JP3516857B2 - Purification method of tetrakis (fluoroaryl) borate magnesium halide - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for purifying tetrakis (fluoroaryl) borate / magnesium halide, as well as a cocatalyst for a metallocene catalyst (polymerization catalyst) used in a cationic complex polymerization reaction, and a silicone. The present invention relates to a method for producing a tetrakis (fluorinated aryl) borate derivative, which is useful as a photopolymerization catalyst or the like.

[0002]

2. Description of the Related Art Tetrakis (fluoroaryl) borate derivatives are compounds useful as, for example, cocatalysts for enhancing the activity of metallocene catalysts (polymerization catalysts) used in cationic complex polymerization reactions, and catalysts for photopolymerization of silicones. Is.
Further, tetrakis (fluoroaryl) borate / magnesium halide is the above-mentioned tetrakis (fluoroaryl)
It is a compound useful as an intermediate for producing a borate derivative. In recent years, metallocene catalysts have attracted particular attention as catalysts for polyolefin polymerization.

For example, in Japanese Unexamined Patent Publication (Kokai) No. 6-247980, tetrakis (pentafluorophenyl) borate / magnesium, which is a kind of tetrakis (fluoroaryl) borate / magnesium halide, is obtained by a Grignard reaction from bromopentafluorobenzene. A method of making bromide is disclosed.

As a method for producing a tetrakis (pentafluorophenyl) borate derivative which is one of tetrakis (fluoroaryl) borate derivatives, for example, Japanese Patent Laid-Open No. 6-247981 discloses an organic lithium compound and a boron halide. A method for synthesizing tetrakis (pentafluorophenyl) borate / lithium from pentafluorobenzene by using and then reacting the compound with N, N-dimethylaniline / hydrochloride is disclosed.

Further, for example, US Pat. No. 398,23.
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. 6-247980 discloses a method for separating and removing magnesium halide, which is a by-product with tetrakis (pentafluorophenyl) borate.magnesium bromide, from the reaction system. Has not been disclosed at all and has no suggestive description. When a tetrakis (pentafluorophenyl) borate derivative produced by using tetrakis (pentafluorophenyl) borate / magnesium bromide containing magnesium halide as an impurity is used as a cocatalyst for a metallocene catalyst, the activity of the catalyst is significantly reduced. To do. The method described in the publication is a method for producing tetrakis (pentafluorophenyl) borate magnesium bromide containing magnesium halide as an impurity. Therefore, the tetrakis (pentafluorophenyl) obtained by this method is obtained.
Borate magnesium bromide is unsuitable as an intermediate for producing the tetrakis (pentafluorophenyl) borate derivative.

In order to remove the magnesium halide contained in the tetrakis (pentafluorophenyl) borate magnesium bromide obtained by the method described in the above publication, for example, a general alkali treatment is performed with tetrakis (pentafluorophenyl). When applied to borate-magnesium bromide, magnesium hydroxide is produced. Then, since the magnesium hydroxide causes the solution after treatment to gel, the solution cannot be filtered. That is, since magnesium halide cannot be removed by general alkali treatment, isolation of tetrakis (pentafluorophenyl) borate magnesium bromide obtained by the above method, or
It is difficult to obtain a highly pure tetrakis (fluoroaryl) borate compound after the treatment.

Therefore, tetrakis (fluoroaryl)
There has been a strong demand 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) the temperature of the reaction system must be maintained at -65 ° C. or lower, so special equipment is required and the cost required for cooling. 2) an expensive organolithium compound must be used, and the compound is liable to be ignited by a reaction with water, so that handling thereof is dangerous; 3) expensive boron halide is used. Must be used, and the compound is gaseous,
And it is corrosive, so its handling is difficult;
There is a problem. Therefore, the method described in the publication is difficult to carry out industrially.

Further, in the method described in US Pat. No. 398,236, magnesium hydroxide is by-produced together with the target tetrakis (pentafluorophenyl) borate derivative, so that the solution after the reaction is magnesium hydroxide. To gel. Therefore, since it is difficult to separate (isolate) the tetrakis (pentafluorophenyl) borate derivative from the solution, there is a problem that the above derivative cannot be efficiently produced.

That is, the above conventional production method has a problem that the tetrakis (fluoroaryl) borate derivative cannot be produced with high purity, efficiently and inexpensively. Therefore, a method capable of producing the derivative with high purity, efficiently and inexpensively is desired.

The present invention has been made in view of the above conventional problems, and an object thereof is to efficiently and easily remove impurities such as magnesium halide contained in tetrakis (fluoroaryl) borate.magnesium halide. It is to provide a purification method that can be separated and removed. Another object of the present invention is to provide a tetrakis (fluorinated aryl) borate derivative useful as, for example, a metallocene catalyst co-catalyst or a silicone photopolymerization catalyst.
It is an object of the present invention to provide a method which can be manufactured with high purity, efficiency and cost.

