth metal or an alkaline earth metal halide, n is 3 or 4, m
Is a compound wherein M is 1 when it is a hydrogen atom, an alkali metal or an alkaline earth metal halide, and 2 when it is an alkaline earth metal.

Accordingly, the tetrakis (fluoroaryl) borate compound is, specifically, an alkali metal salt of tetrakis (fluoroaryl) borate, an alkaline earth metal salt of tetrakis (fluoroaryl) borate, or tetrakis (fluoro) borate. Alkaline earth metal halide salts of aryl (aryl) borate, and hydrogen compounds of tetrakis (fluoroaryl) borate.

The above-mentioned hydrocarbon group includes, specifically, an aryl group, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and a linear alkyl group having 2 to 12 carbon atoms. And a branched or cyclic alkenyl group. In addition, the above-mentioned hydrocarbon group may further have a functional group which is inert to the purification (treatment) and the reaction according to the present invention. As the functional group, specifically, for example,
Examples include a methoxy group, a methylthio group, an N, N-dimethylamino group, an o-anis group, a p-anis group, a trimethylsilyl group, a dimethyl-t-butylsilyloxy group, and a trifluoromethyl group.

The above alkoxy group is represented by the general formula (A) -OR _a (wherein _Ra represents _a hydrocarbon group).
_The hydrocarbon group represented by a is, for example, an aryl group, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and a linear chain having 2 to 12 carbon atoms. , Alkenyl, and the like. In addition, the above-mentioned hydrocarbon group may further have a functional group which is inert to the purification (treatment) and the reaction according to the present invention.

Specific examples of the alkoxy group represented by the general formula (A) include, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec- Butoxy, t-butoxy, cyclohexyloxy, allyloxy, phenoxy and the like.

Here, prior to describing the purification method according to the present invention in detail, an example of a method for producing the above tetrakis (fluoroaryl) borate compound will be described below.

The tetrakis (fluoroaryl) borate compound is represented by, for example, the general formula (4)

[0036]

Embedded image

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ , R ₇ , R ₈ , R ₉ , and R ₁₀ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of R _{1 to} R ₅ is fluorine. And at least one of R _{6 to} R ₁₀ is a fluorine atom, X represents a chlorine atom, a bromine atom or an iodine atom, and n is 3 or 4. A method of treating an aryl halide) borate / magnesium halide with an alkali metal carboxylate and / or an alkaline earth metal carboxylate; a method of treating with an acid;
Alternatively, it can be produced by a method of treating with an alkaline earth metal hydroxide; a method of treating with an acid, followed by a treatment with an alkali metal carboxylate and / or an alkaline earth metal carboxylate.

Accordingly, the tetrakis (fluoroaryl) borate / magnesium halide is converted to an alkali metal carboxylate and / or an alkaline earth metal carboxylate, or an alkali metal hydroxide and / or an alkaline earth metal hydroxide. If processed, that is,
When the treatment is performed by any one of the above methods, an alkali metal salt of tetrakis (fluoroaryl) borate and / or an alkaline earth metal salt of tetrakis (fluoroaryl) borate and / or tetrakis (fluoroaryl) An alkaline earth metal halide salt of borate is obtained. Further, when the tetrakis (fluoroaryl) borate / magnesium halide is treated with an acid, that is, when the magnesium halide is treated by the above method, a hydrogen compound of tetrakis (fluoroaryl) borate is obtained.

The above-mentioned tetrakis (fluoroaryl) borate / magnesium halide is obtained, for example, by reacting an aryl halide with magnesium to form a fluoroarylmagnesium halide which is a Grignard reagent. The fluorinated arylmagnesium halide is mixed with a boron halide in a molar ratio of 4:
It can be easily obtained by the method of reacting in step 1. Therefore, tetrakis (fluoroaryl) borate / magnesium halide is obtained in the form of a reaction solution dissolved in the solvent used for performing the Grignard reaction.

As the solvent, specifically, for example, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, diisoamyl ether, 1,2-dimethoxyethane, 1,2-diethyl ether Ether solvents such as ethoxyethane, anisole, tetrahydrofuran, tetrahydropyran and 1,4-dioxane; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane and methylcyclohexane Solvents; aromatic hydrocarbon solvents such as benzene, toluene and xylene; and the like, but are not particularly limited thereto. These solvents may be used as a mixed solvent.

The reaction solution contains a coloring component as impurities generated by a side reaction or the like. When a tetrakis (fluoroaryl) borate / magnesium halide is produced by reacting a fluoroarylmagnesium halide with a boron halide, a magnesium halide such as magnesium fluorobromide which is a by-product is produced. Are dissolved in the above solution as impurities.

Examples of the alkali metal carboxylate used in the above treatment method include, for example, sodium formate, potassium formate, sodium acetate, potassium acetate,
Such as sodium propionate and potassium propionate,
Alkali metal salts of saturated aliphatic monocarboxylic acids; monosodium oxalate, disodium oxalate, monopotassium oxalate, dipotassium oxalate, monosodium malonate, disodium malonate, monopotassium malonate, dipotassium malonate Mono- or dialkali metal salts of saturated aliphatic dicarboxylic acids, such as, monosodium succinate, disodium succinate, monopotassium succinate, dipotassium succinate;
Alkali metal salts of unsaturated aliphatic monocarboxylic acids such as sodium acrylate, potassium acrylate, sodium methacrylate, potassium methacrylate; monosodium maleate, disodium maleate, monopotassium maleate, dipotassium maleate; Monosodium fumarate,
Mono- or dialkali metal salts of unsaturated aliphatic dicarboxylic acids such as disodium fumarate, monopotassium fumarate and dipotassium fumarate; alkali metal salts of aromatic monocarboxylic acids such as sodium benzoate and potassium benzoate;
Monosodium phthalate, disodium phthalate, monopotassium phthalate, dipotassium phthalate, monosodium isophthalate, disodium isophthalate, monopotassium isophthalate, dipotassium isophthalate, monosodium terephthalate, disodium terephthalate, Mono- or dialkali metal salts of aromatic dicarboxylic acids such as monopotassium terephthalate and dipotassium terephthalate; and the like, but are not particularly limited thereto. In the present invention, the alkali metal carboxylate includes carbonates such as lithium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, and potassium hydrogen carbonate.

Specific examples of the alkaline earth metal carboxylate used in the above-mentioned treatment method include saturated fats such as calcium formate, barium formate, calcium acetate, barium acetate, calcium propionate, and barium propionate. Alkaline earth metal salts of group monocarboxylic acids;
Alkaline earth metal salts of saturated aliphatic dicarboxylic acids such as calcium oxalate, barium oxalate, calcium malonate, barium malonate, calcium succinate, barium succinate; calcium acrylate, barium acrylate, calcium methacrylate; Alkaline earth metal salts of unsaturated aliphatic monocarboxylic acids such as barium methacrylate; alkaline earth metal salts of unsaturated aliphatic dicarboxylic acids such as calcium maleate, barium maleate, calcium fumarate and barium fumarate Alkaline earth metal salts of aromatic monocarboxylic acids such as calcium benzoate and barium benzoate; aromatics such as calcium phthalate, barium phthalate, calcium isophthalate, barium isophthalate, calcium terephthalate, barium terephthalate Dicarboxylic group Alkaline earth metal salts; and the like. However, the invention is not particularly limited. In the present invention, the alkaline earth metal carboxylate includes carbonates such as calcium carbonate and barium carbonate. However, in the present invention, magnesium carboxylate is not included in the alkaline earth metal carboxylate.

These alkali metal carboxylate and alkaline earth metal carboxylate (hereinafter, when both are collectively referred to as carboxylate) may be used alone or in combination of two or more. You may use together. Among the carboxylate salts exemplified above, lithium carbonate, sodium carbonate,
More preferred are potassium carbonate, sodium acetate, disodium succinate, and barium acetate. The amount of the carboxylate used is not particularly limited, and may be at least 1 equivalent to tetrakis (fluoroaryl) borate / magnesium halide. When the alkali metal carboxylate and the alkaline earth metal carboxylate are used in combination, the ratio of the two is not particularly limited.

Examples of the acid used in the above treatment method include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid; formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, and succinic acid And the like, but are not particularly limited.

