JP2021151994A - Method for producing olefin multimer - Google Patents

Abstract

To provide a method for producing olefin multimers that is conducted in the presence of a catalyst for olefin multimerization, the resultant olefin multimers having excellent activity and particularly exhibiting high 1-octene selectivity and/or production efficiency.SOLUTION: In a specific reaction temperature range, in the presence of a catalyst for olefin multimerization including a chromium compound (A), a specific amine compound (B), and a compound such as an organic metal compound (C), the olefin multimerization reaction is caused to occur, so that olefin multimers can be produced that has excellent activity and particularly exhibits high 1-octene selectivity and/or production efficiency.SELECTED DRAWING: None

Description

The present invention relates to a method for producing an olefin multimer, which is carried out in the presence of a catalyst for olefin quantification, which has excellent activity and has high selectivity and / or production efficiency of a specific olefin multimer.

α-olefins are, for example, important compounds widely and industrially used 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 of using organoaluminum or a transition metal compound as a catalyst as an industrialized method. However, in industrialized methods, mixtures of many 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 desired 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). ).

Further, as a catalyst for selectively producing 1-octene, a chromium-based catalyst using a ligand containing a phosphorus atom is disclosed (for example, Patent Documents 2 to 4).

International Publication No. 2009/005003 International Publication No. 2004/056479 International Publication No. 2013/137676 International Publication No. 2009/022770

According to the studies by the present inventors, it cannot be said that the performance of one or more of the reaction activity, the thermal stability, and the selectivity of the α-olefin produced is sufficient with the conventional catalyst, and further improvement is desired. In some cases. In particular, when a conventional catalyst for selectively producing 1-hexene is used, the selectivity of 1-octene is low (or no 1-octene is obtained) as compared with the selectivity of 1-hexene. It seems that there are many cases.

Like 1-hexene, 1-octene is an important component as a raw material for polyolefin, and is an important component particularly when producing high-performance polyolefin. In addition, 1-octene may be important as a raw material for lubricating oil.

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

As a result of diligent studies to solve the above problems, the present inventors have found that catalysts containing a specific transition metal compound, an amine compound having a specific structure, and a co-catalyst have excellent activity and / or high 1-octene. In the presence of this catalyst, the olefin massification reaction can be suitably carried out, and particularly when ethylene is used as the olefin, 1-octene, which is a tetramer of ethylene, is highly active. We found that we could obtain it, and completed the present invention. That is, the present invention is specified by the following matters.

[1] A method for producing an olefin multimer, which carries out an olefin quantification reaction in the presence of an olefin quantification catalyst containing the following components (A) to (C).
(A) Chromium compound,
(B) The amine compound represented by the following general formula (1),

(In the general formula (1), R ^{1 to} R ³ are independently hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, and 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 R ¹ to R ³ may be linked to each other.
(C) (C-1) Organometallic compound,
(C-2) Organoaluminium 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] The method for producing an olefin multimer according to [1], wherein in the general formula (1), R ¹ uses an ^{amine compound (B) that is not linked to R 2} and R ^3.
[3] The method for producing an olefin multimer according to [1] or [2], which comprises the following carrier (D) in addition to the components (A) to (C).
(D) A carrier for supporting at least one compound selected from the group consisting of components (A) to (C).
[4] The method for producing an olefin multimer according to any one of [1] to [3], wherein the olefin quantification reaction is carried out in the presence of an antistatic agent.
[5] The method for producing an olefin multimer according to any one of [1] to [4], wherein the olefin is ethylene.
[6] The method for producing an olefin multimer according to any one of [1] to [5], wherein the olefin multimer is 1-octene.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for producing an olefin multimer, which is carried out in the presence of a catalyst for olefin augmentation, which has excellent activity and particularly high selectivity and / or production efficiency of 1-octene.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto. In the present invention, increasing the amount of olefin means making the olefin into a 2 to 10 quantifier, and preferably making the olefin into a trimer to a tetramer.

<Chromium compound (A)>
The chromium compound (A) 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 bromide (III), chromium bromide (II), chromium iodide (III), and chromium iodide (II). , Chromium Fluoride (III), Chromium Fluoride (II), Chromium Trichloride tetrahydrofuran, Chromium (III) 2-Ethylhexanoate, Chromium (III) Acetylacetonate, Chromium (III) Trifluoroacetylacetonate, Chromium (III) hexafluoroacetylacetonate can be mentioned. However, the chromium compound (A) is not limited to these. Among these, a trivalent chromium compound is preferable. A chromium compound containing a halogen atom is also preferable.

<Amine compound (B)>
The amine compound as the component (B) (hereinafter, also referred to as “amine compound (B)”) is represented by the following general formula (1).

In the general formula (1), R ^{1 to} R ³ independently contain 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, and an aluminum. It represents a 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 to} R ³ are independently hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, hydrocarbon-substituted silyl group, hydrocarbon-substituted syroxy group, alkoxy group, respectively. Alkylthio group, aryloxy group, arylthio group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group, sulfo group, It is preferably a mercapto group, an aluminum-containing group or a hydroxy group.
R ^{1 to} R ³ may be the same as each other, R ^{1 to} R ³ may contain one or more combinations of different groups, and R ^{1 to} R ³ may be different from each other.

Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine.

