JPH09295985A - Production of tetrakis(pentaflurophenyl) borate derivative by using halogenated alkyl - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress coloring of a catalyst component in producing a polyolefin such as polystryene, and therefore suppress coloring of a polymer in producing a polyolefin, etc. SOLUTION: The objective borate derivative expressed by the formula A[B(C6 F5 )4 ] (A is R<1> R<2> R<3> NH, etc., R<1> , R<2> and R<3> are the same or mutually different 1-6C alkyl group.) and having an excellent color toner is obtained by adding a halogenated alkyl of the formula R<5> X (R<5> is a 1-5C lower alkyl group) in preparing a Grignard reagent of the formula C6 F5 MgX (X is chlorine, etc.), in producing the borate derivative by preparing a derivative expressed by the formula C6 F5 MgX from a compound of the formula C6 F5 X (X is same as above) and Mg 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-based 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-C1 (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 pentafluorophenyl magnesium 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 to Lewis acids such as borane, and is not always preferable as a method for economically producing the desired borane derivative.

The Grignard method using halogenated pentafluorobenzene as a starting material is an excellent method with few defects as described above, but sometimes the Grignard reagent is colored when the Grignard reagent is prepared.
It is often recognized that this coloring impairs the color tone of the borate derivative which is the final product. For example, dimethylanilinium tetrakis (pentafluorophenyl) borate is originally white, but when coloring of the solution is observed at the time of preparing the Grignard reagent, it is recognized that it is gray to light black. It is an object of the present invention to provide a new manufacturing method that solves this problem.

[0007]

Hereinafter, the present invention will be described in detail. The present inventors have recognized that the boron derivative prepared by the Grignard method sometimes exhibits an unfavorable color tone, and various measures have been investigated. that time,
Coincidentally, it was found that the Grignard reagent prepared by using an alkyl halide as a catalyst at the time of preparing the Grignard reagent was significantly improved in coloration of the reaction solution as compared with that prepared by pentafluorobromobenzene alone. The present inventors have found that the borate derivative prepared by this method does not have the color tone such as darkening that is observed when the Grignard reagent prepared by pentafluorobromobenzene alone is used as the starting material, and the present invention has been completed.

That is, in the first step of the present invention, a halogen 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 the prepared pentafluorobenzene and magnesium, and then the second step is carried out. As a solution of a boron compound represented by the general formula [3] BX ₃ [3] (wherein X represents fluorine, chlorine, bromine or iodine) having a boiling point of 60 ° C. or higher, and the pentafluorophenyl magnesium derivative. After mixing with a solution of the ether solvent of 50 ° C. to the boiling point of the solvent or refluxing, the compound of the general formula [4] A—Cl [4] (In the formula, A is R ¹ R ² R ³ NH or Ar ₃ Represents 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. Represented by adding hydrochloric acid salt or chlorinated triarylmethane of amine), the general formula [5] A [B (C 6 F 5) 4] [5] ( wherein, A is the same.) To the In the method for efficiently producing the borate derivative represented by the formula, in the preparation of the Grignard reagent represented by the formula [2], the formula [6] R ⁵ X [6] (in the formula, R ⁵ is a C _{1 to} C ₆ lower group). Represents an alkyl group, X
Represents chlorine, bromine or iodine. The present invention relates to a method for producing a borate represented by the formula [5], which maintains the whiteness, characterized by adding an alkyl halide represented by the formula (1).

As a method for mixing 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 mixing 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.

Examples of the ether solvent used in the first step include chain ethers such as diethyl ether, isopropyl ether, n-butyl ether and isoamyl ether. Preferred are diethyl ether, isopropyl ether, and n-butyl ether. Cyclic ethers such as tetrahydrofuran and dioxane are also known to be useful in the preparation of so-called Grignard reagents represented by the general formula [3], 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.

The second step is a solution of a boron halide compound represented by the general formula [3] having a boiling point of 60 ° C. or higher and the pentafluorophenyl represented by the general formula [2] prepared in the first step. A magnesium derivative at -20 to 50 ° C,
Preferably, after mixing at 0 to 30 ° C., the solution is heated to 50 ° C. or higher and up to the boiling point of the solvent used in the second step, and then triallyl chloride chloride or amine hydrochloride represented by the general formula [4]. Salt is added to produce the desired borate derivative of the general formula [5].

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 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 boron halide, but preferably 4.0 to 5.0 molar equivalents of pentafluorophenyl magnesium per 1 molar equivalent of the boron halide. Preference is given to using derivatives. 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 is 1 to 2 with respect to 1 part by weight of the boron halide compound.
00 parts can be used. The heat treatment time after the addition of the pentafluorophenyl magnesium derivative is not particularly limited, but 1 to 5 hours is suitable. 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.

The amine hydrochloride or triallylmethane chloride represented by the general formula [4] includes, for example, triarylmethane chloride, tri-allyl 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 with respect to 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.