[0013]

[Means for Solving the Problems] The inventors of the present application have proposed a method for purifying tetrakis (fluoroaryl) borate / magnesium halide, and tetrakis (fluoroaryl)
The method for producing the borate derivative was earnestly studied. As a result, the tetrakis (fluoroaryl) borate magnesium halide is treated with, for example, a carboxylic acid alkali metal salt and / or a carboxylic acid alkaline earth metal salt to give the tetrakis (fluoroaryl) borate magnesium halide. It has been found that the contained impurities such as magnesium halide can be separated and removed efficiently and easily. Then, by reacting the tetrakis (fluoroaryl) borate compound obtained by the above-mentioned purification method with a compound that generates a monovalent cation species, for example, a cocatalyst for a metallocene catalyst, a catalyst for photopolymerization of silicone, etc. As a result, they have found that a tetrakis (fluoroaryl) borate derivative useful as the above can be produced with high purity, efficiency and 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 general formula (1) in order to solve the above problems.

[0015]

[Chemical 6]

(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, X represents a chlorine atom, a bromine atom or an iodine atom, and n is 2 or 3). Aryl) borate magnesium halide is treated with an alkali metal carboxylic acid salt and / or an alkaline earth metal carboxylic acid salt.

In order to solve the above-mentioned problems, the method for purifying tetrakis (fluoroaryl) borate · magnesium halide according to the second aspect of the present invention is tetrakis (fluoroaryl) represented by the general formula (1). It is characterized in that borate / magnesium halide is treated with an acid.

In order to solve the above-mentioned problems, the method for purifying tetrakis (fluoroaryl) borate · magnesium halide according to the third aspect of the present invention is tetrakis (fluoroaryl) represented by the general formula (1). It is characterized in that the borate / magnesium halide is treated with an acid and then with an alkali metal hydroxide and / or an alkaline earth metal hydroxide.

In order to solve the above-mentioned problems, the method for purifying tetrakis (fluoroaryl) borate · magnesium halide according to the fourth aspect of the present invention is the tetrakis (fluoroaryl) represented by the general formula (1). It is characterized in that the borate / magnesium halide is treated with an acid and then with a carboxylic acid alkali metal salt and / or a carboxylic acid alkaline earth metal salt.

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

It should be noted that tetrakis (fluoroaryl) borate magnesium halide is an alkali metal carboxylic acid salt and / or an alkaline earth metal carboxylic acid salt, or an alkali metal hydroxide and / or an alkaline earth metal hydroxide. When processed, that is, the above claim 1,
When processed by the method described in any one of 3 and 4,
An alkali metal salt and / or an alkaline earth metal salt of tetrakis (fluoroaryl) borate is obtained. Further, when tetrakis (fluoroaryl) borate / magnesium halide is treated with an acid, that is, by the method described in claim 2, a hydrogen compound of tetrakis (fluoroaryl) borate is obtained.

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

[0023]

[Chemical 7]

(Wherein R1, R2, R3, R4, R5,
R6, R7, R8, R9 and R10 each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of R1 to R5 is a fluorine atom, and R6 to At least one of R10 is a fluorine atom, and Z + is an ammonium cation or an anion.
Rinium cation, pyridinium cation, quinolinium
Mu cation, phosphonium cation, sulphonium
Mu cation, iodonium cation, carbenium cation
On and less than alkali metal and alkaline earth metal
The invention relates to a method for producing a tetrakis (fluorinated aryl) borate derivative represented by a monovalent cation selected from monovalent cations of other metals and n is 2 or 3. To a tetrakis (fluoroaryl) borate compound obtained by the purification method according to any one of 1 to 4, and an ammonium cation and an anilinium cation.
On, pyridinium cation, quinolinium cation,
Phosphonium cation, sulfonium cation,
Iodonium cation, carbenium cation, and
And metals other than alkali metals and alkaline earth metals
It is characterized by reacting with a compound that generates a monovalent cation species selected from monovalent cations .

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 or the alkaline earth metal 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. Since the derivative does not contain impurities such as magnesium halide, it has a high purity and can be suitably used as, for example, a cocatalyst for a metallocene catalyst used in a cationic complex polymerization reaction, a catalyst for photopolymerization of silicone, and the like. it can.

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

Further, the method for producing the tetrakis (fluoroaryl) borate derivative represented by the general formula (2) according to the present invention includes the tetrakis (fluoroaryl) borate compound obtained by the above-mentioned purification methods: It is a method of reacting with a compound that generates a monovalent cation 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. A hydrogen compound of (fluoroaryl) borate is shown. Tetrakis (fluoroaryl) borate · magnesium halide and tetrakis (fluoroaryl) borate compounds are suitable as intermediates for tetrakis (fluoroaryl) borate derivatives.

In the tetrakis (fluoroaryl) borate magnesium halide to be treated in the present invention, the substituents represented by R _{1 to} R ₁₀ in the formula are each independently a hydrogen atom, a fluorine atom or a hydrocarbon group. Alternatively, it is composed of an alkoxy group, and at least one of the substituents represented by R _{1 to} R ₅ is a fluorine atom, and R ₆
At least one of the substituents represented by R ₁₀ to R ₁₀ is a fluorine atom, the substituent represented by X is a chlorine atom, a bromine atom or an iodine atom, and n is 2 or 3.

