JP2022156184A - Method for producing olefin multimer - Google Patents

Abstract

To provide a method that suppresses by-production of an olefin polymer and enables selective production of an olefin multimer with high activity and, particularly when using ethylene, to provide a method that enables efficient production of 1-octene (a tetramer).SOLUTION: An olefin multimerization reaction is performed in the presence of an olefin multimerization catalyst that comprises: a chromium compound (A); an amine compound (B) of general formula (1); and a compound (C) obtained by contacting a magnesium halide compound with an alcohol, which are thereafter contacted with an organic aluminum. (R1-R4 each denote a group such as a hydrocarbon group, Y is a structure represented by -CR5R6-, R5 and R6 each denote a group such as a hydrogen atom, Z is an integer of 1-10).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a method for producing olefin multimers in the presence of an olefin multimerization catalyst having excellent activity and high selectivity and/or production efficiency for specific olefin multimers.

α-Olefins are important compounds that are widely used industrially as raw materials for polyolefins, for example. For example, 1-hexene and 1-octene are in high demand as raw materials for polyolefins. Among the methods for producing α-olefins, industrialized methods include methods using organoaluminum or transition metal compounds as catalysts. However, in industrialized processes, mixtures of various α-olefins are usually obtained. For this reason, it may be difficult to flexibly respond to changes in the market conditions of each component. Therefore, a method for producing the target α-olefin with high selectivity is desired.

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

In addition, chromium-based catalysts using ligands containing phosphorus atoms have been disclosed as catalysts for selectively producing 1-octene (eg, Patent Documents 2 to 4).
The present applicant also discloses an olefin multimerization process using a chromium-based catalyst. (Patent document 5)

WO2009/005003 WO2004/056479 WO2013/137676 WO2009/022770 WO2019/009390

According to the studies of the present inventors, many of the conventional catalysts exhibit high efficiency and olefin selectivity, but depending on the reaction conditions, the α-olefin selectivity decreases (the amount of ethylene polymer produced as a by-product increases. ). Therefore, it is desirable to prepare a catalyst with high α-olefin selectivity and an olefin polymerization method under various reaction conditions. Preferably, a method with high selectivity for 1-octene is desired.

Like 1-hexene, 1-octene is an important component as a raw material for polyolefins, and is an especially important component when producing high-performance polyolefins. 1-Octene may also become important as a raw material for lubricating oils.

The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a method for producing an olefin multimer having excellent activity, particularly high selectivity for 1-octene and/or high production efficiency.

The present inventors have made intensive studies to solve the above problems, and as a result, a catalyst containing a specific transition metal compound, an amine compound having a specific structure, and a co-catalyst prepared by a specific method is excellent. It has activity and/or high selectivity for 1-octene, and in the presence of this catalyst can favorably carry out multimerization reactions of olefins, and in particular when ethylene is used as the olefin, it is an ethylene tetramer. The inventors have found that 1-octene can be obtained with high activity and completed the present invention. That is, the present invention is specified by the following matters.

[1] A method for producing an olefin multimer, wherein an olefin multimerization reaction is carried out in the presence of an olefin multimerization catalyst containing the following components (A) to (C).
(A) a chromium compound (B) an amine compound represented by the following general formula (1)

(In general formula (1), R ¹ to R ⁴ may be the same or different, and are hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron contains groups, aluminum-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, or tin-containing groups, two or more of which may be linked together.

Y represents a carbon atom having substituents R ⁵ and R ⁶ (structure represented by —CR ⁵ R ⁶ —). R ⁵ and R ⁶ may be the same or different from each other, and may be 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, phosphorus ^- containing group, silicon ^- containing group, germanium ^- containing group, or tin ^- containing group; good.
Z represents an integer of 1-10. )

(C) A component obtained by contacting a magnesium halide with an alcohol having 1 to 20 carbon atoms and then with an organoaluminum compound represented by the following general formula (α):

(In the formula, R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom or a hydrogen atom, n is a real number of 1 to 3, and when there are multiple Rs, each R may be the same or different. Well, when there are multiple Xs, each X may be the same or different.)

[2] In the general formula (1), R ¹ is not linked to R ³ and R ⁴ and R ² is not linked to R ³ and R ⁴ using an amine compound (B) [1] The method for producing the olefin multimer according to .

[3] The method for producing an olefin multimer according to [1], which uses an amine compound (B) in which Z is an integer of 1 to 3 in general formula (1).
[4] The method for producing an olefin multimer according to [1], which uses an amine compound (B) in which Z is 1 in the general formula (1).

[5] The method for producing an olefin multimer according to [1], wherein the olefin multimerization catalyst contains 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).

[6] The method for producing an olefin multimer according to [1], wherein the olefin multimerization reaction is carried out in the presence of an antistatic agent.
[7] The method for producing an olefin multimer according to [1], wherein the olefin is ethylene.
[8] The method for producing an olefin multimer according to [1], wherein the olefin multimer is 1-octene.

The present invention provides a method for producing an olefin multimer in the presence of an olefin multimerization catalyst that exhibits excellent activity even at low reaction temperatures, particularly high selectivity and/or production efficiency for 1-octene. can provide.

Embodiments of the present invention will be described below, but the present invention is not limited to these. In the present invention, olefin polymerization means conversion of olefins into dimers to decamers, preferably trimers to tetramers.

<Chromium compound (A)>
The chromium compound (A) used in the present invention is usually an inorganic salt, organic salt or 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, and chromium (II) iodide. , chromium (III) fluoride, chromium (II) fluoride, chromium trichloride tristetrahydrofuran, chromium (III) 2-ethylhexanoate, chromium (III) acetylacetonate, chromium (III) trifluoroacetylacetonate, Chromium (III) hexafluoroacetylacetonate may be mentioned. However, the chromium compound (A) is not limited to these. Among these, trivalent chromium compounds are preferred. Chromium compounds containing halogen atoms are also preferred.

<Amine compound (B)>
The amine compound (B) used in the present invention is represented by the following general formula (1).

In general formula (1), R ¹ to R ⁴ may be the same or different, and are hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, 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, two or more of which may be linked together. More specifically, R ¹ to R ⁴ are hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, hydrocarbon-substituted silyl groups, hydrocarbon-substituted siloxy groups, alkoxy groups, alkylthio groups, aryloxy groups, Arylthio group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfonester group, sulfonamide group, cyano group, nitro group, carboxyl group, sulfo group, mercapto group, aluminum-containing group or preferably a hydroxy group.

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

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

When at least one of R ¹ to R ⁴ is a hydrocarbon group, the hydrocarbon group may have a hydrogen atom substituted with another hydrocarbon group. Specific examples thereof include aryl group-substituted alkyl groups such as benzyl, cumyl, diphenylethyl and trityl.

When at least one of R ¹ to R ⁴ is a hydrocarbon group, the hydrocarbon group may further be a heterocyclic compound residue; an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate Oxygen-containing groups such as groups, hydroxy groups, peroxy groups, carboxylic acid anhydride groups; Nitrogen-containing groups such as acid ester groups, amidino groups, diazo groups, and ammonium salts of amino groups; boron-containing groups such as boranediyl groups, boranetriyl groups, and diboranyl groups; group, arylthio group, thioacyl group, thioether group, thiocyanate ester group, isothiocyanate ester group, sulfone ester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group, sulfonyl group, sulfinyl group, sulfenyl group, etc. 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, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, adamantyl, etc., having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 20 carbon atoms. is 1 to 10, particularly preferably 2 to 10, linear or branched alkyl groups; groups; these aryl groups have halogen atoms, alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, alkoxy groups or amino groups, aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms or aryloxy groups A substituted aryl group substituted with 1 to 5 substituents such as is preferred.

When at least one of R ¹ to R ⁴ is an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group and/or a phosphorus-containing group, specific examples of these groups are substituents that may be contained in the hydrocarbon group. The same as those exemplified above can be mentioned. 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.

