JP2018188572A - Method for producing oligomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an oligomer that can efficiently produce an oligomer having a desired molecular weight, in the oligomerization of ethylene.SOLUTION: A method for producing an oligomer includes the step for the oligomerization of ethylene, in the presence of a catalyst containing (A) rac-ethylidene indenyl zirconium compound represented by general formula (1), (B) iron compound represented by general formula (2), (C) methylaluminoxane and/or boron compound, and (D) organic zinc compound and/or organic aluminum compound other than methylaluminoxane.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an oligomer, and more particularly to a method for producing an oligomer from ethylene.

  As a catalyst used for copolymerization of ethylene and α-olefin, a catalyst comprising a metallocene compound and methylaluminoxane, a palladium-based catalyst, an iron complex, a cobalt complex and the like are known (Non-Patent Documents 1 to 3, Patent Documents). 1-3).

  Moreover, an iron complex is also known as a catalyst for ethylene polymerization (Non-Patent Documents 4 to 6).

  Further, as a catalyst for producing a block copolymer, a catalyst comprising diethyl zinc, a metallocene compound, a palladium catalyst and a dialkyl zinc is known (Non-patent Document 7 and Patent Document 4).

Special Table 2000-516295 JP 2002-302510 A Chinese Patent Application No. 10243415 JP-T-2007-529616

“Macromol. Chem. Phys.”, 197, 1996, p. 3907 “J. Am. Chem. Soc.”, 117, 1995, p. 6414 “J. Am. Chem. Soc.”, 120, 1998, p. 7143 “J. Mol. Cat. A: Chemical”, 179, 2002, p. 155 “Appl. Cat. A: General”, 403, 2011, p. 25 “Organometallics”, 28, 2009, p. 3225 “Science”, 312 volume, 2006, p. 714

  An object of the present invention is to provide an oligomer production method capable of efficiently obtaining an oligomer having a desired molecular weight in ethylene oligomerization.

  That is, the present invention provides (A) a rac-ethylideneindenylzirconium compound represented by the following general formula (1), (B) an iron compound represented by the following general formula (2), (C) methylaluminoxane and / or Alternatively, the present invention provides a method for producing an oligomer, comprising a step of oligomerizing ethylene in the presence of a boron compound and a catalyst containing (D) an organoaluminum compound other than (D) an organozinc compound and / or methylaluminoxane.

［式（１）中、Ｘはハロゲン原子、水素原子または炭素数１〜６のヒドロカルビル基を示す。］

[In Formula (1), X shows a halogen atom, a hydrogen atom, or a C1-C6 hydrocarbyl group. ]

［式（２）中、Ｒは炭素数１〜６のヒドロカルビル基または炭素数６〜１２の芳香族基を示し、同一分子中の複数のＲは同一でも異なっていてもよく、Ｒ’は酸素原子および／または窒素原子を有する炭素数０〜６の遊離基を示し、同一分子中の複数のＲ’は同一でも異なっていてもよく、Ｙは塩素原子または臭素原子を示す。］

[In the formula (2), R represents a hydrocarbyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms, a plurality of R in the same molecule may be the same or different, and R ′ represents oxygen A C 0-6 free radical having an atom and / or a nitrogen atom is shown, a plurality of R ′ in the same molecule may be the same or different, and Y represents a chlorine atom or a bromine atom. ]

  According to the production method of the present invention, in the oligomerization of ethylene, the obtained oligomer can be efficiently improved to a desired molecular weight, and the progress of polymerization can be sufficiently suppressed.

  In the said manufacturing method, the number average molecular weight (Mn) of the oligomer obtained can be 200-5000.

  The organoaluminum compound is selected from the group consisting of trimethylaluminum, triethylaluminum, triisopropylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triphenylaluminum, diethylaluminum chloride, ethylaluminum dichloride and ethylaluminum sesquichloride. It can be at least one selected.

  The organozinc compound can be at least one selected from the group consisting of dimethylzinc, diethylzinc and diphenylzinc.