These acids may be used alone.
Further, two or more kinds may be used in combination. Of the acids exemplified above, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, and malonic acid are more preferred. The amount of the acid used is not particularly limited, and may be at least 1 equivalent to the magnesium used in the production of the tetrakis (fluoroaryl) borate / magnesium halide (charged into the reaction system). In addition, when an inorganic acid and an organic acid are used in combination, the ratio between the two is not particularly limited.

Specific examples of the alkali metal hydroxide used in the above treatment method include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. In addition, specific examples of the alkaline earth metal hydroxide used in the above treatment method include calcium hydroxide and barium hydroxide. However, in the present invention, magnesium hydroxide is not included in the alkaline earth metal hydroxide.

These alkali metal hydroxides and alkaline earth metal hydroxides (hereinafter collectively referred to as hydroxides) may be used alone or in combination.
Two or more types may be used in combination. The amount of the hydroxide used is not particularly limited, and may be at least 1 equivalent to tetrakis (fluoroaryl) borate / magnesium halide. In the case where the alkali metal hydroxide and the alkaline earth metal hydroxide are used in combination, the ratio of both is not particularly limited.

Tetrakis (fluoroaryl) borate
When the magnesium halide is treated with a carboxylate (the above-described treatment method), the tetrakis (fluoroaryl) borate / magnesium halide and the carboxylate may be mixed and stirred. When the tetrakis (fluoroaryl) borate / magnesium halide is treated with an acid (the above-described treatment method), the tetrakis (fluoroaryl) borate / magnesium halide is mixed with the acid.
What is necessary is just to stir. In the case of treating with a hydroxide after treating with an acid (the treatment method described above), the hydroxide may be mixed and stirred after separating and removing the acid. Further, in the case of treating with a carboxylate after treating with an acid (the treatment method described above), the carboxylate may be mixed and stirred after separating and removing the acid.

Tetrakis (fluoroaryl) borate
The method of mixing the magnesium halide solution with the carboxylate, acid, or hydroxide is not particularly limited. The carboxylate, acid and hydroxide may be mixed as is (solid or liquid) with a solution of tetrakis (fluoroaryl) borate / magnesium halide, or, if necessary, in a solution. May be.

As the solvent suitably used when the carboxylate, acid, or hydroxide is in the form of a solution, specifically, for example, water; the above-mentioned ether-based solvent; Hydrogen-based solvents; alicyclic hydrocarbon-based solvents described above; ester-based solvents such as methyl acetate and ethyl acetate; aromatic hydrocarbon-based solvents described above; alcohol-based solvents such as methyl alcohol and ethyl alcohol; acetone and methyl ethyl ketone And the like, but are not particularly limited. These solvents are
Only one type may be used, or two or more types may be used in combination.

The method of mixing the carboxylate, acid, and hydroxide, and the mixing order are not particularly limited. For example, tetrakis (fluoroaryl) borate
A carboxylate, an acid, or a hydroxide may be mixed with the magnesium halide solution, or a carboxylate, an acid,
For hydroxides, tetrakis (fluoroaryl) borate
A solution of magnesium halide may be mixed.

Tetrakis (fluoroaryl) borate
Temperature and time when mixing and stirring the magnesium halide solution, carboxylate, acid, and hydroxide, that is,
Processing conditions are not particularly limited. In the above treatment method, a solution of tetrakis (fluoroaryl) borate / magnesium halide, a carboxylate or an acid,
After mixing with the hydroxide, the mixture is stirred at room temperature for a predetermined time, whereby the tetrakis (fluoroaryl) borate / magnesium halide can be easily treated. In the case of treating with a hydroxide or a carboxylate after treating with an acid, the method of separating and removing the acid is not particularly limited. The acid can be separated from the solution of the tetrakis (fluoroaryl) borate compound by performing a simple operation such as liquid separation (oil-water separation). After the treatment, the tetrakis (fluoroaryl) borate compound is obtained in the form of a solution dissolved in a solvent (organic solvent).

If the solution of the tetrakis (fluoroaryl) borate compound contains a carboxylate, an acid, or a hydroxide, the carboxylate or the acid may be washed as necessary. , Hydroxide may be removed. Also,
When the carboxylate, acid, hydroxide, or a solution thereof contains a tetrakis (fluoroaryl) borate compound, extraction is performed as necessary to obtain a tetrakis (fluoroaryl) borate compound. Should be collected. Further, when water is contained in the solution of the tetrakis (fluoroaryl) borate compound, a desiccant such as anhydrous magnesium sulfate is added to the solution if necessary.
It may be removed (dried).

Tetrakis (fluoroaryl) borate
By treating the magnesium halide by the above-mentioned treatment methods, the tetrakis (fluoroaryl) borate compound to be purified in the present invention is obtained. That is, when tetrakis (fluoroaryl) borate / magnesium halide is treated with a carboxylate or hydroxide, that is, when treated with the treatment method of the above-mentioned, M in the general formula (1) becomes Tetrakis (fluoroaryl) borate, which is an alkali metal, alkaline earth metal or alkaline earth metal halide, is obtained. On the other hand, when tetrakis (fluoroaryl) borate / magnesium halide is treated with an acid, that is, when treated with the above-described treatment method, tetrakis (fluoride) in which M in the general formula (1) is a hydrogen atom is used. A hydrogen compound of (aryl) borate is obtained.

As to which one of the above-mentioned treatment methods should be adopted, for example, the obtained tetrakis (fluoroaryl) borate compound is in a desired form (alkali metal salt, alkaline earth metal salt, alkaline earth metal salt). Metal halide salts or hydrogen compounds), or
In order to further facilitate the separation operation performed after the treatment, for example, the operation of liquid separation, tetrakis (aryl fluoride)
What is necessary is just to select suitably based on the kind of borate / magnesium halide, the kind of solvent, etc.

According to the above-mentioned treatment method, for example, a magnesium halide by-produced in the process of producing tetrakis (fluoroaryl) borate / magnesium halide by a Grignard reaction is replaced with a water-soluble magnesium salt or an insoluble magnesium salt. Salt condition (that is,
Other than magnesium hydroxide). Therefore, the salt contained in the tetrakis (fluoroaryl) borate / magnesium halide can be efficiently and easily separated from the solution of the tetrakis (fluoroaryl) borate compound by performing an operation such as liquid separation or filtration. Can be removed. That is, impurities such as, for example, magnesium halide contained in the tetrakis (fluoroaryl) borate / magnesium halide can be efficiently and easily separated and removed.

The method of separating and removing impurities from the solution of the tetrakis (fluoroaryl) borate compound is not particularly limited. When a tetrakis (fluoroaryl) borate derivative is produced using a tetrakis (fluoroaryl) borate compound containing a magnesium halide as an impurity, the tetrakis (fluoroaryl) borate derivative also contains a magnesium halide as an impurity. become. When a tetrakis (fluoroaryl) borate derivative containing a magnesium halide is used, for example, as a co-catalyst of a metallocene catalyst, the activity of the catalyst is significantly reduced. Therefore, a tetrakis (fluoroaryl) borate compound containing a magnesium halide is not suitable as an intermediate for producing a tetrakis (fluoroaryl) borate derivative.

Even when the tetrakis (fluoroaryl) borate / magnesium halide does not contain impurities such as magnesium halide, the above-mentioned treatment is applied to the hydrogen compound of tetrakis (fluoroaryl) borate, tetrakis (fluoroaryl) borate. It is preferable to obtain an alkali metal salt of (fluoroaryl) borate, an alkaline earth metal salt of tetrakis (fluoroaryl) borate, or an alkaline earth metal halide salt of tetrakis (fluoroaryl) borate. Thereby, the reaction with the compound generating a monovalent cation species can be promptly and efficiently performed.

The method for producing the tetrakis (fluoroaryl) borate compound is not limited to the above-described method. Tetrakis (fluoroaryl) borate / magnesium halide, which is a kind of tetrakis (fluoroaryl) borate compound, is obtained, for example, by reacting a fluoroarylmagnesium halide with tris (fluoroaryl) boron at a molar ratio of 1: 1. It can also be produced by a method.