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

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

When at least one of R ¹ to R ⁴ is a heterocyclic compound residue, specific examples of the heterocyclic compound residue include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, furan and pyran. Residues of oxygen-containing compounds such as, sulfur-containing compounds such as thiophene, etc., and substituents such as alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, alkoxy groups, etc. in these heterocyclic compound residues Further substituted groups are mentioned.

When at least one of R ¹ to R ⁴ is a boron-containing group, specific examples of the boron-containing group are the same as those previously exemplified as substituents which may be contained in the hydrocarbon group. be done. Furthermore, groups of alkyl group-substituted boron, aryl group-substituted boron, boron halide, and alkyl group-substituted boron halide are also included. Examples of alkyl-substituted boron groups include (Et) ₂ B-, (iPr) ₂ B-, (iBu) ₂ B-, (Et) ₃ B, (iPr) ₃ B, and (iBu) ₃ B. be. Examples of aryl group-substituted boron groups include (C ₆ H ₅ ) ₂ B—, (C ₆ H ₅ ) ₃ B, (C ₆ F ₅ ) ₃ B, (3,5-(CF ₃ ) ₂ C _There is _6H3 ) _3B . Boron halide radicals include, for example, BCl ₂ -, BCl ₃ . Examples of alkyl-substituted boron halide groups include (Et)BCl-, (iBu)BCl-, and (C ₆ H ₅ ) ₂ BCl. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group. Trisubstituted boron may also be in a coordinated state.

When at least one of R ¹ to R ⁴ is an aluminum-containing group, specific examples of the aluminum-containing group include alkyl-substituted aluminum, aryl-substituted aluminum, halogenated aluminum and alkyl-substituted aluminum halide groups. be done. Examples of alkyl-substituted aluminum groups include (Et) ₂ Al-, (iPr) ₂ Al-, (iBu) ₂ Al-, (Et) ₃ Al, (iPr) ₃ Al and (iBu) ₃ Al. be. The group of aryl group-substituted aluminum includes, for example, (C ₆ H ₅ ) ₂ Al-. Aluminum halide radicals include, for example, AlCl ₂ —, AlCl ₃ . Examples of groups of alkyl group-substituted aluminum halide include (Et)AlCl- and (iBu)AlCl-. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group. Trisubstituted aluminum may also be in a coordinated state.

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

When at least one of R ¹ to R ⁴ is a germanium-containing group and/or a tin-containing group and a silicon-containing group, specific examples of these groups are those in which silicon in the silicon-containing groups exemplified above is replaced with germanium or tin. things are mentioned.

In general formula (1), Y represents a carbon atom having substituents R ⁵ and R ⁶ (structure represented by —CR ⁵ R ⁶ —). R ⁵ and R ⁶ , which may be the same or different, are 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 It represents a containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and examples of each of these groups are the same as the examples of R ¹ to R ⁴ . R ⁵ and R ⁶ may be linked to each other, or may be linked to R ¹ to R ⁴ .

In general formula (1), Z represents an integer of 1-10. Z may preferably be 2-10. On the other hand, Z is preferably an integer from 1 to 3, more preferably 1 or 2, particularly preferably 1. When Z is 2 or more, multiple Y's may be the same or different.

In general formula (1), two or more of R ¹ to R ⁴ may be linked together. However, R ¹ is preferably not linked to R ³ and R ⁴ and R ² is preferably not linked to R ³ and R ⁴ . Preferred amine compounds to which such a specific group is not linked include, for example, three modes of amine compounds represented by the following general formulas (1A) to (1C).

（一般式（１Ａ）中、各基の定義は一般式（１）の各基の定義と同じである。ただし、Ｒ¹～Ｒ⁴は何れの基とも連結していない。）

(In general formula (1A), the definition of each group is the same as the definition of each group in general formula (1). However, R ¹ to R ⁴ are not connected to any group.)

（一般式（１Ｂ）中、各基の定義は一般式（１）の各基の定義と同じである。ただし、Ｒ¹とＲ²は連結し、Ｒ³とＲ⁴は連結している。）

(In general formula (1B), the definition of each group is the same as the definition of each group in general formula (1). However, R ¹ and R ² are connected, and R ³ and R ⁴ are connected. )

（一般式（１Ｃ）中、各基の定義は一般式（１）の各基の定義と同じである。ただし、Ｒ¹とＲ²は何れの基とも連結しておらず、Ｒ³とＲ⁴は連結している。）

(In general formula (1C), the definition of each group is the same as the definition of each group in general formula (1). However, R ¹ and R ² are not connected to any group, R ³ and R ⁴ are concatenated.)

In general formula (1), R ¹ to R ⁴ may be linear or branched groups or groups containing a cyclic structure, and two of R ¹ to R ⁴ The above may be connected to each other to form a ring structure. For example, when either one of R ¹ and R ³ or R ² and R ⁴ is linked (bonded), the number of bonds is preferably 4 or more, and both R ¹ and R ³ and R ² and R ⁴ When is linked (bonded), the number of bonds is preferably 3 or more. However, as represented by general formulas (1A) to (1C), R ¹ is not linked to R ³ and R ⁴ and R ² is not linked to R ³ and R ⁴ . preferable. Each of R ¹ to R ⁴ preferably has no cyclic substituent, that is, it is a linear or branched group. When R ¹ to R ⁴ are linear or branched groups (for example, linear or branched hydrocarbon groups optionally having substituents), the linear or branched groups The number of carbon atoms is preferably 3-20, more preferably 3-15, particularly preferably 3-10. In that case, the total number of carbon atoms of R ¹ to R ⁴ is preferably 8 or more. The R ¹ -R ⁴ are preferably linear.

When R ¹ to R ⁴ are any of the above preferred groups, the reaction activity of the olefin tends to be higher, and an olefin dimer to pentamer (preferably trimer to tetramer) It tends to facilitate more efficient production of certain relatively low boiling alpha-olefins. Here, when the raw material is ethylene, its trimers and tetramers correspond to hexene and octene. That is, it tends to be suitable for producing olefins having 10 or less carbon atoms.

When the olefin multimerization catalyst containing the amine compound (B) of the present invention is used, the total production of the above-mentioned olefin multimers, that is, olefin dimers to pentamers (preferably trimers to tetramers) is produced. There is a tendency for the ratio to the amount of product produced to be high. Specifically, this proportion is desirably 85% by weight or more, preferably 88% by weight or more, more preferably 90% by weight or more, and particularly preferably 91% by weight or more. Thus, for example, when the proportion of 2- to 5-mers (preferably 3- to 4-mers) produced is high, the types of multimers produced tend to be small. In addition, since the difference in boiling points between the components is relatively large, separation by distillation is facilitated (eg, 1-hexene has a boiling point of 63° C. and 1-octene has a boiling point of 122-123° C.). As a result, it is thought that the manufacturing cost can be suppressed and it is easy to cope with the influence of market conditions.

On the other hand, it is also preferred that R ¹ and R ² have the same structure and/or R ³ and R ⁴ have the same structure. In this case, the selectivity for the tetramer of ethylene, ie 1-octene, may be high. For example, amine compounds (B-1) and (B-11) in which R ¹ to R ⁴ are all methyl groups among the amine compounds (B) used in Examples described later correspond to this case.

When R ¹ and R ² are linked to form a ring structure and/or when R ³ and R ⁴ are linked to form a ring structure, R ¹ and R ² have the same structure, and /or preferably R ³ and R ⁴ have the same structure. In this case, the “same structure” means that the ring structure seen from N is left-right symmetrical, that is, the structure on the R ¹ side (or R ³ side) of the ring structure and the structure on the R ² side (or R ⁴ side) structure is the same. Again, the selectivity for the tetramer of ethylene, ie 1-octene, can be high. For example, ^among the amine compounds ^{( B} ) used in the examples described later, the amine compound ⁽ B- 2), and the amine compound (B-10) in which R ¹ and R ² are linked and R ³ and R ⁴ are linked to form a 6-membered ring respectively.

