JPH10310589A - Purification of tetrakis(fluorinated aryl)borate/ magnesium halide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To purify the subject compound useful as a raw material, etc., for a co-catalyst, etc., of a metallocene catalyst efficiently and simply by treating tetrakis(fluorinated aryl)borate/magnesium halide with an alkali (alkaline earth) metal salt of a carboxylic acid. SOLUTION: This method for effectively purifying tetrakis(fluorinated aryl) borate/magnesium halide comprises treating the tetrakis(fluorinated aryl)borate/ magnesium halide expressed by formula I [R1 to R10 are each H, F, a hydrocarbon or an alkoxy provided that among the R1 to R5 , at least one is F and among the R6 to R10 at least one is F; X is Cl, Br or I; (n) is 2, 3] with an alkali metal salt of a carboxylic acid and/or an alkaline earth metal salt of the carboxylic acid. Further, by reacting the above compound with a compound generating a monovalent cation, a co-catalyst for a metallocene catalyst (a polymerization catalyst) and a compound useful as a catalyst for photopolymerization of a silicone expressed by formula II (Z+ is a monovalent cationic group) are efficiently obtained at a low cost.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for purifying tetrakis (fluoroaryl) borate / magnesium halide, as well as, for example, a co-catalyst for a metallocene catalyst (polymerization catalyst) to be subjected to a cationic complex polymerization reaction, and a silicone. The present invention relates to a method for producing a tetrakis (fluoroaryl) borate derivative useful as a photopolymerization catalyst or the like.

[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.
In addition, the tetrakis (fluoroaryl) borate / magnesium halide is the above-mentioned tetrakis (fluoroaryl) borate.
It is a compound useful as an intermediate for producing a borate derivative. Incidentally, metallocene catalysts have been particularly noted in recent years as polyolefin polymerization catalysts.

For example, JP-A-6-247980 discloses that tetrakis (fluorofluoro) borate / magnesium, a kind of tetrakis (fluoroaryl) borate / magnesium halide, is obtained by a Grignard reaction from bromopentafluorobenzene. A method for producing bromide is disclosed.

As a method for producing a tetrakis (pentafluorophenyl) borate derivative, which is a kind of a tetrakis (fluoroaryl) borate derivative, for example, JP-A-6-247981 discloses an organic lithium compound and a boron halide. Discloses a method of synthesizing lithium tetrakis (pentafluorophenyl) borate from pentafluorobenzene using, and reacting the compound with N, N-dimethylaniline hydrochloride.

Further, for example, US Pat.
No. 6 discloses a method for producing a tetrakis (pentafluorophenyl) borate derivative by reacting tetrakis (pentafluorophenyl) borate / magnesium bromide with N, N-dimethylaniline / hydrochloride.

[0006]

However, Japanese Patent Application Laid-Open No. Hei 6-247980 discloses that magnesium halide by-produced with tetrakis (pentafluorophenyl) borate / magnesium bromide is separated and removed from the reaction system. Has not been disclosed and does not indicate any suggestion. When a tetrakis (pentafluorophenyl) borate derivative produced using tetrakis (pentafluorophenyl) borate / magnesium bromide containing a magnesium halide as an impurity is used as, for example, a co-catalyst of a metallocene catalyst, the activity of the catalyst is remarkably reduced. I do. The method described in this publication is a method for producing tetrakis (pentafluorophenyl) borate / magnesium bromide containing a magnesium halide as an impurity. Therefore, tetrakis (pentafluorophenyl) obtained by this method is used.
Borate magnesium bromide is unsuitable as an intermediate for producing the tetrakis (pentafluorophenyl) borate derivative.

Incidentally, in order to remove the magnesium halide contained in the tetrakis (pentafluorophenyl) borate / magnesium bromide obtained by the method described in the above-mentioned publication, for example, a general alkali treatment is carried out using tetrakis (pentafluorophenyl) When applied to borate magnesium bromide, magnesium hydroxide is produced. Then, since the solution after the treatment is gelled by the magnesium hydroxide, the solution cannot be filtered. That is, since magnesium halide cannot be removed by a general alkali treatment, tetrakis (pentafluorophenyl) borate / magnesium bromide obtained by the above method is isolated, or
It is difficult to obtain a high purity tetrakis (fluoroaryl) borate compound after the treatment.

[0008] Therefore, tetrakis (aryl fluoride)
There is a strong need for a purification method capable of efficiently and easily separating and removing impurities such as magnesium halide contained in borate / magnesium halide.

On the other hand, in the method described in JP-A-6-247981, 1) since the temperature of the reaction system must be maintained at -65 ° C. or lower, special equipment is required and cooling costs are required. 2) an expensive organolithium compound must be used, and the compound may be ignited by reaction with water or the like, so that there is a danger in handling the compound; and 3) expensive boron halide is used. Must be used and the compound is gaseous,
Difficult to handle because of its corrosiveness;
There is a problem that. Therefore, the method described in this publication is difficult to implement industrially.

In the method described in US Pat. No. 398,236, magnesium hydroxide is by-produced together with the desired tetrakis (pentafluorophenyl) borate derivative. Gelation. Therefore, it is difficult to separate (isolate) the tetrakis (pentafluorophenyl) borate derivative from the solution, and thus there is a problem that the derivative cannot be efficiently produced.

That is, the above-mentioned conventional production method has a problem that a tetrakis (fluoroaryl) borate derivative cannot be produced with high purity, efficiently and inexpensively. Therefore, there is a strong need for a method capable of producing the derivative with high purity, efficiently and at low cost.

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 simply remove impurities such as magnesium halide contained in tetrakis (fluoroaryl) borate / magnesium halide. Another object of the present invention is to provide a purification method that can be separated and removed. Another object of the present invention is to provide a tetrakis (fluoroaryl) borate derivative useful as, for example, a co-catalyst for a metallocene catalyst or a catalyst for photopolymerization of silicone.
It is an object of the present invention to provide a method that can be manufactured with high purity, efficiently and at low cost.

