JP2014159391A - Method for producing alpha-olefin low polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an α-olefin low polymer by a low polymerization reaction of α-olefin, particularly, a method for producing 1-hexene by a trimerization reaction of ethylene, in which method the selectivity of an objective product can be made higher than before and which method is made industrially advantageous.SOLUTION: The method for producing the α-olefin low polymer comprises the steps of: performing the low polymerization reaction of α-olefin being a raw material in a solvent in the presence of a catalyst, which comprises a transition metal-containing compound-derived component, an aluminum-containing compound-derived component and a halogen-containing compound-derived component at the least, to obtain the α-olefin low polymer being a reaction product; and forcing a compound shown by general formula (I) to exist in the solvent together with the catalyst before the step of performing the low polymerization reaction is carried out so that a molar ratio of the compound shown by general formula (I) to the amount of a transition metal-containing compound in the transition metal-containing compound-derived component is set within a range equal to or larger than 20 and smaller than 200.

Description

  The present invention relates to a method for obtaining an α-olefin low polymer by subjecting α-olefin to a low polymerization reaction in a solvent in the presence of a catalyst, and more specifically, a raw material ethylene is subjected to a low polymerization reaction to produce 1-hexene. On how to get.

  α-Olefin low polymer is a useful substance widely used as a raw material for olefin polymer monomers, as a comonomer for various polymers, and as a raw material for plasticizers, surfactants, lubricating oils and the like. is there. Among these, 1-hexene that can be obtained by a low polymerization reaction using ethylene as a raw material is known to be useful as a raw material for linear low-density polyethylene.

  Usually, a low polymer of an α-olefin is produced by a method in which a α-olefin is subjected to a low polymerization reaction in the presence of a solvent using a catalyst, particularly a homogeneous catalyst. For example, when 1-hexene is produced by a trimerization reaction of ethylene, various catalyst systems including transition metal-containing compounds, aluminum-containing compounds, and halogen-containing compounds have been conventionally studied as catalyst constituents. . Among them, as a transition metal-containing compound, a catalyst system using a chromium-containing compound (chromium-based catalyst) is known as a catalyst that is highly active and can obtain 1-hexene with high selectivity in the trimerization reaction of ethylene. Yes. It is known that the halogen-containing compound used as one of the components of this catalyst system contributes to the improvement of the catalytic activity and the selectivity of the reaction product, and various halogen-containing compounds have been studied. For example, Patent Document 1 describes that an inorganic or organic halogen compound can be used as the halogen-containing compound, and Patent Document 2 discloses an organic halide such as 2-fluoro-6-chlorobenzotrichloride. Are exemplified as effective halogen-containing compounds. Further, Patent Document 3 exemplifies halides of linear hydrocarbons as halogen-containing compounds. Patent Document 4 describes that when 1-hexene is produced by trimerizing ethylene using a chromium-based catalyst, an organic halide is contained in the 1-hexene. Halides are by-produced by decomposition products of halogen-containing compounds used in chromium-based catalysts, and examples include unsaturated organic halides.

JP-A-6-239920 Chinese Patent No. 1256968 Specification JP-A-8-134131 JP 2008-179801 A

In producing an α-olefin low polymer such as 1-hexene using α-olefin such as ethylene as a raw material on an industrial scale, further improvement in selectivity of 1-hexene is desired. The halogen-containing compound used in the chromium-based catalyst described in 4 has a problem that the selectivity cannot be sufficiently improved.
In view of the above-mentioned problems, the present invention provides a method for producing an α-olefin low polymer by a low polymerization reaction of α-olefin, particularly a method for producing 1-hexene by a trimerization reaction of ethylene, which has a higher target product than before. An object of the present invention is to provide an industrially advantageous method for producing an α-olefin low polymer that can achieve selectivity.

  As a result of intensive studies to solve the above problems, the present inventors have determined that halogens having a specific structure that is different from conventional halogen-containing compounds as halogen-containing compounds as catalyst components in homogeneous catalysts, particularly chromium-based catalysts. The present inventors have found that the selectivity of the target product can be improved by carrying out the reaction in the presence of a catalyst containing a compound together with a catalyst in the reaction system, thereby completing the present invention. That is, the gist of the present invention resides in the following [1] to [5].

  [1] A reaction product obtained by performing a low polymerization reaction of a raw material α-olefin in a solvent in the presence of a catalyst composed of components derived from at least a transition metal-containing compound, an aluminum-containing compound, and a halogen-containing compound. When the α-olefin low polymer is obtained, the compound represented by the following general formula (I) is present together with the catalyst, and the compound represented by the following general formula (I) is added to the amount of the transition metal-containing compound. The manufacturing method of the alpha-olefin low polymer whose molar ratio is the range of 20-200.

(In the above formula (I), X represents a halogen atom. R _{1 to} R ₃ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group which may have a substituent. R ₁ and R ₂ , R ₂ and R ₃ may be linked to each other to form a ring, provided that the compound represented by the above formula (I) is different from the halogen-containing compound.
[2] The method for producing an α-olefin low polymer according to [1], wherein the catalyst further contains a nitrogen-containing compound as a constituent component.

[3] The method for producing an α-olefin low polymer as described in [1] or [2], wherein the halogen atom in the general formula (I) is chlorine.
[4] The method for producing an α-olefin low polymer according to any one of [1] to [3], wherein the transition metal of the transition metal-containing compound is chromium.
[5] The method for producing an α-olefin low polymer according to any one of [1] to [4], wherein the α-olefin is ethylene and the α-olefin low polymer is 1-hexene.

  According to the present invention, in producing an α-olefin low polymer by a low polymerization reaction of α-olefin, the selectivity of the α-olefin low polymer can be improved.

It is a figure explaining the example of a manufacture flow of the alpha olefin low polymer (1-hexene) in this Embodiment.

The best mode for carrying out the present invention (hereinafter, an embodiment of the present invention) will be described in detail below. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention.
(catalyst)
The catalyst used in the present invention is not particularly limited as long as the raw material α-olefin can be subjected to a low polymerization reaction to produce an α-olefin low polymer, but at least a transition metal-containing compound, an aluminum-containing compound, and a halogen-containing compound. Is used as a constituent component of the catalyst, and refers to a catalyst system composed of components derived from these compounds. Moreover, it is more preferable to contain a nitrogen-containing compound as a constituent component of the catalyst from the viewpoint of improving the catalytic activity.

