JPH09295984A - Production of tetrakis(pentafluorophenyl) borate derivative using pentafluorophenylmagnesiium derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To devantageously and efficiently produce a borate derivative useful as a catalyst component in producing a polyolefin such as polyethylene, polypropylene or poilystyrene. SOLUTION: The objective borate derivative expressed by the formula A[B(C6 F5 )4 ] (A is R<1> R<2> R<3> NH, etc., R1 , R2 and R3 are the same or mutually different 1-6C alkyl group, etc.) is obtained by preparing a derivative of a compound of the formula C6 F5 MgX (X is chlorine, etc.) from a compound expressed by the formula C6 F5 X and magnesium in an ether-based solvent, mixing a solution of a boron compound of the formula BX3 in a solvent having >=60 deg.C boiling point with a solution of the derivative in an ether-base solvent, and heating the resultant solution at from 50 deg.C to boiling point of the solvent, then adding a hydrochloric acid salt of amine, etc., of the formula A-Cl (A is same as above).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a tetrakis (pentafluorophenyl) borate derivative (hereinafter abbreviated as a boron derivative) using a pentafluorophenylmagnesium derivative. The boron derivative obtained in the present invention is a substance useful as a catalyst component in the production of polyolefin such as polyethylene, polypropylene and polystyrene.

[0002]

2. Description of the Related Art In recent years, a polyolefin polymerization method using a Kaminsky catalyst using a cyclopentadienyl complex of a transition metal has been developed. A large number of documents, patents and the like disclose that the boron derivative is useful as a catalyst component in the present polymerization system.

A method for producing a boron derivative is described in, for example, Journal of Organometallic Chemistry, No. 2
Volume, 245, 1964 (Journal of Oraganometall
ic Chemistry, 1964, 2, 245), Asahi Glass Industrial Technology Promotion Association Research Report, 1983, vol. 42, p. 137, etc., and a method for producing by reaction of pentafluorophenyllithium with tris (pentafluorophenyl) borane is reported. . Further, for example, JP-A-6-247980 discloses a method using a Grignard reagent produced from pentafluorobenzene.

[0004]

The method using pentafluorophenyllithium is such that after separately preparing tris (pentafluorophenyl) borane as a reaction reagent,
It is a method of reacting pentafluorophenyllithium, and the pentafluorophenyllithium used is-
It is known that it decomposes easily at 20 ° C or higher, which is not always preferable as an industrial production method.

Further, in the method using the Grignard reagent prepared from pentafluorobenzene, the reactivity of the starting material pentafluorobenzene is inferior, so that a solvent such as tetrahydrofuran must be used as a reaction solvent when preparing the Grignard reagent. . Tetrahydrofuran has a high coordination ability for Lewis acids such as borane, and is not preferable as a method for economically producing the desired borane derivative. The present invention provides a novel method for producing a tetrakis (pentafluorophenyl) borate derivative that solves this problem.

[0006]

Hereinafter, the present invention will be described in detail. That is, in the first step of the present invention, a halogenated pentafluoro represented by the general formula [1] C ₆ F ₅ X [1] (wherein, X represents chlorine, bromine or iodine) in an ether solvent. A pentafluorophenylmagnesium derivative represented by the general formula [2] C ₆ F ₅ MgX [2] (in the formula, X is the same as above) is prepared from benzene and magnesium. [3] BX ₃ [3] (wherein, X represents fluorine, chlorine, bromine, or iodine), a solvent solution of a boron compound having a boiling point of 60 ° C. or higher, and an ether system of the pentafluorophenyl magnesium derivative. After mixing the solution of the solvent and heating or refluxing at 50 ° C to the boiling point of the solvent, the compound is represented by the general formula [4] A-Cl [4] (wherein A represents R ¹ R ² R ³ NH or Ar ₃ C). ,
R ¹ , R ² and R ³ are the same or different from each other and are C ₁ to
A C ₆ alkyl group or an unsubstituted or optionally substituted phenyl group is shown, and Ar is an unsubstituted or optionally substituted phenyl group. ) Added amine hydrochloride or chlorinated triallylmethane, and represented by the general formula [5] A [B (C ₆ F ₅ ) ₄ ] [5] (wherein A is the same as above). It was found that this borate derivative can be efficiently produced, and the present invention has been completed.