  Boron compounds include trispentafluorophenylborane, lithium tetrakispentafluorophenylborate, sodium tetrakispentafluorophenylborate, N, N-dimethylanilinium tetrakispentafluorophenylborate, trityltetrakispentafluorophenylborate, lithium tetrakis (3,5 -Trifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (3,5-trifluoromethylphenyl) borate and trityltetrakis (3,5-trifluoromethylphenyl) borate It can be.

  ADVANTAGE OF THE INVENTION According to this invention, in the oligomerization of ethylene, the manufacturing method of the oligomer which can obtain the oligomer which has a desired molecular weight efficiently can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

[catalyst]
The catalyst for oligomerization of ethylene according to this embodiment includes (A) rac-ethylideneindenylzirconium compound, (B) iron compound, (C) methylaluminoxane and / or boron compound, and (D) organic An organoaluminum compound other than a zinc compound and / or methylaluminoxane.

  Hereinafter, each component will be described.

<(A) rac-ethylideneindenylzirconium compound>
In the present embodiment, (A) rac-ethylideneindenylzirconium compound is represented by the following general formula (1).

  In the formula (1), X represents a halogen atom, a hydrogen atom, or a hydrocarbyl group having 1 to 6 carbon atoms. Specific examples of such compounds include rac-ethylidene indenyl zirconium dichloride, rac-ethylidene indenyl zirconium dibromide, rac-ethylidene indenyl zirconium dihydride, rac-ethylidene indenyl zirconium hydride chloride, rac-ethylidene indenyl. Zirconium dimethyl etc. are mentioned. Among these, rac-ethylideneindenylzirconium dichloride is preferable from the viewpoint of availability. These rac-ethylideneindenylzirconium compounds can be used alone or in combination of two or more.

<(B) Iron compound>
In this embodiment, the (B) iron compound is represented by the following general formula (2).

  In the formula (2), R represents a hydrocarbyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms, and a plurality of R in the same molecule may be the same or different. Specific examples of R include a methyl group and a phenyl group. R ′ represents an oxygen atom and / or nitrogen-containing free radical having 0 to 6 carbon atoms, and a plurality of R ′ in the same molecule may be the same or different. Specific examples of R ′ include hydrogen atom, methoxy group, ethoxy group, isopropoxy group, nitro group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, hexyl group, A phenyl group, a cyclohexyl group, etc. are mentioned. Y represents a chlorine atom or a bromine atom. Specific examples of such compounds include the compounds represented by the following general formulas (2a) to (2h). These iron compounds can be used alone or in combination of two or more.

  In the iron compound represented by the general formula (2), the diimine compound constituting the ligand (hereinafter sometimes simply referred to as diimine compound) is, for example, dibenzoylpyridine and aniline compound dehydrated in the presence of an acid. It can be synthesized by condensation.

  A preferred embodiment of the method for producing the diimine compound includes a first step in which 2,6-dibenzoylpyridine, an aniline compound, and an acid are dissolved in a solvent and subjected to dehydration condensation under solvent heating under reflux,

  Separating and purifying the reaction mixture after the first step to obtain a diimine compound.

  As the acid used in the first step, for example, an organoaluminum compound can be used. Examples of organoaluminum compounds include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum chloride, ethylaluminum sesquichloride, methylaluminoxane. Etc.

  As the acid used in the first step, a protonic acid can be used in addition to the organoaluminum compound. Protic acid is used as an acid catalyst for donating protons. The proton acid used is not particularly limited, but is preferably an organic acid. Examples of such a protonic acid include acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, and the like. When using these protonic acids, it is preferable to remove water with a Dean-Stark water separator or the like from the viewpoint of suppressing the by-product of water. It is also possible to carry out the reaction in the presence of an adsorbent such as molecular sieves. The addition amount of the protonic acid is not particularly limited, and may be a catalytic amount.

  Examples of the solvent used in the first step include hydrocarbon solvents and alcohol solvents. Examples of the hydrocarbon solvent include hexane, heptane, octane, benzene, toluene, xylene, cyclohexane, methylcyclohexane, and the like. Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, and the like.

  The reaction conditions in the first step can be appropriately selected according to the types and amounts of the raw material compound, acid and solvent.