In the present invention, when R ¹ and R ² are linked and/or when R ³ and R ⁴ are linked, the number of carbon atoms of each of R ¹ and R ² (and/or The number of carbon atoms of each of R ³ and R ⁴ ) is defined as a boundary point at which the number of carbon atoms constituting the connecting structure is 1/2. For example, among the amine compounds (B) used in the examples described later, each of R ¹ to R ⁴ in the amine compound (B-4) has 3 carbon atoms, and the number of carbon atoms in the amine compound (B-3) is 3. Each of R ¹ and R ³ has 3.5 carbon atoms, and each of R ² and R ⁴ has 2.5 carbon atoms.

It is not necessarily clear why better effects are obtained when R ¹ and R ² have the same structure and/or R ³ and R ⁴ have the same structure. However, since R ¹ to R ⁴ are considered to be located relatively close to the chromium atom of the central metal chromium compound (A), the steric influence of R ¹ to R ⁴ in the above structure may It is presumed that the ease of ethylene coordination to the cycle and the activation energy of the insertion reaction are properly controlled.

In the present invention, one of the indices for comprehensively evaluating the performance of the olefin-enriching catalyst is the catalytic activity of 1-octene described in the examples below. The catalytic activity of 1-octene is the amount of 1-octene produced per unit time and per unit amount of catalyst, that is, the production efficiency of 1-octene. The 1-octene production efficiency is an index different from the 1-octene selectivity.

Furthermore, in each of the preferred embodiments described above, not only is the efficiency of producing trimers (1-hexene) and tetramers (1-octene) of ethylene further improved, but the reaction activity of ethylene and 1-octene It is also preferable in terms of efficient production of

In the production of ethylene polymers in the present invention, 1-hexene and 1-octene are the main products. Both are relatively easy to separate 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, when using a production facility for co-producing 1-hexene and 1-octene, this may be an important item.

Specific examples of the amine compound (B) are shown below. However, the amine compound (B) is not limited to these.

In each of the above compounds, Me is a methyl group, Et is an ethyl group, ⁿ Pr is a normal propyl group, ⁱ Pr is an isopropyl group, and Ph is a phenyl group. The number of carbon atoms between N and N in each of the above compounds is 1 or 2, but compounds in which the number of carbon atoms between N and N is changed to 3 or more can also be used.

A commercially available amine compound may be used as the amine compound (B). When synthesizing the amine compound (B), the amine compound (B) can be obtained, for example, by alkylating or arylating a specific amine compound by a general method. Alternatively, the amine compound (B) can be obtained by reducing the imine compound by a general method. Moreover, in this invention, multiple types of amine compounds (B) can also be used together.

When the olefin multimerization catalyst containing the amine compound (B) of the present invention is used, 1-octene tends to be produced efficiently as described above. For example, in the olefin polymer having 10 or less carbon atoms to be produced, the proportion of 1-octene is desirably 40% by weight or more, preferably 50% by weight or more, more preferably 60% by weight or more, and particularly preferably 65% by weight or more, most preferably 70% by weight or more.

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

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

The transition metal complex is obtained dissolved or suspended in a solvent. The transition metal complex solution or suspension may be used as it is, or the transition metal complex may be isolated once and dissolved or suspended again in a solvent before use.

<Compound (C)>
In the method for producing the olefin multimer of the present invention, the compound (C) obtained by the following method is used in combination with the chromium compound (A) and the amine compound (B).

The compound (C) is a component obtained by contacting a magnesium halide with an alcohol having 1 to 20 carbon atoms and then with an organoaluminum compound represented by the following general formula (α).

（式中、Ｒは炭素数１～２０の炭化水素基、Ｘはハロゲン原子または水素原子、ｎは１～３の実数を示し、Ｒが複数ある場合は各々のＲは同じでも異なっていてもよく、Ｘが複数ある場合は、各々のＸは同じでも異なっていてもよい。）

(In the formula, R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom or a hydrogen atom, n is a real number of 1 to 3, and when there are multiple Rs, each R may be the same or different. Well, when there are multiple Xs, each X may be the same or different.)

The method for obtaining the compound (C) of the present invention is explained below.
The compound (C) of the present invention is obtained by contacting a magnesium halide and an alcohol having 1 to 20 carbon atoms (hereinafter, this contact may be referred to as "first contact"), and then is obtained by contacting with an organoaluminum compound represented by (hereinafter, this contact may be referred to as "second contact"). The method is described in more detail below, but is not limited to that method.

Magnesium chloride and magnesium bromide are preferably used as the magnesium halide. Such a magnesium halide may be used as a commercially available product as it is, or may be separately prepared from an alkylmagnesium, and in the latter case, the magnesium halide may be used without isolation.

Examples of alcohols having 1 to 20 carbon atoms include alcohols corresponding to the above alkoxy groups having 1 to 20 carbon atoms, such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, n-pentanol, i-amyl alcohol, n-hexanol, n-heptanol, 2-ethylhexanol, n-octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenyl ethanol, cumyl alcohol, i - Halogen-containing alcohols such as trichloromethanol, trichloroethanol and trichlorohexanol such as propylbenzyl alcohol, lower alkyl group-containing phenols such as phenol, cresol, ethylphenol, nonylphenol, cumylphenol and naphthol. Among these, methanol, ethanol, propanol, butanol, pentanol, i-amyl alcohol, hexanol, heptanol, 2-ethylhexanol, octanol and dodecanol are preferred.

When the magnesium halide and the alcohol having 1 to 20 carbon atoms are brought into contact with each other, they may be carried out in the presence of a solvent. Solvents include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; Examples include halogenated hydrocarbons such as ethylene dichloride, chlorobenzene, dichloromethane, and mixtures thereof.

It is usually preferable to carry out the contact under heating. When heating, the temperature can be arbitrarily selected up to the boiling point of the solvent used. The above heating time depends on the temperature and the ratio of the magnesium compound to the alcohol, but for example, if the molar ratio of the magnesium compound/alcohol is about 1/3, n-decane is used as the solvent, and the heating temperature is 130 ° C. Under these conditions, it can be made into a solution in about 4 hours. Further, it is preferable to use a stirring device when preparing the solution.

The thus prepared contact product of magnesium halide and an alcohol having 1 to 20 carbon atoms (hereinafter sometimes referred to as "first contact product") is used after removing the solvents used during contact. or may be used without distilling off the solvent. It is usually subjected to the next step without distilling off the solvent.

The first contact product obtained by the above method is then contacted (=second contact) with an organoaluminum compound represented by the following general formula (α).

In general formula (α), R is a hydrocarbon group having 1 to 20 carbon atoms, specifically methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, can be exemplified. . X represents a halogen atom such as a chlorine atom or a bromine atom, or a hydrogen atom. n represents a real number of 1 to 3, preferably 2 or 3; When there are multiple Rs, each R may be the same or different, and when there are multiple Xs, each X may be the same or different. As the organoaluminum compound, the following compounds are specifically used. Organoaluminum compounds meeting such requirements include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; Dialkylaluminum halides such as aluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide; alkylaluminum sesquihalides; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide; alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; , trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and diisobutylaluminum hydride.

The contact method in this second contact is not particularly limited, but it is usually carried out by adding the organoaluminum compound represented by the general formula (α) to the first contact product under stirring. At this time, the first contact product may be diluted with a solvent, and as such a solvent, any hydrocarbons that do not have active hydrogen can be used without particular limitation, but usually the solvent used in the first contact It is efficient to use it as it is as a solvent at the time of the second contact without distilling off. The organoaluminum compound added to the first contact product may be used after being diluted with a solvent, or may be added without being diluted with a solvent. It is used in a form diluted with a hydrocarbon or an aromatic hydrocarbon solvent such as toluene or xylene. When adding the organoaluminum compound, it is usually added to the first contact product over 5 minutes to 5 hours. If the heat-releasing capacity in the contact system is sufficient, the addition can be completed in a short period of time. The organoaluminum compound may be added all at once, or may be added in several batches. When split additions are made, the organoaluminum compound in each addition may be the same or different, and the temperature of the first contact in each addition may be the same or different.