(Transition metal-containing compounds)
In the method for producing an α-olefin low polymer of the present invention, the metal contained in the transition metal-containing compound used as a catalyst is not particularly limited as long as it is a transition metal, but among them, transitions in Groups 4 to 6 of the periodic table Metal is preferably used. Specifically, it is preferably at least one metal selected from the group consisting of chromium, titanium, zirconium, vanadium and hafnium, more preferably chromium or titanium, and most preferably chromium.

In the present invention, the transition metal-containing compound used as a raw material for the catalyst is at least one compound represented by the general formula MEZ _n. Here, in the general formula, Me is a transition metal element, Z is any organic group, inorganic group, or negative atom, n is an integer of 1 to 6, and 2 or more is preferable. When n is 2 or more, Z may be the same or different from each other. The organic group may be a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and specifically includes a carbonyl group, an alkoxy group, a carboxyl group, a β-diketonate group, a β-keto. Examples include a carboxyl group, a β-ketoester group, an amide group, and the like. In addition, examples of the inorganic group include metal salt forming groups such as a nitrate group and a sulfate group. Examples of negative atoms include oxygen and halogen. In addition, the transition metal containing compound containing a halogen is not contained in the halogen containing compound mentioned later.

In the case of a transition metal-containing compound whose transition metal is chromium (hereinafter sometimes referred to as a chromium-containing compound), specific examples include chromium (IV) -tert-butoxide, chromium (III) acetylacetonate, chromium (III ) Trifluoroacetylacetonate, chromium (III) hexafluoroacetylacetonate, chromium (III) (2,2,6,6-tetramethyl-3,5-heptanedionate), Cr (PhCOCHCOPh) ₃ (where Ph represents a phenyl group.), Chromium (II) acetate, chromium (III) acetate, chromium (III) 2-ethylhexanoate, chromium (III) benzoate, chromium (III) naphthenate, chromium (III) _{heptanoate, Cr (CH 3 COCHCOOCH 3)} 3, a first chromium chloride, chromic chloride, bromide first click Arm, bromide chromic, first chromium iodide, chromic iodide, first chromium fluoride, and the second chromium fluoride.

In the case of a transition metal-containing compound in which the transition metal is titanium (hereinafter sometimes referred to as a titanium-containing compound), specific examples include TiCl ₄ , TiBr ₄ , TiI ₄ , TiBrCl ₃ , TiBr ₂ Cl ₂ , Ti (OC _{2 H 5) 4, Ti (} OC 2 H 5) 2 Cl 2, Ti (O-n-C 3 H 7) 4, Ti (O-n-C 3 H 7) 2 Cl 2, Ti (O-iso -C ₃ H _{7) 4,
Ti (O-iso-C 3} H 7) 2 Cl 2, Ti (O-n-C 4 H 9) 4, Ti (O-n-C 4 H 9) 2 Cl 2, Ti (O-iso-C _{4 H 9) 4, Ti (} O-iso-C 4 H 9) 2 Cl 2, Ti (O-tert-C 4 H 9) 4, Ti (O-tert-C 4 H 9) 2 Cl 2, TiCl ₄ (thf) ₂ (wherein thf represents tetrahydrofuran), Ti ((CH ₃ ) ₂ N) ₄ , Ti ((C ₂ H ₅ ) ₂ N) ₄ , Ti ((n-C ₃ H ₇ ) ₂ N) ₄ , Ti ((iso-C ₃ H ₇ ) ₂ N) ₄ , Ti ((n-C ₄ H ₉ ) ₂ N) ₄ , Ti ((tert-C ₄ H ₉ ) ₂ N) ₄ , Ti (OSO ₃ CH ₃ ) ₄ , Ti (OSO ₃ C ₂ H ₅ ) ₄ , Ti (OSO ₃ C ₃ H ₇ ) ₄ , Ti (OSO ₃ C ₄ H ₉ ) ₄ , TiCp ₂ Cl ₂ , T
iCp ₂ ClBr, Ti (OCOC ₂ H ₅ ) ₄ , Ti (OCOC ₂ H ₅ ) ₂ Cl ₂ , Ti
(OCOC ₃ H ₇ ) ₄ , Ti (OCOC ₃ H ₇ ) ₂ Cl ₂ , Ti (OCOC ₃ H ₇ ) ₄ , Ti (OCOC ₃ H ₇ ) ₂ Cl ₂ , Ti (OCOC ₄ H ₉ ) ₄ , Ti ( OCOC ₄ H ₉ ) ₂ Cl _{2 and the} like.

In the case of a transition metal-containing compound in which the transition metal is zirconium (hereinafter, sometimes referred to as a zirconium-containing compound), specific examples include ZrCl ₄ , ZrBr ₄ , ZrI ₄ , ZrBrCl ₃ , ZrBr ₂ Cl ₂ , Zr (OC _{2 H 5) 4, Zr (} OC 2 H 5) 2 Cl 2, Zr (O-n-C 3 H 7) 4, Zr (O-n-C 3 H 7) 2 Cl 2, Zr (O-iso _{-C 3 H 7) 4, Zr} (O-iso-C 3 H 7) 2 Cl 2, Zr (O-n-C 4 H 9) 4, Zr (O-n-C 4 H 9) 2 Cl 2 , Zr (O-iso-C ₄ H ₉ ) ₄ , Zr (O-iso-C ₄ H ₉ ) ₂ Cl ₂ , Zr (O-tert-C ₄ H ₉ ) ₄ , Zr (O-tert-C ₄ H ₉ ) ₂ Cl ₂ , Zr ((CH ₃ ) ₂ N) ₄ , Zr ((C ₂ H ₅ ) ₂ N) ₄ , Zr ((n
_{-C 3 H 7) 2 N)} 4, Zr ((iso-C 3 H 7) 2 N) 4, Zr ((n-C 4 H 9) 2 N) 4, Zr ((tert-C 4 H 9 ) ₂ N) ₄ , Zr (OSO ₃ CH ₃ ) ₄ , Zr (OSO ₃ C ₂ H ₅ ) ₄ , Zr (OSO ₃ C ₃ H ₇ ) ₄ , Zr (OSO ₃ C ₄ H ₉ ) ₄ , Z
rCp ₂ Cl ₂ , ZrCp ₂ ClBr, Zr (OCOC ₂ H ₅ ) ₄ , Zr (OCOC ₂ H ₅ ) ₂ Cl ₂ , Zr (OCOC ₃ H ₇ ) ₄ , Zr (OCOC ₃ H ₇ ) ₂ Cl ₂ , Zr (OCOC ₃ H ₇ ) ₄ , Zr (OCOC ₃ H ₇ ) ₂ Cl ₂ , Zr (OCOC ₄ H ₉ ) ₄ , Zr
(OCOC ₄ H ₉ ) ₂ Cl ₂ , ZrCl ₂ (HCOCFCOF) ₂ , ZrCl ₂ (CH ₃
COCFCOCH ₃ ) _{2 and the} like.