  In addition, the separation / purification treatment in the second step is not particularly limited, and examples thereof include silica gel column chromatography and a recrystallization method. In particular, when the above-described organoaluminum compound is used as the acid, it is preferable to purify after mixing the reaction solution with a basic aqueous solution to decompose and remove aluminum.

The iron compound according to the present embodiment contains iron as a central metal. The mixing method of the diimine compound and iron is not particularly limited, for example,
(I) A method of adding and mixing an iron salt (hereinafter sometimes simply referred to as “salt”) to a solution in which a diimine compound is dissolved,
(Ii) a method of mixing a solution in which a diimine compound is dissolved and a solution in which a salt is dissolved;
(Iii) a method of physically mixing a diimine compound and a salt without using a solvent;
Etc.

In addition, the method for taking out the complex from the mixture of the diimine compound and iron is not particularly limited, for example,
(A) a method of distilling off the solvent when a solvent is used in the mixture and filtering off the solid,
(B) a method of filtering the precipitate formed from the mixture,
(C) a method of purifying the precipitate by adding a poor solvent to the mixture and filtering it off;
(D) a method of taking out the solventless mixture as it is,
Etc. Thereafter, a washing treatment with a solvent capable of dissolving the diimine compound, a washing treatment with a solvent capable of dissolving the metal, a recrystallization treatment using an appropriate solvent, and the like may be performed.

  Examples of the iron salt include iron chloride (II), iron chloride (III), iron bromide (II), iron bromide (III), acetylacetone iron (II), acetylacetone iron (III), iron acetate (II) ), Iron (III) acetate, and the like. You may use what has ligands, such as a solvent and water, in these salts. Among these, a salt of iron (II) is preferable, and iron (II) chloride is more preferable.

  Moreover, it does not restrict | limit especially as a solvent which makes a diimine compound and iron contact, Any of a nonpolar solvent and a polar solvent can be used. Nonpolar solvents include hydrocarbon solvents such as hexane, heptane, octane, benzene, toluene, xylene, cyclohexane, and methylcyclohexane. Examples of the polar solvent include polar protic solvents such as alcohol solvents, polar aprotic solvents such as tetrahydrofuran, and the like. Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, and the like. In particular, when the mixture is used as a catalyst as it is, it is preferable to use a hydrocarbon solvent that does not substantially affect ethylene polymerization.

  Further, the mixing ratio of the diimine compound and iron when they are brought into contact with each other is not particularly limited. The lower limit of the diimine compound / iron ratio is preferably a molar ratio of 0.2 / 1 or more, more preferably 0.3 / 1 or more, and even more preferably 0.5 / 1 or more. The upper limit of the ratio is preferably 5/1 or less, more preferably 3/1 or less, and even more preferably 2/1 in terms of molar ratio. The ratio of diimine compound / iron is a molar ratio, particularly preferably 1.

  The two imine sites in the diimine compound are preferably both E-forms, but may contain a diimine compound containing a Z-form as long as the diimine compound is an E-form. Since the diimine compound containing Z form is difficult to form a complex with a metal, it can be easily removed by a purification step such as solvent washing after forming a complex in the system.

<(C) methylaluminoxane, boron compound>
The catalyst according to this embodiment includes (C) methylaluminoxane and / or a boron compound.

  As the methylaluminoxane, a commercially available product diluted with a solvent can be used, and a product obtained by partially hydrolyzing trimethylaluminum in a solvent can also be used. When unreacted trimethylaluminum remains in the methylaluminoxane, the unreacted trimethylaluminum may be used as the component (D) described in detail below, or the trimethylaluminum and the solvent are distilled under reduced pressure. It may be used as a dried dry methylaluminoxane. Further, in the partial hydrolysis of trimethylaluminum, modified methylaluminoxane obtained by co-hydrolysis by coexisting trialkylaluminum other than trimethylaluminum such as triisobutylaluminum can also be used. In this case as well, when residual trialkylaluminum exists, the unreacted trialkylaluminum may be used as the component (D) described in detail below, or the trialkylaluminum and the solvent are distilled off. It may be used as a dry modified methylaluminoxane.