As a mixing method of each solution of the Grignard reagent represented by the formula [2] and the boron compound represented by the formula [3], a method of adding an ether solution of the Grignard reagent to the solution of the boron compound and a method of adding the boron compound Although there is a method of adding the solution to an ether solution of the Grignard reagent, any method can be used in the present invention. First
Diethyl ether as an ether solvent used in the step,
Chain ethers such as isopropyl ether, n-butyl ether and isoamyl ether can be mentioned. Preferably, diethyl ether, isopropyl ether,
It is n-butyl ether. Cyclic ethers such as tetrahydrofuran and dioxane are known to be useful for the preparation of the so-called Grignard reagent represented by the general formula [2], but the borane derivative produced in the borate derivative production process as the final product of the present invention. It has a high complex-forming ability with and is not necessarily a preferable solvent.

Examples of the halogenated pentafluorobenzene represented by the general formula [1] include pentafluorobenzene chloride, pentafluorobenzene bromide and pentafluorobenzene iodide. Pentafluorobenzene bromide is preferable from the viewpoint of reactivity. Reaction is usually -1
It is carried out at 0 ° C. to the boiling point of the solvent, preferably 0 to 10 ° C., and if necessary, it can be carried out in an atmosphere of an inert gas such as nitrogen or argon.

When carrying out the reaction of the first step, an activator such as iodine for preparing a Grignard reagent can be used if necessary. In the second step, a solution of a boron halide compound represented by the general formula [3] having a boiling point of 60 ° C. or higher and a pentafluorophenyl magnesium derivative represented by the general formula [2] prepared in the first step are prepared. After mixing with a solution of an ether solvent at −20 to 50 ° C., preferably 0 to 30 ° C., the solution is heated at a temperature of 50 ° C. or higher and up to the boiling point of the solvent used in the second step, and then the compound of the general formula [ 4] and adding amine hydrochloride or triallyl chloride chloride,
The desired borate derivative of the general formula [5] is produced.

Examples of the boron halide compound represented by the general formula [3] include boron trichloride, boron tribromide, boron trifluoride / ether complex and the like. It is preferable to use a borohydride / ether complex.

Solvents having a boiling point of 60 ° C. or higher which are used by dissolving the boron halide compound represented by the general formula [3] are n-hexane, heptane, isoheptane, n
Include octane, a C ₆ or more linear or branched isooctane aliphatic hydrocarbons or mixtures thereof, toluene, the appropriate C ₁ -C alkyl group substituted or aromatic hydrocarbon of ₆ and xylene - be able to. R ⁴ O
The R ⁴ (wherein R ⁴ represents. A linear or branched alkyl group of C ₃ -C ₆₎ R ⁴ chain ether represented by, isopropyl group, n- butyl group, an isobutyl radical, n
-Pentyl group, isopentyl group, t-amyl group, neopentyl group, n-hexyl group, isohexyl group and the like can be mentioned. Specific examples thereof include diisopropyl ether, di-n-butyl ether, diisobutyl ether and the like. The pentafluorophenyl magnesium derivative is not particularly limited as long as it is 4 times the molar equivalent of the boron halide compound, but is preferably 4.0 to 5.0 molar equivalents of the pentafluorophenyl magnesium derivative with respect to 1 molar equivalent of the boron halide compound. Is preferably used. The amount of the solvent having a boiling point of 60 ° C. or higher is not particularly limited as long as the reaction can be carried out, but 1 to 200 parts can be used per 1 part by weight of the boron halide compound.

The heat treatment time after the addition of the pentafluorophenylmagnesium derivative is not particularly limited, but 1 to 5
Time is appropriate. At this time, when a boron trifluoride ether complex is used as the boron halide or when diethyl ether is used as the reaction solvent in the first step, the diethyl ether present in the reaction system is distilled off in the heat treatment step. It is preferable to let it go.

As the amine hydrochloride or triallylmethane chloride represented by the general formula [4], for example, triallyl chloride such as triphenylmethane chloride and tri-p-tolylmethane chloride, triethylamine, tributylamine,
Benzyldimethylamine, N, N-dimethylaniline,
Hydrochloride such as N, N-diethylaniline can be mentioned. Preferred are triphenylmethane chloride, tributylamine · hydrochloride, and N, N-dimethylaniline · hydrochloride.

The compound represented by the general formula [4] is not particularly limited as long as it is used in an amount of 1 molar equivalent or more based on the boron halide used, but for economic reasons, it is preferably 1.0 to 1.2. It is preferred to use molar equivalents. Also,
The compound represented by the formula [4] can be used as it is, but it is usually added by dissolving it in the solvent used in the second step, water or the like. Especially when adding amine hydrochloride,
It is preferably added as an aqueous solution.

