Catalyst for olefin oligomerization and method for producing olefin oligomers carried out in the presence of the catalyst

Abstract

To provide: an olefin multimerization catalyst having high production efficiency, which has high oligomer production activity and provides not only 1-hexene but also a significant amount of 1-octene; and a method for producing an olefin multimer performed in the presence of the olefin multimerization catalyst.SOLUTION: Provided are: a method for producing an olefin multimer, comprising performing an olefin multimerization reaction in the presence of an olefin multimerization catalyst containing a chromium compound (A), a phosphorus compound of general formula (1), and a compound (C) such as an organometallic compound and the like; and the olefin multimerization catalyst. (In the formula, R1 to R4 represent a group such as hydrocarbon groups and the like; Y shows a structure represented by -CR5R6-, where R5 and R6 show a group such as a hydrogen atom and the like. However, one or more of R1 to R4 are aliphatic hydrocarbon groups.)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a catalyst for olefin oligomerization having excellent activity and high selectivity and production efficiency for specific olefin oligomers, and a method for producing an olefin oligomer carried out in the presence of the catalyst for olefin oligomerization.

Background Art

[0002] α-olefins are important compounds widely used industrially, for example, as raw materials for polyolefins. For example, 1-hexene and 1-octene are in high demand as raw materials for polyolefins. Among the methods for producing α-olefins, there is a method that uses an organoaluminum or a transition metal compound as a catalyst. However, in the industrialized methods, usually, a mixture of various types of α-olefins is obtained. For this reason, it may be difficult to flexibly respond to business situations due to changes in the market conditions of each component. Therefore, a production method with high selectivity for the target α-olefin is desired.

[0003] In recent years, the present inventors have reported a catalyst that can selectively produce 1-hexene by a trimerization reaction of ethylene using a transition metal complex compound having a phenoxyimine ligand (for example, Patent Document 1).

[0004] In addition, as a catalyst for selectively producing 1-octene, a chromium-based catalyst using a ligand containing a phosphorus atom has been disclosed (for example, Patent Documents 2 to 4). In these documents, structures in which a plurality of phosphorus atoms are bonded via a carbon chain having 2 or more carbon atoms or structures in which a plurality of phosphorus atoms are bonded via a nitrogen atom are disclosed. In addition, many substituents having an aromatic structure are disclosed as substituents bonded to the phosphorus atom.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0006] According to the studies of the present inventors, in the case of conventional catalysts, one or more of the performance among reaction activity, thermal stability, and selectivity of the α-olefin to be produced is not sufficient, and further improvement is desired. In particular, when using a conventional catalyst for selectively producing 1-hexene, the selectivity of 1-octene is low (or 1-octene cannot be obtained at all) compared to the selectivity of 1-hexene in many cases.

[0007] 1-Octene is an important component as a polyolefin raw material like 1-hexene, and is particularly important when producing high-performance polyolefins. Also, 1-octene may be important as a raw material for lubricating oils.

[0008] The present invention has been made in view of these problems. Since 1-hexene and 1-octene have a boiling point difference of 50 °C or more even under normal pressure, separation is relatively easy even if they are co-produced. Therefore, an object of the present invention is to provide a catalyst for olefin oligomerization having excellent oligomer production activity and capable of obtaining not only 1-hexene but also a considerable amount of 1-octene, and a method for producing an olefin oligomer carried out in the presence of the catalyst for olefin oligomerization.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that a catalyst containing a specific transition metal compound, a phosphorus compound having a specific structure, and a cocatalyst has excellent activity and selectivity, and in the presence of this catalyst, an oligomerization reaction of olefins can be carried out with high activity. In particular, when ethylene is used as the olefin, it has been found that not only 1-hexene but also a considerable amount of 1-octene, which is a tetramer of ethylene, can be produced, and the present invention has been completed. That is, the present invention is specified by the following matters.

[0010] [1] A method for producing an olefin oligomer by carrying out an olefin oligomerization reaction in the presence of a catalyst for olefin oligomerization containing the following components (A) to (C). (A) A chromium compound (B) A phosphorus compound represented by the following general formula (1)

[0011] [Chemical formula]

[0012] (In the general formula (1), R 1 ~R 4 may be the same as or different from each other, and represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other. However, one or more of R 1 ~R 4 is an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Y represents a carbon atom having substituents R 5 and R 6 (a structure represented by -CR 5 R 6 -). R 5 and R 6 may be the same as or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and R 5 and R6 may be connected to each other, and may also be connected to any one of R 1 ~R 4 .) (C)(C-1) organometallic compound, (C-2) organoaluminum oxy compound, and at least one compound selected from the group consisting of compounds that react with (C-3) transition metal compounds to form ion pairs

[0013] [2] The method for producing an olefin polymer according to [1], wherein a phosphorus compound (B) in which a plurality of R 1 ~R 4 are alicyclic hydrocarbon groups is used.

[0014] [3] The method for producing an olefin polymer according to [1], wherein a phosphorus compound (B) in which all of R 1 ~R 4 are alicyclic hydrocarbon groups is used.

[0015] [4] The method for producing an olefin polymer according to any one of [1] to [3], further comprising the following component (D) in addition to components (A) to (C). (D) A carrier for supporting at least one compound selected from the group consisting of components (A) to (C)

[0016] [5] The method for producing an olefin polymer according to any one of [1] to [4], wherein the oligomerization reaction of olefin is carried out in the presence of an antistatic agent.

[0017] [6] The method for producing an olefin polymer according to any one of [1] to 5, wherein the olefin is ethylene.

[0018] [7] The method for producing an olefin polymer according to any one of [1] to [6], wherein the olefin polymer is 1-hexene and 1-octene.

[0019] [8] An olefin polymerization catalyst comprising the following components (A) and (B). (A) Chromium compound (B) The phosphorus compound represented by the following general formula (1)

[0020]

Chemical formula

[0021] (In general formula (1), R 1 ~R 4 may be the same as or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other. However, one or more of R 1 ~R 4 is an alicyclic hydrocarbon group having 3 to 20 carbon atoms.) Y represents a carbon atom having substituents R 5 and R 6 (the structure represented by -CR 5 R 6 -). R 5 and R 6 may be the same as or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. R 5 and R 6 may be linked to each other, and may also be linked to any one of R 1 ~R 4 .)

[0022] [9] The olefin polymerization catalyst according to [8], wherein component (A) is a trivalent chromium compound.

[0023]

[10] The olefin polymerization catalyst according to [8] or [9], which contains the following component (C) in addition to components (A) and (B). (C) (C-1) An organometallic compound (C-2) An organoaluminum oxy compound, and At least one compound selected from the group consisting of compounds that react with a transition metal compound to form an ion pair

Advantages of the Invention

[0024] According to the present invention, it is possible to provide a catalyst for olefin oligomerization having excellent activity, particularly high selectivity and production efficiency for 1-hexene and 1-octene, and a method for producing an olefin oligomer carried out in the presence of the catalyst for olefin oligomerization.

Modes for Carrying Out the Invention

[0025] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto. In the present invention, the oligomerization of olefins means converting olefins into dimers to decamers, preferably into trimers to tetramers.