  Examples of the boron compound include aryl boron compounds such as trispentafluorophenylborane. As the boron compound, a boron compound having an anionic species can be used. Examples thereof include aryl borates such as tetrakispentafluorophenyl borate and tetrakis (3,5-trifluoromethylphenyl) borate. Specific examples of the aryl borate include lithium tetrakis pentafluorophenyl borate, sodium tetrakis pentafluorophenyl borate, N, N-dimethylanilinium tetrakis pentafluorophenyl borate, trityl tetrakis pentafluorophenyl borate, lithium tetrakis (3,5-tri Fluoromethylphenyl) borate, sodium tetrakis (3,5-trifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (3,5-trifluoromethylphenyl) borate, trityltetrakis (3,5-trifluoromethyl) Phenyl) borate and the like. Among these, N, N-dimethylanilinium tetrakispentafluorophenylborate, trityltetrakispentafluorophenylborate, N, N-dimethylanilinium tetrakis (3,5-trifluoromethylphenyl) borate or trityltetrakis (3,5 -Trifluoromethylphenyl) borate is preferred. These boron compounds can be used alone or in combination of two or more.

<(D) Organozinc compound, Organoaluminum compound>
The catalyst according to the present embodiment includes (D) an organoaluminum compound other than (D) an organozinc compound and / or methylaluminoxane.

  Specific examples of the organic zinc compound include alkyl zinc such as dimethyl zinc and diethyl zinc, and aryl zinc such as diphenyl zinc. In addition, the organic zinc compound is reacted in the reaction system by reacting zinc halide such as zinc chloride, zinc bromide, zinc iodide and the like, alkyllithium, arylgrineer, alkylgrineer, and the following organoaluminum compound. An organic zinc compound may be formed. These organozinc compounds can be used alone or in combination of two or more.

  Specific examples of organoaluminum compounds include trimethylaluminum, triethylaluminum, triisopropylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triphenylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride. Etc. These organoaluminum compounds can be used alone or in combination of two or more.

  In addition, when the total number of moles of the contents of (A) and (B) is Y, the content ratio of Y and (C) is the molar ratio when only methylaluminoxane is used as (C). The lower limit of Y / (C—Al) is preferably 1/1000 or more, and more preferably 1/500 or more. On the other hand, the upper limit of Y / (C-A1) is preferably 1/10 or less, and more preferably 1/20 or less. If the total content of (A) and (B) and the content ratio of (C-Al) are within the above ranges, the cost increase factor can be suppressed while expressing more sufficient polymerization activity. In addition, (C-Al) represents the number of moles of aluminum atoms in methylaluminoxane.

  On the other hand, when only a boron compound is used as (C), the lower limit of Y / (CB) in terms of molar ratio is preferably 1/10 or more, and more preferably 1/2 or more. On the other hand, the upper limit of Y / (C−B) is preferably 10/1 or less, and more preferably 2/1 or less. If the total content of (A) and (B) and the content ratio of (C-B) are within the above range, the cost increase factor can be suppressed while expressing more sufficient polymerization activity. Note that (CB) represents the number of moles of the boron compound. When only a boron compound is used as (C), it is particularly preferable to add an operation of using an alkyl complex or converting it to an alkyl complex for (A) and (B). Examples of the method for converting to an alkyl complex include, for example, conversion to a methyl complex, such as an organoaluminum compound such as trimethylaluminum, an organozinc compound such as dimethylzinc, an organolithium compound such as methyllithium, and methylmagnesium chloride. By bringing the Grineer compound and the like into contact with (A) or (B), conversion into a methyl complex of (A) or (B) can be mentioned. In addition, the thing as described in said (D) can be used for the organoaluminum compound and organozinc compound which were mentioned here.

  When (C) is used in combination with methylaluminoxane and a boron compound, the molar ratio of Y / (C—Al) is 1/100 or more and Y / (C—B) is 1/10 or more. It is more preferable that Y / (C—Al) is 1/50 or more and Y / (C—B) is more than 1/2. Moreover, as for the upper limit of molar ratio, it is preferable that Y / (C-Al) is 1/1 or less and Y / (CB) is 1/1 or less. If the total amount of (A) and (B), the content ratio of (C-Al), the total amount of (A) and (B), and the content ratio of (CB) are within the above ranges, The factor of cost increase can be suppressed while expressing more sufficient polymerization activity. Furthermore, the conversion to the alkyl complexes of (A) and (B) described above can be performed simultaneously.