[0013]

Means for Solving the Problems The present inventors have developed a method for purifying tetrakis (fluoroaryl) borate / magnesium halide, and a method for purifying tetrakis (aryl fluoride).
The production method of borate derivatives was studied diligently. As a result, the tetrakis (fluoroaryl) borate / magnesium halide is treated with, for example, an alkali metal carboxylate and / or an alkaline earth metal carboxylate to give the tetrakis (fluoroaryl) borate / magnesium halide. It has been found that impurities such as magnesium halide contained therein can be separated and removed efficiently and easily. By reacting the tetrakis (fluoroaryl) borate compound obtained by the above-mentioned purification method with a compound generating a monovalent cation species, for example, a co-catalyst of a metallocene catalyst, a catalyst for photopolymerization of silicone, etc. Have found that a tetrakis (fluoroaryl) borate derivative useful as a compound can be produced with high purity, efficiently and at low cost, and have completed the present invention.

That is, the method for purifying tetrakis (fluoroaryl) borate / magnesium halide according to the first aspect of the present invention has the following general formula (1):

[0015]

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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 2 or 3. (Aryl halide) borate / magnesium halide is treated with an alkali metal carboxylate and / or an alkaline earth metal carboxylate.

According to a second aspect of the present invention, there is provided a method for purifying tetrakis (fluoroaryl) borate / magnesium halide in order to solve the above-mentioned problem. It is characterized in that borate magnesium halide is treated with an acid.

According to a third aspect of the present invention, there is provided a method for purifying a tetrakis (fluoroaryl) borate / magnesium halide in order to solve the above-mentioned problems. It is characterized in that borate / magnesium halide is treated with an acid and then treated with an alkali metal hydroxide and / or an alkaline earth metal hydroxide.

According to a fourth aspect of the present invention, there is provided a method for purifying tetrakis (fluoroaryl) borate / magnesium halide in order to solve the above-mentioned problems. The method is characterized in that the borate / magnesium halide is treated with an acid and then treated with an alkali metal carboxylate and / or an alkaline earth metal carboxylate.

According to the above-mentioned method, for example, magnesium halide such as magnesium fluorobromide, which is by-produced in the process of producing tetrakis (fluoroaryl) borate / magnesium halide by Grignard reaction, It can be converted to a water-soluble or insoluble magnesium salt state (that is, a salt state other than magnesium hydroxide).
Therefore, the salt contained in the tetrakis (fluoroaryl) borate / magnesium halide can be efficiently and easily separated and removed by performing an operation such as oil-water separation or filtration. 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 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. When processed, that is, in claim 1,
When processed by the method described in any one of items 3 and 4,
An alkali metal salt and / or an alkaline earth metal salt of tetrakis (fluoroaryl) borate is obtained. In addition, when the tetrakis (fluoroaryl) borate / magnesium halide is treated with an acid, that is, when the treatment is performed by the method described in claim 2, a hydrogen compound of tetrakis (fluoroaryl) borate is obtained.

In order to solve the above-mentioned problems, a method for producing a tetrakis (fluoroaryl) borate derivative according to the invention of claim 5 is represented by the general formula (2)

[0023]

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;
5 is a tetrakis (fluoroaryl) borate derivative represented by the formula (2) or (3), and the tetrakis (fluoroaryl) fluoride obtained by the purification method according to any one of claims 1 to 4. A) reacting a borate compound with a compound that generates a monovalent cationic species.

According to the above method, the tetrakis (fluoroaryl) borate compound obtained by the above-mentioned purification method, that is, the alkali metal salt of tetrakis (fluoroaryl) borate and the alkaline earth salt of tetrakis (fluoroaryl) borate A tetrakis (fluoroaryl) borate derivative can be efficiently and inexpensively produced from a metal salt and a hydrogen compound of tetrakis (fluoroaryl) borate. The derivative has high purity because it does not contain impurities such as magnesium halide, for example, and is preferably used as a co-catalyst of a metallocene catalyst provided for a cation complex polymerization reaction or a catalyst for photopolymerization of silicone. it can.

Hereinafter, the present invention will be described in detail. The purification method of the tetrakis (fluoroaryl) borate / magnesium halide represented by the general formula (1) according to the present invention is a method of treating with an alkali metal carboxylate and / or an alkaline earth metal carboxylate; A method of treating with an acid, followed by a treatment with an alkali metal hydroxide and / or an alkaline earth metal hydroxide;
After treatment with an acid, an alkali metal carboxylate and / or
Or a method of treating with an alkaline earth metal carboxylate;
It is.

The method for producing the tetrakis (fluoroaryl) borate derivative represented by the general formula (2) according to the present invention comprises the tetrakis (fluoroaryl) borate compound obtained by the above-mentioned purification method, This is a method of reacting a compound generating a monovalent cationic species.

The tetrakis (fluoroaryl) borate compound is, specifically, an alkali metal salt of tetrakis (fluoroaryl) borate, an alkaline earth metal salt of tetrakis (fluoroaryl) borate, and tetrakis (fluoroaryl) borate. 1 shows a hydrogen compound of (fluoroaryl) borate. The tetrakis (fluoroaryl) borate magnesium halide and the tetrakis (fluoroaryl) borate compound are suitable as intermediates of the tetrakis (fluoroaryl) borate derivative.

In the tetrakis (fluoroaryl) borate / magnesium halide to be treated in the present invention, the substituents represented by R _{1 to} R ₁₀ are each independently a hydrogen atom, a fluorine atom, a hydrocarbon group. or it is composed of an alkoxy group, and at least one fluorine atom of the substituents represented by the R ₁ to R _5, the R ₆
At least one of the substituents represented by to R ₁₀ is a fluorine atom, substituent represented by X is composed of a chlorine atom, a bromine atom or an iodine atom, a compound n is 2 or 3.

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. Incidentally, the above-mentioned hydrocarbon group may further have a functional group which is inactive to the treatment and the reaction according to the present invention. Specific examples of the functional group 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 fluoromethyl 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. Incidentally, the above-mentioned hydrocarbon group may further have a functional group which is inactive to the treatment and the reaction according to the present invention.