[0026] <Chromium compound (A)> The chromium compound (A) used in the present invention is usually an inorganic salt, an organic salt or a metal organic complex of chromium. Specific examples of the chromium compound (A) include chromium(III) chloride, chromium(II) chloride, chromium(III) bromide, chromium(II) bromide, chromium(III) iodide, chromium(II) iodide, chromium(III) fluoride, chromium(II) fluoride, chromium(III) trichloride tris-tetrahydrofuran, chromium(III) 2-ethylhexanoate, chromium(III) acetylacetonate, chromium(III) trifluoroacetylacetonate, and chromium(III) hexafluoroacetylacetonate. However, the chromium compound (A) is not limited thereto. Among these, trivalent chromium compounds are preferred. Also, chromium compounds containing halogen atoms are preferred.

[0027] <Phosphorus compound (B)> The phosphorus compound (B) used in the present invention is represented by the following general formula (1).

[0028]

Chemical formula

[0029] In general formula (1), R 1 ~R 4 may be the same as or different from each other, and represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other. More specifically, R 1 ~R 4 is preferably a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester group, an amide group, an imide group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group, a carboxyl group, a sulfo group, a mercapto group, an aluminum-containing group, or a hydroxy group.

[0030] R 1 ~R 4 When at least one of them is a halogen atom, specific examples thereof include fluorine, chlorine, bromine, and iodine.

[0031] R 1 ~R 4When at least one of them is a hydrocarbon group, specific examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl; linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as vinyl, allyl, isopropenyl; linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethynyl, propargyl; cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl; cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms, such as cyclopentadienyl, indenyl, fluorenyl; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl; alkyl-substituted aryl groups such as tolyl, isopropylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl; alkylidene groups having 1 to 30 carbon atoms, preferably 5 to 10 carbon atoms, such as benzylidene, methylidene, ethylidene.

[0032] R 1 ~R 4 When at least one of them is a hydrocarbon group, the hydrogen atoms of the hydrocarbon group may be substituted with halogen atoms. Specific examples thereof include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as trifluoromethyl, pentafluorophenyl, chlorophenyl.

[0033] R 1 ~R 4 When at least one of them is a hydrocarbon group, the hydrogen atoms of the hydrocarbon group may be substituted with other hydrocarbon groups. Specific examples thereof include aryl group-substituted alkyl groups such as benzyl, cumyl, diphenylethyl, trityl.

[0034] R 1 ~R4 When at least one of them is a hydrocarbon group, the hydrocarbon group may further have a heterocyclic compound residue; an oxygen-containing group such as an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, a carboxylic anhydride group; a nitrogen-containing group such as an amino group, an imino group, an amide group, an imide group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, and an ammonium salt of an amino group; a boron-containing group such as a borandiyl group, a borantriyl group, a diboranyl group; a sulfur-containing group such as a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, an isothiocyanate ester group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, a sulfenyl group; a phosphorus-containing group such as a phosphide group, a phosphoryl group, a thiophosphoryl group, a phosphato group, a silicon-containing group, a germanium-containing group, or a tin-containing group. Among them, a linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, adamantyl; an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl; a substituted aryl group having 1 to 5 substituents such as a halogen atom, an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an alkoxy group or an amino group, an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, or an aryloxy group, is preferred.

[0035] R 1 ~R 4When at least one of them is an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group and / or a phosphorus-containing group, specific examples of these groups include the same ones as those exemplified above as substituents that may be contained in the hydrocarbon group. Among them, an oxygen-containing group, a nitrogen-containing group, and a sulfur-containing group are preferable, and an oxygen-containing group and a nitrogen-containing group are more preferable.

[0036] Examples of the nitrogen-containing group include an amide group, an amino group, an imide group, and an imino group. Specific examples of the amide group include acetamide, N-methylacetamide, and N-methylbenzamide. Specific examples of the amino group include dimethylamino, ethylmethylamino, and diphenylamino. Specific examples of the imide group include acetimide and benzimide. Specific examples of the imino group include methylimino, ethylimino, propylimino, butylimino, and phenylimino.

[0037] Examples of the sulfur-containing group include an alkylthio group, an arylthio group, a thioester group, a sulfonate ester group, and a sulfonamide group. Specific examples of the alkylthio group include methylthio and ethylthio. Specific examples of the arylthio group include phenylthio, methylphenylthio, and naphthylthio. Specific examples of the thioester group include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl. Specific examples of the sulfonate ester group include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate. Specific examples of the sulfonamide group include phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide.

[0038] R 1 ~R 4When at least one of them is a heterocyclic compound residue, specific examples of the heterocyclic compound residue include residues of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and groups in which these heterocyclic compound residues are further substituted with substituents such as an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

[0039] R 1 ~R 4 When at least one of R 1 to R 4 is a boron-containing group, specific examples of the boron-containing group include the same ones as those exemplified above as substituents that may be contained in a hydrocarbon group. Further, groups such as alkyl group-substituted boron, aryl group-substituted boron, boron halide, and alkyl group-substituted boron halide are also included. Examples of the alkyl group-substituted boron group include (Et)2B-, (iPr)2B-, (iBu)2B-, (Et)3B, (iPr)3B, and (iBu)3B. Examples of the aryl group-substituted boron group include (C6H5)2B-, (C6H5)3B, (C6F5)3B, and (3,5-(CF3)2C6H3)3B. Examples of the boron halide group include BCl2- and BCl3. Examples of the alkyl group-substituted boron halide group include (Et)BCl-, (iBu)BCl-, and (C6H5)2BCl. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group. Also, trisubstituted boron may be in a coordinately bonded state.

[0040] R 1 ~R 4When at least one of them is an aluminum-containing group, specific examples of the aluminum-containing group include an alkyl group-substituted aluminum, an aryl group-substituted aluminum, a halogenated aluminum, and an alkyl group-substituted halogenated aluminum group. Examples of the alkyl group-substituted aluminum group include (Et)2Al-, (iPr)2Al-, (iBu)2Al-, (Et)3Al, (iPr)3Al, and (iBu)3Al. Examples of the aryl group-substituted aluminum group include (C6H5)2Al-. Examples of the halogenated aluminum group include AlCl2- and AlCl3. Examples of the alkyl group-substituted halogenated aluminum group include (Et)AlCl- and (iBu)AlCl-. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group. Also, trisubstituted aluminum may be in a coordinatively bonded state.

[0041] R 1 ~R 4 When at least one of them is a silicon-containing group, specific examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. Examples of the hydrocarbon-substituted silyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, and dimethyl(pentafluorophenyl)silyl. Among them, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, and triphenylsilyl are preferred, and trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are more preferred. Examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

[0042] R 1 ~R 4 When at least one of them is a germanium-containing group and / or a tin-containing group silicon-containing group, specific examples of those groups include those in which silicon in the silicon-containing group exemplified above is substituted with germanium or tin.

[0043] However, R 1 ~R 4 One or more of them are alicyclic hydrocarbon groups having 3 to 20 carbon atoms. Specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, cyclotetradecyl group, cyclohexadecyl group, cyclooctadecyl group, eicosenyl group, and structures in which the carbon atoms forming the ring are bonded to substituents such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, and substituents containing elements of Groups 15 to 17 of the periodic table can be exemplified. Further, as elements forming the three-membered ring to twenty-membered ring as described above, a structure containing an element selected from elements of Groups 15, 16, and 17 of the periodic table (so-called hetero elements) may also be used. Among these, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group can be mentioned as preferable examples.

[0044] In the present invention, it is preferable that two or more of R 1 ~R 4 are the above alicyclic hydrocarbon groups, and more preferably all of R 1 ~R 4 are the above alicyclic hydrocarbon groups.