  Moreover, as for the content ratio of Y and (D), the lower limit of Y / (D) in terms of molar ratio is preferably 1/1000 or more, and more preferably 1/800 or more. On the other hand, the upper limit of Y / (D) is preferably 1 or less, and more preferably 1/10 or less. If the total content of (A) and (B) and the content ratio of (D) are within the above range, the effect of the chain recombination polymerization by the complexes (A) and (B) will remarkably appear, and the reaction efficiency will be further improved. While improving effectively, the oligomer which has more suitable molecular weight can be manufactured. In addition, the content rate of said (D) represents the number-of-moles of the aluminum atom in an organoaluminum compound, when using an organoaluminum compound as (D).

[Method for producing oligomer]
The production method according to the present embodiment includes a step of oligomerizing ethylene in the presence of the catalyst.

  In the method for producing an oligomer in the present embodiment, the reaction solvent is preferably a nonpolar solvent from the viewpoint of favorably performing the polymerization reaction. Examples of the nonpolar solvent include normal hexane, isohexane, heptane, octane, isooctane, cyclohexane, methylcyclohexane, benzene, toluene, xylene and the like.

  Although reaction temperature in this embodiment is not specifically limited, For example, it is preferable that a minimum is 0 degreeC or more, It is more preferable that it is 10 degreeC or more, It is further more preferable that it is 20 degreeC or more. On the other hand, the upper limit of the reaction temperature is, for example, preferably 100 ° C. or less, more preferably 90 ° C. or less, and further preferably 80 ° C. or less. If reaction temperature is 0 degreeC or more, it can react efficiently, without requiring enormous energy for cooling, and if it is 100 degrees C or less, the activity fall of (B) iron compound can be suppressed. . Also, the reaction pressure is not particularly limited, but for example, the lower limit is preferably 100 kPa or more, and the upper limit is preferably 5 MPa or less. The reaction time is not particularly limited, but for example, the lower limit is preferably 1 minute or more, and the upper limit is preferably 24 hours or less.

  Since the oligomer obtained by the above production method in the present embodiment is further colorless and transparent, it can be suitably used, for example, as a component of a lubricating oil composition.

  The lower limit of the number average molecular weight (Mn) of the oligomer obtained by the above production method in the present embodiment is, for example, 200 or more, preferably 300 or more. Moreover, the upper limit of Mn is 5000 or less, for example, Preferably it is 4000 or less. In addition, the number average molecular weight (Mn) of an oligomer can be calculated | required as a polystyrene conversion amount based on the analytical curve created from standard polystyrene, for example using a GPC apparatus.

  The following examples illustrate the invention, but the following examples are not intended to limit the invention.

<Manufacture of catalyst and oligomer>
[Preparation of materials]
The rac-ethylidene bisindenyl zirconium chloride used was purchased from Wako Pure Chemicals as it was. The iron compound was synthesized by the method shown in the synthesis examples described later. The purchased reagents were used as they were. Trimethylaluminum was made of Japanese alkylaluminum diluted with dry toluene. For diethyl zinc, a toluene solution manufactured by Tokyo Chemical Industry was used as it was. As the methylaluminoxane, TMAO-341 manufactured by Tosoh Finechem was used as it was. The trityl tetrakis pentafluorophenyl borate used as it was made by Tokyo Chemical Industry.
Ethylene used was a high-purity liquefied ethylene manufactured by Sumitomo Seika and dried through molecular sieve 4A.
As the solvent toluene, Aldrich dehydrated toluene was used as it was.

[Measurement of number average molecular weight (Mn)]
Two columns (Polymer Laboratories, trade name: PL gel 10 μm MIXED-B LS) were connected to a high temperature GPC apparatus (Polymer Laboratories, trade name: PL-20) to obtain a differential refractive index detector. To 5 mg of sample, 5 ml of orthodichlorobenzene solvent was added, and the mixture was stirred with heating at 140 ° C. for about 1 hour. The sample dissolved in this way was measured at a flow rate of 1 ml / min and the temperature of the column oven set at 140 ° C. The molecular weight was converted based on a calibration curve prepared from standard polystyrene, and the molecular weight converted to polystyrene was determined.