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

Tetrakis (fluoroaryl) borate
The method for producing magnesium halide is not particularly limited. Tetrakis (fluoroaryl) borate ・
The magnesium halide can be prepared, for example, by a method of reacting i) a fluoroarylmagnesium halide, which is a Grignard reagent, with a boron halide at a molar ratio of 4: 1; ii) a fluoroarylmagnesium halide, and tris (fluorinated). Aryl) boron in a molar ratio of 1: 1
The reaction can be easily obtained. The reaction conditions for the Grignard reaction in these methods are not particularly limited.

Tetrakis (fluoroaryl) borate
Magnesium halide is obtained in the form of a solution dissolved in the solvent used for performing the Grignard reaction. Specific examples of the solvent include ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether and anisole; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicycles such as cyclopentane and cyclohexane Formula hydrocarbon solvents; aromatic hydrocarbon solvents such as benzene and toluene; and the like, but are not particularly limited thereto. These solvents may be used as a mixed solvent. When a tetrakis (fluoroaryl) borate / magnesium halide is produced by reacting a fluoroarylmagnesium halide with a boron halide, the by-product magnesium halide such as magnesium fluorobromide is produced. Are dissolved in the above solution as impurities.

The alkali metal carboxylate used in the purification method of the present invention includes, for example,
Alkali metal salts of saturated aliphatic monocarboxylic acids such as sodium formate, potassium formate, sodium acetate, potassium acetate, sodium propionate, potassium propionate; monosodium oxalate, disodium oxalate, monopotassium oxalate, oxalic acid Saturated aliphatic dicarboxylic acids such as dipotassium, monosodium malonate, disodium malonate, monopotassium malonate, dipotassium malonate, monosodium succinate, disodium succinate, monopotassium succinate, dipotassium succinate Mono- or dialkali metal salts of the following: alkali metal salts of unsaturated aliphatic monocarboxylic acids such as sodium acrylate, potassium acrylate, sodium methacrylate and potassium methacrylate;
Monomers of unsaturated aliphatic dicarboxylic acids such as monosodium maleate, disodium maleate, monopotassium maleate, dipotassium maleate, monosodium fumarate, disodium fumarate, monopotassium fumarate and dipotassium fumarate Or a dialkali metal salt; an alkali metal salt of an aromatic monocarboxylic acid 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,
Lithium carbonate, sodium carbonate, sodium bicarbonate,
Carbonates such as potassium carbonate and potassium hydrogen carbonate are also included.

As the alkaline earth metal carboxylate used in the purification method of the present invention, specifically, for example, calcium formate, barium formate, calcium acetate,
Alkaline earth metal salts of saturated aliphatic monocarboxylic acids such as barium acetate, calcium propionate, barium propionate; calcium oxalate, barium oxalate, calcium malonate, barium malonate, calcium succinate, barium succinate, etc. Alkaline earth metal salts of saturated aliphatic dicarboxylic acids; alkaline earth metal salts of unsaturated aliphatic monocarboxylic acids, such as calcium acrylate, barium acrylate, calcium methacrylate, barium methacrylate; calcium maleate; Alkaline earth metal salts of unsaturated aliphatic dicarboxylic acids such as barium maleate, calcium fumarate and barium fumarate; alkaline earth metal salts of aromatic monocarboxylic acids such as calcium benzoate and barium benzoate; Calcium acid, barium phthalate, Calcium phthalate, barium isophthalate, calcium terephthalate, and barium terephthalate, alkaline earth metal salts of aromatic dicarboxylic acids;
And the like, but are not particularly limited. still,
In the present invention, the alkaline earth metal carboxylate,
Carbonates such as calcium carbonate and barium carbonate are also included. 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 purification method of the present invention 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 and malonic acid And organic acids such as succinic acid, 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.

As the alkali metal hydroxide used in the purification method according to the present invention, specifically, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide and the like can be mentioned. Further, specific examples of the alkaline earth metal hydroxide used in the purification method according to the present invention include calcium hydroxide, barium hydroxide and the like. 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, when both are collectively referred to as hydroxides) may be used alone,
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 treating magnesium halide with a carboxylate (the purification method), tetrakis (aryl fluoride)
The borate / magnesium halide and the carboxylate may be mixed and stirred. When treating tetrakis (fluoroaryl) borate / magnesium halide with acid (
Purification method), tetrakis (fluoroaryl) borate / magnesium halide and an acid may be mixed and stirred. In the case of treating with a hydroxide after treating with an acid (a purification method thereof), the hydroxide may be mixed and stirred after separating and removing the acid. Furthermore, after treatment with acid,
When treating with a carboxylate (the purification method), 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; ethers such as diethyl ether, diisopropyl ether, dibutyl ether and anisole Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; Ester solvents such as methyl acetate and ethyl acetate; Aromatic hydrocarbons such as benzene and toluene Hydrogen solvents; alcohol solvents such as methyl alcohol and ethyl alcohol; ketone solvents such as acetone and methyl ethyl ketone; and the like, but are not particularly limited. These solvents may be used alone or in combination of two or more.

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 purification method according to the present invention, a tetrakis (fluoroaryl) borate / magnesium halide solution is mixed with a carboxylate, an acid, or a hydroxide, and the mixture is stirred at room temperature for a predetermined time to obtain tetrakis (fluoroaryl) borate / magnesium halide. (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 obtained by performing a simple operation such as liquid separation (oil-water separation).
It can be separated from the solution of the tetrakis (fluoroaryl) borate compound. After the treatment, the tetrakis (fluoroaryl) borate compound is obtained in the form of a solution dissolved in a solvent.

In the case where the solution of the tetrakis (fluoroaryl) borate compound contains a carboxylate, an acid, or a hydroxide, the carboxylate or the acid may be washed if 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 a magnesium halide by the above purification method, the general formula (3)

[0049]

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(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, M represents a hydrogen atom, an alkali metal or an alkaline earth metal, n is 2 or 3, and m is hydrogen (1 when the compound is an atom or an alkali metal, and 2 when the compound is an alkaline earth metal).

That is, when tetrakis (fluoroaryl) borate / magnesium halide is treated with a carboxylate or hydroxide, that is, when treated by the above-mentioned purification method, the above formula (3) Is obtained, wherein M is an alkali metal or an alkaline earth metal.