According to the above-mentioned production method, a tetrakis (fluoroaryl) borate compound containing no magnesium halide such as magnesium fluorobromide, that is, a solution containing a crude tetrakis (fluoroaryl) borate compound and an organic solvent ( Hereinafter, simply referred to as a solution).
However, the above solution contains a coloring component which is an impurity. Tetrakis (aryl fluoride) in the solution
The concentration (content) of the borate compound is not particularly limited, but it is desirable that the concentration be higher in order to carry out the purification method according to the present invention.

Next, the purification method according to the present invention will be described. In the purification method according to the present invention, the above solution is mixed with water. The tetrakis (fluoroaryl) borate compound dissolves in water. On the other hand, a coloring component which is an impurity produced as a by-product in the process of producing a tetrakis (fluoroaryl) borate compound by, for example, a Grignard reaction does not dissolve in water. Therefore, when the solution is brought into contact with water by, for example, mixing and stirring, the tetrakis (fluoroaryl) borate compound moves to the aqueous layer side, whereas the coloring component is in the solution side (organic solvent side), that is, the oil layer. Remains on the side. Therefore, for example, after the mixture obtained by mixing and stirring the solution with water is separated into two layers, the aqueous layer and the oil layer are separated (oil-water separation), so that the tetrakis (fluoroaryl) borate compound is It is possible to efficiently and easily separate and remove coloring components. That is, since the coloring component can be separated and removed, the tetrakis (fluoroaryl) borate compound can be purified.

The mixing ratio between the solution and water, that is, the amount of water used relative to the tetrakis (fluoroaryl) borate compound, depends on the mixing temperature (described later), the solubility of the tetrakis (fluoroaryl) borate compound at that temperature, and the like. Is not particularly limited. For example, the use amount is such that the ratio of the tetrakis (fluoroaryl) borate compound to the total amount of the tetrakis (fluoroaryl) borate compound and water is more preferably in the range of 0.1% by weight to 90% by weight. The amount may be set to an amount which is more preferably in the range of 1% to 50% by weight, and particularly preferably an amount which is in the range of 10% to 50% by weight. If a large amount of water is used outside the above range, the amount of the aqueous layer increases, and it may not be possible to efficiently purify the water. If the amount of water used is smaller than the above range, the tetrakis (fluoroaryl) borate compound to be transferred to the aqueous layer remains on the oil layer side, so that it may not be possible to purify efficiently. .

The method of mixing the solution with water and the mixing order are not particularly limited. For example, water may be mixed and stirred in the solution, or the solution may be mixed and stirred in water. At this time, the solution may be introduced into the water by an operation such as dripping, or the water may be introduced into the solution by an operation such as dripping. Alternatively, a method of continuously extracting a tetrakis (fluoroaryl) borate compound from a solution using water as an extractant and using a device such as a Soxhlet extractor for heavy and specific gravity can be employed as the mixing method. Therefore, "mixing a solution with water" in the present invention includes:
Also included is "separating the solution while in continuous contact with water."

Further, the mixing temperature and the time when the solution is mixed with water, that is, the purification conditions are not particularly limited. In the purification method according to the present invention, after the solution is mixed with water, the temperature exceeds the freezing point of water and is equal to or lower than the boiling point, that is, within the range of 0 ° C to 100 ° C, more preferably tetrakis (fluoroaryl) borate. Within the range of 50 ° C. to 100 ° C. where the solubility of the compound increases and becomes more efficient,
The stirring may be performed for a predetermined time, for example. Then, the solution and the water may be adjusted to a predetermined temperature (that is, the mixing temperature) prior to the mixing. Alternatively, the mixture obtained by mixing may be adjusted to a predetermined temperature. In short, in the purification method according to the present invention, at least at the time of separating the aqueous layer and the oil layer (oil-water separation), it is sufficient that both layers have reached the mixing temperature. In addition, a solution and water, or
The method for adjusting the temperature of the mixture to a predetermined temperature is not particularly limited.

In the purification method of the present invention, if necessary, the solution is mixed with water, and then the organic solvent is distilled off from the mixture, or the organic solvent is distilled off from the mixture. By mixing the resulting aqueous solution with an aromatic hydrocarbon, the tetrakis (fluoroaryl) borate compound can be purified more efficiently. In other words, by distilling off the organic solvent,
Specifically, the tetrakis (fluoroaryl) borate compound dissolved in the oil layer (organic solvent) is removed by distilling the organic solvent so that the weight of the organic solvent with respect to the weight of water is 30% by weight or less. Can be more dissolved in water. Therefore, the tetrakis (fluoroaryl) borate compound can be purified more efficiently.

The method for distilling off the organic solvent or the conditions such as temperature, pressure and time are not particularly limited, but the temperature is such that the organic solvent forms an azeotropic composition with water. In such a case, the azeotropic temperature may be set. When the organic solvent does not form an azeotropic composition with water, the temperature is preferably set to a temperature equal to or higher than the boiling point of the organic solvent. And when the organic solvent forms an azeotropic composition with water, the water distilled off together with the organic solvent may be returned to the mixture after separation, may be discarded, or may be distilled off. Fresh water corresponding to the amount of water may be added to the mixture. The pressure may be normal pressure (atmospheric pressure) or reduced pressure. Therefore, when the organic solvent is distilled off, the organic solvent is a compound which forms an azeotropic composition with water, or has a boiling point of 10 at normal pressure.
Desirably, the compound is below 0 ° C. The organic solvent may be distilled off from the mixture after the solution is mixed with water, or may be distilled off while introducing the solution into water by an operation such as dropping. The heating method for distilling off the organic solvent is not particularly limited.

After the organic solvent is distilled off, if an aqueous layer and an oil layer are present, the oil layer usually becomes the upper layer and the aqueous layer becomes the lower layer. The method for separating the aqueous layer and the oil layer (oil-water separation), or conditions such as temperature and time are not particularly limited, but the temperature is determined by tetrakis (fluorinated) dissolved in the aqueous layer. In order to prevent the precipitation of (aryl) borate compounds,
Alternatively, in order to suppress a decrease in the fluidity of the aqueous layer, the temperature may be set to a temperature higher than the freezing point of the aqueous layer and lower than the boiling point, more preferably about 50 ° C. When the organic solvent forms an azeotropic composition with water, the temperature may be set to be higher than the freezing point of the aqueous layer and lower than the azeotropic temperature.

By the way, when the organic solvent is almost completely distilled off, the coloring component becomes, for example, oil droplets, and the droplets sink because they have a higher specific gravity than the aqueous layer (aqueous solution). In this case, the tetrakis (fluoroaryl) borate compound and the coloring component can be separated by extracting the aqueous layer or the droplet. Alternatively, in order to further separate the coloring component, an aromatic hydrocarbon is mixed in the aqueous layer to dissolve the coloring component in the aromatic hydrocarbon, and then the aqueous layer and the aromatic hydrocarbon layer are separated. It can also be liquid.

The aromatic hydrocarbon may be any compound that dissolves the coloring component but does not dissolve the tetrakis (fluoroaryl) borate compound. As the aromatic hydrocarbon, specifically, for example, benzene, toluene,
Xylene, mesitylene, durene, ethylbenzene, cumene and the like can be mentioned, but not particularly limited.
These aromatic hydrocarbons may be used alone,
Further, two or more kinds may be used in combination.

The amount of the aromatic hydrocarbon used is not particularly limited as long as it is at least an amount capable of sufficiently dissolving the coloring components. For example, the amount used is such that the weight ratio of the tetrakis (fluoroaryl) borate compound to the aromatic hydrocarbon is more preferably 1: 0.01 to 1: 1.
0, particularly preferably 1: 0.1 to 1:
The amount may be set to be within the range of 5. If a large amount of aromatic hydrocarbon is used outside the above range, the amount of the aromatic hydrocarbon layer increases, so that it may not be possible to purify efficiently.

The method of mixing the aqueous layer with the aromatic hydrocarbon and the mixing order are not particularly limited. For example, an aromatic hydrocarbon may be mixed and stirred in the aqueous layer, or an aqueous layer may be mixed and stirred in the aromatic hydrocarbon.
Alternatively, using a device such as a Soxhlet extractor for heavy specific gravity,
A method of continuously extracting a coloring component from an aqueous layer using an aromatic hydrocarbon as an extractant can also be adopted as the mixing method. Therefore, in the present invention, "mixing the aqueous layer with the aromatic hydrocarbon" includes "separating the aqueous layer while continuously contacting the aqueous layer with the aromatic hydrocarbon".