The amount of the organoaluminum compound represented by the general formula (α) used in the second contact is usually 0.1 to 50 times the amount of magnesium atoms in the first contact, preferably 0. .5 to 30-fold mol, more preferably 1.0 to 20-fold mol, still more preferably 1.5 to 15-fold mol, particularly preferably 2.0 to 10-fold mol of aluminum atoms. used.

Preferred examples of the method and conditions for the second contact are described below.
When the first contact product and the organoaluminum compound represented by the general formula (α) are brought into contact with each other, for example, a solution of a magnesium compound diluted in a hydrocarbon and an organoaluminum compound diluted in a hydrocarbon solvent are brought into contact with each other. Means by reaction of substances are preferred. The amount of the organoaluminum compound used at that time varies depending on the type and contact conditions, but it is usually preferably 2 to 10 mol per 1 mol of the magnesium compound. In view of the reactivity of the compound (C) to be obtained, as well as the shape and particle size of solid products that may be generated in this step, it is preferable to carry out the contact of these components under mild conditions. For example, when a magnesium compound and an organoaluminum compound are brought into contact with each other in the liquid state to form a solid product by mutual reaction, after the two are mixed at a temperature so low that they do not rapidly change upon contact, , the temperature is raised and the reaction is allowed to proceed gradually. According to this method, when a solid product is obtained, it is easy to obtain a granular or spherical solid product having a relatively narrow particle size distribution and a component having homogeneous reactivity.

The above compound (C) may become solid, and in that case, it can also be used as a carrier for the olefin multimerization catalyst of the present invention. When the above compound (C) is in a solid state, it contains both a magnesium atom, an aluminum atom and an alkoxy group having 1 to 20 carbon atoms, is insoluble in a hydrocarbon solvent, and has an average particle size of 3 to 80 μm. is preferred. The molar ratio of magnesium atoms to aluminum atoms (Mg/Al) in the support component is within the range of 1.0<Mg/Al≦300.0, and the molar ratio of alkoxy groups to aluminum atoms (OR/Al) is Preferably, 0.05<OR/Al<2.0.

Insoluble in a hydrocarbon solvent means that at least one solvent selected from hexane, decane and toluene is dissolved in at least one solvent selected from hexane, decane and toluene at a temperature range of 0 ° C. to the inherent boiling point of the solvent under normal pressure for 1 minute to 1 minute. Stirring at room temperature for 1 minute to 1 hour under normal pressure in at least one solvent selected from hexane, decane, and toluene and having a dissolved amount of magnesium atoms of 0.5% by weight or less even after stirring for a period of time However, it means that the dissolved amount of aluminum atoms and alkoxy groups is each 1% by weight or less.

The compound (C) of the present invention may contain other metal atoms and other organic groups in addition to magnesium, aluminum and alkoxy groups as described above. Preferably no group 4 transition metal atoms such as titanium, zirconium, hafnium are included. If such a component is contained, the olefin polymer may be replicated during the multimerization reaction of the olefin, which will be described later.

When the compound (C) is a solid component as described above, the total amount of the magnesium atom, the aluminum atom and the alkoxy group having 1 to 20 carbon atoms is usually in the range of 10 to 90% by weight. From the viewpoint of the olefin polymerization activity of the polymerization catalyst containing the component and the powder properties of the polyolefin obtained as a result of the polymerization, the content is preferably 15 to 60% by weight, particularly preferably 20 to 40% by weight. Among components other than magnesium atoms, aluminum atoms and alkoxy groups having 1 to 20 carbon atoms in the carrier component, halogen atoms occupy the largest weight. When the halogen atom is a chlorine atom, the amount of chlorine atoms in the carrier component reaches about 20% by weight at a low level and about 80% by weight at a high level. The compound (C) may also contain an alcohol corresponding to an alkoxy group having 1 to 20 carbon atoms or a hydrocarbon compound used as a dispersion medium (also referred to as a solvent).

In the case of the solid compound (C) as described above, the alkoxy group having 1 to 20 carbon atoms therein originates from the alcohol having 1 to 20 carbon atoms used as a raw material component when preparing the carrier component described later. is the base. Alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, t-butoxy, n-pentoxy and i-amyloxy. group, n-hexoxy group, n-heptoxy group, 2-ethylhexoxy group, n-octoxy group, dodecoxy group, octadecyloxy group, oleyloxy group, benzyloxy group, phenylethoxy group, cumyloxy group, i-propylbenzyloxy group, etc. , trichloromethoxy group, trichloroethoxy group, trichlorohexoxy group and other halogen-containing alkoxy groups, phenoxy group, cresoxy group, ethylphenoxy group, nonylphenoxy group, cumylphenoxy group, naphthoxy group and other lower alkyl group-containing phenoxy groups, etc. Among them, methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, i-amyloxy group, hexoxy group, heptoxy group, 2-ethylhexoxy group, octoxy group, dodecoxy group preferable.

In the case of the solid compound (C) as described above, the molar ratio (Mg/Al) of magnesium atoms and aluminum atoms therein is usually within the range of 1.0<Mg/Al≤300.0. , preferably 30.0 < Mg/Al ≤ 250.0, more preferably 30.0 < Mg/Al ≤ 200.0, still more preferably 35.0, from the viewpoint of olefin polymerization activity and powder properties of the produced polyolefin. <Mg/Al≤200.0, particularly preferably 40.0<Mg/Al≤150.0. The molar ratio (OR/Al) between the alkoxy group and the aluminum atom is usually 0.05<OR/Al<2.0, and preferably 0.1≦OR/Al<1 from the viewpoint of further increasing the olefin polymerization activity. .8, particularly preferably in the range 0.2≤OR/Al<1.0.

When the solid compound (C) as described above has an average particle diameter of 3 to 80 μm, preferably 3 to 50 μm, the by-product olefin polymer described later tends to be granular, and the inner wall of the reactor It is a preferred embodiment because it may be difficult to adhere to pipes and cooling equipment during the reaction process. The microcrystal size is usually 3 to 80 (Å), preferably 10 to 75 (Å), more preferably 12 to 70 (Å), still more preferably 15 to 60 (Å), particularly preferably 20 to 55 (Å).

As the compound (C) used in the present invention, in addition to the above compounds, the following compounds can be used in combination as long as they do not contradict the object of the present invention.
at least one compound selected from the group consisting of an organometallic compound (C-1), an organoaluminumoxy compound (C-2), and a compound (C-3) that forms an ion pair by reacting with a transition metal compound; be. These compounds (C-1) to (C-3) are described below. In the following description, compound (C-3) is referred to as "ionized ionic compound (C-3)".

[Organometallic compound (C-1)]
Organometallic compounds (C-1) include, for example, compounds of Groups 1, 2, 12 and 13 of the periodic table, such as compounds (C-1a), (C-1b) and (C-1c) described below. of organometallic compounds can be used. Further, these compounds include compounds represented by the general formula (α).
In the present invention, the organometallic compound (C-1) does not include the organoaluminumoxy compound (C-2) described later.

(C-1a): general formula R ^a _m Al(OR ^b ) _n H _p X _q (wherein R ^a and R ^b may be the same or different and have 1 to 15 carbon atoms, preferably represents a hydrocarbon group of 1 to 4, X represents a halogen atom, m is 0 < m ≤ 3, n is 0 ≤ n < 3, p is 0 ≤ p < 3, q is a number of 0 ≤ q < 3 and m+n+p+q=3).

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

(C-1c): general formula R ^a R ^b M ³ (wherein R ^a and R ^b may be the same or different from each other and have 1 to 15 carbon atoms, preferably 1 to 4 hydrocarbon groups and M ³ is Mg, Zn or Cd).