[0045] In the general formula (1), Y represents a carbon atom having substituents R 5 , R 6 (a structure represented by -CR 5 R 6 -). R 5 , R 6 may be the same as or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. Examples of each of these groups are the same as those of R 1 ~R 4 . R 5 and R 6 may be linked to each other, and also R 1 ~R4 may also be connected.

[0046] R 1 ~R 4 When R is any of the above preferred groups, the reaction activity of the olefin tends to be higher, and it tends to be easier to selectively produce low-boiling olefins including octene and hexene. The reason is not clear, but the following hypothesis can be put forward. R 1 ~R 4 In the selection of substituents, in order to improve the catalytic activity, sterically bulky substituents that increase the ion separation between the cationic complex, which is the active species, and the counter anion and enhance the cationicity of the central metal are effective. On the other hand, in order to synthesize 1-hexene and 1-octene selectively, small substituents that can secure a wide reaction (coordination) space suitable for the formation of metallacycles are presumed to be preferred. R 1 ~R 4 When one or more of the substituents are alicyclic hydrocarbon groups, it is considered that the rotation of the alicyclic hydrocarbon group enables both the steric bulk and the securing of the reaction space, and a catalyst having both high activity and high selectivity is obtained. Although the aromatic hydrocarbon group satisfies both requirements of steric bulk and securing of the reaction space, the cationicity of the central metal is lowered by the π-electron donation from the aromatic moiety to the central metal, and the aromatic moiety coordinates to the central metal to inhibit the coordination of the olefin, which is not preferable. Also, the fact that two phosphorus atoms are bonded via one carbon atom is considered to contribute to the realization of a highly selective reaction to 1-hexene and 1-octene by securing the reaction (coordination) space.

[0047] On the other hand, 1 R 2 and 3 R 4 having the same structure, and / or 1 R 4 and

[0048] In addition, R 1 and R 2 The structure in which they are connected may be regarded as an alicyclic structure in the present application. R 3 and R 4と The same applies when they are connected. In the present invention, for each of R 1 and R 2 the number of carbon atoms (and / or for each of R 3 and R 4 the number of carbon atoms) is defined with the point being half the number of carbon atoms constituting the connected structure as the boundary.

[0049] In the present invention, as one of the indexes for comprehensively judging the performance of the catalyst for olefin oligomerization, the catalytic activity of 1-octene described in the examples below can be mentioned. The catalytic activity of 1-octene is the production amount of 1-octene per unit time and per unit amount of the catalyst, that is, the production efficiency of 1-octene.

[0050] Furthermore, in each of the preferred embodiments described above, not only is the production efficiency of the trimer (1-hexene) and tetramer (1-octene) of ethylene further improved, but it is also preferable in terms of the reaction activity of ethylene and the efficient production of 1-octene.

[0051] When producing an ethylene oligomer in the present invention, 1-hexene and 1-octene tend to be the main products. And it is relatively easy to separate both by distillation. Therefore, the production efficiency of 1-octene described above is considered to be an important index from an industrial point of view. In particular, it may be an important item when using a production facility for co-producing 1-hexene and 1-octene.

[0052] Specific examples of the phosphorus compound (B) are shown below. However, the phosphorus compound (B) is not limited to these.

[0053]

Chemical formula

[0054] [Chemical formula]

[0055] In each of the above compounds, Me represents a methyl group, Et represents an ethyl group, n Pr represents a normal propyl group, i Pr represents an isopropyl group, and Ph represents a phenyl group.

[0056] As the phosphorus compound (B), commercially available phosphorus compounds may be used. When synthesizing the phosphorus compound (B), for example, the phosphorus compound (B) can be obtained by subjecting a specific phosphorus compound to alkylation, cycloalkylation, arylation, etc. by a general method.

[0057] The phosphorus compound (B) and the chromium compound (A) may be added to the reactor separately. However, it is preferable to add a transition metal complex formed by reacting the phosphorus compound (B) and the chromium compound (A) in advance to the reactor. For example, the phosphorus compound (B) is dissolved in a solvent, mixed with the chromium compound (A), and stirred under an inert gas atmosphere such as nitrogen or argon at -78°C to room temperature or reflux conditions for about 5 minutes to 48 hours to obtain a transition metal complex.

[0058] The solvent used when synthesizing the transition metal complex is not particularly limited. General solvents known to be usable in such reactions can be used. Specific examples of the solvent include polar solvents such as ether and tetrahydrofuran; hydrocarbon solvents such as toluene, methylcyclohexane, and heptane; and halogenated hydrocarbon solvents such as methylene chloride.

[0059] The transition metal complex is obtained in a state dissolved or suspended in a solvent. This solution or suspension of the transition metal complex may be used as it is, or the transition metal complex may be isolated once and then dissolved or suspended in a solvent again for use.

[0060] <Compound (C)> The compound (C) used in the present invention is at least one compound selected from the group consisting of an organometallic compound (C-1), an organoaluminum oxy compound (C-2), and a compound (C-3) that reacts with a transition metal compound to form an ion pair. Hereinafter, these compounds (C-1) to (C-3) will be described. In the following description, the compound (C-3) is referred to as an "ionizable ionic compound (C-3)".

[0061] [Organometallic compound (C-1)] As the organometallic compound (C-1), for example, organometallic compounds of Groups 1, 2, 12, and 13 of the periodic table such as the compounds (C-1a), (C-1b), and (C-1c) described below can be used. In the present invention, the organometallic compound (C-1) is assumed not to contain the organoaluminum oxy compound (C-2) described later.

[0062] (C-1a): General formula R a m Al(OR b ) n H p X q (In the formula, R a and R b each represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other; X represents a halogen atom; m is a number where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 0 ≦ q < 3, and m + n + p + q = 3) represents an organoaluminum compound.

[0063] (C-1b): General formula M 2 AlR a 4 (In the formula, M 2 represents Li, Na, or K; R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) represents a complex alkylate of a Group 1 metal of the periodic table and aluminum.

[0064] (C-1c): General formula R a R b M 3 (In the formula, R a and R brepresents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other, and M 3 is a dialkyl compound of a Group 2 or 12 metal in the periodic table represented by (where M is Mg, Zn or Cd).

[0065] Examples of the organoaluminum compound (C-1a) include an organoaluminum compound represented by the general formula R a m Al(OR b ) 3-m (wherein R a and R b represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other, and m is preferably a number such that 1.5 ≦ m ≦ 3.), an organoaluminum compound represented by the general formula R a m AlX 3-m (wherein R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably a number such that 0 < m < 3.), an organoaluminum compound represented by the general formula R a m AlH 3-m (wherein R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably a number such that 2 ≦ m < 3), and an organoaluminum compound represented by the general formula R a m Al(OR b ) n X q (wherein R a and R b represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other, X represents a halogen atom, m is a number such that 0 < m ≦ 3, n is a number such that 0 ≦ n < 3, q is a number such that 0 ≦ q < 3, and m + n + q = 3) can be used.