In the case of a transition metal-containing compound whose transition metal is hafnium (hereinafter sometimes referred to as a hafnium-containing compound), a specific example is dimethylsilylene bis {1- (2-methyl-4-isopropyl-4H-azurenyl)}. Hafnium dichloride, dimethylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} hafnium dichloride, dimethylsilylenebis [1- {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] Hafnium dichloride, dimethylsilylenebis [1- {2-methyl-4- (4-fluorophenyl) -4H-azurenyl}] hafnium dichloride, dimethylsilylenebis [1- {2-methyl-4- (3-chlorophenyl)- 4H-azulenyl}] hafnium dichloride, dimethylsilylene bis [1 {2-Methyl-4- (2,6-dimethylphenyl) -4H-azurenyl}] hafnium dichloride, dimethylsilylenebis {1- (2-methyl-4,6-diisopropyl-4H-azurenyl)} hafnium dichloride, diphenyl Silylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} hafnium dichloride, methylphenylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} hafnium dichloride, methylphenylsilylenebis [1- {2-Methyl-4- (1-naphthyl) -4H-azurenyl}] hafnium dichloride, dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-azurenyl)} hafnium dichloride, dimethylsilylenebis [1- {2-ethyl-4- (1-anthraceni ) -4H-azurenyl}] hafnium dichloride, dimethylsilylenebis [1- {2-ethyl-4- (2-anthracenyl) -4H-azurenyl}] hafnium dichloride, dimethylsilylenebis [1- {2-ethyl-4- (9-phenanthryl) -4H-azurenyl}] hafnium dichloride, dimethylmethylenebis [1- {2-methyl-4- (4-biphenylyl) -4H-azurenyl}] hafnium dichloride, dimethylgermylenebis [1- {2 -Methyl-4- (4-biphenylyl) -4H-azurenyl}] hafnium dichloride, dimethylsilylenebis {1- (2-ethyl-4- (3,5-dimethyl-4-trimethylsilylphenyl-4H-azurenyl)} hafnium Dichloride, dimethylsilyl 2 [1- {2-methyl-4- (4 -Biphenylyl) -4H-azurenyl}] [1- {2-methyl-4- (4-biphenylyl) indenyl}] hafnium dichloride, dimethylsilylene {1- (2-ethyl-4-phenyl-4H-azurenyl)} { 1- (2-methyl-4,5-benzoindenyl)} hafnium dichloride, dimethylsilylenebis {1- (2-methyl-4-phenylindenyl)} hafnium dichloride, dimethylsilylenebis {1- (2-methyl) -4,5-benzoindenyl)} hafnium dichloride, dimethylsilylene bis [1- {2-methyl-4- (1-naphthyl) indenyl}] hafnium dichloride, and the like.
Among these transition metal-containing compounds, chromium-containing compounds are preferable, and among chromium-containing compounds, chromium (III) 2-ethylhexanoate is particularly preferable.

(Α-olefin)
In the method for producing an α-olefin low polymer to which the present embodiment is applied, examples of the α-olefin used as a raw material include substituted or unsubstituted α-olefins having 2 to 30 carbon atoms. Specific examples of such α-olefins include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene and the like. Among these, ethylene is suitable as the α-olefin of the raw material of the present invention. When ethylene is used as the raw material, 1-hexene, which is a trimer of ethylene, can be obtained with high yield and high selectivity.

  Moreover, when using ethylene as a raw material, impurity components other than ethylene may be included in the raw material. Specific components include methane, ethane, nitrogen, acetylene, carbon dioxide, carbon monoxide, oxygen, sulfur content, moisture, and the like. Although it does not specifically limit about methane, ethane, and nitrogen, It is preferable that it is 0.1 mol% or less with respect to ethylene of a raw material, and other impurities are 1 molppm or less with respect to ethylene of a raw material.

(solvent)
In the method for producing an α-olefin low polymer of the present invention, the α-olefin low polymerization reaction can be carried out in a solvent. Although it does not specifically limit as such a solvent, A saturated hydrocarbon is used suitably, Preferably, for example, butane, pentane, 3-methylpentane, n-hexane, n-heptane, 2-methylhexane, octane, It is a chain saturated hydrocarbon having 1 to 20 carbon atoms such as cyclohexane, methylcyclohexane, 2,2,4-trimethylpentane, decalin, or an alicyclic saturated hydrocarbon having 1 to 20 carbon atoms. In addition, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, mesitylene, and tetralin may be used as a solvent for the α-olefin low polymer. Furthermore, 1-hexene, decene and the like produced by low polymerization reaction of α-olefin can be used as a reaction solvent. These can be used alone or as a mixed solvent.
Among these solvents, chain saturated hydrocarbons having 4 to 10 carbon atoms from the point that production or precipitation of by-products such as polyethylene can be suppressed, and further high catalytic activity tends to be obtained. It is preferable to use an alicyclic saturated hydrocarbon. Specifically, n-heptane or cyclohexane is preferable, and n-heptane is most preferable.

(Aluminum-containing compound)
Examples of the aluminum-containing compound used in the present invention include a trialkylaluminum compound, an alkoxyalkylaluminum compound, and an alkylaluminum hydride compound. Examples of the trialkylaluminum compound include trimethylaluminum, triethylaluminum, and triisobutylaluminum. Specific examples of the alkoxyaluminum compound include diethylaluminum ethoxide. Specific examples of the alkylaluminum hydride compound include diethylaluminum hydride. Among these, trialkylaluminum compounds are preferable, and triethylaluminum is more preferable. These compounds may be used as a single compound or as a mixture of a plurality of compounds.