Specific examples of the borate derivative represented by the general formula [5] produced by the above method include N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate N, N-diethylanilinium tetrakis (pentafluoro). Phenyl) borate trimethylammonium tetrakis (pentafluorophenyl) borate triethylammonium tetrakis (pentafluorophenyl) borate tributylammonium tetrakis (pentafluorophenyl) borate trityl tetrakis (pentafluorophenyl) borate.

[0016]

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) 1.21 g (48.8 mmol) of magnesium metal piece was added to a 200 ml three-necked flask equipped with a magnetic stirrer, a thermometer and a dropping funnel, and the inside of the flask was sufficiently replaced with nitrogen, followed by diethyl ether. 64 ml was added. Then, the temperature of the reaction solution was adjusted to 10 ° C. or lower, and 1.2 g (4.9 mmol) of pentafluorobenzene bromide was added dropwise. After confirming the exotherm of the reaction system,
1.1 g (44.9 mmol) of pentafluorobenzene bromide was further added dropwise. After completion of dropping, further 1 at room temperature under nitrogen stream
After stirring for an hour, boron trifluoride ether complex 1.67
A 58 ml toluene solution of g (11.7 mmol) was added dropwise at room temperature. After that, the dropping funnel was switched to a distillation apparatus to heat the reaction solution to 85 ° C., and the effluent was distilled off. Reaction temperature is 8
After reaching 5 ° C., heating was continued for 2 hours. The reaction solution was allowed to cool to room temperature, 13 ml of a 1 M aqueous solution of N, N-dimethylaniline hydrochloride was added to the reaction solution, and the mixture was further stirred for 30 minutes. Then, the organic layer was separated, and the organic layer was washed 3 times with water. The organic layer was dried over anhydrous sodium sulfate, and the desiccant was filtered off. Hexane (50 ml) was added to the dried organic layer to precipitate a solid, and the suspension was cooled to 0 ° C. and stirred at the same temperature for 2 hours. The precipitated solid was collected by filtration and then dried by heating under reduced pressure to obtain 8.67 g of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. The yield was 92%.

Example 2 Except that the molar ratio of pentafluorobenzene bromide to boron trifluoride ether complex was 4.13, the heat treatment temperature was 110 ° C., and anhydrous magnesium sulfate was used as a desiccant in the final step. Example 1
By substantially the same operation as above, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was obtained with a yield of 83%.

(Example 3) Almost the same as Example 1 except that diisopropyl ether was used as the boron trifluoride ether complex solution and the heat treatment was carried out at 69 ° C for 2 hours. , N-dimethylanilinium
Tetrakis (pentafluorophenyl) borate was obtained.

Example 4 Dibutyl ether was used as a boron trifluoride ether complex solution, and heat treatment was performed at 110
N, N-Dimethylanilinium tetrakis (pentafluorophenyl) borate was obtained in a yield of 87.7% in substantially the same manner as in Example 1 except that the temperature was 2 hours.

Example 5 Almost the same as Example 1 except that hexane was used as the boron trifluoride ether complex solution and the heat treatment was carried out at 50 ° C. for 2 hours, and the yield was 66.8.
% N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was obtained.

Example 6 N, N-with a yield of 93.3% was obtained in substantially the same manner as in Example 1 except that hexane was used as a boron trifluoride ether complex solution and the heat treatment was refluxed for 2 hours. Dimethylanilinium tetrakis (pentafluorophenyl) borate was obtained.

Example 7 Almost the same as Example 1 except that hexane was used as the boron trifluoride ether complex solution and the heat treatment was refluxed for 3.5 hours, and the yield was 94.1.
% N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was obtained.

(Example 8) Cyclohexane was used as the boron trifluoride ether complex solution, and the heat treatment was carried out under reflux for 3 hours, in substantially the same manner as in Example 1 except that the yield was 9
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was obtained at 6.4%.

(Example 9) As a solution of boron trifluoride ether complex, Isopar E (manufactured by Exxon Co.) consisting of hydrocarbon having a boiling point of 115 to 123 ° C was used, and heat treatment was conducted at 115 ° C for 3.0 hours. N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was obtained in a yield of 94.6% in substantially the same manner as in Example 1 except for the above.

(Example 10) Except for using xylene as a boron trifluoride ether complex solution and heating for 2 hours under reflux, the same procedure as in Example 1 was performed to obtain a yield of 87.
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was obtained at 6%.