On the other hand, when tetrakis (fluoroaryl) borate / magnesium halide is treated with an acid, that is, when it is treated by the above-mentioned purification method, tetrakis in which M in the general formula (3) is a hydrogen atom is used. (Fluoroaryl) borate is obtained.

Regarding which of the above-mentioned purification methods according to the present invention is to be adopted, for example, the obtained tetrakis (fluoroaryl) borate compound has a desired form (alkali metal salt, alkaline earth metal). Salt or hydrogen compound) or the kind of tetrakis (fluoroaryl) borate / magnesium halide and the kind of solvent so that the separation operation performed after the treatment, for example, the operation of liquid separation, etc., becomes much easier. What is necessary is just to select suitably on the basis of etc.

According to the purification method of the present invention, for example, a magnesium halide by-produced in the process of producing tetrakis (fluoroaryl) borate / magnesium halide by a Grignard reaction is converted into a water-soluble magnesium salt or an insoluble magnesium salt. (I.e., a salt state 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 for separating and removing impurities from the solution of the tetrakis (fluoroaryl) borate compound is not particularly limited.

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

As described above, the purification method of tetrakis (fluoroaryl) borate / magnesium halide according to the present invention includes a method of treating with a carboxylate; a method of treating with an acid; A method of treating with an acid, followed by a treatment with a carboxylate;
It is.

Thus, it is possible to provide a purification method capable of efficiently and easily separating and removing impurities such as magnesium halide contained in tetrakis (fluoroaryl) borate / magnesium halide. Further, for example, the reaction between the tetrakis (fluoroaryl) borate compound obtained by the purification method and the compound generating a monovalent cation species can be promptly and efficiently performed. The tetrakis (fluoroaryl) borate compound can be isolated and purified as crystals by removing (distilling off) the solvent as necessary.

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.

As the monovalent cation species generated by the cation species generating compound, specifically, 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; dimethylphenylphosphonium, triphenylphosphonium, tetraethyl Phosphonium cations such as phosphonium and tetraphenylphosphonium; sulfonium cations such as trimethylsulfonium and triphenylsulfonium; iodonium cations such as diphenyliodonium and di-4-methoxyphenyliodonium; triphenyl Carbenium cations such as carbenium and tri-4-methoxyphenylcarbenium; monovalent cations of metals other than alkali metals and alkaline earth metals; Although the like, but is not particularly limited.

Of these, trialkylammonium cation, tetraalkylammonium cation, dialkylanilinium cation, alkylpyridinium cation, tetraalkylphosphonium cation, tetraarylphosphonium cation, and diaryliodonium cation are included. 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
Quaternary ammonium compounds such as dimethylaniline / hydrochloride, N, N-dimethylaniline / sulfate, tetramethylammonium chloride; pyridine / hydrochloride, quinoline / hydrochloride, iodide-N-methylpyridine, iodide-N Nitrogen-containing aromatic heterocyclic compounds such as -methylquinoline; tetrabromide-
quaternary phosphonium compounds such as n-butylphosphonium and tetraphenylphosphonium bromide; sulfonium compounds such as trimethylsulfonium iodide;
Iodonium compounds such as diphenyliodonium chloride;
Carbenium compounds such as trityl chloride; and the like.

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; ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether and anisole; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; methyl acetate Ester solvents such as acetic acid and ethyl acetate; aromatic hydrocarbon solvents such as benzene and toluene;
Alcohol solvents such as methyl alcohol and ethyl alcohol; ketone solvents such as acetone and methyl ethyl ketone; and the like, but are not particularly limited.
These reaction solvents may be used alone,
Two or more types may be used in combination.

When the reaction is carried out using a solution of the tetrakis (fluoroaryl) borate compound obtained by the above treatment, the tetrakis (fluoroaryl) borate compound is dissolved as a reaction solvent (or a part thereof). Solvents used can be used. Therefore, in the production method according to the present invention, after treating tetrakis (fluoroaryl) borate / magnesium halide,
The tetrakis (fluoroaryl) borate derivative can be produced using the solution of the obtained tetrakis (fluoroaryl) borate compound without isolating the compound from the solution.

As a method of mixing the tetrakis (fluoroaryl) borate compound and the cationic species generating compound, specifically, for example, a tetrakis (fluoroaryl) borate compound and a cationic species generating compound are mixed in a reaction solvent. A method of mixing a cationic species generating compound or a solution thereof with a solution of a tetrakis (fluoroaryl) borate compound;
A method of mixing a tetrakis (fluoroaryl) borate compound or a solution thereof; and the like, but is not particularly limited. When a solution of a cationic species generating compound is mixed with a solution of a tetrakis (fluoroaryl) borate compound,
When a solution of a tetrakis (fluoroaryl) borate compound is mixed, 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, the tetrakis (fluoroaryl) borate compound is an alkali metal salt of tetrakis (fluoroaryl) borate or an alkaline earth metal salt of tetrakis (fluoroaryl) borate, and the cationic species generating compound is N, N. In the case of N-dimethylaniline hydrochloride, the target compound N, N-
Dimethylanilinium tetrakis (aryl fluoride)
While borate is obtained, 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 easily separated from the solution of N, N-dimethylanilinium.tetrakis (fluoroaryl) borate by performing operations such as liquid separation, filtration and washing.・ Can be removed.

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

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

According to the above method, tetrakis (fluoroaryl) borate compounds, that is, alkali metal salts of tetrakis (fluoroaryl) borate, alkaline earth metal salts of tetrakis (fluoroaryl) borate, and tetrakis (fluoroaryl) borate A tetrakis (fluoroaryl) borate derivative can be efficiently and inexpensively produced from a hydrogen compound of (fluoroaryl) borate. The derivative has high purity because it does not contain impurities such as magnesium halide, for example, and is preferably used as a co-catalyst of a metallocene catalyst provided for a cation complex polymerization reaction or a catalyst for photopolymerization of silicone. it can.

[0073]

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 Tetrakis (pentafluorophenyl) borate / magnesium bromide as tetrakis (fluoroaryl) borate / magnesium halide was placed in a reactor equipped with a thermometer, a dropping funnel, a stirrer and a reflux condenser. 100 ml of a mixed solution of diethyl ether and toluene containing 0.0257 mol was charged. The mixing volume ratio of the above-mentioned diethyl ether and toluene as solvents was 1: 1. The mixed solution contained 0.0771 mol of magnesium bromide as an impurity. On the other hand, 100 ml (0.100 mol) of an aqueous solution of sodium carbonate as a carboxylate was charged into the dropping funnel.