(Halogen-containing compounds)
In the present invention, the halogen-containing compound includes a halogenated alkylaluminum compound, a benzyl chloride skeleton-containing compound, a linear halogenated hydrocarbon having 1 or more carbon atoms having 3 or more halogen atoms, and 3 or more halogen atoms. Examples thereof include one or more cyclic halogenated hydrocarbon compounds having 3 or more carbon atoms (the halogenated alkylaluminum compound is not included in the aluminum-containing compound). For example, diethylaluminum chloride, ethylaluminum sesquichloride, benzyl chloride, (1-chloroethyl) benzene, 2-methylbenzyl chloride, 3-methylbenzyl chloride, 4-methylbenzyl chloride, 4-ethylbenzyl chloride, 4-isopropylbenzyl chloride 4-tert-butylbenzyl chloride, 4-vinylbenzyl chloride, α-ethyl-4-methylbenzyl chloride, α, α′-dichloro-o-xylene, α, α′-dichloro-m-xylene, α, α '-Dichloro-p-xylene, 2,4-dimethylbenzyl chloride, 2,5-dimethylbenzyl chloride, 2,6-dimethylbenzyl chloride, 3,4-dimethylbenzyl chloride, 2,3,5,6-tetramethyl Benzyl chloride, 1- (chloromethyl) ) Naphthalene, 1- (chloromethyl) -2-methylnaphthalene, 1,4-bis-chloromethyl-2,3-dimethylnaphthalene, 1,8-bis-chloromethyl-2,3,4,5,6 7-hexamethylnaphthalene, 9- (chloromethyl) anthracene, 9,10-bis (chloromethyl) anthracene, 7- (chloromethyl) benzanthracene, 7-chloromethyl-12-methylbenzanthracene, carbon tetrachloride, 1 , 1,1-trichloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, hexachloroethane, 1,2,3-trichlorocyclopropane, 1,2,3,4,5,6-hexachlorocyclohexane, , 4-bis (trichloromethyl) -2,3,5,6-tetrachlorobenzene and the like. However, the halogen-containing compound of the present invention does not include a compound represented by the following general formula (I).

(Nitrogen-containing compounds)
In the present invention, in addition to the above transition metal-containing compound, aluminum-containing compound, and halogen-containing compound, it is preferable to further contain a nitrogen-containing compound as a catalyst component. In the present invention, examples of the nitrogen-containing compound include amines, amides, and imides. Examples of amines include pyrrole compounds. Specific examples include pyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, 2,5-diethylpyrrole, 2,4-diethylpyrrole, 2,5. -Di-n-propyl pyrrole, 2,5-di-n-butyl pyrrole, 2,
5-di-n-pentylpyrrole, 2,5-di-n-hexylpyrrole, 2,5-dibenzylpyrrole, 2,5-diisopropylpyrrole, 2-methyl-5-ethylpyrrole, 2,5-dimethyl- 3-ethylpyrrole, 3,4-dimethylpyrrole, 3,4-dichloropyrrole, 2,3,4,5-tetrachloropyrrole, 2-acetylpyrrole, indole, 2-methylindole, two pyrrole rings are substituents Pyrrole such as dipyrrole or a derivative thereof bonded through a benzene. Examples of the derivatives include metal pyrolide derivatives, and specific examples include, for example, diethylaluminum pyrolide, ethylaluminum dipyrrolide, aluminum tripyrolide, diethylaluminum (2,5-dimethylpyrrolide), ethylaluminum. Bis (2,5-dimethyl pyrolide), aluminum tris (2,5-dimethyl pyrolide), diethyl aluminum (2,5-diethyl pyrolide), ethyl aluminum bis (2,5-diethyl pyrolide), aluminum tris Aluminum pyrolides such as (2,5-diethyl pyrolide), sodium pyrolide, sodium pyrolides such as sodium (2,5-dimethyl pyrolide), lithium pyrolide, lithium (2,5-dimethyl pyrolide) ) Etc. Umupiroraido acids, potassium pyrrolide, potassium (2,5-dimethyl pyrrolide) potassium pyrrolide such like. Aluminum pyrolides are not included in the above-mentioned aluminum-containing compound. Moreover, the pyrrole compound containing a halogen is not contained in the above-mentioned halogen-containing compound.

Examples of amides include, for example, acetamide, N-methylhexaneamide, succinamide, maleamide, N-methylbenzamide, imidazole-2-carboxamide, di-2-thenoylamine, β-lactam, δ-lactam, ε-caprolactam or Examples thereof include salts of these with metals of Group 1, 2 or 13 of the periodic table.
Examples of the imides include 1,2-cyclohexanedicarboximide, succinimide, phthalimide, maleimide, 2,4,6-piperidinetrione, perhydroazesin-2,10-dione, and 1 of the periodic table, And salts with Group 2 or 13 metals. Examples of the sulfonamides and sulfonamides include, for example, benzenesulfonamide, N-methylmethanesulfonamide, N-methyltrifluoromethylsulfonamide, and salts thereof with a metal of Groups 1 to 2 or 13 in the periodic table. Is mentioned. These compounds may be used as a single compound or a plurality of compounds.
In the present invention, among these, amines are preferable, among which pyrrole compounds are more preferable, and 2,5-dimethylpyrrole or diethylaluminum (2,5-dimethylpyrrolide) is particularly preferable.

(Pre-catalyst preparation)
In the present invention, the catalyst used for the low polymerization reaction is preferably such that the transition metal-containing compound and the aluminum-containing compound do not contact each other in advance, or the raw material α-olefin and the catalyst are contacted in such a manner that the contact time is short. . By such a contact mode, a low polymerization reaction of the raw material α-olefin can be selectively performed, and a low polymer of the raw material α-olefin can be obtained in a high yield. In the present invention, “an aspect in which the transition metal-containing compound and the aluminum-containing compound do not contact with each other in advance or the contact time is short in advance” refers not only to the start of the reaction but also to the raw material α-olefin and each catalyst thereafter. This means that the above-described embodiment is maintained even when the components are additionally supplied to the reactor. However, the specific embodiments described above are preferred embodiments required during catalyst preparation and are irrelevant after the catalyst is prepared. Therefore, when the catalyst already prepared is recovered from the reaction system and reused, the catalyst can be reused regardless of the above preferred embodiment.

The reason why the activity of the low polymerization reaction of the α-olefin is low when the catalyst is used in such a manner that the transition metal-containing compound and the alkylaluminum compound are in contact with each other is not yet clear, but is estimated as follows.
That is, when the transition metal-containing compound is brought into contact with the alkylaluminum, a ligand exchange reaction proceeds between the ligand coordinated to the transition metal-containing compound and the alkyl group in the alkylaluminum compound, It is considered unstable. Therefore, the decomposition-reduction reaction of the alkyl-transition metal-containing compound proceeds preferentially. As a result, metalization inappropriate for the low polymerization reaction of α-olefin occurs, and the activity of the low polymerization reaction of α-olefin decreases. .