The hydrocarbon group is a group containing a hydrocarbon group as a portion to be bonded to another group, and the hydrocarbon group may be substituted with another substituent. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl and the like, preferably having 1 to 30 carbon atoms. Linear or branched alkyl groups from 1 to 20, more preferably 1 to 10; linear or branched groups having 2 to 30, preferably 2 to 20 carbon atoms such as vinyl, allyl, isopropenyl, etc. Branched alkenyl group; linear or branched alkynyl group having 2 to 30 carbon atoms such as ethynyl and propargyl, preferably 2 to 20; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl and the like Cyclic saturated hydrocarbon groups of 3 to 30, preferably 3 to 20; cyclic unsaturated hydrocarbon groups of 5 to 30 carbon atoms such as cyclopentadienyl, indenyl, fluorenyl; phenyl, naphthyl, biphenyl, terphenyl, phenanthryl , Anthracenyl and the like; aryl groups having 6 to 30, preferably 6 to 20 carbon atoms; these aryl groups have halogen atoms, 1 to 30 carbon atoms, preferably 1 to 20 alkyl groups and alkoxy groups. Alternatively, a substituted aryl group substituted with 1 to 5 substituents selected from the group consisting of substituents such as an amino group, an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 or an aryloxy group; benzyl, cumyl. , Diphenylethyl, trityl and other aryl group-substituted alkyl groups having 7 to 19 carbon atoms; benzylidene, methylidene, ethylidene and the like having 1 to 30 carbon atoms, preferably 5 to 10 alkylidene groups. Examples of the alkyl-substituted aryl group include an alkyl-substituted aryl group having 7 to 14 carbon atoms such as tolyl, isopropylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl.

The hydrocarbon group may be a group in which at least one hydrogen atom of the hydrocarbon group is substituted with a group other than the hydrocarbon group.
Examples of the group other than the hydrocarbon group substituted with the hydrocarbon group include a halogen atom, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, and a silicon-containing group. At least one selected from the group consisting of a germanium-containing group and a tin-containing group can be mentioned.
Examples of the halogen-substituted hydrocarbon group include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl and chlorophenyl.

Preferred hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, adamantyl and the like, with 1 to 30 carbon atoms, preferably 1 ~ 20, more preferably 1-10, particularly preferably 2-10 linear or branched alkyl groups; 6-30 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc., preferably 6 to 20 aryl groups; examples thereof include substituted aryl groups in which 1 to 5 substituents are substituted on these aryl groups. The substituent of the substituted aryl group is a halogen atom, an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20, an alkoxy group or an amino group, and an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 atoms. Alternatively, it is selected from the group consisting of substituents such as allyloxy groups.

Examples of the oxygen-containing group, the nitrogen-containing group, the sulfur-containing group and the phosphorus-containing group include a group containing at least one selected from an oxygen atom, a nitrogen atom, an ionic atom and a phosphorus atom. In the present invention, these groups are mainly classified by atoms that characterize the properties and bonding modes of the groups. For example, a group consisting of an oxygen atom alone, and a group whose characteristics and bonding mode are characterized by an oxygen atom, such as a group consisting of at least one of a carbon atom and a hydrogen atom and an oxygen atom, are classified as oxygen-containing groups. being classified. Even if a group having a nitrogen atom has an oxygen atom, a group whose characteristics and bonding mode are characterized by a nitrogen atom is classified as a nitrogen-containing group. Groups with sulfur or phosphorus atoms are similarly classified. Boron-containing groups, aluminum-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, and tin-containing groups, which will be described later, are also classified in the same manner.
Among the oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups and phosphorus-containing groups, oxygen-containing groups, nitrogen-containing groups and sulfur-containing groups are preferable, and oxygen-containing groups and nitrogen-containing groups are more preferable.

Examples of the oxygen-containing group include a hydroxy group, an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a peroxy group, and a carboxylic acid anhydride group.
Examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group and a tert-butoxy group.
Examples of the aryloxy group include an aryloxy group having an unsubstituted aryl group and an aryloxy group having 1 to 3 alkyl groups having 1 to 4 carbon atoms. Examples of the aryl group contained in the aryloxy group include a phenyl group and the like. Specific examples thereof include a phenoxy group, a 2,6-dimethylphenoxy group, a 2,4,6-trimethylphenoxy group, a 3,5-di-tert-butylphenoxy group and the like.
The ester group is a group containing an ester bond, and examples thereof include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group.
Examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, a p-methoxybenzoyl group and the like.

Examples of the nitrogen-containing group include groups in which nitrogen atoms do not form a cyclic structure. Such groups include an amide group which may be substituted, an amino group which may be substituted, an imide group which may be substituted, an imino group which may be substituted, a hydrazino group, a hydrazono group, and a nitro group. Examples thereof include a group in which a group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, and an amino group are ammonium salts.
The amide group is a group containing an amide bond, and specific examples of the substituted amide group include acetamide, N-methylacetamide, and N-methylbenzamide. Specific examples of the substituted amino group include dimethylamino, ethylmethylamino, and diphenylamino. The imide group is a group having an imide bond, and specific examples of the substituted imide group include acetimide and benzimide. The imino group is a group having an imino bond, and specific examples of the substituted imino group include methylimino, ethylimino, propylimino, butylimino, and phenylimino.

Examples of the sulfur-containing group include an alkylthio group, an arylthio group, a thioester group, a sulfone ester group, an optionally substituted sulfonamide group, a mercapto group, a dithioester group, a thioacyl group, a thioether group, a thiosian acid ester group and an isothiocyanate group. Examples thereof include an acid ester group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group and a sulphenyl group.
Specific examples of the alkylthio group include methylthio and ethylthio. Specific examples of the arylthio group include phenylthio, methylphenylthio, and naphthylthio. The thioester group is a group containing a thioester bond, and specific examples thereof include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl. Specific examples of the sulfone ester group include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate. The sulfonamide group is a group containing a sulfonamide bond, and specific examples of the substituted sulfonamide group include phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide.