[0066] Specific examples of the organoaluminum compound (C-1a) include tri(n-alkyl)aluminums such as trimethylaluminum, triethylaluminum, tri(n-butyl)aluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tri-branched chain alkylaluminums such as triisopropylaluminum, triisobutylaluminum, tri(sec-butyl)aluminum, tri(tert-butyl)aluminum, tri(2-methylbutyl)aluminum, tri(3-methylbutyl)aluminum, tri(2-methylpentyl)aluminum, tri(3-methylpentyl)aluminum, tri(4-methylpentyl)aluminum, tri(2-methylhexyl)aluminum, tri(3-methylhexyl)aluminum, tri(2-ethylhexyl)aluminum; tricycloalkylaluminums such as tricyclohexylaluminum, tricyclooctylaluminum; triarylaluminums such as triphenylaluminum, tritolylaluminum; dialkylaluminum hydrides such as diethylaluminum hydride, diisobutylaluminum hydride; alkenylaluminums such as isoprenylaluminum represented by (iC4H9) x Al y (C5H 10 ) z (wherein x, y, and z are positive numbers, and z ≧ 2x. iC4H9 represents an isobutyl group.) and the like; alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide; for example, R a 2.5 Al(OR b ) 0.5 (wherein R a and R brepresents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other. Partially alkoxylated alkylaluminum having an average composition represented by); dialkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; partially halogenated alkylaluminum such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride; partially hydrogenated alkylaluminum such as ethylaluminum dihydride, propylaluminum dihydride; and partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide.

[0067] Compounds similar to the organoaluminum compound (C-1a), for example, organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom, such as (C2H5)2AlN(C2H5)Al(C2H5)2, can also be used.

[0068] Specific examples of the compound (C-1b) include LiAl(C2H5)4, LiAl(C7H 15 )4.

[0069] Specific examples of the compound (C-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, and butylethylmagnesium.

[0070] Specific examples of the organometallic compound (C-1) other than the compounds (C-1a) to (C-1c) described above include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, and butylmagnesium chloride.

[0071] Compounds in which an organoaluminum compound is formed in the polymerization reaction system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium, can also be used.

[0072] The organometallic compound (C-1) described above can be used alone or in combination of two or more. Among the organometallic compounds (C-1) described above, the organoaluminum compound (C-1a) is particularly preferred.

[0073] [Organoaluminum oxy compound (C-2)] The organoaluminum oxy compound (C-2) may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. The conventionally known aluminoxane can be produced, for example, by the following method and is usually obtained as a solution.

[0074] (1) A method of adding an organoaluminum compound such as trialkylaluminum to a suspension containing a compound containing adsorbed water or a salt containing water of crystallization (for example, magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerium(I) chloride hydrate) and a hydrocarbon solvent, and reacting the adsorbed water or water of crystallization with the organoaluminum compound.

[0075] (2) A method of allowing water, ice or steam to act directly on an organoaluminum compound such as trialkylaluminum in a solvent such as benzene, toluene, ethyl ether, tetrahydrofuran.

[0076] (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a solvent such as decane, benzene, toluene.

[0077] The aluminoxane may contain a small amount of an organometallic component. The solvent and unreacted organoaluminum compound may be removed by distillation from the solution of aluminoxane recovered by each of the above methods, and the aluminoxane may be redissolved in a solvent or suspended in a poor solvent for aluminoxane.

[0078] Specific examples of the organoaluminum compound used for the production of aluminoxane are the same as the specific examples of the organoaluminum compound (C-1a) described above. The organoaluminum compound can be used alone or in combination of two or more. Among them, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.

[0079] As the solvent used for the production of aluminoxane, for example, hydrocarbon solvents and ether solvents can be used. Specific examples of hydrocarbon solvents include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and light oil; and halides (especially chlorides or bromides) of aromatic hydrocarbons, aliphatic hydrocarbons, or alicyclic hydrocarbons. Specific examples of ether solvents include ethyl ether and tetrahydrofuran. Among them, aromatic hydrocarbons and aliphatic hydrocarbons are preferred. When using an organoaluminum oxy compound that is insoluble or poorly soluble in benzene, the amount of Al component dissolved in benzene at 60 °C is usually 10% or less, preferably 5% or less, more preferably 2% or less in terms of Al atoms.

[0080] As the organoaluminum oxy compound (C-2), an organoaluminum oxy compound containing boron represented by the following general formula (2) can also be used.

[0081] [Chemical formula]

[0082] (In general formula (2), R 5 represents a hydrocarbon group having 1 to 10 carbon atoms. R 6 represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different from each other.)

[0083] The organoaluminum oxy compound containing boron represented by general formula (2) can be produced, for example, by reacting an alkylboronic acid represented by the following general formula (3) with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of -80 °C to room temperature for 1 minute to 24 hours.

[0084] R 5-B(OH)2···(3) (In general formula (3), R 5 represents the same group as R 5 in the above general formula (2).)

[0085] Specific examples of the alkylboronic acid represented by general formula (3) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis(trifluoromethyl)phenylboronic acid. Among them, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These alkylboronic acids can be used alone or in combination of two or more.

[0086] Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid are the same as the specific examples of the organoaluminum compound (C-1a) described above. The organoaluminum compound can be used alone or in combination of two or more. Among them, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are more preferred.

[0087] The organoaluminum oxy compound (C-2) described above can be used alone or in combination of two or more.

[0088] [Ionizing ionic compound (C-3)] The ionizing ionic compound (C-3) is a compound that reacts with a transition metal compound to form an ion pair. Therefore, a compound having the property of forming an ion pair when at least contacted with a transition metal compound corresponds to this ionizing ionic compound (C-3).

[0089] As the ionized ionic compound (C-3), for example, Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and U.S. Patent No. 5,321,106 can be used. Further, heteropoly compounds and isopoly compounds can also be used.

[0090] Examples of the Lewis acid include compounds represented by the general formula BR3 (where R is a phenyl group which may have a substituent such as fluorine, a methyl group, or a trifluoromethyl group, or fluorine). Specific examples thereof include trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron, and tris(3,5-dimethylphenyl)boron.

[0091] Specific examples of the ionic compound include, for example, compounds represented by the following general formula (4).

[0092]

Chemical formula

[0093] In general formula (4), R 7+ is, for example, H + , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, or a ferrocenium cation having a transition metal. R 8 ~R 11 may be the same or different from each other and are preferably an organic group, preferably an aryl group or a substituted aryl group.

[0094] R 7+Specific examples of the case where R is a carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0095] R 7+ Specific examples of the case where R is an ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, and tri(n-butyl)ammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N,2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.

[0096] R 7+ Specific examples of the case where R is a phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0097] R 7+ Preferably, R is a carbonium cation or an ammonium cation, more preferably a triphenylcarbonium cation, an N,N-dimethylanilinium cation, or an N,N-diethylanilinium cation.

[0098] In addition to the compound represented by the general formula (4) described above, as the ionic compound, trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts can also be used.

[0099] Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tri(n-propyl)ammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o-tolyl)borate, tri(n-butyl)ammonium tetra(pentafluorophenyl)borate, tri(n-propyl)ammonium tetra(o,p-dimethylphenyl)borate, tri(n-butyl)ammonium tetra(m,m-dimethylphenyl)borate, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)borate, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)borate, and tri(n-butyl)ammonium tetra(o-tolyl)borate.

[0100] Specific examples of the N,N-dialkylanilinium salt include N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, and N,N,2,4,6-pentamethylanilinium tetraphenylborate.

[0101] Specific examples of the dialkylammonium salt include di(n-propyl)ammonium tetra(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate.

[0102] In addition to the salts described above, as the ionic compound, triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following general formula (5) or (6) can also be used.