The above-mentioned hydrocarbon group is specifically 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. , A branched or cyclic alkenyl group and the like. The above hydrocarbon group may further have a functional group which is inactive to the treatment and 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 trifunctional group. Examples thereof include a fluoromethyl group.

[0031] The alkoxy group of the general formula _{(A) -OR a ...... (A} ) ( wherein, R _a represents a hydrocarbon group) is represented by, wherein, R
_The hydrocarbon group represented by a specifically includes, 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. Group, branched chain, or cyclic alkenyl group. The above hydrocarbon group may further have a functional group which is inactive to the treatment and reaction according to the present invention.

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

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

Tetrakis (fluoroaryl) borate
Magnesium halide can be obtained in the form of a solution dissolved in the solvent used for 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, heptane; cycloaliphatic rings such as cyclopentane and cyclohexane. Formula hydrocarbon solvents; aromatic hydrocarbon solvents such as benzene and toluene; and the like, but not limited thereto. These solvents may be used as a mixed solvent. When tetrakis (fluoroaryl) borate / magnesium halide is produced by reacting a fluoroaryl magnesium halide with a boron halide, a by-produced magnesium halide such as magnesium fluorobromide is produced. Are dissolved in the above solution as impurities.

Specific examples of the alkali metal carboxylic acid salt used in the purification method according to the present invention include:
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, etc. Alkali metal salts of unsaturated aliphatic monocarboxylic acids such as sodium acrylate, potassium acrylate, sodium methacrylate, potassium methacrylate, etc .;
Monomers of unsaturated aliphatic dicarboxylic acids such as monosodium maleate, disodium maleate, monopotassium maleate, dipotassium maleate, monosodium fumarate, disodium fumarate, monopotassium fumarate, dipotassium fumarate, etc. Or dialkali metal salts; 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,
Examples thereof include mono- or dialkali metal salts of aromatic dicarboxylic acids such as monopotassium terephthalate and dipotassium terephthalate; however, they are not particularly limited.
In the present invention, the carboxylic acid alkali metal salt,
Lithium carbonate, sodium carbonate, sodium hydrogen carbonate,
Carbonates such as potassium carbonate and potassium hydrogen carbonate are also included.

Specific examples of the alkaline earth metal carboxylic acid salt used in the purification method according to the present invention include 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; phthalate Calcium acid, barium phthalate, a Calcium phthalate, barium isophthalate, calcium terephthalate, and barium terephthalate, alkaline earth metal salts of aromatic dicarboxylic acids;
However, it is not particularly limited. still,
In the present invention, the carboxylic acid alkaline earth metal salt,
Carbonates such as calcium carbonate and barium carbonate are also included. However, in the present invention, the carboxylic acid alkaline earth metal salt does not include a carboxylic acid magnesium salt.

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

Specific examples of the acid used in the purification method of the present invention include 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; however, they are not particularly limited.

Only one of these acids may be used,
Moreover, you may use together 2 or more types. Of the above-exemplified acids, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, and malonic acid are more preferable. The amount of the acid used is not particularly limited, and may be 1 equivalent or more with respect to the magnesium used in the production of tetrakis (fluoroaryl) borate.magnesium halide (charged into the reaction system). Further, when the inorganic acid and the organic acid are used in combination, the ratio of both is not particularly limited.

Specific examples of the alkali metal hydroxide used in the purification method according to the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. Specific examples of the alkaline earth metal hydroxide used in the purification method according to the present invention include calcium hydroxide and barium hydroxide. However, in the present invention, magnesium hydroxide is not included in the alkaline earth metal hydroxide.

Only one kind of these alkali metal hydroxides and alkaline earth metal hydroxides (hereinafter referred to as hydroxides when they are collectively referred to) may be used.
You may use 2 or more types together. The amount of the hydroxide used is not particularly limited, and may be 1 equivalent or more with respect to tetrakis (fluoroaryl) borate.magnesium halide. Further, when 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 (purification method), tetrakis (fluoroaryl)
The borate / magnesium halide and the carboxylate may be mixed and stirred. When tetrakis (fluoroaryl) borate / magnesium halide is treated with acid (
The purification method) may be performed by mixing and stirring tetrakis (fluoroaryl) borate.magnesium halide and an acid. Further, in the case of treating with hydroxide after treatment with acid (the purification method thereof), the acid may be separated and removed, and then the hydroxide may be mixed and stirred. After further treatment with acid,
When treating with a carboxylic acid salt (the purification method thereof), the acid may be separated and removed, and then the carboxylic acid salt may be mixed and stirred.

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 they are (solid or liquid) with a solution of tetrakis (fluoroaryl) borate / magnesium halide, or if necessary, mixed in the form of a solution. You may.