Examples of the heterocyclic compound residue include residues obtained from a polycyclic compound having at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom, such as a monocyclic compound or a bicyclic compound. be able to. Specific examples of heterocyclic compound residues include 5- or 6-membered nitrogen-containing monocyclic compounds such as pyrrole, pyridine, pyrimidine, and triazine, residues of sulfur-containing bicyclic compounds such as quinoline, furan, and pyran. Residues such as 5- or 6-membered oxygen-containing monocyclic compounds such as thiophene, sulfur-containing monocyclic compounds such as thiophene, and these heterocyclic compound residues have 1 to 30 carbon atoms, preferably 1. Examples thereof include groups in which one or more of substituents such as an alkyl group to 20 and an alkoxy group are further substituted.

Specific examples of the boron-containing group include a bolangyl group, a bolantriyl group, a diboranyl group and the like. Further, examples thereof include groups of alkyl group-substituted boron, aryl group-substituted boron, halogenated boron, and alkyl group-substituted boron halide. The group of the alkyl group substituted boron, for _{example, (Et) 2 B -,} (iPr) 2 B -, (iBu) 2 B -, (Et) 3 B, (iPr) 3 B, is _{(iBu) 3} B be. Examples of the aryl group-substituted boron group include (C ₆ H ₅ ) ₂ B-, (C ₆ H ₅ ) ₃ B, (C ₆ F ₅ ) ₃ B, and (3,5- (CF ₃ ) ₂ C. ₆ H ₃ ) There is _{3 B.} Examples of the boron halide group include BCl _2- and BCl ₃ . Examples of the group of the alkyl group-substituted boron halide 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. Further, the trisubstituted boron may be in a coordinated bond state.

Specific examples of the aluminum-containing group include an alkyl group-substituted aluminum, an aryl group-substituted aluminum, an aluminum halide, and an alkyl group-substituted aluminum halogenated group. Examples of the alkyl group-substituted aluminum group include (Et) ₂ Al−, (iPr) ₂ Al−, (iBu) ₂ Al−, (Et) ₃ Al, (iPr) ₃ Al, and (iBu) ₃ Al. be. Examples of the aryl group-substituted aluminum group include (C ₆ H ₅ ) ₂ Al−. Examples of the group of aluminum halide include AlCl _2- and AlCl ₃ . Examples of the group of the 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. Further, the trisubstituted aluminum may be in a coordinated bond state.

Examples of the phosphorus-containing group include a phosphide group, a phosphoryl group, a thiophosphoryl group, a phosphato group and the like.

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. There is. Of these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, and triphenylsilyl are preferable, and trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are more preferable. Hydrocarbon-substituted syroxy groups include trimethylsiloxy.

Specific examples of the germanium-containing group and the tin-containing group include those in which the silicon of the silicon-containing group exemplified above is replaced with germanium or tin.

In the general formula (1), R ² and R ³ may be connected to each other to form an annular structure. When R ² and R ³ are linked (bonded) to form a cyclic structure together with a nitrogen atom, the number of bonds of this cyclic structure is 3 or more, preferably 5 or more.
The number of bonds refers to the number of bonds that the connection from the nitrogen atom to the original nitrogen atom via ^{R 2} and R ^{3 has.} For example, when R ² and R ³ are both methylene groups (−CH ₂₋ ) and they are linked, the number of bonds in the link chain consisting of ^{nitrogen atom, R 2} and R ^{3 is 3.}
Examples of the group having a preferable cyclic structure in which R ² and R ³ are linked to form together with a nitrogen atom include an aziridinyl group, an azetidyl group, a pyrrolidyl group and a piperidyl group, among which the pyrrolidyl group and the piperidyl group can be mentioned. Is more preferable.

When R ^{1 to} R ³ are any of the above preferred groups, the reaction activity of the olefin tends to be higher, and the olefin is a 2 to pentamer (preferably a 3 to tetramer). It tends to facilitate the more efficient production of certain relatively low boiling point α-olefins. Here, when the raw material is ethylene, its 3 to tetramers correspond to hexene and octene. That is, it tends to be suitable for producing an olefin having 10 or less carbon atoms.

When an olefin multimerization catalyst containing an amine compound (B) is used, the production of a total product in an amount of an olefin multimer as described above, that is, a 2 to pentamer (preferably 3 to tetramer) of the olefin is produced. The ratio to the amount tends to be high. Specifically, the lower limit of this ratio is preferably 70% by mass, more preferably 73% by mass, still more preferably 75% by mass, and particularly preferably 77% by mass. On the other hand, the preferable upper limit value is 100% by mass, more preferably 98% by mass, still more preferably 95% by mass, particularly preferably 90% by mass, and particularly preferably 85% by mass. As described above, for example, when the ratio of the amount of 2 to pentamer (preferably 3 to 4) produced is high, the types of multimers produced tend to decrease. Further, since the difference in boiling points of each component is relatively large, it becomes easy to separate by distillation (for example, 1-hexene has a boiling point of 63 ° C. and 1-octene has a boiling point of 122 to 123 ° C.). As a result, manufacturing costs can be suppressed, and it is thought that it is easy to respond to the effects of market conditions.

In the present invention, one of the indexes for comprehensively judging the performance of the catalyst for increasing the amount of olefins is the catalytic activity of 1-octene described in Examples described later. 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 efficiency of 1-octene production. The 1-octene production efficiency is an index different from the 1-octene selectivity.
Further, in each of the preferred embodiments described above, not only the efficiency of producing ethylene trimers (1-hexene) and tetramers (1-octene) is further improved, but also the reaction activity of ethylene and 1-octene are improved. It is also preferable in terms of efficient production of ethylene.