Therefore, when the catalyst is, for example, the above four components, that is, the transition metal-containing compound (a), the nitrogen-containing compound (b), the aluminum-containing compound (c), and the halogen-containing compound (d), The embodiment usually comprises (1) a method of introducing the catalyst component (a) into a solution containing the catalyst components (b), (c) and (d), (2) the catalyst components (a), (b) and ( a method of introducing the catalyst component (c) into the solution containing d), (3) a method of introducing the catalyst components (b) and (c) into the solution containing the catalyst components (a) and (d), (4) ) A method of introducing the catalyst components (a) and (b) into the solution containing the catalyst components (c) and (d); (5) the catalyst component (c) in the solution containing the catalyst components (a) and (b); ) And (d), (6) catalyst components (a) and (d) in a solution containing catalyst components (b) and (c) ), (7) a method of introducing the catalyst components (a), (b) and (d) into the solution containing the catalyst component (c), and (8) a solution containing the catalyst component (a). The catalyst components (b) to (d) are introduced, and (9) the catalyst components (a) to (d) are introduced into the reactor simultaneously and independently. And each said solution is normally prepared using the solvent used for reaction.
The present invention is characterized in that a compound represented by the following general formula (I) is present together with the above-mentioned catalyst in a reaction system in which an α-olefin low polymer is produced.

(In the above formula (I), X represents a halogen atom. R _{1 to} R ₃ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group which may have a substituent. R ₁ and R ₂ , R ₂ and R ₃ may be linked to each other to form a ring, provided that the compound represented by the above formula (I) is different from the structure of the halogen-containing compound.
When the compound represented by the above formula (I) is present in the reaction system together with the above catalyst system, the reason why the selectivity of the target product is improved is not clear, but the following reason is presumed.

In general, it is known that a catalyst catalyst for olefin polymerization includes a multi-site catalyst having many active sites and a single-site catalyst. In the multisite catalyst, polymers having various molecular weights are generated from each active site and the composition distribution is widened. However, in the single site catalyst, a polymer having a target molecular weight is generated and the composition distribution is narrowed. In the present reaction system, the above compounds that can be constituent components of the catalyst are mixed to form a homogeneous catalyst in a solvent. The catalyst formed at this time is highly selective for the desired α-olefin low polymer. Catalyst with the ability to produce
) And a catalyst (B) that produces α-olefin low polymers of various molecular weights. Since this catalyst (B) produces many low polymers other than the target low polymerization in the low polymerization reaction of the raw material α-olefin, the presence of the catalyst (B) reduces the selectivity of the target low polymer. . The compound represented by the above formula (I) is bonded to the catalyst (B) more strongly than the catalyst (A), thereby reducing the function of the catalyst (B) as a catalyst. It is considered that the formation of a low polymer is suppressed, and as a result, the selectivity of the target low polymer is improved.

  In the present invention, the molar ratio of the compound represented by the general formula (I) to the transition metal-containing compound is 20 or more and less than 200, preferably 20 or more and 150 or less, and more preferably 20 or more and 100 or less. When this molar ratio is supplied to the reaction system together with a compound that is a component constituting the catalyst, or after the reaction, the solvent containing the catalyst system is recycled and supplied again to the reaction system for use. In the purification step of the process, it can be adjusted by adjusting the reflux ratio of the distillation column to be used, separating it from the solvent, and reducing the supply amount.

The compound represented by the general formula (I) has a structure different from that of the above-described halogen-containing compound, and the halogen-containing compound used as a constituent component of the catalyst is decomposed in the reaction system and other components (raw materials) By-products produced by reaction with α-olefins).
X in the above formula (I) represents a halogen atom, and specific examples include chlorine, bromine, fluorine, or iodine, preferably chlorine or bromine, and most preferably chlorine.

R _{1 to} R ₃ in the above formula (I) may be the same as or different from each other, and are not particularly limited, but each may independently have a hydrogen atom, a halogen atom, or a substituent. It is a hydrocarbon group. Examples of the hydrocarbon group which may have a substituent include an alkyl group, a cycloalkyl group, a halogenated alkyl group, an allyl group, an aryl group, and a vinyl group, preferably an alkyl group, more preferably , A linear or branched alkyl group having 1 to 10 carbon atoms. Further, when R _{1 to} R ₃ are hydrocarbon groups, they may have a substituent on any carbon atom as long as the effects of the present invention are not significantly impaired. Groups, cycloalkyl groups, or aryl groups. R ₁ and R ₂ , R ₂ and R ₃ may be connected to each other to form a ring.

Specific examples of the halogen additive in which X in the formula (I) is chlorine include tetrachloroethylene, trichloroethylene, 1,2-dichloroethylene, vinyl chloride, 1,3-dichloropropene, 2,3-dichloro-1-propene, 2-chloropropene, 1-chloro-2-methylpropene, hexachloropropene, tetrachlorocyclopropene, 2-chloro-3-methylene-1,4-pentadiene, 3,3-difluorohexachloro-1,4-pentadiene, 1 -Chlorocyclohexene and the like. Tetrachloroethylene and 1,2-dichloroethylene are preferable.

Specific examples of the aromatic halogen-containing compound in which X in the formula (I) is bromine include 1,2-
Examples thereof include dibromoethylene, vinyl bromide, 2-bromo-3,3,3-trifluoropropene.
Specific examples of the aromatic halogen-containing compound in which X in the formula (I) is fluorine or iodine include 1,1-difluoroethylene, vinyl fluoride, vinyl iodide, hexafluoropropene and the like.

(Low polymerization reaction conditions)
Although the ratio of each structural component of the catalyst used in the present invention is not particularly limited, the halogen-containing compound is usually 1 to 50 mol, preferably 1 to 30 mol, per 1 mol of the transition metal-containing compound. Alternatively, when a nitrogen-containing compound or an aluminum-containing compound is included, the nitrogen-containing compound is 1 mol to 50 mol, preferably 1 mol to 30 mol, per 1 mol of the transition metal-containing compound.
The aluminum-containing compound is 1 mol to 200 mol, preferably 10 mol to 150 mol.

In the present invention, the amount of the catalyst used is not particularly limited, but is usually 1.0 × 10 ⁻⁹ mol to 0.5 mol, preferably 5.0 per liter of solvent and per atom of transition metal of the transition metal-containing compound. × 10 ⁻⁹ mol to 0.2 mol, more preferably 1.0 × 10 ⁻⁸ mol to 0.05 mol.
By using such a catalyst, for example, when ethylene is used as a raw material, hexene that is a trimer of ethylene can be obtained with a selectivity of 90% or more. Further, in this case, the ratio of 1-hexene to hexene can be 99% or more.