Examples of the organoaluminum compound (C-1a) include those represented by the general formula R ^a _m Al(OR ^b ) _3-m (wherein R ^a and R ^b may have the same or different number of carbon atoms 1 to 15, preferably 1 to 4, hydrocarbon groups, and m is preferably a number satisfying 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 satisfying 0<m<3.) The 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 2≦m < 3), an organoaluminum compound represented by the general formula R ^a _m Al (OR ^b ) _n X _q (wherein R ^a and R ^b may be the same or different from each other, and the number of carbon atoms represents a hydrocarbon group of 1 to 15, preferably 1 to 4, X represents a halogen atom, m is 0 < m ≤ 3, n is 0 ≤ n < 3, q is a number of 0 ≤ q < 3 and m+n+q=3) can be used.

Specific examples of the organoaluminum compound (C-1a) include trimethylaluminum, triethylaluminum, tri(n-butyl)aluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum. tri(n-alkyl)aluminum; 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 tri-branched alkylaluminum such as; tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminum such as triphenylaluminum and tritolylaluminum; dialkylaluminum hydride such as diethylaluminum hydride and diisobutylaluminum hydride; _iC4H9 ) _{xAly ( C5H10} ) _{z (} wherein, _x , y, and z are positive numbers, z≧ _2x , _iC4H9 represents an isobutyl group), and the like. alkenyl aluminum such as isoprenyl aluminum represented; alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide; dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminum butoxide. alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; for example R ^a _2.5 Al(OR ^b ) _0.5 (wherein R ^a and R ^b may have the same or different number of carbon atoms; represents 1 to 15, preferably 1 to 4 hydrocarbon groups.); (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl- 4-methylphenoxide), dialkylaluminum aryloxides such as isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutyl dialkylaluminum halides such as aluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; partially halogenated alkylaluminum; dialkylaluminum hydride such as diethylaluminum hydride, dibutylaluminum hydride; partially hydrogenated alkylaluminum hydride such as ethylaluminum dihydride, propylaluminum dihydride. partially alkoxylated and halogenated aluminum alkyls such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide;

Compounds similar to organoaluminum compounds (C-1a), for example, two or more aluminum compounds via nitrogen atoms such as (C ₂ H ₅ ) ₂ AlN(C ₂ H ₅ )Al(C ₂ H ₅ ) ₂ can also be used.

Specific examples of the compound (C-1b) include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .
Specific examples of the compound (C-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium and butylethylmagnesium.

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, and methylmagnesium chloride. , ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride.

It is also possible to use compounds in which an organoaluminum compound is formed in the multimerization reaction system, such as a combination of an aluminum halide and an alkyllithium, or a combination of an aluminum halide and an alkylmagnesium.

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

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

(1) Compounds containing adsorbed water or salts containing water of crystallization (e.g., magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate ) and a hydrocarbon solvent, an organoaluminum compound such as trialkylaluminum is added to react the adsorbed water or water of crystallization with the organoaluminum compound.

(2) A method in which water, ice or steam is directly acted on an organoaluminum compound such as trialkylaluminum in a solvent such as benzene, toluene, ethyl ether or tetrahydrofuran.

(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 or toluene.

Aluminoxanes may contain small amounts of organometallic components. The solvent and unreacted organoaluminum compound may be distilled off from the aluminoxane solution recovered in each of the above methods, and the aluminoxane may be redissolved in the solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of the organoaluminum compound used for producing the aluminoxane are the same as the specific examples of the organoaluminum compound (C-1a) described above. An organic aluminum compound can be used individually by 1 type or in combination of 2 or more types. Among them, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.

As the solvent used for producing the 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; cyclopentane, Alicyclic hydrocarbons such as cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and light oil; aromatic hydrocarbons, aliphatic hydrocarbons, or halides of alicyclic hydrocarbons (especially chlorides or bromides). 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 sparingly 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% in terms of Al atoms. It is below.

As the organoaluminumoxy compound (C-2), an organoaluminumoxy compound containing boron represented by the following general formula (5) can also be used.

（一般式（５）中、Ｒ⁷は炭素原子数が１～１０の炭化水素基を示す。Ｒ⁸は、互いに同一でも異なっていてもよい水素原子、ハロゲン原子、炭素原子数が１～１０の炭化水素基を示す。）

(In general formula (5), R ⁷ represents a hydrocarbon group having 1 to 10 carbon atoms; R ⁸ , which may be the same or different, is a hydrogen atom, a halogen atom, or a indicates a hydrocarbon group.)

The organoaluminumoxy compound containing boron represented by the general formula (5) can be obtained, for example, by combining an alkylboronic acid represented by the following general formula (6) and an organoaluminum compound in an inert gas atmosphere. It can be produced by reacting in a solvent at a temperature of −80° C. to room temperature for 1 minute to 24 hours.

（一般式（６）中、Ｒ⁷は上記一般式（５）におけるＲ⁷と同じ基を示す）

(In general formula (6), R ⁷ represents the same group as R ⁷ in general formula (5) above)

Specific examples of alkylboronic acids represented by the general formula (6) 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, preferred are methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid. These alkylboronic acids can be used singly or in combination of two or more.

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. An organic aluminum compound can be used individually by 1 type or in combination of 2 or more types. Among them, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are more preferable.
The organoaluminumoxy compounds (C-2) described above can be used singly or in combination of two or more.

[Ionized ionic compound (C-3)]
The ionized 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 contacted with at least a transition metal compound corresponds to this ionized ionic compound (C-3).

As the ionized ionic compound (C-3), for example, Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-3-207703, JP-A-3-207704 and US Pat. No. 5,321,106 can be used. Furthermore, heteropoly compounds and isopoly compounds can also be used.

Examples of the Lewis acid include compounds represented by the general formula BR ₃ (R is fluorine or a phenyl group optionally having a substituent such as fluorine, methyl group or trifluoromethyl group). Specific examples 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, tris(3,5-dimethylphenyl)boron.

Specific examples of the ionic compound include compounds represented by the following general formula (7).

In general formula (7), R ⁹⁺ includes, for example, H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal. R ¹⁰ to R ¹³ are organic groups which may be the same or different, preferably aryl groups or substituted aryl groups.

Specific examples of carbonium cations in which R ⁹⁺ is a carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

Specific examples of when R ⁹⁺ is an ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, tri(n-butyl)ammonium cation; - N,N-dialkylanilinium cations such as dimethylanilinium cation, N,N-diethylanilinium cation, N,N,2,4,6-pentamethylanilinium cation; di(isopropyl)ammonium cation, dicyclohexylammonium cation; cations such as dialkylammonium cations.

Specific examples of R ⁹⁺ being a phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

R ⁹⁺ is preferably carbonium cation or ammonium cation, more preferably triphenylcarbonium cation, N,N-dimethylanilinium cation or N,N-diethylanilinium cation.

In addition to the compounds represented by the general formula (7) described above, the ionic compounds further include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Available.

Specific examples of the trialkyl-substituted ammonium salts 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, tri (n-Butyl)ammonium tetra(o-tolyl)borate.

Specific examples of the N,N-dialkylanilinium salts include N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N,2,4,6-pentamethylanilinium nium tetraphenyl borate.

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

In addition to the salts described above, the ionic compounds further include triphenylcarbenium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, ferrocenium tetra(pentafluoro Phenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following general formula (8) or (9) can also be used. .

（一般式（８）中、Ｅｔはエチル基を示す。）

(In general formula (8), Et represents an ethyl group.)

（一般式（９）中、Ｅｔはエチル基を示す。）

(In general formula (9), Et represents an ethyl group.)

Specific examples of the borane compound include decaborane (14); bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undeca salts of anions such as borate, bis[tri(n-butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, bis[tri(n-butyl)ammonium]dodecachlorododecaborate; metal borane anions such as tri(n-butyl)ammonium bis(dodecahydride dodecaborate) cobaltate (III) and bis[tri(n-butyl)ammonium]bis(dodecahydride dodecaborate) nickelate (III); salt.