The conditions for mixing the aqueous layer with the aromatic hydrocarbon, such as the mixing temperature and the time, are not particularly limited. For example, the conditions according to the conditions for mixing the solution with water may be used. And it is sufficient. After the mixture obtained by mixing and stirring the aqueous layer with the aromatic hydrocarbon is separated into two layers, the aqueous layer and the aromatic hydrocarbon layer are separated (oil-water separation) to obtain a tetrakis (aryl fluoride). 2.) The borate compound and the coloring component can be efficiently and easily separated and removed.

The water layer and the oil layer may be separated without distilling the organic solvent or the water layer and the oil layer may be separated with the organic solvent removed to a certain extent. In order to further remove impurities contained in the water, the aqueous layer is mixed with an aromatic hydrocarbon to dissolve (extract) the impurities in the aromatic hydrocarbon, and then the aqueous layer and the aromatic The liquid can be separated from the hydrocarbon layer. This makes it possible to purify the tetrakis (fluoroaryl) borate compound with even higher purity.

By the above purification method, an aqueous solution of a tetrakis (fluoroaryl) borate compound containing no coloring component as an impurity, that is, an aqueous solution of a tetrakis (fluoroaryl) borate compound, is obtained.

When the tetrakis (fluoroaryl) borate compound is isolated and purified as a solid (crystal) from an aqueous solution of the tetrakis (fluoroaryl) borate compound, for example, water is completely distilled from the aqueous solution. After the compound is precipitated by concentrating and / or cooling the aqueous solution, a separation operation such as filtration is performed; or the compound is extracted from the aqueous solution by mixing the aqueous solution with an organic extractant. And various other operations such as distilling off the organic extractant. In particular, tetrakis (fluoroaryl)
When a water-soluble impurity is contained in the aqueous solution of the borate compound, it is more preferable to perform the above operation using an organic extractant.

The method of completely removing water from the aqueous solution and various conditions such as temperature, pressure and time in the method are as follows.
There is no particular limitation. Specific examples of the method include a method of concentrating and drying an aqueous solution under normal pressure or reduced pressure. The method of concentrating and / or cooling the aqueous solution to precipitate the compound, the method of separation operation such as filtration, and various conditions such as temperature, pressure, and time in these methods are not particularly limited. Absent.

The organic extractant may be any compound that dissolves the tetrakis (fluoroaryl) borate compound and does not mix uniformly with water. As the organic extractant, specifically, for example, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, t
-Butyl methyl ether, diisoamyl ether, 1,
Ether extractants such as 2-dimethoxyethane, 1,2-diethoxyethane, anisole, 2-methyltetrahydrofuran, and 1,2-dioxane; ester extractants such as methyl acetate and ethyl acetate; diethyl ketone, dipropyl ketone And the like, but are not particularly limited. Examples thereof include a ketone-based extraction medium such as methylene chloride (dichloromethane), chloroform, and 1,2-dichloroethane. Only one kind of these organic solvents may be used, or two or more kinds may be used in combination.

The amount of the organic extractant used is not particularly limited, as long as it is at least an amount capable of sufficiently extracting the tetrakis (fluoroaryl) borate compound from the aqueous solution. When extraction is performed using an organic extractant, the tetrakis (fluoroaryl) borate compound moves to the oil layer side (organic extractant side), while various water-soluble impurities remain in the aqueous layer side (aqueous solution side). I do. Therefore, for example, after a mixture obtained by mixing and stirring an aqueous solution with an organic extractant is separated into two layers, the aqueous layer and the oil layer are separated (oil-water separation) to obtain tetrakis (fluoroaryl) borate. Compounds and water-soluble impurities can be efficiently and easily separated and removed.

The method of extracting an aqueous solution by mixing it with an organic extractant, and the order of mixing are not particularly limited. For example, extraction may be performed by mixing and stirring an organic extractant with an aqueous solution, or may be performed by mixing and stirring an aqueous solution with an organic extractant. At this time, the organic extractant may be introduced into the aqueous solution by an operation such as dropping, or the aqueous solution may be introduced into the organic extractant by an operation such as dropping. Further, in the present invention, "mixing and extracting an aqueous solution with an organic extractant" includes "contacting the aqueous solution with the organic extractant continuously and separating while extracting". The method of distilling off the organic extractant after extracting the compound from the aqueous solution, and various conditions such as temperature, pressure and time in the method are not particularly limited. Therefore, the method of extracting the tetrakis (fluoroaryl) borate compound from the aqueous solution using the organic extractant and the extraction conditions are not particularly limited.

By the above purification method, the tetrakis (fluoroaryl) borate compound can be isolated as a solid from the aqueous solution. That is, a solid tetrakis (fluoroaryl) borate compound containing no impurities can be obtained.

Next, a method of producing a tetrakis (fluoroaryl) borate derivative by reacting a tetrakis (fluoroaryl) borate compound obtained by the above purification method with a compound generating a monovalent cation species is described. explain. Specifically, the tetrakis (fluoroaryl) borate compound represented by the general formula (1) is reacted with a compound that generates a monovalent cation species to form a tetrakis (fluoroalkyl) borate compound represented by the general formula (2). The present invention will be described by way of an example of a method for producing a (fluoroaryl) borate derivative.

The compound capable of generating a monovalent cationic species according to the present invention (hereinafter referred to as a cationic species generating compound) generates a monovalent cationic species in a reaction solvent described below,
In addition, any compound having reactivity with the tetrakis (fluoroaryl) borate compound may be used.

Specific examples of the monovalent cation species generated by the cation species generating compound include, for example, n-
Butyl ammonium, dimethyl ammonium, trimethyl ammonium, triethyl ammonium, triisopropyl ammonium, tri-n-butyl ammonium,
Ammonium cations such as tetramethylammonium, tetraethylammonium, and tetra-n-butylammonium; anilinium, N-methylanilinium,
N, N-dimethylanilinium, N, N-diethylanilinium, N, N-diphenylanilinium, N, N,
Anilinium cations such as N-trimethylanilinium; pyridinium cations such as pyridinium, N-methylpyridinium and N-benzylpyridinium; quinolinium cations such as quinolinium and isoquinolinium; adamantyl cations such as adamantane-2-yl-ammonium; Phosphonium cations such as dimethylphenylphosphonium, triphenylphosphonium, tetraethylphosphonium, and tetraphenylphosphonium; sulfonium cations such as trimethylsulfonium and triphenylsulfonium; diphenyliodonium, Iodonium cations such as 4-methoxyphenyliodonium; carbenium cations such as triphenylcarbenium and tri-4-methoxyphenylcarbenium Alkali metals and alkaline earth metals other than the metal monovalent cation; and the like, but not particularly limited.

Among them, trialkylammonium cation, tetraalkylammonium cation, dialkylanilinium cation, alkylpyridinium cation, tetraalkylphosphonium cation, tetraarylphosphonium cation, and diaryliodonium cation are More preferred. The anionic species to be paired with the monovalent cation species is not particularly limited.

Specific examples of the cationic species generating compound include, for example, tri-n-butylamine.hydrochloride, N, N
-Dimethylaniline / hydrochloride, N, N-dimethylaniline / sulfate, tri-n-butylammonium / hydrochloride,
Quaternary ammonium compounds such as tetramethylammonium chloride (tetramethylammonium / hydrochloride); nitrogen-containing aromatic heterocycles such as pyridine / hydrochloride, quinoline / hydrochloride, N-methylpyridine iodide and N-methylquinoline iodide Adamantane compounds such as 2-aminoadamantane hydrochloride; quaternary phosphonium compounds such as tetra-n-butylphosphonium bromide and tetraphenylphosphonium bromide; trimethylsulfonium chloride;
Sulfonium compounds such as trimethylsulfonium iodide; iodonium compounds such as diphenyliodonium chloride; carbenium compounds such as trityl chloride (triphenylcarbenium chloride);

For example, N, N-dimethylaniline hydrochloride generates an N, N-dimethylanilinium cation as a monovalent cation species. In this case, the anion species is a chloride ion.