In this invention, although it does not specifically limit as reaction temperature, Usually, it is 0-250 degreeC, Preferably it is 50-200 degreeC, More preferably, it is 80-170 degreeC.
The reaction pressure is not particularly limited, but is usually from normal pressure to 250 kgf / cm ² , preferably from 5 to 150 kgf / cm ² , and more preferably from 10 to 100 kgf / cm ² .
In the present invention, the residence time in the reactor is not particularly limited, but is usually in the range of 1 minute to 10 hours, preferably 3 minutes to 3 hours, and more preferably 5 minutes to 40 minutes.
Although the reaction form of this invention is not specifically limited, Any of a batch type, a semibatch type, or a continuous type may be sufficient.

(Production method of α-olefin low polymer)
The α-olefin low polymer in the present invention means an oligomer in which several α-olefins as monomers are bonded. Specifically, it is a polymer in which 2 to 10 α-olefins as monomers are bonded.
Next, a method for producing an α-olefin low polymer will be described using ethylene as an α-olefin and taking as an example low polymerization to 1-hexene which is a trimer of ethylene as an α-olefin low polymer.
FIG. 1 is a diagram for explaining an example of a production flow of an α-olefin low polymer in the present embodiment.

  In the example of the production flow of 1-hexene using ethylene as a raw material shown in FIG. 1, a completely mixed stirring type reactor 10 for polymerizing ethylene in the presence of a catalyst and an unreacted reaction liquid extracted from the reactor 10 Degassing tank 20 for separating ethylene gas, ethylene separation tower 30 for distilling off ethylene in the reaction liquid extracted from degassing tank 20, and high boiling point in the reaction liquid extracted from ethylene separation tower 30 The high boiling separation tower 40 for separating the substances (hereinafter sometimes referred to as HB (high boiler)) and the reaction liquid extracted from the top of the high boiling separation tower 40 are distilled to store 1-hexene. A hexene separation column 50 is shown. Further, a compressor 17 is provided for circulating unreacted ethylene separated in the degassing tank 20 and the condenser 16 to the reactor 10 through a circulation pipe 21.

In FIG. 1, as the reactor 10, for example, a conventionally well-known type equipped with a stirrer 10a, a baffle, a jacket and the like can be mentioned. As the stirrer 10a, a stirring blade in the form of a paddle, a fiddler, a propeller, a turbine, or the like is used in combination with a baffle such as a flat plate, a cylinder, or a hairpin coil.
As shown in FIG. 1, ethylene is continuously supplied to the reactor 10 from the ethylene supply pipe 12 a through the compressor 17 and the first supply pipe 12. Here, when the compressor 17 is, for example, a two-stage compression system, the electricity cost can be reduced by connecting the circulation pipe 31 to the first stage and connecting the circulation pipe 21 to the second stage. A solvent used for the low polymerization reaction of ethylene is supplied to the reactor 10 from the second supply pipe 13.

  On the other hand, the transition metal-containing compound and the nitrogen-containing compound prepared in advance in the catalyst tank 1c are supplied from the second supply pipe 13 to the reactor 10 through the catalyst supply pipe 13a, and the aluminum-containing compound is supplied from the third supply pipe 14. Is supplied, and the halogen-containing compound is supplied from the fourth supply pipe 15. Here, the halogen-containing compound may be supplied to the reactor 10 from the second supply pipe 13 via the supply pipe. Moreover, if the contact time with the transition metal-containing compound is also supplied to the reactor 10 within a few minutes, the aluminum-containing compound may be supplied to the reactor 10 from the second supply pipe 13 via the supply pipe. . In this method, if a static mixer or the like is installed between the second supply pipe 13 and the reactor 10, a homogeneous mixed solution of each catalyst component can be supplied to the reactor 10. Reduced. In addition, as a method for causing the compound represented by the above general formula (I) to exist in the reactor, it is supplied together with the compound as a constituent component of the catalyst from the catalyst supply pipe 13a, the third supply pipe 14, the fourth supply pipe 15, and the like. do it. In addition, the compound represented by the above general formula (I) distilled from the reactor is separated from the solvent by a distillation column in the rear system of the reactor. When the solvent is withdrawn from the bottom of the hexene separation tower 50 and the solvent is circulated and reused from the second supply pipe 13 to the reactor through the solvent circulation pipe 52, the second supply pipe may be used depending on the distillation conditions of the distillation tower. 13 also allows a part of the compound represented by the general formula (I) to be supplied to the reactor. Therefore, in continuous operation, in order to adjust the abundance of the compound represented by the general formula (I) in the reactor, the amount can be adjusted by adjusting the distillation conditions of each distillation column.

In this Embodiment, it does not specifically limit as reaction temperature in the reactor 10, Usually, 0 to 250 degreeC, Preferably it is 50 to 200 degreeC, More preferably, it is 80 to 170 degreeC.
As the reaction pressure is not particularly limited, usually, atmospheric pressure ~250kgf / cm ^{2, preferably, 5kgf / cm 2 ~150kgf / cm} 2, more preferably, 10 kgf
/ Cm ^{2 to} 100 kgf / cm ² .

  Furthermore, the trimerization reaction of ethylene is not particularly limited, but the molar ratio of 1-hexene to ethylene in the reaction solution ((molar concentration of 1-hexene in the reaction solution) / (molar concentration of ethylene in the reaction solution). ) Is preferably 0.05 to 1.5, particularly preferably 0.10 to 1.0. That is, in the case of continuous reaction, it is preferable to adjust the catalyst concentration, reaction pressure, and other conditions so that the molar ratio of ethylene to 1-hexene in the reaction solution falls within the above range. In the case of batch reaction, it is preferable to stop the ethylene trimerization reaction when the molar ratio is in the above range.

By performing the trimerization reaction of ethylene under such conditions, the by-product of a component having a boiling point higher than that of 1-hexene is suppressed, and the selectivity of 1-hexene tends to be further increased.
Next, the reaction solution continuously extracted from the bottom of the reactor 10 through the pipe 11 is stopped by the ethylene trimerization reaction by the quenching agent supplied from the quenching agent supply pipe 11a. It is supplied to the tank 20. In the degassing tank 20, unreacted ethylene is degassed from above and is circulated and supplied to the reactor 10 via the circulation pipe 21, the condenser 16, the compressor 17 and the first supply pipe 12. Further, the reaction liquid from which the unreacted ethylene has been degassed is extracted from the bottom of the degas tank 20. Although the operating conditions of the degassing tank 20 are not particularly limited, the temperature is usually 0 ° C. to 250 ° C., preferably 50 ° C. to 200 ° C., and the pressure is normal pressure to 150 kgf / cm ² , preferably normal pressure to 90 kgf / cm ² .