Specific examples of the carborane compounds 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-dicarbanodecaborane ( 13), 2,7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbaundecaborate, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium 1-trimethylsilyl -1-carbadecaborate, tri(n-butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium 6-carbadecaborate (14), tri(n-butyl)ammonium 6-carbadecaborate (12), tri(n-butyl)ammonium 7-carbaundecaborate (13), tri(n-butyl)ammonium 7,8-dicarbaundecaborate (12), tri(n-butyl)ammonium 2,9 -dicarbaundecaborate (12), tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, 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-dical Boundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate salts of anions such as borates; tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbano naborate) cobaltate (III), 8-Dicalbound decavolley g) ferrate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarboundecaborate) cobaltate (III), tri(n-butyl)ammonium bis(undecahydride) -7,8-dicarbaundecaborate)nickelate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)cuprate (III), tri(n- Butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)aurate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundeca) borate) ferrate (III), tri(n-butyl) ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), tri(n-butyl) ammonium Bis(tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate) chromate ( III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7 - carbaundecaborate) cobaltate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate)nickelate (IV). mentioned.

The heteropoly compound usually consists of atoms of 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, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, Phosphotungstic acid, germanotungstic acid, stannotungstic acid, phosphomolybdovanadate, phosphotungstovanadate, germanotungstovanadate, phosphomolybd tungstovanadate, germanomolybdenum tungstovanadate, phosphomolyb dotungstic acid, phosphomolybdoniobic acid. Salts of these acids may also be used. Specific examples of salts include salts with metals of Group 1 or 2 of the periodic table (e.g., lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium), triphenylethyl salts, and the like. organic salts and isopoly compounds of

The ionized ionic compounds (C-3) described above can be used singly or in combination of two or more.
Compounds (C-1), (C-2), and (C-3) as described above are preferably 10 mol or less, more preferably in terms of aluminum atoms per 1 mol of magnesium atoms in the magnesium compound of compound (C). is 1 mol or less, more preferably 0.5 mol or less, particularly preferably 0.1 mol or less.

<Carrier (D)>
The olefin enrichment 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 the chromium compound (A), amine compound (B) and/or compound (C). As inorganic compounds, porous oxides, inorganic halides, clays, clay minerals, and ion-exchange layered compounds are preferred.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or composites or mixtures containing these (e.g. , natural or synthetic zeolites, SiO ₂ --MgO, SiO ₂ --Al ₂ O ₃ , SiO ₂ --TiO ₂ , SiO ₂ --V ₂ O ₅ , SiO ₂ --Cr ₂ O ₃ , SiO ₂ --TiO ₂ --MgO). mentioned. Among them, porous oxides containing SiO ₂ and/or Al ₂ O ₃ as main components are preferred. Porous oxides include small amounts of _Na2CO3 , _K2CO3 , _CaCO3 , _MgCO3 , _Na2SO4 , Al2 _{( SO4} ) ₃ , _{BaSO4 , KNO3} , Mg _{( NO3} ) _{2 ,} It may contain carbonates, sulfates, nitrates or oxide components such as 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 manufacturing method. In the present invention, the porous oxide preferably has a particle size of 0.5 to 300 μm, more preferably 20 to 200 μm, and a specific surface area of 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 sintered at 100 to 1000°C, more preferably 150 to 700°C, if necessary.

Specific examples of the inorganic halides include MgCl ₂ , MgBr ₂ , MnCl ₂ and MnBr ₂ . The inorganic halide may be used as it is, or may be used after pulverizing with a ball mill or vibration mill. Moreover, after dissolving an inorganic halide in a solvent such as alcohol, it is possible to use a product obtained by depositing fine particles using a precipitating agent.

The clay usually contains clay minerals as a main component. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds are stacked in parallel with a weak bonding force, and is a compound in which ions can be exchanged. As the ion-exchangeable layered compound, for example, an ion-crystalline compound having a layered crystal structure such as a hexagonal close-packing type, an antimony type, a CdCl ₂ type, and a CdI ₂ type can be used. Most clay minerals are ion exchange layered compounds. These clays, clay minerals, and ion-exchange layered compounds are not limited to natural ones, and artificially synthesized ones can also be used.

Specific examples of clay and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hisingerite, pyrophyllite, mica, montmorillonite, vermiculite, hectorite, teniolite, ryokudeite, palygorskite, kaolinite, and nacrite. , dickite and halloysite. Specific examples of the ion-exchange layered compound include α-Zr(HAsO ₄ ) ₂ ·H ₂ O, α-Zr(KPO ₄ ) ₂ ·3H ₂ O, α-Ti(HPO ₄ ) ₂ , α-Ti( _HAsO4 ) _2.H2O , α-Sn(HPO4) _2.H2O , γ _- Zr(HPO4) ₂ , γ _{-Ti(HPO4)2 , γ - Ti ( NH4PO4} ) ₂ - Crystalline acid salts of polyvalent metals such as _H2O . Among them, clay and clay minerals are preferable, and synthetic mica, montmorillonite, vermiculite, hectorite, and teniolite are more preferable.

The pore volume of the clay, clay mineral and ion-exchange 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 in the range of pore radius from 20 to 3×10 ⁴ angstroms by mercury porosimetry using a mercury porosimeter. When a carrier having a pore volume of less than 0.1 cc/g and having a radius of 20 angstroms or more is used, it tends to be difficult to obtain high multimerization activity.

It is also preferable to chemically treat clay and clay minerals. Chemical treatments include, for example, surface treatments for removing impurities adhering to the surface and treatments for affecting the crystal structure of clay. Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. The acid treatment not only removes surface impurities, but also elutes cations such as Al, Fe, and Mg in the crystal structure, thereby increasing the surface area. Alkaline treatment can change the structure of the clay by destroying the crystalline structure of the clay. Salt treatment and organic substance treatment can change the surface area and interlayer distance by forming ionic complexes, molecular complexes, or organic derivatives.

The ion-exchangeable layered compound may be a layered compound in which the interlayer spacing is expanded by exchanging the interlayer exchangeable ions with other large bulky ions. These bulky ions play a role of support supporting the layered structure and are usually called pillars. Also, introducing another substance between layers of a layered compound in this way is called intercalation. Specific examples of intercalating guest compounds (other substances) include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ , B( metal alkoxides (R is a hydrocarbon group, etc.) such as OR) ₃ , [ _{Al13O4 (} OH) ₂₄ ] ⁷⁺ , [ _Zr4 (OH) ₁₄ ] ²⁺ , [ _Fe3O ( _OCOCH3 ) ₆ ] ⁺ and other metal hydroxide ions. A guest compound can be used individually by 1 type or in combination of 2 or more types. Dimerization obtained by hydrolyzing a metal alkoxide (R is a hydrocarbon group, etc.) such as Si(OR) ₄ , Al(OR) ₃ , Ge(OR) ₄ when intercalating a guest compound Colloidal inorganic compounds such as SiO ₂ can also coexist. Specific examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them by heating.

Clays, clay minerals, and ion-exchangeable layered compounds may be used as they are, or may be used after being subjected to treatments such as ball milling and sieving. Moreover, it may be used after newly adding water for adsorption, or may be used after heat dehydration treatment.

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

<Organic compound component (E)>
The olefin enrichment catalyst of the present invention may further contain an organic compound component (E) as necessary.

In the present invention, the organic compound component (E) is used, for example, for the purpose of improving multimerization performance. Examples of such organic compounds that can be used include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates. However, the organic compound component (E) is not limited to this.

As the alcohols and the phenolic compounds, compounds represented by R ¹⁴ —OH are usually 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 alcohols, compounds in which R ¹⁴ is a halogenated hydrocarbon are preferred. As the phenolic compound, a compound in which the α,α'-position of the hydroxyl group is substituted with a hydrocarbon having 1 to 20 carbon atoms is preferred.