Specific examples of the solvent that is preferably used when the carboxylic acid salt, the acid, and the hydroxide are brought into a solution state include, for example, water; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, and anisole. -Based solvents; aliphatic hydrocarbon-based solvents such as pentane, hexane, heptane; alicyclic hydrocarbon-based solvents such as cyclopentane, cyclohexane; ester-based solvents such as methyl acetate and ethyl acetate; aromatic carbonization such as benzene and toluene Examples thereof include, but are not limited to, hydrogen-based solvents; alcohol-based solvents such as methyl alcohol and ethyl alcohol; ketone-based solvents such as acetone and methyl ethyl ketone. These solvents may be used alone or in combination of two or more.

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

Tetrakis (fluoroaryl) borate
Temperature and time when mixing and stirring a solution of magnesium halide, a carboxylic acid salt, an acid, and a hydroxide, that is,
The processing conditions are not particularly limited. In the purification method according to the present invention, a solution of tetrakis (fluoroaryl) borate / magnesium halide is mixed with a carboxylic acid salt, an acid, or a hydroxide, and then tetrakis ( The fluorinated aryl) borate magnesium halide can be easily treated. Moreover, when treating with a hydroxide or a carboxylate after treating with an acid, the method of separating / removing the acid is not particularly limited. Acid can be separated by simple operations 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.

When the solution of the tetrakis (fluoroaryl) borate compound contains a carboxylic acid salt, an acid, or a hydroxide, washing or the like is performed as necessary to remove the carboxylic acid salt or acid. The hydroxide should be removed. Also,
When the tetrakis (fluorinated aryl) borate compound is contained in the carboxylate, the acid, the hydroxide, or the solution thereof, the tetrakis (fluorinated aryl) borate compound is extracted as necessary. Should be collected. Further, when the solution of the tetrakis (fluoroaryl) borate compound contains water, a drying agent 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 with the above-mentioned purification methods, the compound represented by the general formula (3)

[0049]

[Chemical 8]

(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 or an alkaline earth metal, n is 2 or 3, and m is M is hydrogen. A tetrakis (fluorinated aryl) borate compound represented by 1 when it is an atom or an alkali metal and 2 when it is an alkaline earth metal is obtained.

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

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

Regarding which of the above-mentioned purification methods (1) to (3) according to the present invention should be adopted, for example, the obtained tetrakis (fluoroaryl) borate compound should have a desired form (alkali metal salt, alkaline earth metal). Salt or hydrogen compound), or the type of tetrakis (fluoroaryl) borate / magnesium halide, the type of solvent so that the separation operation performed after the treatment, for example, the operation such as liquid separation, can be further facilitated. It may be appropriately selected based on the above.

According to the purification method of the present invention, for example, magnesium halide by-produced in the process of producing tetrakis (fluoroaryl) borate.magnesium halide by Grignard reaction is used as a water-soluble magnesium salt or insoluble magnesium halide. Can be converted into a magnesium salt state (that is, a salt state other than magnesium hydroxide). Therefore, the salt contained in tetrakis (fluoroaryl) borate / magnesium halide can be efficiently and easily separated from the solution of the tetrakis (fluoroaryl) borate compound by carrying out operations such as liquid separation or filtration. Can be removed.
That is, impurities such as magnesium halide contained in tetrakis (fluoroaryl) borate.magnesium halide can be separated and removed efficiently and easily. The method for separating and removing impurities from the solution of the tetrakis (fluoroaryl) borate compound is not particularly limited.

Even when the tetrakis (fluoroaryl) borate / magnesium halide does not contain impurities such as magnesium halide, the above-mentioned treatment is carried out to obtain the hydrogen compound of tetrakis (fluoroaryl) borate, tetrakis ( It is preferable to obtain an alkali metal salt of fluorinated aryl) borate or an alkaline earth metal salt of tetrakis (fluorinated aryl) borate. As a result, the reaction with the compound that generates a monovalent cation species can proceed rapidly and in good yield.

As described above, the method for purifying tetrakis (fluoroaryl) borate magnesium halide according to the present invention is as follows: a method of treating with a carboxylic acid salt; a method of treating with an acid; A method of treating with an acid; a method of treating with an acid and then a carboxylate;
Is.

This makes it 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. In addition, 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 rapidly and efficiently performed. The tetrakis (fluoroaryl) borate compound can be isolated and purified as crystals by removing (distilling) the solvent as necessary.

The compound which generates a monovalent cation species according to the present invention (hereinafter referred to as a cation species generating compound) generates a monovalent cation species in a reaction solvent described later,
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-
Butylammonium, dimethylammonium, trimethylammonium, triethylammonium, triisopropylammonium, tri-n-butylammonium,
Ammonium cations such as tetramethylammonium, tetraethylammonium, 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, N-benzylpyridinium; quinolinium cations such as quinolinium, 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 cations, tetraalkylammonium cations, dialkylanilinium cations, alkylpyridinium cations, tetraalkylphosphonium cations, tetraarylphosphonium cations, diaryliodonium cations are More preferable. The anion species that should be paired with the monovalent cation species is not particularly limited.

Specific examples of the cation species generating compound include tri-n-butylamine.hydrochloride, N, N
-Quaternary ammonium compounds such as dimethylaniline / hydrochloride, N, N-dimethylaniline / sulfate, tetramethylammonium chloride; pyridine / hydrochloride, quinoline / hydrochloride, iodo-N-methylpyridine, iodo-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 N, N-dimethylanilinium cation as a monovalent cation species. The anion species in this case is chlorine ion.