When producing a multimer of ethylene in the present invention, 1-hexene and 1-octene are the main products. And both are relatively easy to separate by distillation. Therefore, the 1-octene production efficiency 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 manufacturing facility for co-producing 1-hexene and 1-octene.

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 ⁿ Bu is a normal butyl group.

As the amine compound (B), a commercially available amine compound may be used. When synthesizing an amine compound (B), the amine compound (B) can be obtained, for example, by alkylating or arylating a specific amine compound by a general method. The amine compound (B) can also be obtained by reducing the imine compound by a general method. Further, in the present invention, a plurality of types of amine compounds (B) can be used in combination.

When an olefin quantification catalyst containing an amine compound (B) is used, 1-octene tends to be efficiently produced as described above. For example, among the olefin multimers having 10 or less carbon atoms to be produced, the proportion of 1-octene is preferably 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably. It is 65% by mass or more, most preferably 70% by mass or more.

The amine compound (B) and the chromium compound (A) may be added to the reactor separately. However, it is preferable to add the 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 under an atmosphere of an inert gas such as nitrogen or argon, from −78 ° C. to room temperature or reflux conditions for about 5 minutes to The 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 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.
The transition metal complex is obtained in a state of being dissolved or suspended in a solvent. The 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.

<Compound (C)>
As the component (C), the organometallic compound (C-1) (hereinafter, also referred to as “component (C-1)”) and the organoaluminum oxy compound (C-2) (hereinafter, also referred to as “component (C-2)”). At least one compound selected from the group consisting of a compound (C-3) (hereinafter, also referred to as "component (C-3)") that reacts with a transition metal compound to form an ion pair (hereinafter, also referred to as "component (C-3)"). Also referred to as "compound (C)") is used. Hereinafter, these compounds (C-1) to (C-3) will be described. In the following description, compound (C-3) will be referred to as "ionized ionic compound (C-3)".

[Organometallic compound (C-1)]
Examples of the organometallic compound (C-1) include the compounds (C-1a), (C-1b) and (C-1c) described below, which are Group 1, 2, 12, and 13 of the Periodic Table. Organometallic compounds can be used. In the present invention, the organometallic compound (C-1) does not include the organoaluminum oxy compound (C-2) described later.

(C-1a): the general formula ^{_{R a m Al (OR b)}} n H p X q ( wherein, ^{R a} and ^{R b} may carbon atoms may be the same or different 1 to 15, preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, m is a number of 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is a number of 0 ≦ q <3. And m + n + p + q = 3).

(C-1b): shows the general formula ^M 2 ^AlR _{a 4} (wherein, ^{M 2} represents a Li, Na or K, ^{R a} is the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups ) Is a complex alkylated product of Group 1 metal and aluminum.

(C-1c): General formula ^Ra R ^b M ³ (In the formula, ^Ra 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. ³ is Mg, Zn or Cd), which is a dialkyl compound of a Group 2 or 12 metal of the periodic table.
Examples of the organoaluminum compounds (C-1a), for example, in the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, ^{R a} and ^{R b} are optionally carbon atoms may be the same or different 15, preferably an 1-4 hydrocarbon group, m is preferably a number 1.5 ≦ m ≦ 3.) an organoaluminum compound represented by the general formula ^R _{a m AlX 3-m} (In the formula, Ra represents ^a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably a number of 0 <m <3). an organoaluminum compound represented by the general formula ^R _{a m AlH 3-m} (wherein, ^{R a} is the number of carbon atoms 1 to 15, preferably an 1-4 hydrocarbon group, m is preferably 2 ≦ m <organoaluminum compound represented by the 3 number of a is), the general formula _{^{R a m Al (oR b)}} n X q ( wherein, ^{R a} and ^{R b} are optionally carbon atoms may be the same or different Indicates a hydrocarbon group of 1 to 15, preferably 1 to 4, X represents a halogen atom, m is a number of 0 <m ≦ 3, n is 0 ≦ n <3, and q is a number of 0 ≦ q <3. Yes, and an organoaluminum compound represented by m + n + q = 3) can be used.

Specific examples of the organic aluminum compound (C-1a) include trimethylaluminum, triethylaluminum, tri (n-butyl) aluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum. Tri (n-alkyl) aluminum; triisopropyl aluminum, triisobutyl aluminum, tri (sec-butyl) aluminum, tri (tert-butyl) aluminum, tri (2-methylbutyl) aluminum, tri (3-methylbutyl) aluminum, tri (tri (3-methylbutyl) aluminum. 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 chain alkyl aluminum such as; tricycloalkyl aluminum such as tricyclohexylaluminum, tricyclooctylaluminum; triarylaluminum such as triphenylaluminum, tritrylaluminum; dialkylaluminum hydride such as diethylaluminum hydride, diisobutylaluminum hydride; iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (In the formula, x, y, z are positive numbers and z ≧ 2x. iC ₄ H ₉ represents an isobutyl group). Represented alkenyl aluminum such as isoprenyl aluminum; alkylaluminum alkoxides such as isobutylaluminum methoxyd, isobutylaluminum ethoxide, isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxyde, diethylaluminum ethoxide, dibutylaluminum butoxide. Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxydo, butylaluminum sesquibutoxide; for example ^Ra _2.5 Al (OR ^b ) _0.5 (in the formula, ^Ra and R ^b may be the same or different from each other. Partially alkoxylated alkylaluminum having an average composition represented by a good carbon number of carbon atoms 1-15, preferably 1-4 hydrocarbon groups; 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), 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 sesquibramide; like alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromid Partially halogenated alkylaluminum; dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; partially hydrogenated alkylaluminum such as ethylaluminum dihydrides and alkylaluminum dihydrides. Examples include partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butokicyclolide, and ethylaluminum ethoxybromid.