The amount of the cationic species generating compound to be used is not particularly limited, and tetrakis (aryl fluoride) may be used.
What is necessary is just 0.8 equivalent or more with respect to a borate compound.

In the production method according to the present invention, a reaction solvent is used. As the above reaction solvent, specifically,
For example, water; diethyl ether, dipropyl ether,
Diisopropyl ether, dibutyl ether, t-butyl methyl ether, diisoamyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, anisole, tetrahydrofuran, tetrahydropyran, 1,4
Ether solvents such as dioxane; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane and methylcyclohexane; ester solvents such as methyl acetate and ethyl acetate; Examples thereof include, but are not particularly limited to, aromatic hydrocarbon solvents such as benzene, toluene, and xylene; alcohol solvents such as methyl alcohol and ethyl alcohol; ketone solvents such as acetone and methyl ethyl ketone. One of these reaction solvents may be used alone, or two or more of them may be used in combination.

Further, obtained by the above-mentioned purification method,
When the reaction is performed using an aqueous solution of a tetrakis (fluoroaryl) borate compound, water in which the tetrakis (fluoroaryl) borate compound is dissolved can be used as a reaction solvent (or a part thereof). Therefore,
In the production method according to the present invention, the tetrakis (fluoroaryl) borate derivative is produced using the aqueous solution of the purified tetrakis (fluoroaryl) borate compound without isolating the compound from the purified aqueous solution. Can be.

As a method of mixing the tetrakis (fluoroaryl) borate compound and the cationic species generating compound, specifically, for example, mixing the tetrakis (fluoroaryl) borate compound and the cationic species generating compound in a reaction solvent A method of mixing a cationic species generating compound or a solution thereof with an aqueous solution of a tetrakis (fluoroaryl) borate compound; a method of mixing a tetrakis (fluoroaryl) borate compound or an aqueous solution thereof with a solution of a cationic species generating compound And the like, but are not particularly limited. In the case of mixing a solution of a cationic species generating compound with an aqueous solution of a tetrakis (fluoroaryl) borate compound, and in the case of mixing an aqueous solution of a tetrakis (fluoroaryl) borate compound with a solution of a cationic species generating compound, It is more preferable to drop the solution to be added.

The temperature and time, ie, the reaction conditions, in the reaction between the tetrakis (fluoroaryl) borate compound and the cationic species generating compound are not particularly limited. In the production method according to the present invention, the reaction proceeds easily by stirring a reaction solution obtained by dissolving a tetrakis (fluoroaryl) borate compound and a cationic species generating compound in a reaction solvent at room temperature for a predetermined time. Can be done. Therefore, the desired tetrakis (fluoroaryl) borate derivative can be easily obtained.

For example, when the tetrakis (fluoroaryl) borate compound is an alkali metal salt of tetrakis (fluoroaryl) borate, an alkaline earth metal salt of tetrakis (fluoroaryl) borate, or an alkali metal salt of tetrakis (fluoroaryl) borate When the compound is an earth metal halide salt and the cation species generating compound is N, N-dimethylaniline hydrochloride, the target compound, N, N-dimethylanilinium tetrakis (aryl fluoride) ) A borate is obtained, and an alkali metal chloride such as sodium chloride or an alkaline earth metal chloride such as calcium chloride is by-produced. These alkali metal chlorides or alkaline earth metal chlorides can be converted to N, N- by performing operations such as liquid separation, filtration, and washing.
Dimethylanilinium tetrakis (aryl fluoride)
It can be easily separated and removed from the borate solution.

For example, when the tetrakis (fluoroaryl) borate compound is a hydrogen compound of tetrakis (fluoroaryl) borate and the cationic species generating compound is N, N-dimethylaniline hydrochloride, The reaction yields N, N-dimethylanilinium tetrakis (fluoroaryl) borate, which is the desired product, and produces hydrochloric acid as a by-product. The hydrochloric acid can be easily separated and removed from N, N-dimethylanilinium.tetrakis (fluoroaryl) borate by performing operations such as liquid separation and washing.

That is, for the tetrakis (fluoroaryl) borate derivative, simple operations such as liquid separation and filtration are performed, and then, if necessary, simple operations such as removal (distillation) of the reaction solvent are performed. Can easily be isolated and purified as crystals.

As described above, in the method for producing a tetrakis (fluoroaryl) borate derivative according to the present invention, a tetrakis (fluoroaryl) borate compound obtained by the above-mentioned purification method is reacted with a cationic species generating compound. Is the way.

According to the above method, a tetrakis (fluoroaryl) borate compound, that is, an alkali metal salt of tetrakis (fluoroaryl) borate, an alkaline earth metal salt of tetrakis (fluoroaryl) borate, tetrakis (fluoro) Alkaline earth metal halide salts of aryl) borates and tetrakis (aryl fluorides)
A tetrakis (fluoroaryl) borate derivative can be efficiently and inexpensively produced from a borate hydrogen compound. The derivative has high purity because it does not contain impurities such as a coloring component and, for example, magnesium halide, and is used as a co-catalyst of a metallocene catalyst provided for a cationic complex polymerization reaction, a catalyst for photopolymerization of silicone, and the like. It can be suitably used.

[0098]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 A crude tetrakis (pentafluorophenyl) borate / hydrogen compound 10 as a tetrakis (fluoroaryl) borate compound was placed in a 1-L container equipped with a thermometer, a stirrer, and a reflux condenser.
400 ml of a xylene (organic solvent) solution containing 8.8 g (0.160 mol) and 500 ml of ion-exchanged water were charged. The purity of the tetrakis (pentafluorophenyl) borate / hydrogen compound in the solution was 95.4%. The solution was colored black by the coloring component.

Next, the above mixture was heated and stirred at 100 ° C. for 4 hours. Thereafter, stirring was stopped and the mixture was cooled to 70 ° C. Then, the mixture was separated into two layers, that is, a black xylene layer and a colorless and transparent aqueous layer. Therefore, only the aqueous layer was taken out of the container by liquid separation (oil-water separation).

The content of the tetrakis (pentafluorophenyl) borate / hydrogen compound in the aqueous layer was determined to be ¹⁹ F
-It was determined by measuring an NMR (nuclear magnetic resonance) spectrum. That is, ¹⁹ F-NMR was measured under predetermined conditions using p-fluorotoluene as an internal standard. In the measurement, trifluoroacetic acid was used as a standard substance, and the position of the signal was 0 ppm. And got
^{From the 19} F-NMR chart, the integral value of the fluorine atom of p-fluorotoluene and the integral value of the fluorine atom at the ortho position of the pentafluorophenyl group in the tetrakis (pentafluorophenyl) borate / hydrogen compound were determined.
The amount of tetrakis (pentafluorophenyl) borate / hydrogen compound was calculated from both integral values. As a result, the aqueous layer contained 79.4 g of a colorless tetrakis (pentafluorophenyl) borate / hydrogen compound, and the purity was 9%.
It was 9.0%. The recovery of tetrakis (pentafluorophenyl) borate / hydrogen compound was 73.0%.
Met.

Example 2 A crude (purity: 95.4%) tetrakis (pentafluorophenyl) borate / hydrogen compound was placed in a 1-L container equipped with a thermometer, a dropping funnel, a stirrer, and a distillation apparatus. 8g (0.160
Mol) and 320 ml of xylene, and 400 ml of ion-exchanged water. The solution was colored black by the coloring components.

Next, the above mixture was stirred for 10 minutes.
The mixture was heated to 0 ° C. to distill off xylene. Water distilled out by forming an azeotropic composition with xylene was returned to the container via a dropping funnel after liquid separation. Then, when 200 ml of xylene was distilled off, the heating was stopped, and the mixture was cooled to 70 ° C. Then, the mixture was separated into two layers, that is, a black xylene layer and a white aqueous layer. By separating the mixture, only the aqueous layer was taken out of the container.

As a result of analysis by the same method as in Example 1, the aqueous layer contained 98.1 g of a colorless tetrakis (pentafluorophenyl) borate / hydrogen compound, and the purity was 99.0%. there were. The recovery of tetrakis (pentafluorophenyl) borate / hydrogen compound was 90.2%.