Next, while stirring the above mixed solution,
After the above aqueous solution was added dropwise at room temperature over 10 minutes, the mixture was stirred at the same temperature for 30 minutes. That is, the purification method according to the present invention was performed. After completion of the stirring, the precipitate (magnesium carbonate) was removed by suction filtration of the solution.

After separating the obtained filtrate into an organic layer and an aqueous layer, the aqueous layer was extracted twice with 50 ml of ethyl acetate.
Then, the ethyl acetate (approximately 100 ml) as an extract was added to the organic layer, and anhydrous magnesium sulfate as a desiccant was added to the organic layer, followed by drying.

After drying, diethyl ether,
Toluene and ethyl acetate were distilled off under reduced pressure. Thus, sodium tetrakis (pentafluorophenyl) borate as a tetrakis (fluoroaryl) borate compound was obtained as brown crystals.

The residual ratio of magnesium in the above crystals was measured by X-ray fluorescence analysis. As a result, magnesium was not detected from the crystals. Therefore, it was found that the crystal did not contain impurities such as magnesium halide.

Further, the yield of sodium tetrakis (pentafluorophenyl) borate was determined by measuring ¹⁹ F-NMR. That is, ¹⁹ F-NMR was measured under predetermined conditions using p-fluorotoluene as an internal standard. Then, from the obtained ¹⁹ F-NMR chart, the integrated value of the fluorine atom of p-fluorotoluene,
The integral value of the fluorine atom at the ortho position of the pentafluorophenyl group in sodium tetrakis (pentafluorophenyl) borate was determined, and the amount of sodium tetrakis (pentafluorophenyl) borate was calculated from both integral values. As a result, the yield of sodium tetrakis (pentafluorophenyl) borate was 89.1 mol%.
And the purity was 96.0%.

Example 2 A reactor similar to that of Example 1 was charged with 100 ml of a mixed solution of diethyl ether and toluene containing 0.025 mol of tetrakis (pentafluorophenyl) borate / magnesium bromide. . The mixing volume ratio of the above diethyl ether and toluene was 1: 1. On the other hand, 100 ml (0.100 mol) of an aqueous solution of sodium acetate as a carboxylate was charged into the dropping funnel.

Next, while stirring the above mixed solution,
After the above aqueous solution was added dropwise at room temperature over 10 minutes, the mixture was stirred at the same temperature for 60 minutes. That is, the purification method according to the present invention was performed. After completion of the stirring, the obtained solution was separated into an organic layer and an aqueous layer, and the aqueous layer was extracted once with 50 ml of ethyl acetate. Then, the ethyl acetate as an extract was added to the organic layer, and anhydrous magnesium sulfate was added to the organic layer, followed by drying.

After drying, diethyl ether,
Toluene and ethyl acetate were distilled off under reduced pressure. Thus, sodium tetrakis (pentafluorophenyl) borate was obtained as brown crystals. The yield of sodium tetrakis (pentafluorophenyl) borate determined by the same method as in Example 1 was 92.1 mol%.
And the purity was 97.4%.

Example 3 In a 500 ml separating funnel,
160 ml (concentration: 29.5 mol%) of a di-n-butyl ether solution containing 0.047 mol of tetrakis (pentafluorophenyl) borate / magnesium bromide and 300 ml (0.300 mol) of 1N hydrochloric acid as an acid were charged. . Next, the above-mentioned separating funnel was shaken sufficiently, and then allowed to stand to separate the solution into an organic layer and an aqueous layer. That is, the purification method according to the present invention was performed. Anhydrous magnesium sulfate was added to the obtained organic layer and dried.

After drying, di-n as a solvent is removed from the organic layer.
-Butyl ether was distilled off under reduced pressure to obtain a tetrakis (pentafluorophenyl) borate / hydrogen compound. The yield of the tetrakis (pentafluorophenyl) borate / hydrogen compound determined by the same method as in Example 1 was 89.7 mol%.

Example 4 In a 300 ml separating funnel,
47.9 g (concentration: 38.7 mol%) of a toluene solution containing 0.018 mol of tetrakis (pentafluorophenyl) borate / magnesium bromide and 160 ml (0.160 mol) of 1N hydrochloric acid were charged. Then
After sufficiently shaking the above separating funnel, the solution was separated into an organic layer and an aqueous layer by allowing to stand still.

Next, the above-mentioned organic layer and 30 ml (0.030 mol) of a 1N aqueous solution of sodium hydroxide as a hydroxide were charged into a 200 ml Erlenmeyer flask equipped with a stirrer. Stirred at room temperature for 1 hour. After completion of the stirring, the solution was separated into an organic layer and an aqueous layer. That is, the purification method according to the present invention was performed. Anhydrous magnesium sulfate was added to the obtained organic layer and dried.

After drying, toluene was distilled off from the organic layer under reduced pressure to obtain sodium tetrakis (pentafluorophenyl) borate as crystals. The yield of sodium tetrakis (pentafluorophenyl) borate determined by a method similar to that of Example 1 was 93.5.
Mole%.

Example 5 In a 300 ml separating funnel,
45.6 g (concentration: 37.4 mol%) of a toluene solution containing 0.017 mol of tetrakis (pentafluorophenyl) borate / magnesium bromide and 75 ml (0.150 mol) of 0.5N-sulfuric acid as an acid were charged. . Next, the above-mentioned separating funnel was shaken sufficiently, and then allowed to stand to separate the solution into an organic layer and an aqueous layer.

Next, the above organic layer and 20 ml (0.020 mol) of a 1N aqueous solution of sodium hydroxide were charged into a 200 ml Erlenmeyer flask equipped with a stirrer, and the solution was stirred at room temperature for 1 hour. did. After completion of the stirring, the solution was separated into an organic layer and an aqueous layer. That is, the purification method according to the present invention was performed. Anhydrous magnesium sulfate was added to the obtained organic layer and dried.