A compound represented by R ¹⁵ —COOH is usually used as the carboxylic acid. R ¹⁵ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms. Particularly preferred are compounds in which R ¹⁵ is a halogenated hydrocarbon group having 1 to 50 carbon atoms.

As the phosphorus compound, phosphoric acids having a P—O—H bond, phosphates or phosphine oxide compounds having a P—OR bond or P═O bond are preferred.
As the sulfonate, for example, a compound represented by the following general formula (10) can be used.

In general formula (10), M ² is an element of Groups 1 to 14 of the periodic table, and R ¹⁴ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. 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 satisfying 1≦u≦7 and tu≧1.

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

<Method for producing olefin multimer>
The method for producing an olefin multimer of the present invention is a method of performing an olefin multimerization reaction (preferably a trimerization to a tetramerization reaction, more preferably a tetramerization reaction) in the presence of the olefin multimerization catalyst described above. .

Specific examples of the olefin to be multimerized are as described above, with ethylene being preferred. Specifically, it is preferable to produce multimers by multimerization reaction of ethylene, more preferably to produce 1-hexene and 1-octene with high selectivity by trimerization and tetramerization reaction of ethylene. It is particularly preferred to produce 1-octene with high selectivity by a tetramerization reaction.

During polymerization, the order of adding the chromium compound (A), amine compound (B), compound (C) and other components (e.g. carrier (D), organic compound component (E)) to the reactor is not particularly limited. not. A specific example of the addition method is as follows.

(1) A method in which component (A) and component (B) are directly added to a reactor in any order.
(2) A method in which a transition metal complex formed by contacting component (A) and component (B) in advance is added to a reactor.
(3) A method of adding the component (A), the component (B) and the component (C) as they are to the reactor in any order.
In addition, the method described in Patent Document 5 can be exemplified.

In the present invention, an olefin multimer is obtained by multimerizing an olefin in the presence of the olefin multimerization catalyst described above. Enrichment can be carried out by either a liquid phase reaction method such as dissolution reaction or suspension reaction, or a gas phase reaction method.

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

Using an olefin multimerization catalyst, for example, when producing 1-hexene or 1-octene mainly by tri- to tetra-merization reaction of ethylene, chromium atoms in component (A) are usually It is used in an amount of 10 ^-12 to 10 ^-2 mol, preferably 10 ^-10 to 10 ^-3 mol. In the present invention, a highly active olefin polymer can be obtained even when the component (A) is used at a relatively low concentration.

Component (B) is used in such an amount that the molar ratio [(B)/M] to chromium atoms (M) in component (A) is usually 0.1 to 10, preferably 0.5 to 2. be done.
The molar ratio of aluminum atoms in component (C) to chromium atoms (M) in component (A) is usually such that the Al/Cr ratio is 0.01 to 100,000, preferably 0.05 to 50,000. Used in quantity.

Component (D) has a ratio (g/mol) of the mass (g) of component (D) per mole of chromium atoms (M) in component (A) is usually 100 to 10000, preferably 1000 to 5000. used in such amounts.

Component (C) and component (E) are used in amounts such that the (E)/Al molar ratio is generally 0.01-10, preferably 0.1-5.
The polymerization reaction temperature is usually -50 to 200°C, preferably 0 to 170°C, more preferably 20 to 120°C. It may be preferable to carry out the olefin multimerization reactions of the present invention at relatively low temperatures. More preferably in the range of 0 to 50°C, more preferably in the range of 10 to 40°C, in the case of the multimerization reaction of ethylene, the by-production of ethylene polymer is small, and the selectivity for the production of 1-octene, which is a tetramer of ethylene. tends to be high.

According to studies by the present inventors, in the case of known olefin polymerization catalysts, there is a tendency that the amount of by-products of olefin polymers increases as the reaction temperature decreases. Although the cause of such a tendency is not clear, the present inventors consider it as follows.

Olefin multimerization containing a chromium compound (A), which is a conventional embodiment, an amine compound (B), and one or more components selected from the above (C-1), (C-2), and (C-3) In the catalyst, interaction between the so-called promoter components such as (C-1), (C-2), and (C-3), the chromium compound (A), and the amine compound (B) is low. At the reaction temperature, it decreases, for example, it becomes difficult for the reaction to proceed by the metallacycle mechanism that selectively produces 1-hexene and 1-octene from ethylene, and the production of polymers is relatively dominant. Maybe.

On the other hand, the compound (C) of the present invention has an effect that the (finely dispersed) magnesium component contained therein adjusts the reactivity of the organoaluminum compound, and the magnesium component has a chromium compound (A) even at a relatively low temperature. ), the amine compound (B), and the organoaluminum compound, the reaction is likely to proceed in the metallacycle mechanism, so that good reaction activity and α-olefin selectivity are achieved. I'm assuming it shows.

In the olefin multimerization reaction of the present invention. The reaction pressure is usually normal pressure to 10 MPa, preferably normal pressure to 6 MPa, more preferably normal pressure to 5 MPa. Also, the lower limit is preferably 0.5 MPa, more preferably 0.9 MPa, and particularly preferably 1.5 MPa. The most preferable upper limit is 4 MPa.

The multimerization reaction can be carried out in any of a batch system, a semi-continuous system and a continuous system.
The multimerization reaction may be carried out with the addition of an antistatic agent. Specific examples of antistatic agents include polypropylene glycol, polypropylene glycol distearate, ethylenediamine-PEG-PPG-block copolymer, stearyldiethanolamine, lauryldiethanolamine, alkyldiethanolamide, polyoxyalkylene (e.g. polyethylene glycol, polypropylene glycol, polyethylene glycol block copolymers (PEG-PPG-PEG)). Among them, polyoxyalkylene (eg, PEG-PPG-PEG) is preferred. The antistatic agent is used in an amount such that the ratio (g/mol) of mass (g) per mole of chromium atoms (M) in component (A) is usually 100 to 10000, preferably 100 to 1000. .

The multimerization reaction may be carried out by adding hydrogen. The hydrogen pressure for the reaction is usually 0.01 MPa to 5 MPa, preferably 0.01 MPa to 1 MPa.
The α-olefins, preferably 1-hexene and 1-octene, obtained by the olefin multimerization reaction of the present invention can be used without limitation in conventional applications using α-olefins. For example, it can be used as a raw material for synthesizing a variety of organic compounds, taking advantage of the reactivity of its double bond, in addition to the main monomer component and comonomer component for the production of olefin polymers.

Hereinafter, the present invention will be specifically described based on Synthesis Examples and Examples, but the present invention is not limited to these Examples.

[Quantification of reaction product]
The reaction product was quantified by gas chromatography using nonane as an internal standard (Shimadzu GC-14A apparatus, J&WS Scientific DB-5 column).

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

[Selectivity of 1-hexene or 1-octene]
The selectivity of 1-hexene or 1-octene was obtained according to the following formula.
S (%) = Wp/Wr x 100
S (%): 1-hexene or 1-octene selectivity (mass fraction)
Wr (mass): total mass of products having 4 or more carbon atoms produced by the reaction Wp (mass): mass of 1-hexene or 1-octene produced by the reaction Below, catalyst synthesis examples and ethylene An example of multimerization is shown.

[Synthesis Example 1]
(Preparation of chromium compound)

0.698 g (3.829 mmol) of compound (B1) identified by the above structural formula, 1.305 g (3.483 mmol) of chromium trichloride tristetrahydrofuran, and 70 mL of dichloromethane were added to a sufficiently dried 100 mL Schlenk tube. , under an argon atmosphere for 16 h. After concentrating the reaction solution under reduced pressure to about 1/7 in weight ratio, 15 mL of diethyl ether was added, and after stirring for a while, the insoluble matter was collected by filtration through a glass filter, washed with 20 mL of diethyl ether, and dried under reduced pressure to remove chromium. 0.67 g of compound (I) was obtained.