The amount of the cation species-generating compound used is not particularly limited, and may be tetrakis (fluoroaryl).
It may be 0.8 equivalent or more with respect to the borate compound.

A reaction solvent is used in the production method according to the present invention. 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, heptane; alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; methyl acetate , Ester solvents such as ethyl acetate; aromatic hydrocarbon solvents such as benzene and toluene;
Examples thereof include alcohol solvents such as methyl alcohol and ethyl alcohol; ketone solvents such as acetone and methyl ethyl ketone; however, the solvent is not particularly limited.
These reaction solvents may be used alone, or
You may use 2 or more types together.

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

As a method of mixing the tetrakis (fluoroaryl) borate compound and the cation species generating compound, specifically, for example, the tetrakis (fluoroaryl) borate compound and the cation species generating compound are mixed in a reaction solvent. A method of mixing a cation species generating compound or a solution thereof with a solution of a tetrakis (fluoroaryl) borate compound; a solution of a cation species generating compound,
Examples thereof include a method of mixing a tetrakis (fluoroaryl) borate compound or a solution thereof, but are not particularly limited. When a solution of a cation species generating compound is mixed with a solution of a tetrakis (fluoroaryl) borate compound, and a solution of a cation species generating compound,
When the solution of the tetrakis (fluoroaryl) borate compound is mixed, it is more preferable to drop the solution on the addition side.

The temperature and time in the reaction between the tetrakis (fluoroaryl) borate compound and the cation species generating compound, that is, the reaction conditions are not particularly limited. In the production method according to the present invention, a reaction solution prepared by dissolving a tetrakis (fluoroaryl) borate compound and a cation species generating compound in a reaction solvent is stirred at room temperature for a predetermined time to facilitate the reaction. Can be made. Therefore, the target 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 cation species generating compound is N, In the case of N-dimethylaniline / hydrochloride, the reaction product of N-dimethylaniline and 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.

Further, for example, when the tetrakis (fluoroaryl) borate compound is a hydrogen compound of tetrakis (fluoroaryl) borate and the cation species generating compound is N, N-dimethylaniline.hydrochloride, both By the reaction of (1), N, N-dimethylanilinium tetrakis (fluoroaryl) borate, which is the target product, is obtained, and hydrochloric acid is by-produced. 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, if necessary, simple operations such as removal (distillation) of the reaction solvent. Thus, the crystals can be easily isolated and purified.

As described above, in the method for producing a tetrakis (fluoroaryl) borate derivative according to the present invention, the tetrakis (fluoroaryl) borate compound obtained by the above purification method is reacted with the cation 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, and tetrakis (fluoroaryl) borate A tetrakis (fluoroaryl) borate derivative can be efficiently and inexpensively produced from a hydrogen compound of (fluoroaryl) borate. Since the derivative does not contain impurities such as magnesium halide, it has a high purity and can be suitably used as, for example, a cocatalyst for a metallocene catalyst used in a cationic complex polymerization reaction, a catalyst for photopolymerization of silicone, and the like. it can.

[0073]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 In a reactor equipped with a thermometer, a dropping funnel, a stirrer, and a reflux condenser, tetrakis (pentafluorophenyl) borate / magnesium bromide as tetrakis (fluoroaryl) borate / magnesium halide was added. 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 as a solvent and toluene was set to 1: 1. The mixed solution contained 0.0771 mol of magnesium bromide fluoride as an impurity. On the other hand, 100 ml (0.100 mol) of an aqueous sodium carbonate solution as a carboxylic acid salt was charged into the dropping funnel.

Next, while stirring the above mixed solution,
The above aqueous solution was added dropwise at room temperature over 10 minutes and then stirred at the same temperature for 30 minutes. That is, the purification method according to the present invention was carried out. After completion of stirring, the solution was suction-filtered to remove the precipitate (magnesium carbonate).

The obtained filtrate was separated into an organic layer and an aqueous layer, and the aqueous layer was extracted twice with 50 ml of ethyl acetate.
Then, the ethyl acetate (about 100 ml) as an extract was added to the above organic layer, and anhydrous magnesium sulfate as a desiccant was added to dry the organic layer.

After drying, diethyl ether was added to the organic layer,
Toluene and ethyl acetate were distilled off under reduced pressure. As a result, tetrakis (pentafluorophenyl) borate / sodium as a tetrakis (fluoroaryl) borate compound was obtained as brown crystals.

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

The yield of tetrakis (pentafluorophenyl) borate.sodium 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 integral value of the fluorine atom of p-fluorotoluene,
The integral value of the fluorine atom at the ortho position of the pentafluorophenyl group in tetrakis (pentafluorophenyl) borate.sodium was obtained, and the amount of tetrakis (pentafluorophenyl) borate.sodium was calculated from both integral values. As a result, the yield of tetrakis (pentafluorophenyl) borate / sodium was 89.1 mol%.
And the purity was 96.0%.