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. Organoaluminium compounds bound to 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 organic metal 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.

Compounds such as those in which organoaluminum compounds are formed in the augmentation reaction system, such as a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium, can also be used.
The organometallic compound (C-1) described above can be used alone or in combination of two or more. Further, among the organometallic compounds (C-1) described above, the organoaluminum compound (C-1a) is particularly preferable.

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

(1) Compounds containing adsorbed water or salts containing water of crystallization (for example, magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate) ) And an organic aluminum compound such as trialkylaluminum are added to a suspension containing a hydrocarbon solvent to cause the adsorbed water or water of crystallization to react with the organic aluminum compound.

(2) A method in which water, ice or water vapor is allowed to act directly 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.

Alminoxane may contain a small amount of organometallic components. The solvent and the unreacted organoaluminum compound may be distilled and removed from the solution of aluminoxane recovered in each of the above methods, and the aluminoxane may be further redissolved in the solvent or suspended in a poor solvent of aluminoxane.

Specific examples of the organoaluminum compound used for producing alminoxane are the same as those of the organoaluminum compound (C-1a) described above. The organoaluminum compound can be used alone or in combination of two or more. Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.

As the solvent used for producing alminoxane, for example, a hydrocarbon solvent or an ether solvent can be used. Specific examples of hydrocarbon solvents include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and simen; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; cyclopentane, Alicyclic hydrocarbons such as cyclohexane, cyclooctane, methylcyclopentane; petroleum distillates such as gasoline, kerosene, light oil; halides of aromatic hydrocarbons, aliphatic hydrocarbons or alicyclic hydrocarbons (especially chlorinated or Brobride). Specific examples of the ether solvent include ethyl ether and tetrahydrofuran. Of these, aromatic hydrocarbons and aliphatic hydrocarbons are preferable. When an organic aluminum oxy compound that is insoluble or sparingly soluble in benzene is used, the amount of the 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 as follows.

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

(In the general formula (2), ^{R 4} is a hydrocarbon group having 1 to 10 carbon atoms or .4 one ^{R 5} in which the number of carbon atoms is a halogenated hydrocarbon group of 1 to 10, are each independently a hydrogen atom, a halogen atom, is the .4 one R ⁵ showing 1-10 hydrocarbon group having carbon atoms may be identical to each other, may be included combinations of these different groups are one or more, These may be different from each other.)

The organoaluminum oxy compound containing boron represented by the general formula (2) is, for example, the alkylboronic acid represented by the following general formula (3) and the organoaluminum compound being inert under 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.

R ^4- B (OH) ₂ ... (3)
(In the general formula (3), ^{R 4} represents the same group as ^{R 4} in the general formula (2))

Specific examples of the alkylboronic acid represented by the general formula (3) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, and the like. Examples thereof include cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, and 3,5-bis (trifluoromethyl) phenylboronic acid. Of these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferable. These alkylboronic acids can be used alone or in combination of two or more.

Specific examples of the organoaluminum compound to be reacted with alkylboronic acid are the same as those 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 preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are more preferable.

The organoaluminum oxy compound (C-2) described above can be used alone 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, at least a compound having a property of forming an ion pair when contacted with a transition metal compound corresponds to this ionized ionic compound (C-3).

Examples of the ionized ionic compound (C-3) include JP-A-1-501950, JP-A-1-502306, JP-A-3-179005, JP-A-3-179006, and JP-A-3-179006. Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A-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 a phenyl group or fluorine which may have a substituent such as a fluorine, a methyl group, or a trifluoromethyl group). Specific examples thereof include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, and tris (pentafluorophenyl). Examples thereof include boron, tris (p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.

Specific examples of the ionic compound include compounds represented by the following general formula (4).

In the general formula (4), examples of ^{R 6+ include H +} , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptiltyrienyl cation, and ferrosenium cation having a transition metal. R ^{7 to} R ¹⁰ each independently represent an organic group, preferably an aryl group or a substituted aryl group. These groups may be the same as each other, may contain one or more combinations of different groups, and may be different from each other.

Specific examples of the case where R ⁶⁺ is a carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

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

Specific examples of the case where R ⁶⁺ is a phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

As R ⁶⁺ , a carbonium cation and an ammonium cation are preferable, and a triphenylcarbonium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are more preferable.

In addition to the compound represented by the general formula (4) described above, the ionic compound also includes a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, a dialkylammonium salt, and a triarylphosphonium salt. Can be used.

Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tri (n-propyl) ammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, and 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 Examples include (n-butyl) ammonium tetra (o-tolyl) borate.

Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N, 2,4,6-pentamethylaniri. Nium tetraphenylborate can be mentioned.

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

In addition to the salts described above, examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferrosenium tetra (pentafluoro). Phenyl) 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. ..

(In the general formula (5), Et represents an ethyl group.)

(In the general formula (6), Et represents an ethyl group.)

Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonabolate, bis [tri (n-butyl) ammonium] decaboleate, and bis [tri (n-butyl) ammonium] undeca. Anion salts such as borate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachloro dodecaborate; Metal borane anions such as tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III) Salt is mentioned.