After drying, toluene was distilled off from the organic layer under reduced pressure to obtain sodium tetrakis (pentafluorophenyl) borate as crystals. The yield of sodium tetrakis (pentafluorophenyl) borate determined by the same method as in Example 1 was 91.5.
Mole%.

Example 6 In a reactor similar to the reactor of Example 1, 50 ml of an aqueous solution of oxalic acid as an acid (0.10
(0 mol). On the other hand, tetrakis (pentafluorophenyl) borate / magnesium bromide 0.0
100 ml of di-n-butyl ether solution containing 25 mol
Was charged into a dropping funnel.

Next, the above solution was added dropwise over 10 minutes at room temperature while stirring the above aqueous solution, and then stirred at the same temperature for 60 minutes. After the completion of stirring, the obtained solution was separated into an organic layer and an aqueous layer, and the organic layer was washed with a 10% by weight aqueous solution of sodium hydroxide as an alkali metal hydroxide. Next, the solution after washing was separated into an organic layer and an aqueous layer. That is, the purification method according to the present invention was performed. Anhydrous magnesium sulfate was added to the obtained organic layer and dried.

After drying, di-n-butyl ether was distilled off from the organic layer under reduced pressure. Thus, sodium tetrakis (pentafluorophenyl) borate was obtained as crystals. The yield of sodium tetrakis (pentafluorophenyl) borate determined by the same method as in Example 1 was 95.0 mol%.

Example 7 A mixed solution of diethyl ether and di-n-butyl ether containing 0.042 mol of tetrakis (pentafluorophenyl) borate / magnesium bromide was placed in a reactor similar to the reactor of Example 1. 100 ml was charged. The mixing volume ratio of the above diethyl ether and di-n-butyl ether as the solvent was 1:
6. On the other hand, 132 g of a 10% by weight aqueous solution of hydrochloric acid was charged into the dropping funnel.

Next, while stirring the above mixed solution,
After the above aqueous solution was added dropwise at room temperature over 10 minutes, the mixture was stirred at the same temperature for 60 minutes. After completion of the stirring, the obtained solution was separated into an organic layer and an aqueous layer. The organic layer was washed with a 15% by weight aqueous solution of disodium succinate as a carboxylate. After washing, the solution was separated into an organic layer and an aqueous layer. That is, the purification method according to the present invention was performed. Anhydrous magnesium sulfate was added to the obtained organic layer and dried.

After drying, diethyl ether and di-n-butyl ether were distilled off from the organic layer under reduced pressure to obtain sodium tetrakis (pentafluorophenyl) borate as crystals. Tetrakis (pentafluorophenyl) obtained by the same method as in Example 1.
The yield of sodium borate was 97.9 mol%.

Example 8 A mixed solution of diethyl ether and di-n-butyl ether containing 0.041 mol of tetrakis (pentafluorophenyl) borate / magnesium bromide was placed in a reactor similar to the reactor of Example 1. 100 ml was charged. The above diethyl ether and di-n
The mixing volume ratio with -butyl ether was 1: 6. On the other hand, 132 g of a 10% by weight aqueous solution of hydrochloric acid was charged into the dropping funnel.

Next, while stirring the above mixed solution,
After the above aqueous solution was added dropwise at room temperature over 10 minutes, the mixture was stirred at the same temperature for 60 minutes. After completion of the stirring, the obtained solution was separated into an organic layer and an aqueous layer. Then, the organic layer was washed with a 10% by weight aqueous solution of sodium carbonate. After washing, the solution was separated into an organic layer and an aqueous layer. That is, the purification method according to the present invention was performed. Anhydrous magnesium sulfate was added to the obtained organic layer and dried.

After drying, diethyl ether and di-n-butyl ether were distilled off from the organic layer under reduced pressure to obtain sodium tetrakis (pentafluorophenyl) borate as crystals. Tetrakis (pentafluorophenyl) obtained by the same method as in Example 1.
The sodium borate yield was 95.6 mol%.

Example 9 In a reactor similar to that of Example 1, 16.1 g of sodium tetrakis (pentafluorophenyl) borate obtained in Example 1 and 100 ml of ethyl acetate as a reaction solvent were placed. And was charged. On the other hand, 100 ml (0.025 mol) of an aqueous solution of N, N-dimethylaniline.hydrochloride as a cationic species generating compound
Was charged into a dropping funnel.

Next, while the above solution was stirred, the above aqueous solution was added dropwise at room temperature over 10 minutes, and the mixture was stirred at the same temperature for 1 hour to react. After completion of the reaction, the reaction solution was separated into an organic layer and an aqueous layer, and the aqueous layer was extracted once with 50 ml of ethyl acetate. Then, the ethyl acetate as an extract was added to the organic layer, and anhydrous magnesium sulfate was added to the organic layer, followed by drying.

After drying, ethyl acetate was distilled off from the organic layer under reduced pressure to obtain black crystals. The crystals are washed with 50 ml of diisopropyl ether to give a light brown N, N-dimethylanilinium · tetrakis (fluoroaryl) borate derivative.
Tetrakis (pentafluorophenyl) borate was obtained. As in the method of Example 1, the yield of N, N-dimethylanilinium.tetrakis (pentafluorophenyl) borate determined by measuring ¹⁹ F-NMR using p-fluorotoluene as an internal standard was 89. .9
Mole%.

Example 10 16.6 g of sodium tetrakis (pentafluorophenyl) borate obtained in Example 2 was placed in a reactor similar to the reactor of Example 1.
100 ml of ethyl acetate was charged. On the other hand, 100 ml of an aqueous solution of N, N-dimethylaniline / hydrochloride (0.025
Mol) was charged to a dropping funnel.

Next, while stirring the above solution, the above aqueous solution was added dropwise at room temperature over 10 minutes, and the mixture was stirred and reacted at the same temperature for 1 hour. After completion of the reaction, the reaction solution was separated into an organic layer and an aqueous layer, and the aqueous layer was extracted once with 50 ml of ethyl acetate. Then, the ethyl acetate as an extract was added to the organic layer, and anhydrous magnesium sulfate was added to the organic layer, followed by drying.