Example 2 A reactor similar to the reactor 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 sodium acetate solution as a carboxylic acid salt was charged into the dropping funnel.

Then, while stirring the above mixed solution,
The above aqueous solution was added dropwise at room temperature over 10 minutes and then stirred at the same temperature for 60 minutes. That is, the purification method according to the present invention was carried out. After completion of 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, ethyl acetate as an extract was added to the above organic layer, and anhydrous magnesium sulfate was added and dried.

After drying, diethyl ether was added to the organic layer.
Toluene and ethyl acetate were distilled off under reduced pressure. This gave sodium tetrakis (pentafluorophenyl) borate as brown crystals. The yield of tetrakis (pentafluorophenyl) borate.sodium 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 of a di-n-butyl ether solution containing 0.047 mol of tetrakis (pentafluorophenyl) borate magnesium bromide (concentration 29.5 mol%), and 300 ml of 1N hydrochloric acid as an acid (0.300 mol) were charged. . Next, the above 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 carried out. Anhydrous magnesium sulfate was added to the obtained organic layer to dry it.

After drying, the organic layer was treated with di-n as a solvent.
-Butyl ether was distilled off under reduced pressure to obtain 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
The above separating funnel was shaken sufficiently and then allowed to stand to separate the solution into an organic layer and an aqueous layer.

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

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

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 separating funnel was shaken sufficiently and then allowed to stand to separate the solution into an organic layer and an aqueous layer.

Then, the above organic layer and 20 ml (0.020 mol) of a 1N sodium hydroxide aqueous solution 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 stirring, the solution was separated into an organic layer and an aqueous layer. That is, the purification method according to the present invention was carried out. Anhydrous magnesium sulfate was added to the obtained organic layer to dry it.

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

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) was charged. On the other hand, tetrakis (pentafluorophenyl) borate / magnesium bromide 0.0
100 ml of di-n-butyl ether solution containing 25 mol
Was placed in a dropping funnel.

Then, while stirring the above aqueous solution, the above solution was added dropwise at room temperature over 10 minutes and then stirred at the same temperature for 60 minutes. After 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. Then, the washed solution was separated into an organic layer and an aqueous layer. That is, the purification method according to the present invention was carried out. Anhydrous magnesium sulfate was added to the obtained organic layer to dry it.

After drying, di-n-butyl ether was distilled off from the organic layer under reduced pressure. As a result, tetrakis (pentafluorophenyl) borate sodium was obtained as crystals. The yield of tetrakis (pentafluorophenyl) borate.sodium 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 in a reactor similar to that of Example 1. 100 ml was charged. The mixing volume ratio of the above-mentioned diethyl ether and di-n-butyl ether as a solvent is 1:
It was set to 6. On the other hand, 132 g of a 10 wt% aqueous solution of hydrochloric acid was placed in the dropping funnel.

Next, while stirring the above mixed solution,
The above aqueous solution was added dropwise at room temperature over 10 minutes and then stirred at the same temperature for 60 minutes. After completion of stirring, the obtained solution was separated into an organic layer and an aqueous layer. Then, the organic layer was washed with a 15% by weight aqueous solution of disodium succinate as a carboxylic acid salt. 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 carried out. Anhydrous magnesium sulfate was added to the obtained organic layer to dry it.

After drying, diethyl ether and di-n-butyl ether were distilled off from the organic layer under reduced pressure to obtain tetrakis (pentafluorophenyl) borate.sodium as crystals. Tetrakis (pentafluorophenyl) determined by the same method as in Example 1.
The yield of borate sodium 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 in a reactor similar to the reactor of Example 1. 100 ml was charged. Diethyl ether and di-n
The mixing volume ratio with -butyl ether was 1: 6. On the other hand, 132 g of a 10 wt% aqueous solution of hydrochloric acid was placed in the dropping funnel.

Next, while stirring the above mixed solution,
The above aqueous solution was added dropwise at room temperature over 10 minutes and then stirred at the same temperature for 60 minutes. After completion of stirring, the obtained solution was separated into an organic layer and an aqueous layer. Then, the above organic layer was washed with a 10 wt% sodium carbonate aqueous solution. 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 carried out. Anhydrous magnesium sulfate was added to the obtained organic layer to dry it.

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

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

Then, while stirring the above solution, the above aqueous solution was added dropwise at room temperature over 10 minutes, and then stirred at the same temperature for 1 hour to react. After the reaction was completed, 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, ethyl acetate as an extract was added to the above organic layer, and anhydrous magnesium sulfate was added and dried.

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

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

Next, while stirring the above solution, the above aqueous solution was added dropwise at room temperature over 10 minutes, and then stirred at the same temperature for 1 hour to react. After the reaction was completed, 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, ethyl acetate as an extract was added to the above organic layer, and anhydrous magnesium sulfate was added and dried.

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

Example 11 In a 500 ml separating funnel, 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) was charged. Then, the above separating funnel was sufficiently shaken and then left still to separate the solution into an organic layer and an aqueous layer, and the aqueous layer was extracted. Then, 2N-lithium hydroxide aqueous solution 7 as a hydroxide was added to the organic layer.
0 ml (0.014 mol) was mixed, shaken well, 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 carried out.
Then, anhydrous magnesium sulfate was added to the above organic layer and dried.