[0103]

Chemical formula

[0104] (In general formula (5), Et represents an ethyl group.)

[0105] [Chemical formula]

[0106] (In general formula (6), Et represents an ethyl group.)

[0107] Specific examples of the borane compound include decaborane(14); salts of anions such as bis[tributylammonium] nonaborate, bis[tributylammonium] decaborate, bis[tributylammonium] undecaborate, bis[tributylammonium] dodecaborate, bis[tributylammonium] decachlorodecaborate, bis[tributylammonium] dodecachlorododecaborate; salts of metal borane anions such as tributylammonium bis(dodecahydrododecaborate) cobaltate(III), bis[tributylammonium] bis(dodecahydrododecaborate) nickelate(III).

[0108] Specific examples of the carborane compound include 4-carbanonaborane(14), 1,3-dicarbanonaborane(13), 6,9-dicarbadecaborane(14), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane(13), 2,7-dicarboundecaborane(13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium 1-carbaundecaborate, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadodecaborate, tri(n-butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium 6-carbadodecaborate(14), tri(n-butyl)ammonium 6-carbadodecaborate(12), tri(n-butyl)ammonium 7-carbaundecaborate(13), tri(n-butyl)ammonium 7,8-dicarboundecaborate(12), tri(n-butyl)ammonium 2,9-dicarboundecaborate(12), tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate, and salts of anions such as these;Salts of metal carborane anions such as tris(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate(III), tris(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)ferrate(III), tris(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)cobaltate(III), tris(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)nickelate(III), tris(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)cuprate(III), tris(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)aurate(III), tris(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)ferrate(III), tris(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)chromate(III), tris(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarbaundecaborate)cobaltate(III), tris[tris(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)chromate(III), bis[tris(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)manganate(IV), bis[tris(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)cobaltate(III), bis[tris(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)nickelate(IV), etc.

[0109] The heteropoly compound usually consists of an atom selected from silicon, phosphorus, titanium, germanium, arsenic or tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specific examples thereof include phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, silicomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphotungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid, and phosphomolybdoniobic acid. Further, salts of these acids may also be used. Specific examples of the salts include, for example, salts with metals of Group 1 or 2 of the periodic table (e.g., lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium), organic salts such as triphenylethyl salts, and isopoly compounds.

[0110] The ionized ionic compound (C-3) described above can be used alone or in combination of two or more.

[0111] By using the above catalyst for olefin oligomerization, a high-activity olefin oligomer can be obtained. In particular, when ethylene is used as the olefin, the selectivity for 1-octene is high. For example, when an organoaluminum oxy compound (C-2) such as methylaluminoxane is used in combination as a cocatalyst component, it shows higher activity with respect to ethylene and 1-octene can be produced. Further, even when an ionized ionic compound (C-3) such as triphenylcarbonium tetrakis(pentafluorophenyl)borate is used as a cocatalyst component, 1-octene can be obtained from ethylene with better activity and higher selectivity.

[0112] <Support (D)> The olefin oligomerization catalyst of the present invention may contain a carrier (D). The carrier (D) is an inorganic compound or an organic compound, and is usually a granular or particulate solid. In the present invention, the carrier (D) supports a chromium compound (A), a phosphorus compound (B) and / or a compound (C). As the inorganic compound, porous oxides, inorganic halides, clays, clay minerals, and ion-exchangeable layered compounds are preferred.

[0113] Specific examples of the porous oxide include SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, or a composite or mixture containing these (for example, natural or synthetic zeolite, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO). Among them, a porous oxide mainly composed of SiO2 and / or Al2O3 is preferred. The porous oxide may contain a small amount of carbonate, sulfate, nitrate or oxide components such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, Li2O. The particle size, specific surface area, and pore volume of the porous oxide are not particularly limited and may be appropriately determined according to the type of material and the manufacturing method. In the present invention, the particle size of the porous oxide is preferably 0.5 to 300 μm, more preferably 20 to 200 μm, the specific surface area is preferably 50 to 1000 m 2 / g, more preferably 100 to 700 m 2 / g, and the pore volume is preferably 0.3 to 3.0 cm 3 / g. The porous oxide is preferably calcined at 100 to 1000 °C, more preferably 150 to 700 °C, if necessary.

[0114] Specific examples of the inorganic halide include MgCl2, MgBr2, MnCl2, and MnBr2. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, after dissolving the inorganic halide in a solvent such as alcohol, a precipitate obtained by precipitation into fine particles with a precipitating agent can also be used.

[0115] The clay usually contains clay minerals as a main component. Further, the ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds are stacked parallel to each other with a weak binding force, and is a compound in which the contained ions are exchangeable. As the ion-exchangeable layered compound, for example, an ion-crystalline compound having a layered crystal structure such as a hexagonal close-packed type, an antimony type, a CdCl2 type, or a CdI2 type can be used. Most clay minerals are ion-exchangeable layered compounds. These clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural ones, and synthetic products can also be used.

[0116] Specific examples of the clay and the clay mineral include kaolin, bentonite, kibushi clay, gaylussite clay, allophane, hisingerite, pyrophyllite, mica, montmorillonite, vermiculite, hectorite, teniolite, ryokudite, palygorskite, kaolinite, nacrite, dickite, and halloysite. Specific examples of the ion-exchangeable layered compound include crystalline acidic salts of polyvalent metals such as α-Zr(HAsO4)2·H2O, α-Zr(KPO4)2·3H2O, α-Ti(HPO4)2, α-Ti(HAsO4)2·H2O, α-Sn(HPO4)2·H2O, γ-Zr(HPO4)2, γ-Ti(HPO4)2, and γ-Ti(NH4PO4)2·H2O. Among them, clay and clay minerals are preferable, and synthetic mica, montmorillonite, vermiculite, hectorite, and teniolite are more preferable.

[0117] The pore volume of the clay, clay mineral, and ion-exchangeable layered compound is preferably 0.1 cc / g or more, more preferably 0.3 to 5 cc / g. This pore volume is the volume measured by the mercury intrusion method using a mercury porosimeter in the range of pore radius from 20 to 3×10 4 angstroms. When a carrier with a pore volume of less than 0.1 cc / g for pores with a radius of 20 angstroms or more is used, it tends to be difficult to obtain high polymerization activity.

[0118] It is also preferable to perform chemical treatment on the clay and clay mineral. Examples of chemical treatment include surface treatment for removing impurities adhering to the surface and treatment that affects the crystal structure of the clay. Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. Acid treatment can increase the surface area not only by removing surface impurities but also by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment can destroy the crystal structure of the clay and change the structure of the clay. Salt treatment and organic substance treatment can change the surface area and interlayer distance by forming an ion complex, a molecular complex, or an organic derivative.

[0119] The ion-exchangeable layered compound may be a layered compound in a state where the interlayer is expanded by exchanging the exchangeable ions in the interlayer with another large and bulky ion. This bulky ion plays a pillar-like role in supporting the layered structure and is usually called a pillar. Also, introducing another substance into the interlayer of the layered compound in this way is called intercalation. Specific examples of the guest compound (another substance) to be intercalated include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (where R is a hydrocarbon group, etc.), [Al 13 O4(OH) 24 7+ 、[Zr4(OH) 14 2+ 、[Fe3O(OCOCH3)6] + ​​Examples of such metal hydroxide ions include. The guest compound can be used alone or in combination of two or more. When intercalating the guest compound, for example, dimers obtained by hydrolyzing metal alkoxides such as Si(OR)4, Al(OR)3, Ge(OR)4 (R is a hydrocarbon group etc.), and colloidal inorganic compounds such as SiO2 can also coexist. Specific examples of the pillar include oxides formed by heating and dehydrating after intercalating the above metal hydroxide ions between layers.