Example 3 In a container similar to that in Example 2, 108.8 g (0.16%) of crude (purity: 95.4%) tetrakis (pentafluorophenyl) borate / hydrogen compound was added.
(0 mol) and 400 ml of ion-exchanged water. The solution was colored black by the coloring components.

Next, the above mixture was stirred for 10 minutes.
The mixture was heated to 0 ° C. to distill off xylene. Water distilled out by forming an azeotropic composition with xylene was returned to the container via a dropping funnel after liquid separation. When the distillation of xylene is completed, the heating is stopped, and the mixture is stirred for 7 minutes.
Cooled to 0 ° C. Then, the mixture was separated into two layers, that is, a white aqueous layer and a black oil layer accumulated at the bottom of the container. Only the aqueous layer was extracted from the container.

As a result of analysis by the same method as in Example 1, the aqueous layer contained 105.5 g of a colorless tetrakis (pentafluorophenyl) borate / hydrogen compound, and the purity was 99.0%. there were. The recovery of tetrakis (pentafluorophenyl) borate / hydrogen compound was 97.0%.

Example 4 In a container similar to that of Example 2, 108.8 g (0.16 g) of a crude (purity: 95.5%) tetrakis (pentafluorophenyl) borate / hydrogen compound was prepared.
0 mol) in a di-n-butyl ether solution 400 ml
And 500 ml of ion-exchanged water. The solution was colored black by the coloring components.

Next, the above mixture was stirred for 10 minutes.
The mixture was heated to 0 ° C. to distill off di-n-butyl ether. Further, water distilled out by forming an azeotropic composition with di-n-butyl ether was returned to a container via a dropping funnel after liquid separation. When the distillation of di-n-butyl ether was completed, the heating was stopped, and the mixture was cooled to 70 ° C. Then, a black oil layer accumulated at the bottom of the container.

Thereafter, 100 ml of toluene as an aromatic hydrocarbon was charged into the container via a dropping funnel,
For 1 hour. When the stirring was stopped, the mixture was separated into two layers, that is, a black toluene layer and a colorless and transparent aqueous layer. By separating the layers, only the aqueous layer was taken out of the container.

As a result of analysis by the same method as in Example 1, the aqueous layer contained 103.4 g of a colorless tetrakis (pentafluorophenyl) borate / hydrogen compound, and the purity was 99.0%. there were. The recovery of tetrakis (pentafluorophenyl) borate / hydrogen compound was 95.0%.

Example 5 230 ml of ion-exchanged water was charged into a 1 L container equipped with a thermometer, a stirrer, and a Soxhlet extractor for specific gravity. Further, the crude (purity 95.0%) tetrakis (pentafluorophenyl) borate / hydrogen compound 16.3 was added to the Soxhlet extractor.
g (0.024 mol) of a xylene solution containing 65 ml
400 ml of ion-exchanged water was charged. The solution was colored black by the coloring components.

Next, the ion-exchanged water in the container was intermittently refluxed for 60 hours while stirring to perform an extraction operation.
Heating and stirring were stopped. The aqueous solution in the container and the aqueous layer in the Soxhlet extractor were colorless and transparent. Then, the aqueous solution was extracted from the container, and only the aqueous layer was extracted from the Soxhlet extractor, and the two were mixed.

As a result of analysis by the same method as in Example 1, the mixed solution contained 11.0 g of a colorless tetrakis (pentafluorophenyl) borate / hydrogen compound, and the purity was 99.0%. Met. The recovery of tetrakis (pentafluorophenyl) borate / hydrogen compound was 64.7%.

Example 6 In the same container as in Example 2, crude (purity: 95.5%) tetrakis (aryl fluoride) was added.
Sodium tetrakis (pentafluorophenyl) borate as a borate compound 112.3 g (0.16 g)
0 mol) in a di-n-butyl ether solution 400 ml
And 600 ml of ion-exchanged water. The solution was colored black by the coloring components.

Next, the above mixture was stirred for 10 minutes.
The mixture was heated to 0 ° C. to distill off di-n-butyl ether. Further, water distilled out by forming an azeotropic composition with di-n-butyl ether was returned to a container via a dropping funnel after liquid separation. When the distillation of di-n-butyl ether was completed, the heating was stopped, and the mixture was cooled to 70 ° C. Then, a black oil layer accumulated at the bottom of the container.

Thereafter, 200 ml of toluene was charged into the vessel via a dropping funnel, heated and stirred at 70 ° C. for 1 hour, and then the mixture was cooled to 50 ° C. When stirring is stopped,
Since the mixture was separated into two layers, a black toluene layer and an aqueous layer, only the aqueous layer was taken out of the container by liquid separation.

As a result of analysis by the same method as in Example 1, the aqueous layer contained 104.6 g of colorless sodium tetrakis (pentafluorophenyl) borate and had a purity of 99.0%. Was. The recovery of sodium tetrakis (pentafluorophenyl) borate was 93.1%.

Example 7 In the same container as in Example 2, crude (purity 95.5%) tetrakis (aryl fluoride) was added.
Tetrakis (pentafluorophenyl) borate magnesium bromide as borate compound 103.4
g (0.132 mol) of a xylene solution containing 80 ml;
125 ml of ion-exchanged water was charged. The solution was colored black by the coloring components.

Next, the above mixture was stirred for 10 minutes.
The mixture was heated to 0 ° C. to distill off xylene. When the distillation of xylene was completed, the heating was stopped and the mixture was heated to 70 ° C.
And cooled. Then, the mixture was separated into two layers, that is, a white aqueous layer and a black oil layer accumulated at the bottom of the container. Only the aqueous layer was extracted from the container.

As a result of analysis in the same manner as in Example 1, the aqueous layer was found to contain 55.0 g of colorless tetrakis (pentafluorophenyl) borate / magnesium bromide.
And a purity of 99.0%. The recovery of tetrakis (pentafluorophenyl) borate / magnesium bromide was 61.3%.

Example 8 A 1 L reactor equipped with a thermometer, a dropping funnel, a stirrer, and a reflux condenser was charged with
An aqueous solution containing 79.4 g (0.117 mol) of the tetrakis (pentafluorophenyl) borate / hydrogen compound purified in Example 1 was charged. On the other hand, N, N-dimethylaniline sulfate 0.1 as a cationic species generating compound
130 ml of an aqueous solution containing 55 mol was charged into the dropping funnel.

Next, the aqueous solution in the reaction vessel was heated to 70 ° C. while stirring, and the aqueous solution in the dropping funnel was dropped at the same temperature over 30 minutes. After the addition was completed, the reaction solution was cooled to room temperature. Then, crystals were precipitated from the reaction solution, and the crystals were separated by suction filtration. Then, the obtained cake (crystal) was washed with 160 ml of ion-exchanged water, and then dried under reduced pressure.

Thus, N, N-dimethylanilinium.tetrakis (pentafluorophenyl) borate as a tetrakis (fluoroaryl) borate derivative was obtained as a white powder. As a result of analysis in the same manner as in Example 1, the yield of N, N-dimethylanilinium.tetrakis (pentafluorophenyl) borate based on tetrakis (pentafluorophenyl) borate.hydrogen compound was 95.0. Mole% and a purity of 9
It was 9.0%.

Example 9 In a reaction vessel similar to that of Example 8, 105.5 g of tetrakis (pentafluorophenyl) borate / hydrogen compound purified in Example 3 (0.1
(55 mol). On the other hand, an aqueous solution 1 containing 0.155 mol of N, N-dimethylaniline sulfate
30 ml was charged into the dropping funnel.

Next, the same reaction and operation as in Example 8 were performed to obtain N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate as a white powder. As a result of analysis by the same method as in Example 1, the yield of N, N-dimethylanilinium.tetrakis (pentafluorophenyl) borate based on tetrakis (pentafluorophenyl) borate.hydrogen compound was 90.0%. Mole% and a purity of 9
It was 9.0%.