After drying, ethyl acetate was distilled off from the organic layer under reduced pressure to obtain brown crystals. The crystals are washed with 50 ml of diisopropyl ether to give light gray N, N-dimethylanilinium.
Tetrakis (pentafluorophenyl) borate was obtained. The yield of N, N-dimethylanilinium.tetrakis (pentafluorophenyl) borate determined by the same method as in Example 9 was 83.0 mol%.

Example 11 Tetrakis (pentafluorophenyl) borate.
Di-n- containing 0.021 mol of magnesium bromide
59.8 g of butyl ether solution (concentration: 35.7 mol%) and 250 ml of 1N-formic acid as an acid (0.1%).
(250 mol). Next, the above-mentioned separating funnel was shaken sufficiently, and then allowed to stand, whereby the solution was separated into an organic layer and an aqueous layer, and the aqueous layer was extracted. Then, a 2N aqueous solution of lithium hydroxide as a hydroxide 7 was added to the organic layer.
0 ml (0.014 mol) was mixed, shaken sufficiently, and allowed to stand to separate the solution into an organic layer and an aqueous layer. That is, the purification method according to the present invention was performed.
Then, anhydrous magnesium sulfate was added to the organic layer and dried.

Next, a 200 ml four-necked flask equipped with a thermometer, a dropping funnel, a stirrer, and a reflux condenser was placed
The above organic layer was charged. On the other hand, 2.84 g (0.0%) of N, N-dimethylaniline as a cationic species generating compound
23 mol) was charged to a dropping funnel.

Next, while stirring the above organic layer,
After N, N-dimethylaniline was added dropwise at room temperature over 15 minutes, the mixture was stirred and reacted at the same temperature for 1 hour. After completion of the reaction, di-n-butyl ether was distilled off from the organic layer under reduced pressure to obtain N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.
N, N-dimethylanilinium tetrakis (pentafluorophenyl) obtained by the same method as in Example 9.
The borate yield was 91.2 mol%.

Example 12 A 500 ml separatory funnel was charged with tetrakis (pentafluorophenyl) borate.
Di-n- containing 0.023 mol of magnesium bromide
80 ml of a butyl ether solution (concentration: 29.5 mol%),
And 150 ml (0.150 mol) of 1N hydrochloric acid was charged. Next, the above-mentioned separating funnel was shaken sufficiently, and then allowed to stand, whereby the solution was separated into an organic layer and an aqueous layer, and the aqueous layer was extracted. Thereafter, 33.0 ml (0.031 mol) of a 10% by weight aqueous solution of sodium carbonate was mixed with the organic layer, shaken sufficiently, and allowed to stand to separate the solution into an organic layer and an aqueous layer. . That is, the purification method according to the present invention was performed. Then, anhydrous magnesium sulfate was added to the organic layer and dried.

Next, the above organic layer and 3.72 g of N, N-dimethylaniline hydrochloride were placed in a 200 ml four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser.
(0.024 mol). Then, the organic layer was reacted by stirring at room temperature for 1 hour. After completion of the reaction, di-n-butyl ether was distilled off from the organic layer under reduced pressure to obtain N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. Example 9
The yield of N, N-dimethylanilinium.tetrakis (pentafluorophenyl) borate determined by the same method as in the above method was 86.7 mol%.

Example 13 Instead of 33.0 ml of a 10% by weight aqueous solution of sodium carbonate in Example 12, 83.0 ml of a 20% by weight aqueous solution of disodium succinate (0.1%) were used.
031 mol) and the amount of N, N-dimethylaniline hydrochloride was changed from 3.72 g (0.024 mol) to 3.99 g (0.025 mol). The same reaction and operation as those described above were performed to obtain N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. N, N-dimethylanilinium. Obtained by the same method as in Example 9
The yield of tetrakis (pentafluorophenyl) borate was 87.3 mol%.

Example 14 A 500 ml separatory funnel was charged with tetrakis (pentafluorophenyl) borate.
Di-n- containing 0.016 mol of magnesium bromide
50.0 g of a butyl ether solution and 1N hydrochloric acid 1
40 ml was charged. Next, the above-mentioned separating funnel was shaken sufficiently, and then allowed to stand to separate the solution into an organic layer and an aqueous layer. That is, the purification method according to the present invention was performed. Then, anhydrous magnesium sulfate was added to the organic layer and dried.

Next, into a 200 ml four-necked flask equipped with a thermometer, a dropping funnel, a stirrer, and a reflux condenser,
The above organic layer was charged. On the other hand, 2.06 g (0.017 mol) of N, N-dimethylaniline was charged into the dropping funnel.

Next, while stirring the above organic layer,
After N, N-dimethylaniline was added dropwise at room temperature over 10 minutes, the mixture was stirred and reacted at the same temperature for 1 hour. After completion of the reaction, di-n-butyl ether was distilled off from the organic layer under reduced pressure to obtain N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.
N, N-dimethylanilinium tetrakis (pentafluorophenyl) obtained by the same method as in Example 9.
The borate yield was 94.8 mol%.

Example 15 A 500 ml separatory funnel was charged with tetrakis (pentafluorophenyl) borate.
Di-n- containing 0.021 mol of magnesium bromide
130.6 g of butyl ether solution (concentration: 15.8 mol%) and 180 ml of 1N sulfuric acid as an acid (0.1 ml).
180 mol). Next, the above-mentioned separating funnel was shaken sufficiently, and then allowed to stand to separate the solution into an organic layer and an aqueous layer. That is, the purification method according to the present invention was performed. Then, anhydrous magnesium sulfate was added to the organic layer and dried.

Next, into a 200 ml four-necked flask equipped with a thermometer, a dropping funnel, a stirrer, and a reflux condenser,
The above organic layer was charged. On the other hand, 2.74 g (0.027 mol) of N, N-dimethylaniline was charged into the dropping funnel.

Next, while stirring the above organic layer,
After N, N-dimethylaniline was added dropwise at room temperature over 15 minutes, the mixture was stirred and reacted at the same temperature for 1 hour. After completion of the reaction, di-n-butyl ether was distilled off from the organic layer under reduced pressure to obtain N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.
N, N-dimethylanilinium tetrakis (pentafluorophenyl) obtained by the same method as in Example 9.
The borate yield was 90.3 mol%.