[Calculation of catalyst efficiency]
The catalyst efficiency was calculated by dividing the weight of the obtained oligomer by the total number of moles of the charged catalyst.

[Synthesis of diimine compounds]
2-methyl-4-methoxyaniline (2.0893 g, 15.3 mmol) (manufactured by Tokyo Chemical Industry), 2,6-diacetylpyridine (1.2429 g, 7.6 mmol) (manufactured by Tokyo Chemical Industry), molecular sieve 4A (5. 0 g), a catalytic amount of para-toluenesulfonic acid was dispersed in dry toluene (60 ml), and the mixture was stirred with heating under reflux for 24 hours while removing water using a Dean-Stark water separator.

  The molecular sieve was removed from the reaction solution by filtration, and the molecular sieve was washed with toluene. The washing liquid and the filtered reaction liquid were mixed and concentrated to dryness to obtain a crude solid (2.8241 g). The crude solid (2 g) obtained here was weighed and washed with absolute ethanol (30 ml). The ethanol-insoluble solid was filtered off, and the insoluble solid was further washed with ethanol. The remaining solid was sufficiently dried to obtain the following diimine compound in a yield of 50%.

¹ H-NMR (600 MHz, CDCl ₃ ): 2.1 (s, 6H), 2.4 (s, 6H), 3.8 (s, 6H), 6.6 (m, 2H), 6.7 (M, 2H), 6.8 (m, 2H), 7.9 (m, 1H), 8.4 (m, 2H)
¹³ C-NMR (600 MHz, CDCl ₃ ): 16, 18, 56, 116, 119, 122, 125, 129, 137, 138, 143, 156, 167

[Synthesis of iron compounds]
FeCl ₂ .4H ₂ O (0.2401 g, 1.2 mmol) (manufactured by Kanto Chemical) was dissolved in dehydrated tetrahydrofuran (30 ml) (manufactured by Aldrich), and the previously synthesized diimine compound (0.4843 g, 1.2 mmol) was dissolved. Tetrahydrofuran solution (10 ml) was added. By adding a yellow diimine compound, a dark green tetrahydrofuran solution was instantaneously formed. Furthermore, it stirred at room temperature for 2 hours. The solvent was evaporated from the reaction solution to dryness, and the precipitated solid was washed with dehydrated ethanol until the filtrate had no color. Further, the washed solid was washed with dehydrated diethyl ether, and the solvent was removed to obtain an iron complex. Since the obtained iron compound obtained 527.0820 (calculated value: 527.0831) in FD-MASS, the following structure is suggested.

<Example 1>
The iron compound obtained above was added to dehydrated toluene to prepare a solution (A) having an iron compound concentration of 2 mM. Similarly, rac-ethylideneindenylzirconium dichloride was added to dehydrated toluene to prepare a solution (B) having a concentration of 2 mM. Add 20 ml of dehydrated toluene to a 50 ml eggplant flask, then add 0.5 ml of solution (A) and 0.5 ml of solution (B), and then add TMAO-341 (3.46M hexane solution, 0.03 ml, moles of zirconium and iron). After adding Al / metal = 50), where the total number was “metal”, trimethylaluminum (2M toluene solution, 0.05 ml, Al / metal = 50) was added to prepare a catalyst.

  The catalyst prepared above was added to an autoclave into which dry toluene (80 ml) was introduced, and 0.19 MPa of ethylene was continuously introduced at room temperature (25 ° C.). After 30 minutes, the introduction of ethylene was stopped, unreacted ethylene was removed, the ethylene in the autoclave was purged with nitrogen, and a very small amount of ethanol was added. The autoclave was opened, the contents were transferred to a 200 ml eggplant flask, and the solvent was distilled off under reduced pressure to obtain a semi-solid oligomer. The catalyst efficiency (CE) was 3343 kg / mol metal. Moreover, Mn of the obtained oligomer was 320.