Specific examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbanoborane (14), and dodecahydride-1-phenyl-1,3. -Dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbanonaborane (7,8-dicarbanonaborane ( 13) 2,7-Dicarbaundecaborane (13), Undecahydride-7,8-dimethyl-7,8-dicarbundecaborane, Dodecahydride-11-methyl-2,7-dicarbaundecaborane, Tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilylate -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-carbundecaborate (13), tri (n-butyl) ammonium 7,8-dicarbundecaborate (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 -Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dical Borane de Caborate, Tri (n-Butyl) Ammonium Undeca Hydlide-9-trimethylsilyl-7,8-Dicarba Undecaborate, Tri (n-Butyl) Ammonium Undeca Hydlide-4,6-dibromo-7-Carba Undeca Anion salts such as borate; tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonabolate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7, 8-Dicarbound de cabole G) Iron salt (III), tri (n-butyl) ammonium bis (undecahydrate-7,8-dicarba undecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride) -7,8-dicarbaundecaborate) Niklate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) copper salt (III), tri (n-) Butyl) ammonium bis (undecahydride-7,8-dicarbundecaborate) hydroxide (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundeca) Borate) iron salt (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbundecaborate) chromate (III), tri (n-butyl) ammonium Bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydrate-7-carbaundecarbolate) chromate ( III), bis [tri (n-butyl) ammonium] bis (undecahydrate-7-carbaundecarbolate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydrate-7) -Carboundecabolate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbundecaborate) nickelate (IV) and other salts of metal carborane anions Can be mentioned.

The heteropoly compound usually consists of an atom consisting of silicon, phosphorus, titanium, germanium, arsenic or tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specific examples thereof include limvanadic acid, germanovanadic acid, arsenic vanadic acid, linniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdenum acid, germanomolybdic acid, arsenic molybdic acid, tin molybdenum acid, Phosphoridtoxyic acid, germanotungstate, tintungstate, phosphoribdvanadic acid, lintangustovanadinic acid, germanotangstvanadinic acid, phosphoribbed tonguestovanadic acid, germanomoribed tonguestovanadic acid, phosphorib Examples thereof include dotung acid and phosphoribdoniobic acid. Further, it may be a salt of each of these acids. Specific examples of the salt include salts with metals of Group 1 or 2 of the Periodic Table (eg, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium), triphenylethyl salts and the like. Organic salts and isopoly compounds of.

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

When the above catalyst for increasing the amount of olefin is used, an olefin multimer can be obtained with high activity, and particularly when ethylene is used as the olefin, the selectivity of 1-octene is high. For example, when an organoaluminum oxy compound (C-2) such as methylaluminoxane is used in combination as a co-catalyst component, it exhibits higher activity against ethylene and 1-octene can be produced. Also, when an ionized ionic compound (C-3) such as triphenylcarbenium tetrakis (pentafluorophenyl) borate is used as a co-catalyst component, 1-octene can be obtained from ethylene with better activity and higher selectivity. ..

<Carrier (D)>
The catalyst for increasing the amount of olefin may contain a carrier (D). The carrier (D) is an inorganic compound or an organic compound, and is usually a solid in the form of granules or fine particles. In the present invention, the carrier (D) carries at least one component selected from the group consisting of the chromium compound (A), the amine compound (B) and the compound (C). Further, the organic compound (E) used may be supported as needed. As the inorganic compound for the carrier (D), a porous oxide, an inorganic halide, clay, a clay mineral, and an ion-exchange layered compound are preferable.

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 a composite or mixture containing these (for example,). , 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) is Can be mentioned. Of these, _{a porous oxide containing SiO 2} and / or Al ₂ O ₃ as a main component is preferable. Porous oxides include small amounts of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ , It may contain carbonates such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O, sulfates, nitrates or oxide components. 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 production 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, and the specific surface area is preferably 50 to 1000 m ² / g, more preferably 100 to 700 m ² / g. The pore volume is preferably 0.3 to 3.0 cm ³ / g. The porous oxide is calcined at preferably 100 to 1000 ° C., more preferably 150 to 700 ° C., if necessary.

Specific examples of the inorganic halide include MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ . 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, it is also possible to use a product obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating it in the form of fine particles with a precipitant.
The clay usually contains a clay mineral as a main component. Further, the ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds are stacked in parallel with each other with a weak bonding force, and the contained ions are exchangeable compounds. As the ion-exchangeable layered compound, for example, an ionic crystalline compound having a layered crystal structure such as _{hexagonal fine packing type, antimony type, CdCl 2} type, and CdI _{2 type can be used.} Most clay minerals are ion-exchange layered compounds. As these clays, clay minerals and ion-exchange layered compounds, not only natural ones but also artificial synthetic compounds can be used.

Specific examples of clay and clay minerals include kaolin, bentonite, knot clay, gailome clay, allophane, hisingel stone, pyrophyllite, mica, montmorillonite, vermiculite, hectorite, teniolite, ryokudei stone, parigolskite, kaolinite, and nacrite. , Dickite, Halloysite. Specific examples of the ion-exchangeable layered _{compound, α-Zr (HAsO 4)} 2 · H 2 O, α-Zr (KPO 4) 2 · 3H 2 O, α-Ti (HPO 4) 2, α-Ti ( HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄ PO ₄ ) ₂ · H 2 _O polyvalent metal crystalline acid salts of the like. Of these, clay and clay minerals are preferable, and synthetic mica, montmorillonite, vermiculite, hectorite, and teniolite are more preferable.

The pore volume of clay, clay minerals and ion-exchange layered compounds is preferably 0.1 cc / g or more, more preferably 0.3 to 5 cc / g. This pore volume is a volume measured in a ^{pore radius range of 20 to 3} × 104 angstroms by a mercury intrusion method using a mercury porosimeter. When a carrier having a pore volume of 20 angstroms or more and a pore volume smaller than 0.1 cc / g is used as a carrier, it tends to be difficult to obtain high quantification activity.