[Synthesis Example 2]
(Preparation of magnesium chloride-alcohol reactant component (C1))
95.2 g (1.0 mol) of anhydrous magnesium chloride, 242 ml of decane, 260.4 g (2.0 mol) of 2-ethylhexyl alcohol and 298.6 g (1.0 mol) of 2-octyldodecanol were heated at 155° C. for 4 hours. A reaction was carried out to obtain a homogeneous solution [component (C1)].

[Synthesis Example 3]
(Preparation of Mg-containing carrier component (C1-1))
50 ml of component (B1) (50 millimoles in terms of magnesium atom) and 400 ml of decane were charged into a flask with an internal volume of 1000 ml which was sufficiently replaced with nitrogen, and the liquid temperature was raised to 20 while stirring at 500 rpm using a three-one motor. C., 52 mmol of triethylaluminum diluted with decane were added dropwise over a period of 30 minutes. After that, the liquid temperature was raised to 80° C. over 3.5 hours, and the reaction was carried out for 1 hour. Next, while maintaining the temperature at 80° C., 98 millimoles of decane-diluted triethylaluminum was again added dropwise over 30 minutes, and then the reaction was further heated for 1 hour. After completion of the reaction, the solid portion was collected by filtration, thoroughly washed with toluene, and 100 ml of toluene was added to prepare a toluene slurry of the solid catalyst component (C1-1).

[Example 1]
(Ethylene multimerization reaction)
30 mL of toluene was put into an autoclave having an inner volume of 100 mL which was sufficiently purged with nitrogen, and 0.03 mmol (in terms of aluminum atom) of triisobutylaluminum was added. Further, a toluene slurry of the Mg-containing carrier component (C1-1) was added so as to make 0.4 mmol in terms of magnesium atom. After replacing the gas phase with ethylene, the temperature of this slurry liquid was raised to 30°C. Separately, under an argon atmosphere, 0.02 mmol (in terms of chromium atom) of the chromium compound (I) obtained in Synthesis Example 1 and 19.5 mL of toluene were added to a sufficiently dried Schlenk tube to form a 1 mol/L triethylaluminum/toluene solution. 0.5 mL (0.5 mmol in terms of aluminum atom) was contacted, and 0.5 mL (0.5 μmol in terms of chromium atom) of the mixture was added to the autoclave. The reactor was kept at 30° C. for 60 minutes while supplying ethylene so that the pressure in the reactor was maintained at 0.8 MPa-G. Thereafter, the pressure was released to remove unreacted ethylene, and a small amount of isopropanol was added to stop the reaction. After completion of the reaction, the reaction mixture was washed with 0.1N aqueous hydrochloric acid and pure water, and low boiling point components (components with 10 or less carbon atoms) were separated from high boiling point components and polyethylene using a liquid nitrogen trap under reduced pressure. , analyzed by gas chromatography. The amount of low boiling point components produced (the amount of components with 10 or less carbon atoms) was 636 mg, and the amount of polyethylene produced was 50 mg. )Met. The selectivity for 1-hexene was 5.4% by mass, the selectivity for 1-octene was 86.8% by mass, and the catalytic activity for 1-octene was 1190 (g/mmol-Cr·hr).

[Example 2]
The reaction was carried out under the same conditions as in Example 1, except that the reaction temperature was changed from 30°C to 25°C. The amount of low boiling point components produced (the amount of components with 10 or less carbon atoms) was 764 mg, and the amount of polyethylene produced was 79 mg. )Met. The selectivity for 1-hexene was 4.2% by mass, the selectivity for 1-octene was 86.0% by mass, and the catalytic activity for 1-octene was 1450 (g/mmol-Cr·hr).

[Comparative Example 1]
The reaction was carried out under the same conditions as in Example 1, except that the toluene slurry of the Mg-containing carrier component (C1-1) was not added. The amount of low boiling point components produced (the amount of components with 10 or less carbon atoms) was 92 mg, and the amount of polyethylene produced was 62 mg. )Met. The 1-hexene selectivity was 31.7% by mass, the 1-octene selectivity was 27.4% by mass, and the 1-octene catalytic activity was 85 (g/mmol-Cr·hr).

[Comparative Example 2]
30 mL of toluene was placed in an autoclave having an internal volume of 100 mL which was sufficiently purged with nitrogen, and methylaluminoxane (Tosoh Finechem MMAO-3A, 5.7 mass % hexane solution) was added in an amount of 0.5 mmol in terms of aluminum atom. After replacing the gas phase with ethylene, the temperature of this slurry liquid was raised to 25°C. Separately, under an argon atmosphere, the chromium compound (I) obtained in Synthesis Example 1 was dissolved in toluene in a sufficiently dried Schlenk tube to prepare a toluene solution (catalyst solution) having a concentration of 0.001 mmol/mL in terms of chromium atoms. did. 0.1 mL of this solution (0.1 μmol in terms of Cr atom) was added to the autoclave. The reactor was kept at 25° C. for 60 minutes while supplying ethylene so that the pressure in the reactor was maintained at 0.8 MPa-G. After that, the product was analyzed in the same manner as in Example 1. The amount of low boiling point components produced (the amount of components with 10 or less carbon atoms) was 147 mg, and the amount of polyethylene produced was 59 mg. )Met. The selectivity of 1-hexene was 3.2% by mass, the selectivity of 1-octene was 67.6% by mass, and the catalytic activity of 1-octene was 1390 (g/mmol-Cr·hr).

From the above results, it can be seen that the olefin multimer production method of the present invention can selectively produce olefin multimers with less by-products of olefin polymers. In particular, it tends to be suitable for the production of 1-octene, which is a tetramer in the multimerization reaction of ethylene.

The method for producing an olefin multimer of the present invention has excellent reaction activity even at a relatively low temperature, produces little olefin polymer by-products, that is, has a high selectivity for producing an olefin multimer, and produces an olefin multimer. It is extremely useful in In addition, in the multimerization reaction of ethylene, the selectivity of 1-octene, which is the tetramer, tends to be high. Therefore, the present invention is industrially of extremely high value.

Claims (8)

A method for producing an olefin multimer, comprising conducting an olefin multimerization reaction in the presence of an olefin multimerization catalyst containing the following components (A) to (C).
(A) a chromium compound (B) an amine compound represented by the following general formula (1)

(In general formula (1), R ¹ to R ⁴ may be the same or different, and are hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron contains groups, aluminum-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, or tin-containing groups, two or more of which may be linked together.
Y represents a carbon atom having substituents R ⁵ and R ⁶ (structure represented by —CR ⁵ R ⁶ —). R ⁵ and R ⁶ may be the same or different from each other, and may be 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, phosphorus ^- containing group, silicon ^- containing group, germanium ^- containing group, or tin ^- containing group; good.
Z represents an integer of 1-10. )
(C) A component obtained by contacting a magnesium halide with an alcohol having 1 to 20 carbon atoms and then with an organoaluminum compound represented by the following general formula (α):

(In the formula, R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom or a hydrogen atom, n is a real number of 1 to 3, and when there are multiple Rs, each R may be the same or different. Well, when there are multiple Xs, each X may be the same or different.) 2. The amine compound (B) according to claim 1, wherein R ¹ is not connected to R ³ and R ⁴ and R ² is not connected to R ³ and R ⁴ in general formula (1). A method for producing an olefin multimer. The method for producing an olefin multimer according to claim 1, wherein the amine compound (B) in which Z is an integer of 1 to 3 in the general formula (1) is used. The method for producing an olefin multimer according to claim 1, wherein the amine compound (B) in which Z is 1 in the general formula (1) is used. The method for producing olefin multimers according to claim 1, wherein the olefin multimerization catalyst contains 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). The method for producing an olefin multimer according to claim 1, wherein the olefin multimerization reaction is carried out in the presence of an antistatic agent. The method for producing an olefin multimer according to claim 1, wherein the olefin is ethylene. The method for producing an olefin multimer according to claim 1, wherein the olefin multimer is 1-octene.