Example 10 In the same reaction vessel as in Example 8, 103.4 g (0.1%) of the tetrakis (pentafluorophenyl) borate / hydrogen compound purified in Example 4 was added.
(52 mol). On the other hand, an aqueous solution 1 containing 0.155 mol of N, N-dimethylaniline sulfate
30 ml was charged into the dropping funnel.

Next, by carrying out the same reaction and operation as in Example 8, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was obtained as a white powder. As a result of analysis in the same manner as in Example 1, the yield of N, N-dimethylanilinium.tetrakis (pentafluorophenyl) borate based on tetrakis (pentafluorophenyl) borate.hydrogen compound was 95.0. Mole% and a purity of 9
It was 9.0%.

Example 11 10.5 g (0.01%) of sodium tetrakis (pentafluorophenyl) borate purified in Example 6 was placed in the same reaction vessel as in Example 8.
(5 mol). On the other hand, an aqueous solution 13 containing 0.015 mol of N, N-dimethylaniline sulfate
ml was charged into the dropping funnel.

Then, N, N-dimethylanilinium tetrakis (N, N-dimethylanilinium tetrakis) was obtained by performing the same reaction and operation as in Example 8 except that the amount of ion exchanged water for washing the cake was changed to 60 ml. (Pentafluorophenyl) borate was obtained as a white powder. As a result of analysis in the same manner as in Example 1, N, N was determined based on sodium tetrakis (pentafluorophenyl) borate.
The yield of N-dimethylanilinium tetrakis (pentafluorophenyl) borate is 95.0 mol%,
Purity was 99.0%.

Example 12 The procedure of Example 12 was repeated, except that 20 ml of an aqueous solution containing 0.018 mol of tetramethylammonium hydrochloride as a cation species generating compound was used instead of the aqueous N, N-dimethylaniline sulfate solution. The same reaction and operation as those of No. 11 were performed.

As a result, tetramethylammonium tetrakis (pentafluorophenyl) borate as a tetrakis (fluoroaryl) borate derivative was obtained as a white powder. As a result of analysis by the same method as in Example 1, the yield of tetramethylammonium tetrakis (pentafluorophenyl) borate based on sodium tetrakis (pentafluorophenyl) borate was 97.4 mol%, Purity was 99.0%.

Example 13 Instead of an aqueous solution of N, N-dimethylaniline / sulfate, 0.015 tri-n-butylammonium / hydrochloride as a cation species generating compound was used.
Example 11 except that 20 ml of an aqueous solution containing mol was used.
The same reaction and operation as those described above were performed.

Thus, tri-n-butylammonium tetrakis (pentafluorophenyl) borate as a tetrakis (fluoroaryl) borate derivative was obtained as a white powder. As a result of analysis in the same manner as in Example 1, the yield of tri-n-butylammonium tetrakis (pentafluorophenyl) borate based on sodium tetrakis (pentafluorophenyl) borate was 96.5 mol%. And a purity of 9
It was 9.0%.

[Example 14] Except that 20 ml of an aqueous solution containing 0.015 mol of tetra-n-butylphosphonium bromide as a cationic species generating compound was used instead of the aqueous solution of N, N-dimethylaniline sulfate. Is
The same reaction and operation as those in Example 11 were performed.

As a result, tetra-n-butylphosphonium.tetrakis (pentafluorophenyl) borate as a tetrakis (fluoroaryl) borate derivative was obtained as a white powder. As a result of analysis by the same method as in Example 1, tetra-n based on sodium tetrakis (pentafluorophenyl) borate was used.
The yield of -butylphosphonium tetrakis (pentafluorophenyl) borate was 83.9 mol%,
Purity was 99.0%.

Example 15 The procedure of Example 15 was repeated except that 20 ml of an aqueous solution containing 0.016 mol of trimethylsulfonium iodide as a cationic species generating compound was used in place of the aqueous solution of N, N-dimethylaniline sulfate. The same reaction and operation as those of No. 11 were performed.

As a result, trimethylsulfonium tetrakis (pentafluorophenyl) borate as a tetrakis (fluoroaryl) borate derivative was obtained as a white powder. As a result of analysis in the same manner as in Example 1, the yield of trimethylsulfonium tetrakis (pentafluorophenyl) borate based on sodium tetrakis (pentafluorophenyl) borate was 89.5 mol%. And the purity was 99.0%.

Example 16 An aqueous solution containing 0.015 mol of pyridine / hydrochloride as a cationic species generating compound instead of the aqueous solution of N, N-dimethylaniline / sulfate was used.
The same reaction and operation as in Example 11 were performed except for using ml.

As a result, pyridinium tetrakis (pentafluorophenyl) borate as a tetrakis (fluoroaryl) borate derivative was obtained as a white powder. As a result of analysis by the same method as that of Example 1,
The yield of pyridinium tetrakis (pentafluorophenyl) borate based on sodium tetrakis (pentafluorophenyl) borate was 89.2 mol%, and the purity was 99.0%.

Example 17 8.2 g of sodium tetrakis (pentafluorophenyl) borate (0.01 g)
Aqueous solution containing 2 mol) of N, N
-Instead of dimethylaniline / sulfate aqueous solution, iodide N-methylquinoline iodide as a cationic species generating compound is used.
The same reaction and operation as in Example 11 were performed except that 20 ml of an aqueous solution containing 012 mol was used.

Thus, N-methylquinolinium · tetrakis (fluoroaryl) borate derivative was obtained.
Tetrakis (pentafluorophenyl) borate was obtained as a white powder. As a result of analysis in the same manner as in Example 1, the yield of N-methylquinolinium tetrakis (pentafluorophenyl) borate based on sodium tetrakis (pentafluorophenyl) borate was 93.5 mol%. And the purity was 99.0%.

Example 18 Water was distilled off under reduced pressure from an aqueous solution containing 14.04 g (0.020 mol) of sodium tetrakis (pentafluorophenyl) borate purified in Example 6 to obtain the tetrakis (pentafluorophenyl) borate. 13.18 g of sodium (pentafluorophenyl) borate
(0.019 mol) was obtained as a white solid. The purity of the obtained sodium tetrakis (pentafluorophenyl) borate is 99%, and the recovery from the aqueous solution is 9%.
It was 3.9%.

Next, in a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, the above-mentioned sodium tetrakis (pentafluorophenyl) borate and 0.1% of triphenylcarbenium chloride as a cationic species generating compound were added. 019 mol and n-hexane (reaction solvent) 200 m
l was charged. Next, the above-mentioned contents were heated with stirring and reacted under reflux for 6 hours.

After completion of the reaction, the reaction solution was cooled to room temperature. Then, yellow crystals were precipitated from the reaction solution, and the crystals were separated by suction filtration. Then, the obtained cake (crystal) was dissolved in 100 ml of dichloromethane, and insolubles were removed by filtration using celite.
The obtained filtrate was concentrated and dried to obtain a solid, and this solid was suspended in 100 ml of n-hexane and stirred for 16 hours. Thereafter, stirring was stopped and the precipitate was separated by filtration under reduced pressure. Next, the obtained cake was washed with 100 ml of n-hexane and dried under reduced pressure.

Thus, triphenylcarbenium tetrakis (pentafluorophenyl) borate as a tetrakis (fluoroaryl) borate derivative was obtained as a yellow powder. As a result of analysis by the same method as in Example 1, the yield of triphenylcarbenium tetrakis (pentafluorophenyl) borate based on sodium tetrakis (pentafluorophenyl) borate was 30.2 mol%. And the purity was 99.0%.

Example 19 An aqueous solution 1 containing 10.10 g (0.01439 mol) of sodium tetrakis (pentafluorophenyl) borate purified in Example 6
10.10 g and 30 ml of methylene chloride (organic extractant) were charged into a separating funnel, vigorously shaken, and allowed to stand.
After removing the methylene chloride layer, a new methylene chloride 3
0 ml was charged into a separating funnel and the same operation was performed. The methylene chloride layers taken out were combined and dried over anhydrous sodium sulfate, and then methylene chloride was completely distilled off under reduced pressure. This resulted in a white solid. As a result of analysis by the same method as in Example 1, the solid contained 9.78 g (0.01393 mol) of sodium tetrakis (pentafluorophenyl) borate, and the purity was 99.0%. there were. The recovery of sodium tetrakis (pentafluorophenyl) borate was 96.
8%.