It is also preferable to chemically treat clay and clay minerals. Examples of the chemical treatment include a surface treatment for removing impurities adhering to the surface and a treatment for affecting the crystal structure of clay. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. According to the acid treatment, not only the impurities on the surface can be removed, but also the surface area can be increased by eluting cations such as Al, Fe and Mg in the crystal structure. Alkaline treatment can destroy the crystal structure of clay and change the structure of clay. According to the salt treatment and the organic substance treatment, the surface area and the interlayer distance can be changed by forming an ionic complex, a molecular complex or an organic derivative.

The ion-exchangeable layered compound may be a layered compound in a state in which the layers are expanded by exchanging the exchangeable ions between the layers with another large bulky ion. These bulky ions play a supporting role in supporting the layered structure and are usually called pillars. Further, introducing another substance between the layers 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 _{TiCl 4} , ZrCl _{4 , Ti (OR) 4} , Zr (OR) ₄ , PO (OR) ₃ , and B ( Metal alkoxides such as OR) ₃ (R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ^+, etc. Metal hydroxide ion of. The guest compound can be used alone or in combination of two or more. Dimerization obtained by hydrolyzing metal alkoxides (R is a hydrocarbon group, etc.) such as Si (OR) ₄ , Al (OR) ₃ , and Ge (OR) _{4 when intercalating guest compounds.} A colloidal inorganic compound such as a substance or SiO _{2 can coexist.} Specific examples of the pillars include oxides produced by intercalating the metal hydroxide ions between layers and then heating and dehydrating them.

Clays, clay minerals, and ion-exchange layered compounds may be used as they are, or may be used after being subjected to treatments such as ball milling and sieving. Further, it may be used after newly adding water and adsorbing it, or it may be used after heat dehydration treatment.
Examples of the organic compound for the carrier (D) include granular or fine-grained solid organic compounds having a particle size of 10 to 300 μm. As a specific example of the monomer of the polymer constituting the organic compound, it is produced mainly of α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene. Examples thereof include (co) dimer, vinyl cyclohexane, (co) dimer produced mainly of styrene, and variants thereof.

<Organic compound component (E)>
The catalyst for increasing the amount of olefins according to the present invention may further contain the organic compound component (E), if necessary.

The organic compound component (E) is used, for example, for the purpose of improving the quantification performance. As such an organic compound, for example, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates can be used. However, the organic compound component (E) is not limited to this.

As the alcohols and the phenolic compound, a compound represented by ^{R 11-OH is usually used.} R ¹¹ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms. As the alcohols, ^{a compound in which R 11} is a halogenated hydrocarbon is preferable. As the phenolic compound, a compound in which the α and α'-positions of the hydroxyl groups are substituted with hydrocarbons having 1 to 20 carbon atoms is preferable.

As the carboxylic acid, ^typically, a compound represented by R 12 -COOH are used. R ¹² 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 12} is a halogenated hydrocarbon group having 1 to 50 carbon atoms is preferable.

The phosphorus compound is preferably a phosphoric acid having a P—O—H bond, a phosphate or a phosphine oxide compound having a P—OR bond or a P = O bond.

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

In the general formula (7), M ² is an element of Group 1 to 14 of the periodic table, and R ¹³ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Is the basis. When R ¹³ have more than one plurality of R ¹³ are each independently defined as above. 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, and u is 1 ≦. It is an integer of u ≦ 7 and tu ≧ 1.

<Olefin>
Specific examples of the olefin as a raw material for mulching used in the olefin mulching reaction according to the present invention include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and vinyl. Examples include vinyl compounds such as cyclohexene, styrene, 1-octene and 1-decene, and internal olefins such as 2-butene, cyclopentene, cyclohexene and norbornene. Of these, ethylene is preferable. Two or more kinds of olefins may be co-quantified.

<Method for producing olefin multimers>
The method for producing an olefin multimer according to the present invention includes an olefin mulching reaction (preferably a quantification to quaternization reaction, more preferably a quaternization reaction) in the presence of the olefin mulching catalyst described above.

Specific examples of the olefin to be quantified are as described above, and ethylene is preferable. Specifically, it is preferable to produce a multimer by an ethylene mulching reaction, and it is more preferable to produce 1-hexene and 1-octene by a quantification reaction of ethylene with a high selectivity, and it is more preferable to produce 1-hexene and 1-octene by a quantification reaction of ethylene. It is particularly preferable to produce 1-octene at a high selectivity by the quaternization reaction.

The order in which the chromium compound (A), the amine compound (B), the compound (C) and other components (for example, the carrier (D) and the organic compound component (E)) are added to the reactor is particularly limited when the amount of olefin is increased. Not done. Specific examples of the addition method are as follows. In the following description of the order of addition of each component, the chromium compound (A), the amine compound (B), the compound (C) and the organic compound (E) are abbreviated as the components (A) to (C) and (E), respectively. ..

(1) A method in which the component (A) and the component (B) are added to the reactor as they are in an arbitrary order.
(2) A method of adding a transition metal complex formed by contacting the component (A) and the component (B) in advance to the reactor.
(3) A method in which the component (A), the component (B), and the component (C) are added to the reactor as they are in an arbitrary order.
(4) A method of adding a transition metal complex formed by contacting a component (A) and a component (B) in advance and a component (C) to a reactor in an arbitrary order.
(5) A method of adding to a reactor a catalyst component in which the component (C) is previously contacted with a transition metal complex formed by previously contacting the component (A) and the component (B).
(6) The catalyst component in which the component (C) is previously contacted with the transition metal complex formed by contacting the component (A) and the component (B) in advance, and the component (C) are added to the reactor in an arbitrary order. how to. In this case, each component (C) may be the same or different.
(7) A method of adding a carrier (D) carrying a transition metal complex formed by contacting a component (A) and a component (B) in advance to a reactor.
(8) A method in which a carrier (D) carrying a transition metal complex formed by contacting a component (A) and a component (B) in advance and a component (C) are added to a reactor in an arbitrary order.
(9) A method of adding a transition metal complex formed by contacting the component (A) and the component (B) in advance and a carrier (D) carrying the component (C) to the reactor.
(10) The transition metal complex formed by contacting the component (A) and the component (B) in advance, the carrier (D) carrying the component (C), and the component (C) are added to the reactor in an arbitrary order. how to. In this case, each component (C) may be the same or different.