Example 11 Xylene was used as a boron trifluoride ether complex solution, and heat treatment was performed at 120 ° C. for 2 hours.
The yield was 9 in the same manner as in Example 1 except that the time was set.
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was obtained at 2.9%.

(Example 12) 1M as hydrochloride of amine
Tributylammonium tetrakis (pentafluorophenyl) borate was obtained in a yield of 87.4% in substantially the same manner as in Example 1 except that tributylamine hydrochloride was used.

Example 13 Almost the same as Example 1 except that trityl chloride was used as the amine hydrochloride,
Trityl tetrakis (pentafluorophenyl) borate was obtained with a yield of 80.3%.

(Comparative Example 1) Diethyl ether was used as a boron trifluoride ether complex solution, and heat treatment was performed at 2.5.
The same operation as in Example 1 was carried out except that the heating under reflux was performed, but the desired borate derivative was not produced at all,
Only 74% of tris (pentafluorophenyl) borane was obtained.

(Comparative Example 2) Dimethoxyethane was used as a boron trifluoride ether complex solution, and heat treatment was performed at 2.5.
The same operation as in Example 1 was carried out except that the heating under reflux was performed, but the desired borate derivative was not produced at all,
Only 76% of tris (pentafluorophenyl) borane was obtained.

[0032]

According to the present invention, it is possible to provide a method for easily producing a borate derivative which is an important cocatalyst in a metallocene catalyst system.

Claims (8)

[Claims] 1. A halogenated pentafluorobenzene represented by the general formula [1] C ₆ F ₅ X [1] (wherein X represents chlorine, bromine or iodine) and magnesium in an ether solvent. A pentafluorophenylmagnesium derivative represented by the general formula [2] C ₆ F ₅ MgX [2] (wherein X represents chlorine, bromine or iodine), and then the general formula [3] BX ₃ [3] A solution of a boron compound represented by the formula (wherein X represents fluorine, chlorine, bromine or iodine) having a boiling point of 60 ° C. or higher and a solution of the pentafluorophenyl magnesium derivative in an ether solvent. After mixing, after heating or refluxing at 50 ° C to the boiling point of the solvent, the compound is represented by the general formula [4] A-Cl [4] (wherein A represents R ¹ R ² R ³ NH or Ar ₃ C,
R ¹ , R ² and R ³ are the same or different from each other and are C ₁ to
A C ₆ alkyl group or an unsubstituted or optionally substituted phenyl group is shown, and Ar is an unsubstituted or optionally substituted phenyl group. ) Amine hydrochloride or chlorinated triallylmethane is added to give a compound of the general formula [5] A [B (C ₆ F ₅ ) ₄ ] [5] (wherein A is R ¹ R ² R ³ Represents NH or Ar ₃ C,
R ¹ , R ² and R ³ are the same or different from each other and are C ₁ to
A C ₆ alkyl group or an unsubstituted or optionally substituted phenyl group is shown, and Ar is an unsubstituted or optionally substituted phenyl group. ) The manufacturing method of the borate represented by. 2. A straight-chain or branched aliphatic hydrocarbon having a boiling point of 60 ° C. or higher and a C ₆ or higher, an aromatic hydrocarbon optionally substituted by a C ₁ -C ₆ alkyl group, or R ⁴ OR.
^4. A chain ether represented by the formula ⁴ (in the formula, R ⁴ represents a C ₃ -C ₆ linear or branched alkyl group).
A method for producing the described borate. 3. The method according to claim 1, wherein the ether solvent is diethyl ether, isopropyl ether, n-butyl ether or isoamyl ether. 4. The method according to claim 1, wherein the boron compound is boron trichloride, boron tribromide, boron trifluoride or boron trifluoride ether complex. 5. The hydrocarbon of C ₆ or higher is hexane, heptane, octane, nonane, decane and isomers thereof or a mixture thereof, and any one of claims 2 to 4.
The method described in the section. 6. The method according to claim 2, wherein the solvent having a boiling point of 60 ° C. or higher is toluene or xylene. 7. The method according to claim 2, wherein the solvent having a boiling point of 60 ° C. or higher is diisopropyl ether, di-n-butyl ether or di-isoamyl ether. 8. A compound represented by the general formula [1] C ₆ with respect to 1 equivalent of a boron compound represented by the general formula [3] BX ₃ [3] (wherein X represents fluorine, chlorine, bromine or iodine). 4 equivalents or more of halogenated pentafluorobenzene represented by F ₅ X [1] (wherein X represents chlorine, bromine or iodine),
Preferably, 4 to 5 equivalents are used.
The method described in the section.