Next, in 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, 2.84 g of N, N-dimethylaniline (0.0
23 mol) was charged to the dropping funnel.

Next, while stirring the above organic layer,
N, N-dimethylaniline was added dropwise at room temperature over 15 minutes, and then the mixture was stirred at the same temperature for 1 hour to cause a reaction. 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) determined 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 butyl ether solution (concentration 29.5 mol%),
Also, 150 ml (0.150 mol) of 1N-hydrochloric acid was charged. Then, the above separating funnel was sufficiently shaken and then left still to separate the solution into an organic layer and an aqueous layer, and the aqueous layer was extracted. Thereafter, the organic layer was mixed with 33.0 ml (0.031 mol) of a 10% by weight aqueous solution of sodium carbonate, 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 carried out. Then, anhydrous magnesium sulfate was added to the above organic layer and dried.

Then, in a 200 ml four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, the above organic layer and 3.72 g of N, N-dimethylaniline.hydrochloride were added.
(0.024 mol) was charged. 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 obtained by the same method as in Example 1 was 86.7 mol%.

Example 13 In place of 33.0 ml of 10% by weight aqueous solution of sodium carbonate in Example 12, 83.0 ml of 20% by weight aqueous solution of disodium succinate (0.
(031 mol), and the reaction amount of N, N-dimethylaniline.hydrochloride was changed from 3.72 g (0.024 mol) to 3.99 g (0.025 mol). Then, the same reaction and operation as those described above were carried out 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
Butyl ether solution 50.0 g, and 1N-hydrochloric acid 1
40 ml was charged. Next, the above 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 carried out. Then, anhydrous magnesium sulfate was added to the above organic layer and dried.

Next, in 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 placed in the dropping funnel.

Next, while stirring the above organic layer,
N, N-dimethylaniline was added dropwise at room temperature over 10 minutes, and then the mixture was reacted at the same temperature for 1 hour with stirring. 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) determined 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.
180 mol) was charged. Next, the above 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 carried out. Then, anhydrous magnesium sulfate was added to the above organic layer and dried.

Next, in 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 placed in the dropping funnel.

Next, while stirring the above organic layer,
N, N-dimethylaniline was added dropwise at room temperature over 15 minutes, and then the mixture was stirred at the same temperature for 1 hour to cause a reaction. 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) determined by the same method as in Example 9.
The borate yield was 90.3 mol%.

Example 16 A 500 ml separatory funnel was charged with tetrakis (pentafluorophenyl) borate.
Di-n-containing 0.020 mol of magnesium bromide
Butyl ether solution 120.7 g (concentration 16.6 mol%), and 2N-formic acid 90 ml (0.180 mol)
Was charged. Next, the above 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 carried out. Then, anhydrous magnesium sulfate was added to the above organic layer and dried.

Next, in 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,
N, N-dimethylaniline was added dropwise at room temperature over 15 minutes, and then the mixture was stirred at the same temperature for 1 hour to cause a reaction. 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) determined by the same method as in Example 9.
The borate yield was 89.6 mol%.

[0121]

As described above, the method for purifying tetrakis (fluoroaryl) borate magnesium halide according to the present invention has the general formula (1):

[0122]

[Chemical 9]

(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, X represents a chlorine atom, a bromine atom or an iodine atom, and n is 2 or 3). Aryl) borate magnesium halide is treated with a carboxylic acid alkali metal salt and / or a carboxylic acid alkaline earth metal salt.

The method for purifying tetrakis (fluoroaryl) borate.magnesium halide according to claim 2 of the present invention is, as described above, the tetrakis (fluoroaryl) borate.magnesium represented by the general formula (1). It 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 is, as described above, the tetrakis (fluoroaryl) borate.magnesium represented by the general formula (1). In this method, the halide is treated with an acid and then 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 is, as described above, the tetrakis (fluoroaryl) borate.magnesium represented by the general formula (1). In this method, the halide is treated with an acid and then treated with a carboxylic acid alkali metal salt and / or a carboxylic acid alkaline earth metal salt.

According to the above method, for example, magnesium halide such as magnesium fluorobromide, which is a by-product in the process of producing tetrakis (fluoroaryl) borate magnesium halide by the Grignard reaction, can be dissolved in water. It can be converted into the state of the magnesium salt or the insoluble magnesium salt (that is, the state of salt other than magnesium hydroxide). Therefore, the salt contained in tetrakis (fluoroaryl) borate / magnesium halide can be efficiently and easily separated / removed by performing an operation such as oil / water separation or filtration. That is, it is possible to efficiently and easily separate and remove impurities such as magnesium halide contained in tetrakis (fluoroaryl) borate.magnesium halide.