  Subsequently, the reaction liquid from which the unreacted ethylene has been degassed in the degassing tank 20 is extracted from the tank bottom of the degassing tank 20 and supplied to the ethylene separation tower 30 through the pipe 22. In the ethylene separation tower 30, ethylene is distilled from the top of the tower by distillation and is circulated and supplied to the reactor 10 through the circulation pipe 31 and the first supply pipe 12. Moreover, the reaction liquid from which ethylene has been removed is extracted from the bottom of the column.

Although the operating conditions of the ethylene separation tower 30 are not particularly limited, the pressure at the top of the tower is usually normal pressure to 30 kgf / cm ² , preferably normal pressure to 20 kgf / cm ² , and the reflux ratio (R / D) is Although it does not specifically limit, Usually, it is 0-500, Preferably, it is 0.1-100.
Next, the reaction liquid obtained by distilling ethylene in the ethylene separation tower 30 is extracted from the bottom of the ethylene separation tower 30 and supplied to the high boiling separation tower 40 through the pipe 32. In the high boiling separation tower 40, a high boiling point component (HB: high boiler) is extracted from the bottom of the tower. Moreover, the distillate from which the high boiling point component was separated by the pipe 42 is extracted from the tower top. Operating conditions of the high boiling separation column 40 is not particularly limited, usually, the top portion pressure ^{0.1kgf / cm 2 ~10kgf / cm 2} , ^{preferably, 0.5kgf / cm 2 ~5kgf / cm} 2, also, reflux The ratio (R / D) is not particularly limited, but is usually 0 to 100, preferably 0.1 to 20.

Subsequently, the reaction liquid extracted as a distillate from the top of the high boiling separation tower 40 is supplied to the hexene separation tower 50 through the pipe 41. In the hexene separation tower 50, 1-hexene obtained by distillation is distilled out from the top of the tower through a pipe 51. Further, heptane is extracted from the bottom of the hexene separation tower 50, bypassed to the solvent drum 60 through the solvent circulation pipe 52, and further circulated and supplied to the reactor 10 as the reaction solvent through the second supply pipe 13. The At this time, a nitrogen-containing compound, which is one of the catalyst components, is also circulated in the heptane solvent extracted from the bottom of the hexene separation column 50 and continuously supplied to the reactor 10 in the same manner as the heptane solvent. The vessel 10 may be continuously circulated. The concentration of the nitrogen-containing compound in the solvent to be circulated in a steady state is not particularly limited, but is preferably 5.0 wtppm or more. Operating conditions of the hexene separation column 50 is not particularly limited, usually, the top portion pressure ^{0.1kgf / cm 2 ~10kgf / cm 2} , ^{preferably, 0.5kgf / cm 2 ~5kgf / cm} 2, also, the reflux ratio (R / D) is usually 0 to 100, preferably 0.1 to 20.

Hereinafter, the present invention will be described more specifically based on examples. In addition, this invention is not limited to a following example, unless it deviates from the summary.
[Example 1]
In the production flow shown in FIG. 1, 1-hexene was produced by continuous low polymerization reaction of ethylene using ethylene as a raw material α-olefin. The production flow of FIG. 1 includes a completely mixed stirring type reactor 10 in which ethylene is low-polymerized in the presence of an n-heptane solvent and a catalyst, and a desorption that separates unreacted ethylene gas from the reaction liquid drawn from the reactor 10. Gas tank 20, ethylene separation tower 30 for distilling off ethylene in the reaction liquid extracted from degassing tank 20, high-boiling separation tower for separating high-boiling substances in the reaction liquid extracted from ethylene separation tower 30 40, and a hexene separation column 50 for distilling the reaction liquid extracted from the top of the high boiling separation column 40 and distilling 1-hexene. Further, the n-heptane solvent separated in the hexene separation tower 50 is directly circulated to the reactor 10 via the solvent circulation pipe 52 and the second supply pipe 13 without going through the solvent drum 60. Furthermore, unreacted ethylene separated in the degassing tank 20 and the condenser 16 is circulated to the reactor 10 via the circulation pipe 21 and the compressor 17.

  First, a solution of each component of the catalyst was supplied from a 0.2 MPaG nitrogen seal tank (not shown). From the catalyst supply pipe 13a, chromium (III) 2-ethylhexanoate (a) and 2,5-dimethylpyrrole (b) are 3.0 equivalents with respect to chromium (III) 2-ethylhexanoate (a). Then, it was continuously supplied to the reactor 10 through the second supply pipe 13. Triethylaluminum (c) was continuously supplied from the third supply pipe 14 to the reactor 10. Furthermore, hexachloroethane (d) was continuously supplied from the fourth supply pipe 15 to the reactor 10. The reaction conditions were a reactor internal temperature of 140 ° C. and a reactor internal pressure of 7.0 MPaG.

The reaction liquid continuously withdrawn from the reactor 10 is added with 2-ethylhexanol as a catalyst deactivator from the deactivator supply pipe 11a, and then sequentially, a degassing tank 20, an ethylene separation tower 30, a high boiling point. It processed in the separation tower 40 and the hexene separation tower 50.
The recovered n-heptane solvent separated in the hexene separation tower 50 was continuously supplied to the reactor 10 from the second supply pipe 13 by bypassing the solvent drum 60 (0.2 MPa nitrogen seal). At this time, the reflux ratio of the high boiling separation column 40 was 0.6. In addition, 2,5-dimethylpyrrole (b) was not completely separated in the high-boiling separation column, and part of it was recycled together with the recovered n-heptane solvent and fed again to the reactor. At this time, the concentration of 2,5-dimethylpyrrole (b) in the recovered n-heptane solvent was 10 wtppm.

  The ratio (molar ratio) of the catalyst components (a) to (d) in the reactor 10 in the steady state is (a) :( b) :( c) :( d) = 1: 20: 80. 5 and the molar ratio of perchlorethylene to chromium (III) 2-ethylhexanoate (a) was 20. This perchlorethylene was by-produced by decomposition of the halogen-containing compound and was present in the reactor.