Examples of the alkyl halide represented by the formula [6] include methyl iodide, ethyl bromide, ethyl iodide, propyl iodide, propyl bromide, butyl iodide, butyl bromide and butyl chloride. However, methyl iodide, ethyl bromide and ethyl iodide are preferred. The amount of alkyl halide is 1 to 20 mol%, preferably 2 to 15 mol% of the starting halogenated pentafluorobenzene of the Grignard reagent.

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 (penta Examples thereof include fluorophenyl) borate trimethylammonium tetrakis (pentafluorophenyl) borate triethylammonium tetrakis (pentafluorophenyl) borate tributylammonium tetrakis (pentafluorophenyl) borate trityl tetrakis (pentafluorophenyl) borate.

[0020]

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) A 200 ml three-neck round bottom flask equipped with a mechanical stirrer, a thermometer and a dropping funnel was used. 1.21 g of magnesium (48.8
(mmol), and the inside of the flask was sufficiently replaced with nitrogen. 64 ml of diethyl ether was added, the mixture was cooled to 5 ° C., and 300 mg (2.7 mmol, 5.4 mol% based on pentafluorobromobenzene) of ethyl bromide was added. After stirring at room temperature for 1 hour, pentafluorobromobenzene 1
2.3 g (50 mmol) was added dropwise at room temperature. After completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour, and then 1.67 g (11.7 mmol) of 5 was added to the boron trifluoride ether complex.
8 ml toluene solution was added at room temperature. Then, the dropping funnel was replaced with a distillation apparatus and heated to remove ether. The heating temperature was until the temperature of the reaction solution reached 85 ° C., and after reaching the same temperature, heating and stirring were further performed for 2 hours. afterwards,
The reaction solution was allowed to cool, the reaction solution temperature was brought to room temperature, and then 13 ml of an aqueous solution of N, N-dimethylaniline hydrochloride was added to the reaction solution.
(1.0 M, 13 mmol) was added, and the mixture was stirred at room temperature for 30 minutes. After separating the organic layer, the organic layer was washed with water three times. After drying the organic layer with anhydrous magnesium sulfate, 50 ml of hexane was added to the organic layer from which the desiccant was filtered off to precipitate a solid. The obtained suspension solution was stirred at 0 ° C. for 2 hours, and the precipitated solid was filtered off. The solid separated by filtration is washed with hexane, and then the pressure is reduced to 150.
After drying for 15 hours at ℃, the target white solid N, N-dimethylanilinium tetrakis (pentafluorophenyl)
8.15 g (10.2 mmol) of borate was obtained. The yield was 85%.

(Examples 2 to 4) The results shown in Table 1 were obtained in the same manner as in Example 1 except that the amount of ethyl bromide, the heating temperature and the time were changed.

[0023]

[Table 1]

Comparative Example 5 samples were prepared by substantially the same operation as in Example 1 except that ethyl bromide was not used.
The yield was 80-90%, but 3 samples were gray solids.

[0025]

Industrial Applicability According to the present invention, it is possible to provide a method for suppressing coloration of a borate derivative which is an important cocatalyst in a metallocene catalyst system. It is expected that the present invention will avoid polymer coloring which is often a problem in polyolefin production.

Claims (10)

[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. In the method for producing the borate represented by the formula (4), a formula [6] R ⁵ X [6] (wherein R ⁵ represents a C ₁ -C ₆ lower alkyl group) at the time of preparing the Grignard reagent represented by the formula [2]. , X
Represents chlorine, bromine or iodine. ) An alkyl halide represented by the above formula [5]
A method for producing borate having good color tone 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. A boron compound represented by the general formula [3] BX ₃ [3] (wherein X represents fluorine, chlorine, bromine or iodine), wherein the boron compound is boron trichloride, boron tribromide or trifluoride. 4. The method according to any one of claims 1 to 3, which is a boron trifluoride or a boron trifluoride ether complex, preferably a 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 boron compound represented by the general formula [3] BX ₃ [3] (wherein X represents fluorine, chlorine, bromine, or iodine) with respect to 1 equivalent of the boron halide represented by the general formula [1] C. ₄ F ₅ X [1] (wherein X represents chlorine, bromine or iodine), 4 equivalents or more of halogenated pentafluorobenzene represented by the formula:
Preferably, 4 to 5 equivalents are used.
The method described in the section. 9. A compound of the formula [6] R ⁵ X [6] (wherein R ⁵ represents a C ₁ -C ₆ lower alkyl group, X
Represents chlorine, bromine or iodine. The method according to any one of claims 1 to 8, wherein the alkyl halide represented by) is methyl iodide, ethyl bromide, or ethyl iodide. 10. A starting material for a pentafluorophenylmagnesium derivative represented by the formula [2], which is a target of the alkyl halide represented by the formula [6] used in the preparation of the Grignard reagent.
20 mol%, preferably 2 to 15 mol%, process according to any one of claims 1 to 9.