The method for producing a tetrakis (fluoroaryl) boron derivative according to claim 5 of the present invention is, as described above, represented by the general formula (2):

[0129]

[Chemical 10]

(Wherein R1, R2, R3, R4, R5,
R6, R7, R8, R9 and R10 each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of R1 to R5 is a fluorine atom, and R6 to At least one of R10 is a fluorine atom, and Z + is an ammonium cation or an anion.
Rinium cation, pyridinium cation, quinolinium
Mu cation, phosphonium cation, sulphonium
Mu cation, iodonium cation, carbenium cation
On and less than alkali metal and alkaline earth metal
The invention relates to a method for producing a tetrakis (fluoroaryl) boron derivative represented by a monovalent cation species selected from monovalent cations of other metals and n is 2 or 3. To a tetrakis (fluoroaryl) borate compound obtained by the purification method according to any one of 1 to 4, and an ammonium cation and an anilinium cation.
, Pyridinium cation, quinolinium cation,
Phosphonium cation, sulfonium cation, yo
A donium cation, a carbenium cation, and
Monovalent metals other than alkali metals and alkaline earth metals
It is a method of reacting with a compound that generates a monovalent cation species selected from cations.

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 or the alkaline earth metal tetrakis (fluoroaryl) borate. An effect is obtained that a tetrakis (fluoroaryl) borate derivative can be efficiently and inexpensively produced from a metal salt and a hydrogen compound of tetrakis (fluoroaryl) borate. Since the derivative does not contain impurities such as magnesium halide, it has a high purity and can be suitably used as, for example, a cocatalyst for a metallocene catalyst used in a cationic complex polymerization reaction, a catalyst for photopolymerization of silicone, and the like. it can.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tsunemasa Ueno 5-8 Nishimitabicho, Suita City, Osaka Prefecture Nippon Shokubai Co., Ltd. (56) References JP-A-9-220476 (JP, A) JP-A 6-247981 (JP, A) JP-A-6-247980 (JP, A) US Patent 3468959 (US, A) International Publication 96/027435 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07F 5/02 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A general formula (1): (In the formula, R1, R2, R3, R4, R5, R6, R7,
R8, R9 and R10 each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of R1 to R5 is a fluorine atom, and among R6 to R10, At least one of which is a fluorine atom, X represents a chlorine atom, a bromine atom or an iodine atom, and n is 2 or 3), and tetrakis (fluoroaryl) borate magnesium halide represented by A method for purifying tetrakis (fluoroaryl) borate magnesium halide, which comprises treating with a salt and / or an alkaline earth metal carboxylate. 2. A general formula (1): (In the formula, R1, R2, R3, R4, R5, R6, R7,
R8, R9 and R10 each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of R1 to R5 is a fluorine atom, and among R6 to R10, At least one of which is a fluorine atom, X represents a chlorine atom, a bromine atom or an iodine atom, and n is 2 or 3), and the tetrakis (fluoroaryl) borate magnesium halide represented by the formula (3) is treated with an acid. A method for purifying tetrakis (fluoroaryl) borate / magnesium halide, comprising: 3. General formula (1): (In the formula, R1, R2, R3, R4, R5, R6, R7,
R8, R9 and R10 each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of R1 to R5 is a fluorine atom, and among R6 to R10, At least one of which is a fluorine atom, X represents a chlorine atom, a bromine atom or an iodine atom, and n is 2 or 3), and tetrakis (fluorinated aryl) borate magnesium halide is treated with an acid. Then, a method for purifying tetrakis (fluorinated aryl) borate magnesium halide, which is characterized by treatment with an alkali metal hydroxide and / or an alkaline earth metal hydroxide. 4. General formula (1): (In the formula, R1, R2, R3, R4, R5, R6, R7,
R8, R9 and R10 each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of R1 to R5 is a fluorine atom, and among R6 to R10, At least one of which is a fluorine atom, X represents a chlorine atom, a bromine atom or an iodine atom, and n is 2 or 3), and tetrakis (fluorinated aryl) borate magnesium halide is treated with an acid. Then, a method for purifying tetrakis (fluoroaryl) borate magnesium halide, which is characterized by treatment with a carboxylic acid alkali metal salt and / or a carboxylic acid alkaline earth metal salt. 5. A tetrakis (fluorinated aryl) borate compound obtained by the purification method according to claim 1, an ammonium cation, an anilinium cation, or pyridinium.
Nium cation, quinolinium cation, phosphoni
Umium cation, sulfonium cation, iodonium
Cations, carbenium cations, and alkali gold
Monovalent cations of metals other than genus and alkaline earth metals
A general formula (2) characterized by reacting with a compound that generates a monovalent cation species selected from (In the formula, R1, R2, R3, R4, R5, R6, R7,
R8, R9 and R10 each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of R1 to R5 is a fluorine atom, and among R6 to R10, At least one is a fluorine atom, Z + is an ammonium cation, an anilinium cation
Ion, pyridinium cation, quinolinium cation
Ion, phosphonium cation, sulfonium cation
Ion, iodonium cation, carbenium cation,
And metals other than alkali metals and alkaline earth metals
Represents a monovalent cation species selected from monovalent cations of
n is 2 or 3), The manufacturing method of the tetrakis (fluorinated aryl) borate derivative represented by these.