[0120] The clay, clay mineral, and ion-exchangeable layered compound may be used as they are, or may be used after treatments such as ball milling and sieving. Also, it may be used after newly adding water and adsorbing it, or may be used after heat dehydration treatment.

[0121] Examples of the organic compound include granular or particulate solid organic compounds with a particle size of 10 to 300 μm. Specific examples of the monomers of the polymer constituting the organic compound include (co)dimers mainly composed of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, (co)dimers mainly composed of vinylcyclohexane and styrene, and modified products thereof.

[0122] <Organic compound component (E)> The olefin polymerization catalyst of the present invention may further contain an organic compound component (E) as required.

[0123] In the present invention, the organic compound component (E) is used, for example, for the purpose of improving the polymerization performance. Examples of such organic compounds include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates. However, the organic compound component (E) is not limited thereto.

[0124] The alcohols and the phenolic compounds usually have R 14A compound represented by -OH is used. R 14 represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms. As the alcohols, those in which R 14 is a halogenated hydrocarbon are preferred. As the phenolic compounds, those in which the α,α'-positions of the hydroxyl groups are substituted with a hydrocarbon having 1 to 20 carbon atoms are preferred.

[0125] As the carboxylic acid, usually, a compound represented by R 15 -COOH is used. R 15 represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms. In particular, a compound in which R 15 is a halogenated hydrocarbon group having 1 to 50 carbon atoms is preferred.

[0126] As the phosphorus compound, phosphoric acids having a P-O-H bond, phosphates or phosphine oxide compounds having a P-OR bond or a P=O bond are preferred.

[0127] As the sulfonate, for example, a compound represented by the following general formula (7) can be used.

[0128]

Chemical formula

[0129] In general formula (7), M 2 is an element of Groups 1 to 14 of the periodic table, R 12 is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, t is an integer of 1 to 7, u is an integer of 1 ≦ u ≦ 7, and t - u ≧ 1.

[0130] <Olefin oligomerization catalyst> The catalyst for olefin oligomerization of the present invention is a catalyst used in the oligomerization reaction of olefins. Specific examples of such olefins include vinyl compounds such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, vinylcyclohexene, styrene, 1-octene, and 1-decene, and internal olefins such as 2-butene, cyclopentene, cyclohexene, and norbornene. Among them, ethylene is preferred. Two or more olefins may be co-oligomerized.

[0131] <Method for Producing Olefin Oligomer> The method for producing an olefin oligomer of the present invention is a method of performing an olefin oligomerization reaction (preferably a trimerization to tetramerization reaction, more preferably a tetramerization reaction) in the presence of the above-described catalyst for olefin oligomerization.

[0132] Specific examples of the olefin to be oligomerized are as described above, and among them, ethylene is preferred. Specifically, it is preferable to produce an oligomer by the oligomerization reaction of ethylene, and it is more preferable to produce 1-hexene and 1-octene with high selectivity by the trimerization and tetramerization reactions of ethylene, and it is particularly preferable to produce 1-octene with high selectivity by the tetramerization reaction of ethylene.

[0133] During oligomerization, the order of adding the above chromium compound (A), phosphorus compound (B), compound (C), and other components (for example, carrier (C), organic compound component (E)) to the reactor is not particularly limited. Specific examples of the addition method are as follows.

[0134] (1) A method of adding component (A) and component (B) to the reactor as they are in any order.

[0135] (2) A method of adding to the reactor a transition metal complex formed by previously contacting component (A) and component (B).

[0136] (3) A method of adding component (A), component (B), and component (C) to the reactor as they are in any order.

[0137] (4) A method of adding to a reactor, in any order, a transition metal complex formed by previously contacting component (A) and component (B), and component (C).

[0138] (5) A method of adding to a reactor a catalyst component obtained by previously contacting component (C) with a transition metal complex formed by previously contacting component (A) and component (B).

[0139] (6) A method of adding to a reactor, in any order, a catalyst component obtained by previously contacting component (C) with a transition metal complex formed by previously contacting component (A) and component (B), and component (C). In this case, each component (C) may be the same or different.

[0140] (7) A method of adding to a reactor a carrier (D) supporting a transition metal complex formed by previously contacting component (A) and component (B).

[0141] (8) A method of adding to a reactor, in any order, a carrier (D) supporting a transition metal complex formed by previously contacting component (A) and component (B), and component (C).

[0142] (9) A method of adding to a reactor a carrier (D) supporting a transition metal complex formed by previously contacting component (A) and component (B) and component (C).

[0143] (10) A method of adding to a reactor, in any order, a carrier (D) supporting a transition metal complex formed by previously contacting component (A) and component (B) and component (C), and component (C). In this case, each component (C) may be the same or different.

[0144] (11) A method of adding to a reactor, in any order, a carrier (D) supporting component (C), component (A), and component (B).

[0145] (12) A method of adding to a reactor, in any order, a carrier (D) supporting component (C) and a transition metal complex formed by previously contacting component (A) and component (B).

[0146] (13) A method of adding a carrier (D) supporting component (C), component (A), component (B), and component (C) to a reactor in any order. In this case, each component (C) may be the same or different.

[0147] (14) A method of adding a carrier (D) supporting component (C), a transition metal complex formed by previously contacting component (A) and component (B), and component (C) to a reactor in any order. In this case, each component (C) may be the same or different.

[0148] (15) A method of adding a carrier (D) supporting a transition metal complex formed by previously contacting component (A) and component (B) and a carrier (D) supporting component (C) to a reactor in any order.

[0149] (16) A method of adding a carrier (D) supporting a transition metal complex formed by previously contacting component (A) and component (B), a carrier (D) supporting component (C), and component (C) to a reactor in any order. In this case, each component (C) may be the same or different.

[0150] (17) A method of adding component (A), component (B), and component (E) to a reactor as they are in any order.

[0151] (18) A method of adding a transition metal complex formed by previously contacting component (A) and component (B) and component (E) to a reactor in any order.

[0152] (19) A method of adding component (A), component (B), component (C), and component (E) to a reactor as they are in any order.

[0153] (20) A method of adding a transition metal complex formed by previously contacting component (A) and component (B), component (C), and component (E) to a reactor in any order.

[0154] A method of adding a component obtained by previously contacting component (C) and component (E), component (A), and component (B) to a reactor in any order.

[0155] A method of adding a component obtained by previously contacting component (C) and component (E) and a transition metal complex formed by previously contacting component (A) and component (B) to a reactor in any order.

[0156] A method of adding a carrier (D) supporting component (E), component (A), and component (B) to a reactor in any order.

[0157] A method of adding a carrier (D) supporting component (E) and a transition metal complex formed by previously contacting component (A) and component (B) to a reactor in any order.

[0158] A method of adding a carrier (D) supporting component (C) and component (E), component (A), and component (B) to a reactor in any order.

[0159] A method of adding a carrier (D) supporting component (C) and component (E) and a transition metal complex formed by previously contacting component (A) and component (B) to a reactor in any order.