  The C6 selectivity is determined by analyzing the composition of each of the circulating n-heptane solvent and the bottom liquid of the ethylene separation tower 30 by gas chromatography (manufactured by Shimadzu Corporation, GC-17AAF). Selectivity was calculated. The catalytic activity is the product weight (unit: g) produced in one hour per chromium atomic weight (unit: g) of the catalyst component supplied in one hour. The results are shown in Table-1.

[Example 2]
In Example 1, everything was performed in the same manner except that the molar ratio of perchlorethylene to chromium (III) 2-ethylhexanoate (a) was 53. The results are shown in Table-1.
[Comparative Example 1]
In Example 1, it carried out by the same method except having changed the molar ratio of perchlorethylene with respect to chromium (III) 2-ethylhexanoate (a) to 14. The results are shown in Table-1.

[Example 3]
In Example 1, the molar ratio of the catalyst components in the reactor 10 was (a) :( b) :( c) :( d) = 1: 20: 80: 4, chromium (III) 2-ethylhexano All were carried out in the same manner except that the molar ratio of perchlorethylene to ate (a) was 67. The results are shown in Table-1.
[Comparative Example 2]
In Example 3, everything was performed in the same manner except that the molar ratio of perchlorethylene to chromium (III) 2-ethylhexanoate (a) was 7. The results are shown in Table-1.

[Example 4]
To a glass three-necked flask having a 500 ml stirrer heated and dried at 140 ° C. for 2 hours or more, 0.37 g (3.9 mmol) of 2,5-dimethylpyrrole and 234 ml of n-heptane in a nitrogen atmosphere. Then, 8.91 ml (3.9 mmol) of triethylaluminum diluted to 50 g / L with n-heptane was added thereto. Thereafter, the flask was immersed in an oil bath, the temperature was raised, and n-heptane was refluxed at 98 ° C. for 3 hours in a nitrogen atmosphere to prepare aluminum pyrolide, which is a nitrogen-containing compound. Then, it cooled to 80 degreeC. Subsequently, 6.26 ml (0.65 mmol) of chromium 2-ethylhexanoate diluted to 50 g / L with n-heptane was added. After the addition, the catalyst solution was prepared by heating and stirring at 80 ° C. for 30 minutes in a nitrogen atmosphere.

  Next, a set of 500 ml autoclaves heated and dried at 140 ° C. for 2 hours or more was assembled while being heated, and vacuum nitrogen substitution was performed. The autoclave was fitted with a catalyst feed tube equipped with a pressure rupture disc. The feed tube was charged with 2 ml of the catalyst solution prepared in advance as described above. On the barrel side of the autoclave, 235 ml of n-heptane as a reaction solvent, 2 ml (0.52 mmol) of perchlorethylene diluted to 43 g / L with n-heptane and an internal standard for composition analysis by gas chromatography 5 ml of n-undecane to be used, 5.3 ml (0.31 mmol) of triethylaluminum diluted to 6.67 g / L with n-heptane, and 3 ml of hexachloroethane diluted to 2.76 g / L with n-heptane (0 0.031 mmol).

After heating the autoclave to 140 ° C., ethylene was introduced from the catalyst feed tube to initiate a low polymerization reaction of ethylene. During the reaction, the temperature in the autoclave was maintained at 140 ° C. and the total pressure was maintained at 7 MPaG.
After 60 minutes, ethanol was added to stop the reaction. Then, the reaction liquid and the reaction gas were sampled, and the respective compositions were analyzed by gas chromatography. Moreover, the polymer weight contained in the reaction liquid was measured after filtering and drying the reaction liquid. The catalytic activity was determined by dividing the mass (unit: g) of the reaction product obtained by the reaction for 60 minutes by the amount of transition catalyst metal atom (unit: g) in the transition metal catalyst component used in the reaction. The results are shown in Table-2.

[Comparative Example 3]
In Example 4, 233 ml of n-heptane charged to the barrel side of the autoclave was used, and all the procedures were the same except that perchlorethylene diluted to 43 g / L with n-heptane was not charged. The results are shown in Table-2.
[Comparative Example 4]
In Example 4, 231 ml of n-heptane charged to the barrel side of the autoclave was charged, and all operations were performed in the same manner except that 4 ml (1.04 mmol) of perchlorethylene diluted to 43 g / L with n-heptane was charged. . The results are shown in Table-2.

  From Tables 1 and 2, when the molar ratio of the chromium-containing compound and the perchlorethylene (the compound represented by the general formula (I)) in the reactor is in the range of 20 or more and less than 200, the catalytic activity is to some extent. It can be seen that the C6 selectivity and the 1-hexene content in C6 are improved while keeping.

10 ... reactor,
10a: stirrer,
11, 22, 32, 41, 42, 51 ... piping,
11a ... Deactivating agent supply pipe 12 ... First supply pipe,
12a ... ethylene supply piping,
13 ... second supply pipe,
13a ... catalyst supply piping,
14 ... Third supply piping,
15 ... Fourth supply pipe,
21, 31 ... circulation piping,
16 ... Condenser,
17 ... Compressor,
20 ... degassing tank,
30 ... ethylene separation tower,
40 ... high boiling separation tower,
50 ... hexene separation tower,
52. Solvent circulation piping,
60 ... solvent drum

Claims (5)

The reaction product α is obtained by performing a low polymerization reaction of the raw material α-olefin in a solvent in the presence of a catalyst composed of components derived from at least a transition metal-containing compound, an aluminum-containing compound, and a halogen-containing compound. -In obtaining the olefin low polymer, the compound represented by the following general formula (I) is present together with the catalyst, and the molar ratio of the compound represented by the following general formula (I) to the amount of the transition metal-containing compound is The manufacturing method of the alpha olefin low polymer which is the range of 20 or more and less than 200.

(In the above formula (I), X represents a halogen atom. R _{1 to} R ₃ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group which may have a substituent. R ₁ and R ₂ , R ₂ and R ₃ may be linked to each other to form a ring, provided that the compound represented by the above formula (I) is different from the halogen-containing compound.   The method for producing an α-olefin low polymer according to claim 1, wherein the catalyst further contains a nitrogen-containing compound as a constituent component.   The method for producing an α-olefin low polymer according to claim 1 or 2, wherein the halogen atom in the general formula (I) is chlorine.   The method for producing an α-olefin low polymer according to any one of claims 1 to 3, wherein the transition metal of the transition metal-containing compound is chromium. The method for producing an α-olefin low polymer according to any one of claims 1 to 4, wherein the α-olefin is ethylene and the α-olefin low polymer is 1-hexene.

Images