Example 16 A 500 ml separating funnel was charged with tetrakis (pentafluorophenyl) borate.
Di-n- containing 0.020 mol of magnesium bromide
120.7 g of butyl ether solution (concentration: 16.6 mol%) and 90 ml of 2N-formic acid (0.180 mol)
Was charged. Next, the above-mentioned separating funnel was shaken sufficiently, and then allowed to stand to separate the solution into an organic layer and an aqueous layer. That is, the purification method according to the present invention was performed. Then, anhydrous magnesium sulfate was added to the organic layer and dried.

Next, into a 200 ml four-necked flask equipped with a thermometer, a dropping funnel, a stirrer, and a reflux condenser,
The above organic layer was charged. On the other hand, 2.62 g (0.022 mol) of N, N-dimethylaniline was charged into the dropping funnel.

Next, while stirring the above organic layer,
After N, N-dimethylaniline was added dropwise at room temperature over 15 minutes, the mixture was stirred and reacted at the same temperature for 1 hour. After completion of the reaction, di-n-butyl ether was distilled off from the organic layer under reduced pressure to obtain N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.
N, N-dimethylanilinium tetrakis (pentafluorophenyl) obtained by the same method as in Example 9.
The borate yield was 89.6 mol%.

[0121]

According to the method for purifying tetrakis (fluoroaryl) borate / magnesium halide according to claim 1 of the present invention, as described above, the general formula (1)

[0122]

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 2 or 3. Aryl halide) borate / magnesium halide is treated with an alkali metal carboxylate and / or an alkaline earth metal carboxylate.

The method for purifying tetrakis (fluoroaryl) borate / magnesium halide according to claim 2 of the present invention, as described above, comprises tetrakis (fluoroaryl) borate / magnesium represented by the general formula (1). This is a method of treating a halide with an acid.

The method for purifying tetrakis (fluoroaryl) borate / magnesium halide according to claim 3 of the present invention comprises, as described above, tetrakis (fluoroaryl) borate / magnesium represented by the general formula (1). This is a method in which a halide is treated with an acid and then treated with an alkali metal hydroxide and / or an alkaline earth metal hydroxide.

The method for purifying tetrakis (fluoroaryl) borate / magnesium halide according to claim 4 of the present invention comprises, as described above, tetrakis (fluoroaryl) borate / magnesium represented by the general formula (1). This is a method in which a halide is treated with an acid and then treated with an alkali metal carboxylate and / or an alkaline earth metal carboxylate.

According to the above-mentioned method, for example, a magnesium halide such as magnesium bromobromide produced as a by-product in the process of producing tetrakis (fluoroaryl) borate / magnesium halide by the Grignard reaction is converted into a water-soluble one. It can be converted to a magnesium salt or an insoluble magnesium salt (that is, a salt other than magnesium hydroxide). Therefore, the salt contained in the tetrakis (fluoroaryl) borate / magnesium halide can be efficiently and easily separated and removed by performing an operation such as oil-water separation or filtration. That is, there is an effect that impurities such as magnesium halide contained in tetrakis (fluoroaryl) borate / magnesium halide can be efficiently and easily separated and removed.

Further, the method for producing a tetrakis (fluoroaryl) borane derivative according to claim 5 of the present invention comprises, as described above, the general formula (2)

[0129]

Embedded image

(Wherein R₁, R_Two, R_Three, R_Four, R_Five,
R₆, R₇, R₈, R₉, R_TenAre each independently hydrogen
Atom, fluorine atom, hydrocarbon group or alkoxy group
And the R₁~ R_FiveAt least one of the
And R is₆~ R _TenAt least one of
A fluorine atom, Z⁺Represents a monovalent cation species, and n
Is 2 or 3).
Reel) a method for producing a boron derivative,
A product obtained by the purification method according to any one of claims 1 to 4.
A tetrakis (fluoroaryl) borate compound,
Method for reacting a compound generating a monovalent cationic species
It is.

According to the above method, the tetrakis (fluoroaryl) borate compound obtained by the above-mentioned purification method, that is, the alkali metal salt of tetrakis (fluoroaryl) borate and the alkaline earth salt of tetrakis (fluoroaryl) borate There is an effect that a tetrakis (fluoroaryl) borate derivative can be efficiently and inexpensively produced from a metal salt and a hydrogen compound of tetrakis (fluoroaryl) borate. The derivative has high purity because it does not contain impurities such as magnesium halide, for example, and is preferably used as a co-catalyst of a metallocene catalyst provided for a cation complex polymerization reaction or a catalyst for photopolymerization of silicone. it can.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tsunemasa Ueno 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd.

Claims (5)

[Claims] 1. A compound of the general formula (1) (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, X represents a chlorine atom, a bromine atom or an iodine atom, and n is 2 or 3) tetrakis (fluoroaryl) borate / magnesium A method for purifying a tetrakis (fluoroaryl) borate / magnesium halide, comprising treating a halide with an alkali metal carboxylate and / or an alkaline earth metal carboxylate. 2. A compound of the general formula (1) (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, X represents a chlorine atom, a bromine atom or an iodine atom, and n is 2 or 3) tetrakis (fluoroaryl) borate / magnesium A method for purifying tetrakis (fluoroaryl) borate / magnesium halide, comprising treating the halide with an acid. 3. A compound of the general formula (1) (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, X represents a chlorine atom, a bromine atom or an iodine atom, and n is 2 or 3) tetrakis (fluoroaryl) borate / magnesium A method for purifying tetrakis (fluoroaryl) borate / magnesium halide, comprising treating a halide with an acid and then treating the halide with an alkali metal hydroxide and / or an alkaline earth metal hydroxide. 4. A compound of the general formula (1) (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, X represents a chlorine atom, a bromine atom or an iodine atom, and n is 2 or 3) tetrakis (fluoroaryl) borate / magnesium A method for purifying tetrakis (fluoroaryl) borate / magnesium halide, comprising treating a halide with an acid and then treating the halide with an alkali metal carboxylate and / or an alkaline earth metal carboxylate. 5. 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. 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 2 or 3). .