[0160] A method of adding a catalyst component obtained by previously contacting component (C) with a transition metal complex formed by previously contacting component (A) and component (B) and component (E) to a reactor in any order.

[0161] A method of adding a catalyst component obtained by previously contacting component (C) with a transition metal complex formed by previously contacting component (A) and component (B), component (C), and component (E) to a reactor in any order. In this case, each component (C) may be the same or different.

[0162] A method of adding to a reactor, in any order, a catalyst component obtained by pre - contacting component (C) with a transition metal complex formed by pre - contacting components (A) and (B), and a component obtained by pre - contacting components (C) and (E). In this case, each component (C) may be the same or different.

[0163] (30) A method of adding to a reactor, in any order, a carrier (D) supporting a transition metal complex formed by pre - contacting components (A) and (B), component (C), and component (E).

[0164] (31) A method of adding to a reactor, in any order, a carrier (D) supporting a transition metal complex formed by pre - contacting components (A) and (B), and component (E).

[0165] (32) A method of adding to a reactor, in any order, a carrier (D) supporting a transition metal complex formed by pre - contacting components (A) and (B), and a component obtained by pre - contacting components (C) and (E).

[0166] (33) A method of adding to a reactor a catalyst component obtained by pre - contacting component (E) with a transition metal complex formed by pre - contacting components (A) and (B).

[0167] (34) A method of adding to a reactor a catalyst component obtained by pre - contacting components (C) and (E) with a transition metal complex formed by pre - contacting components (A) and (B) in any order.

[0168] (35) A method of adding to a reactor, in any order, a catalyst component obtained by pre - contacting components (C) and (E) with a transition metal complex formed by pre - contacting components (A) and (B) in any order, and component (C). In this case, each component (C) may be the same or different.

[0169] (36) A method of adding to a reactor a carrier (D) supporting a transition metal complex formed by pre - contacting components (A) and (B) and component (E).

[0170] (37) A method of adding to a reactor a transition metal complex formed by previously contacting component (A) and component (B), component (C), and a carrier (D) supporting component (E).

[0171] (38) A method of adding to a reactor a transition metal complex formed by previously contacting component (A) and component (B), a carrier (D) supporting component (C) and component (E), and component (C) in any order. In this case, each component (C) may be the same or different.

[0172] In the present invention, an olefin multimer is obtained by multimerizing an olefin in the presence of the olefin multimerization catalyst described above. The multimerization can be carried out by any of liquid phase reaction methods such as a solution reaction and a suspension reaction, and a gas phase reaction method.

[0173] In the liquid phase reaction method, usually, an inert hydrocarbon medium is used. Specific examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, xylene, trimethylbenzene, and tetralin; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof. Among them, linear saturated hydrocarbons having 5 to 7 carbon atoms such as pentane, n-hexane, and n-butane; alicyclic saturated hydrocarbons such as methylcyclohexane are preferred.

[0174] When producing 1-hexene or 1-octene by, for example, mainly a trimerization or tetramerization reaction of ethylene using the olefin multimerization catalyst, the chromium atom in component (A) is usually 10 -12 ~10 -2 mol, preferably 10 -10 ~10 -3It is used in an amount such that it becomes a mole. In the present invention, even when component (A) is used at a relatively low concentration, a highly active olefin multimer can be obtained.

[0175] Component (B) is used in an amount such that the molar ratio [(B) / M] with the chromium atom (M) in component (A) is usually 0.1 to 10, preferably 0.5 to 2.

[0176] Among component (C), component (C-1) is used in an amount such that the molar ratio [(C-1) / M] between component (C-1) and the chromium atom (M) in component (A) is usually 0.01 to 100000, preferably 0.05 to 50000.

[0177] Component (C-2) is used in an amount such that the molar ratio [(C-2) / M] between the aluminum atom in component (C-2) and the chromium atom (M) in component (A) is usually 10 to 500000, preferably 20 to 100000.

[0178] Component (C-3) is used in an amount such that the molar ratio [(C-3) / M] between component (C-3) and the chromium atom (M) in component (A) is usually 1 to 10, preferably 1 to 5.

[0179] Component (D) is used in an amount such that the ratio (g / mol) of the mass (g) of component (D) per mole of the chromium atom (M) in component (A) is usually 100 to 10000, preferably 1000 to 5000.

[0180] When component (C-1) is used as component (C), component (E) is used in an amount such that the molar ratio [(E) / (C-1)] is usually from 0.01 to 10, preferably from 0.1 to 5. When component (C-2) is used as component (C), component (E) is used in an amount such that the molar ratio of component (E) to the aluminum atoms in component (D) and component (C-2) [(E) / (C-2)] is usually from 0.001 to 2, preferably from 0.005 to 1. When component (C-3) is used as component (C), component (E) is used in an amount such that the molar ratio [(E) / (C-3)] is usually from 0.01 to 10, preferably from 0.1 to 5.

[0181] The reaction temperature for the oligomerization is usually from -50 to 200 °C, preferably from 0 to 170 °C, more preferably from 10 °C to 130 °C, particularly preferably from 20 °C to 120 °C. Also, the most preferable lower limit is 25 °C and the most preferable upper limit is 100 °C. For the catalyst of the present invention, it is assumed that if the reaction temperature is too low, the activation of the catalyst will not proceed efficiently, and if the reaction temperature is too high, the activity will be lowered due to the decomposition of the catalyst.

[0182] The reaction pressure is usually from atmospheric pressure to 10 MPa, preferably from atmospheric pressure to 6 MPa, more preferably from atmospheric pressure to 5 MPa. Also, the lower limit is preferably 0.2 MPa, more preferably 0.5 MPa, particularly preferably 0.8 MPa. The most preferable upper limit is 4 MPa. For the catalyst of the present invention, there is a tendency that the higher the reaction pressure, the higher the production efficiency of 1-octene. 1-Octene is presumed to be obtained via metallacyclononane formed by the coordination of two ethylene molecules to metallacyclopentane and then the insertion of ethylene concertedly (or sequentially). And although the reason why the higher reaction pressure is more effective is not necessarily clear, it is presumed that the structure of the catalyst of the present invention is a structure in which the coordination of two ethylene molecules to metallacyclopentane becomes more advantageous as the pressure increases.

[0183] The oligomerization reaction can be carried out by any of batch, semi-continuous, and continuous methods.

[0184] The multimerization reaction may be carried out by adding an antistatic agent. Specific examples of the antistatic agent include polypropylene glycol, polypropylene glycol distearate, ethylenediamine-PEG-PPG-block copolymer, stearyldiethanolamine, lauryldiethanolamine, alkyldiethanolamide, polyoxyalkylene (for example, polyethylene glycol·polypropylene glycol·polyethylene glycol block copolymer (PEG-PPG-PEG)). Among them, polyoxyalkylene (for example, PEG-PPG-PEG) is preferred. The antistatic agent is used in an amount such that the ratio (g / mol) of the mass (g) to the number of moles of chromium atoms (M) in component (A) is usually 100 to 10,000, preferably 100 to 1,000.

[0185] The multimerization reaction may be carried out by adding hydrogen. The hydrogen pressure of the reaction is usually 0.01 MPa to 5 MPa, preferably 0.01 MPa to 1 MPa.

Examples

[0186] Hereinafter, the present invention will be specifically described based on synthesis examples and examples, but the present invention is not limited to these examples.

[0187] The analysis of the compound obtained in the synthesis example was performed using an ICP emission spectroscopic analyzer (manufactured by Agilent Technologies, model name 720-ES).