Next, the above-mentioned sodium tetrakis (pentafluorophenyl) borate and 2-aminoadamantane hydrochloride 2 as a cationic species generating compound were placed in a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser. .6
1 g (0.0139 mol) and 100 ml of cyclohexane (reaction solvent) were charged. Next, the contents were reacted at room temperature (26 ° C.) for 1 hour with stirring, and then further reacted under reflux for 3 hours.

After the completion of the reaction, the reaction solution was cooled to room temperature. Then, crystals were precipitated from the reaction solution, and the crystals were separated by suction filtration. Then, after the obtained cake (crystal) is washed with 100 ml of ion-exchanged water, under reduced pressure,
Dry at 70 ° C. for 12 hours.

Thus, adamantan-2-yl- as a tetrakis (fluoroaryl) borate derivative was obtained.
Ammonium tetrakis (pentafluorophenyl)
The borate was obtained as white crystals. As a result of analysis in the same manner as in Example 1, the yield of adamantan-2-yl-ammonium tetrakis (pentafluorophenyl) borate based on sodium tetrakis (pentafluorophenyl) borate was 88.2 mol. % And the purity was 99.0%.

[Example 20] In the same container as in Example 2,
12.3 g of crude (86.5% purity) n-butyl-tris (pentafluorophenyl) borate / hydrogen compound
(0.0216 mol) of di-n-butyl ether solution and 30 ml of ion-exchanged water.
The solution was colored black by the coloring components.

Next, the above mixture was stirred for 10 minutes.
The mixture was heated to 0 ° C. to distill off di-n-butyl ether. Further, water distilled out by forming an azeotropic composition with di-n-butyl ether was returned to a container via a dropping funnel after liquid separation. When the distillation of di-n-butyl ether was completed, the heating was stopped, and the mixture was cooled to 70 ° C. Then, the mixture was separated into two layers, that is, a white aqueous layer and a black oil layer accumulated at the bottom of the container. Only the aqueous layer was extracted from the container. Thus, n-butyl-tris (pentafluorophenyl) borate / hydrogen compound was purified.

Subsequently, an aqueous solution containing n-butyl-tris (pentafluorophenyl) borate / hydrogen compound purified by the above method was charged into the same reaction vessel as in Example 8. On the other hand, 50 ml of an aqueous solution containing 0.025 mol of tetramethylammonium chloride was charged into the dropping funnel.

Next, the same reaction and operation as in Example 8 were performed to obtain 10.30 g of tetramethylammonium / n-butyl-tris (pentafluorophenyl) borate as a white powder. As a result of analysis by the same method as in Example 1, the yield of tetramethylammonium / n-butyl-tris (pentafluorophenyl) borate based on n-butyl-tris (pentafluorophenyl) borate / hydrogen compound was determined. Is 75.
It was 0 mol% and the purity was 96.0%.

Example 21 In the same container as in Example 2,
Crude (purity 90.0%) sodium cyclohexyl-tris (pentafluorophenyl) borate 1.54
g (0.0025 mol) of a di-n-butyl ether solution containing 50 ml of ion-exchanged water.
The solution was colored black by the coloring components.

Next, the above mixture was stirred for 10 minutes.
The mixture was heated to 0 ° C. to distill off di-n-butyl ether. Further, water distilled out by forming an azeotropic composition with di-n-butyl ether was returned to a container via a dropping funnel after liquid separation. When the distillation of di-n-butyl ether was completed, the heating was stopped, and the mixture was cooled to 70 ° C. Then, the mixture was separated into two layers, that is, a white aqueous layer and a black oil layer accumulated at the bottom of the container. Only the aqueous layer was extracted from the container. Thereby, cyclohexyl-
Tris (pentafluorophenyl) borate sodium was purified.

Subsequently, an aqueous solution containing sodium cyclohexyl-tris (pentafluorophenyl) borate purified by the above method was charged into the same reaction vessel as in Example 8. On the other hand, 30 ml of an aqueous solution containing 0.005 mol of tetramethylammonium chloride was charged into the dropping funnel.

Next, the same reaction and operation as in Example 8 were performed to obtain tetramethylammonium cyclohexyl-tris (pentafluorophenyl).
1.54 g of borate was obtained as a white powder. Example 1
As a result of analysis by the same method as in the above method, cyclohexyl-
The yield of tetramethylammonium cyclohexyl-tris (pentafluorophenyl) borate based on sodium tris (pentafluorophenyl) borate was 92.0 mol%, and the purity was 99.0%.

[0159]

According to the method of purifying a tetrakis (fluoroaryl) borate compound according to the present invention, a coloring component which is an impurity contained in the tetrakis (fluoroaryl) borate compound can be efficiently and easily separated. -Since it can be removed, the tetrakis (fluoroaryl) borate compound can be purified. Further, after mixing the solution with water, by distilling the organic solvent from the mixture, or by distilling the organic solvent from the mixture, an aqueous solution obtained by further mixing with an aromatic hydrocarbon, The above coloring components,
There is an effect that separation and removal can be performed more efficiently and easily.

By adopting the method for purifying a tetrakis (fluoroaryl) borate compound according to the present invention, the effect that the tetrakis (fluoroaryl) borate compound can be isolated as a solid (crystal) can be obtained. Play.

Further, by adopting the method for producing a tetrakis (fluoroaryl) borate derivative according to the present invention, the tetrakis (fluoroaryl) borate derivative obtained from the purification method can be converted to a tetrakis (fluoroaryl) borate derivative. Can be efficiently and inexpensively manufactured. The derivative has good color tone and high purity because it does not contain a coloring component which is an impurity, and is suitable as, for example, a co-catalyst of a metallocene catalyst used for a cationic complex polymerization reaction or a catalyst for photopolymerization of silicone. Can be used.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ikuno Ikuyo 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Inventor Naoko Hirano 5-8 Nishi-Mabori-cho, Suita-shi, Osaka Within Nippon Shokubai (72) Inventor Yukiko Ariyoshi 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd.

Claims (7)

[Claims] 1. A method for purifying a tetrakis (fluoroaryl) borate compound, comprising mixing a solution containing an impurity-containing tetrakis (fluoroaryl) borate compound and an organic solvent with water. 2. The compound according to claim 1, wherein the tetrakis (fluoroaryl) borate compound has the general formula (1): ## STR1 ## (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ ,
R ₈ , R ₉ and R ₁₀ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of R _{1 to} R ₅ is a fluorine atom; _At least one of _{6 to} R ₁₀ is a fluorine atom, M represents a hydrogen atom, an alkali metal, an alkaline earth metal or an alkaline earth metal halide, n is 3 or 4, and m is hydrogen. 2. The compound represented by claim 1, wherein the compound is represented by an atom, 1 when the compound is an alkali metal or alkaline earth metal halide, and 2 when the compound is an alkaline earth metal. ) A method for purifying borate compounds. 3. The method according to claim 1, wherein the organic solvent is distilled off from the mixture after mixing the solution with water.
A method for purifying a tetrakis (fluoroaryl) borate compound according to the above. 4. An aqueous solution obtained by mixing said solution with water and then distilling off an organic solvent from said mixture, and further mixing with an aromatic hydrocarbon. A method for purifying a tetrakis (fluoroaryl) borate compound according to the above. 5. The method according to claim 1, wherein the tetrakis (fluoroaryl) borate compound is isolated as a solid from an aqueous solution of the tetrakis (fluoroaryl) borate compound obtained by mixing the solution with water. 5. The method for purifying a tetrakis (fluoroaryl) borate compound according to 2, 3, or 4. 6. A method comprising reacting a tetrakis (fluoroaryl) borate compound obtained by the purification method according to claim 1 with a compound generating a monovalent cation species. For producing a tetrakis (fluoroaryl) borate derivative. 7. The tetrakis (fluoroaryl) borate derivative represented by the general formula (2): (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ ,
R ₈ , R ₉ and R ₁₀ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of R _{1 to} R ₅ is a fluorine atom; _At least one of _{6 to} R ₁₀ is a fluorine atom, Z ⁺ represents a monovalent cation species, and n is 3 or 4). A method for producing the tetrakis (fluoroaryl) borate derivative described above.