<Example 2>
The same operation as in Example 1 was performed except that the introduction time of ethylene was 60 minutes. The catalyst efficiency (CE) was 4645 kg / mol metal. Further, Mn of the obtained oligomer was 310.

<Example 3>
Trityltetrakispentafluorophenylborate (boron compound) was dissolved in dehydrated toluene to prepare a solution (C) having a concentration of 2 mM of the boron compound. After adding 20 ml of dehydrated toluene to a 50 ml eggplant flask, 0.5 ml of solution (A) and 0.5 ml of solution (B) were added, and then solution (C) (1 ml, boron / metal = 1/1) was added. Trimethylaluminum (2M toluene solution, 0.05 ml, Al / metal = 50) was added to prepare a catalyst.

  The catalyst prepared above was added to an autoclave into which dry toluene (80 ml) was introduced, and 0.19 MPa of ethylene was continuously introduced at 10 ° C. After 60 minutes, the introduction of ethylene was stopped, unreacted ethylene was removed, ethylene in the autoclave was purged with nitrogen, and a very small amount of ethanol was added. The autoclave was opened, the contents were transferred to a 200 ml eggplant flask, and the solvent was distilled off under reduced pressure to obtain a semi-solid oligomer. The catalyst efficiency (CE) was 5148 kg / mol metal. Moreover, Mn of the obtained oligomer was 340.

<Comparative Example 1>
20 ml of dehydrated toluene was placed in a 50 ml eggplant flask, followed by addition of 0.5 ml of solution (A), and further trimethylaluminum (2M toluene solution, 0.05 ml, Al / Fe = 500) was added to prepare a catalyst.

  The catalyst prepared above was added to an autoclave into which dry toluene (80 ml) was introduced, and 0.19 MPa of ethylene was continuously introduced at room temperature (25 ° C.). After 30 minutes, the introduction of ethylene was stopped, unreacted ethylene was removed, the ethylene in the autoclave was purged with nitrogen, and a very small amount of ethanol was added. The autoclave was opened, the contents were transferred to a 200 ml eggplant flask, and the solvent was distilled off under reduced pressure to obtain a semi-solid oligomer. The catalyst efficiency (CE) was 1395 kg / Fe mol. Further, Mn of the obtained oligomer was 370.

Claims (5)

(A) a rac-ethylideneindenylzirconium compound represented by the following general formula (1),
(B) an iron compound represented by the following general formula (2),
(C) methylaluminoxane and / or boron compound, and
(D) an organoaluminum compound other than an organozinc compound and / or methylaluminoxane,
The manufacturing method of an oligomer provided with the process of oligomerizing ethylene in presence of the catalyst containing this.

[In Formula (1), X shows a halogen atom, a hydrogen atom, or a C1-C6 hydrocarbyl group. ]

[In the formula (2), R represents a hydrocarbyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms, a plurality of R in the same molecule may be the same or different, and R ′ represents oxygen A C 0-6 free radical having an atom and / or a nitrogen atom is shown, a plurality of R ′ in the same molecule may be the same or different, and Y represents a chlorine atom or a bromine atom. ]   The manufacturing method of Claim 1 whose number average molecular weights (Mn) of the said oligomer are 200-5000.   The organoaluminum compound is made of trimethylaluminum, triethylaluminum, triisopropylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triphenylaluminum, diethylaluminum chloride, ethylaluminum dichloride and ethylaluminum sesquichloride. The manufacturing method of Claim 1 or 2 which is at least 1 sort (s) chosen from.   The manufacturing method as described in any one of Claims 1-3 whose said organic zinc compound is at least 1 sort (s) chosen from the group which consists of dimethyl zinc, diethyl zinc, and diphenyl zinc.   The boron compound is trispentafluorophenylborane, lithium tetrakispentafluorophenylborate, sodium tetrakispentafluorophenylborate, N, N-dimethylanilinium tetrakispentafluorophenylborate, trityltetrakispentafluorophenylborate, lithium tetrakis (3 At least one selected from the group consisting of 5-trifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (3,5-trifluoromethylphenyl) borate and trityltetrakis (3,5-trifluoromethylphenyl) borate The manufacturing method as described in any one of Claims 1-4 which is a seed | species.