[0188] The yield of the reaction product and the selectivity of 1-hexene and 1-octene were analyzed using gas chromatography (Shimadzu GC-14A, J&W Scientific DB-5 column).

[0189] [Catalytic activity] The catalytic activity was determined by dividing the mass of the reaction product obtained per unit time by the atomic weight (millimoles) of the transition metal atoms in the transition metal catalyst component used for multimerization.

[0190] [Selectivity of 1-hexene or 1-octene] The selectivity of 1-hexene or 1-octene was determined according to the following formula. S(%) = Wp / Wr × 100 S(%): Selectivity of 1-hexene or 1-octene (mass fraction) Wr (mass): Total mass of products composed of 4 or more carbon atoms generated by the reaction Wp (mass): Mass of 1-hexene and 1-octene generated by the reaction

[0191] Examples of ethylene oligomerization are shown below.

[0192] [Example 1] To a thoroughly dried 100 mL Schlenk tube, 0.57 g (1.40 mmol) of bis(dicyclohexylphosphino)methane (phosphorus compound (B-1)) represented by the following formula (B-1), 0.44 g (1.17 mmol) of chromium(III) chloride tris(tetrahydrofuran), and 20 mL of dichloromethane were added, and the mixture was stirred for 18 hours under an argon atmosphere. After concentrating the reaction solution, 15 mL of n-hexane was added, and the insoluble matter was filtered off through a glass filter. The filtered solid was washed with 15 mL of n-hexane and dried under reduced pressure to obtain 0.38 g of a chromium compound. Methylcyclohexane was added to this chromium compound to prepare a methylcyclohexane solution (catalyst solution) at 0.001 mmol / mL in terms of chromium atoms.

[0193] [Chemical formula]

[0194] 29.6 mL of methylcyclohexane was placed in an autoclave with an internal volume of 100 mL that had been fully purged with nitrogen. Subsequently, 0.5 mmol of methylaluminoxane (Tosoh Finechem MMAO-3A, 5.7 mass% hexane solution) was added in terms of aluminum atoms. Subsequently, 0.10 mL (0.0001 mmol) of the previously prepared catalyst solution was added, and the reaction was initiated by pressurizing with ethylene (0.8 MPa-G). The reaction was carried out at 60 °C for 60 minutes while supplying ethylene at the same pressure. After the reaction, the reaction was stopped by adding a small amount of isopropanol. After the reaction was completed, the reaction solution was washed with 0.1 N hydrochloric acid water and pure water, and the low-boiling components (products with 12 or fewer carbon atoms) were separated from the high-boiling components and polyethylene using a liquid nitrogen trap under reduced pressure, and analysis was performed using gas chromatography. The production amount of the low-boiling components (production amount of products with 12 or fewer carbon atoms) was 1553 mg, and the production amount of polyethylene was 4 mg. The catalytic activity calculated from the total of these product amounts was 15562 g-product / (mmol-Cr·hr). The selectivity for 1-hexene was 66.6 mass%, the selectivity for 1-octene was 30.0 mass%, and the selectivity for polyethylene was 0.2 mass%. Also, the catalytic activity of 1-hexene was calculated to be 10366 g-product / (mmol-Cr·hr), and the catalytic activity of 1-octene was calculated to be 4670 g-product / (mmol-Cr·hr).

[0195] [Comparative Example 1] The reaction was carried out in the same manner as in Example 1 except that the compound (B-2) represented by the following formula was used instead of the phosphorus compound (B-1).

[0196] [Chemical formula]

[0197] The production amount of low-boiling components (the production amount of products having 12 or less carbon atoms) was 9 mg, the production amount of polyethylene was 4 mg, and the catalytic activity calculated from the total of these product amounts was 88 g-products / (mmol-Cr·hr). The selectivity of 1-hexene was 33.1% by mass, the selectivity of 1-octene was 16.8% by mass, and the selectivity of polyethylene was 50.1% by mass. Also, the catalytic activity of 1-hexene was calculated to be 29 g-products / (mmol-Cr·hr) and the catalytic activity of 1-octene was calculated to be 15 g-products / (mmol-Cr·hr).

Industrial Applicability

[0198] The catalyst for olefin oligomerization of the present invention has excellent activity, and in particular, has high selectivity and production efficiency for olefin oligomers such as 1-hexene and 1-octene, and is extremely useful in the production of olefin oligomers. Therefore, the present invention has extremely high industrial value.

Claims

1. A method for producing an olefin multimer by performing an olefin oligomerization reaction in the presence of a catalyst for olefin oligomerization containing the following components (A) to (C). (A) A chromium compound containing a halogen atom (B) A phosphorus compound represented by the following general formula (1) 【Chemical 1】 (In general formula (1), R 1 ~R 4 may be the same as or different from each other, and represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other. However, one or more of R 1 ~R 4 is an alicyclic hydrocarbon group having 3 to 20 carbon atoms.) Y is a carbon atom having substituents R 5 and R 6 (a structure represented by -CR 5 R 6 -). R 5 and R 6 may be the same as or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. R 5 and R 6 may be linked to each other, and may also be linked to any one of R 1 to R 4 .) (C) (C-1) An organometallic compound, (C-2) An organoaluminum oxy compound, and (C-3) At least one compound selected from the group consisting of compounds that react with a transition metal compound to form an ion pair.

2. In the general formula (1), R 1 ~R 4 The method for producing an olefin multimer according to claim 1, wherein a phosphorus compound (B) in which a plurality of are alicyclic hydrocarbon groups is used.

3. In general formula (1), R 1 ~R 4 The method for producing an olefin multimer according to claim 1, wherein a phosphorus compound (B) in which all of are alicyclic hydrocarbon groups is used.

4. The method for producing an olefin multimer according to any one of Claims 1 to 3, further comprising the following component (D) in addition to components (A) to (C). (D) A carrier for supporting at least one compound selected from the group consisting of components (A) to (C)

5. The method for producing an olefin multimer according to any one of Claims 1 to 4, wherein the olefin oligomerization reaction is carried out in the presence of an antistatic agent.

6. The method for producing an olefin multimer according to any one of Claims 1 to 5, wherein the olefin is ethylene.

7. The method for producing an olefin multimer according to any one of Claims 1 to 6, wherein the olefin multimer is 1-hexene and 1-octene.

8. A catalyst for olefin oligomerization containing the following components (A) and (B). (A) A chromium compound containing a halogen atom (B) A phosphorus compound represented by the following general formula (1) 【Chemical Formula 2】 (In general formula (1), R 1 to R 4 may be the same as or different from each other, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other. However, one or more of R 1 to R 4 is an alicyclic hydrocarbon group having 3 to 20 carbon atoms.) Y represents a carbon atom having substituents R 5 and R 6 (a structure represented by -CR 5 R 6 -). R 5 and R 6 may be the same as or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. R 5 and R 6 may be linked to each other, and may also be linked to any one of R 1 to R 4 .)

9. The catalyst for olefin oligomerization according to Claim 8, wherein component (A) is a trivalent chromium compound.

10. The catalyst for olefin oligomerization according to Claim 8 or 9, further comprising the following component (C) in addition to components (A) and (B). (C) (C-1) An organometallic compound, (C-2) An organoaluminum oxy compound, and (C-3) At least one compound selected from the group consisting of compounds that react with a transition metal compound to form an ion pair.

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