(11) A method of adding a carrier (D) carrying a component (C), a component (A), and a component (B) to a reactor in an arbitrary order.
(12) A method in which a carrier (D) carrying a component (C) and a transition metal complex formed by contacting the component (A) and the component (B) in advance are added to a reactor in an arbitrary order.
(13) A method of adding a carrier (D) carrying a component (C), a component (A), a component (B), and a component (C) to a reactor in an arbitrary order. In this case, each component (C) may be the same or different.
(14) The carrier (D) carrying the component (C), the transition metal complex formed by contacting the component (A) and the component (B) in advance, and the component (C) are placed in a reactor in an arbitrary order. How to add. In this case, each component (C) may be the same or different.
(15) A reactor carrying a transition metal complex formed by contacting the component (A) and the component (B) in advance and a carrier (D) carrying the component (C) in an arbitrary order. How to add to.
(16) A carrier (D) carrying a transition metal complex formed by contacting the component (A) and the component (B) in advance, a carrier (D) carrying the component (C), and the component (C) are provided. A method of adding to the reactor in any order. In this case, each component (C) may be the same or different.
(17) A method in which the component (A), the component (B), and the component (E) are added to the reactor as they are in an arbitrary order.
(18) A method of adding a transition metal complex formed by contacting a component (A) and a component (B) in advance and a component (E) to a reactor in an arbitrary order.
(19) A method in which the component (A), the component (B), the component (C), and the component (E) are added to the reactor as they are in an arbitrary order.
(20) A method of adding a transition metal complex formed by contacting a component (A) and a component (B) in advance, a component (C), and a component (E) to a reactor in an arbitrary order.

(21) A method in which a component (C) and a component (E) that have been brought into contact with each other in advance, a component (A), and a component (B) are added to a reactor in an arbitrary order.
(22) A component in which the component (C) and the component (E) are previously contacted and a transition metal complex formed by contacting the component (A) and the component (B) in advance are added to the reactor in an arbitrary order. Method.
(23) A method in which the carrier (D) carrying the component (E), the component (A), and the component (B) are added to the reactor in an arbitrary order.
(24) A method in which a carrier (D) carrying a component (E) and a transition metal complex formed by contacting the component (A) and the component (B) in advance are added to a reactor in an arbitrary order.
(25) A method in which a carrier (D) carrying a component (C) and a component (E), a component (A), and a component (B) are added to a reactor in an arbitrary order.
(26) The carrier (D) carrying the component (C) and the component (E) and the transition metal complex formed by contacting the component (A) and the component (B) in advance are added to the reactor in an arbitrary order. how to.
(27) The catalyst component in which the component (C) is previously contacted with the transition metal complex formed by contacting the component (A) and the component (B) in advance, and the component (E) are added to the reactor in an arbitrary order. how to.
(28) A catalyst component in which the component (C) is previously contacted with a transition metal complex formed by contacting the component (A) and the component (B) in advance, the component (C), and the component (E) are arbitrarily selected. A method of adding to the reactor in order. In this case, each component (C) may be the same or different.
(29) The catalyst component in which the component (C) is previously contacted with the transition metal complex formed by previously contacting the component (A) and the component (B) is brought into contact with the component (C) and the component (E) in advance. A method of adding components to a reactor in any order. In this case, each component (C) may be the same or different.
(30) A carrier (D) carrying a transition metal complex formed by contacting the component (A) and the component (B) in advance, the component (C), and the component (E) are placed in a reactor in an arbitrary order. How to add.

(31) A method in which a carrier (D) carrying a transition metal complex formed by contacting a component (A) and a component (B) in advance and a component (E) are added to a reactor in an arbitrary order.
(32) An arbitrary component (D) carrying a transition metal complex formed by contacting the component (A) and the component (B) in advance and a component in which the component (C) and the component (E) are previously contacted are used. A method of adding to the reactor in order.
(33) A method of adding to a reactor a catalyst component in which the component (E) is previously contacted with a transition metal complex formed by previously contacting the component (A) and the component (B).
(34) A method of adding a catalytic component in which the component (C) and the component (E) are previously contacted in an arbitrary order to a transition metal complex formed by contacting the component (A) and the component (B) in advance to the reactor. ..
(35) A catalyst component in which the component (C) and the component (E) are previously contacted in an arbitrary order with a transition metal complex formed by contacting the component (A) and the component (B) in advance, and the component (C). To the reactor in any order. In this case, each component (C) may be the same or different.
(36) A method of adding a transition metal complex formed by contacting the component (A) and the component (B) in advance and a carrier (D) carrying the component (E) to the reactor.
(37) A method of adding a transition metal complex formed by contacting the component (A) and the component (B) in advance, a carrier (D) carrying the component (C) and the component (E) to the reactor.
(38) The transition metal complex formed by contacting the component (A) and the component (B) in advance, the carrier (D) carrying the component (C) and the component (E), and the component (C) are arranged in an arbitrary order. How to add to the reactor with. In this case, each component (C) may be the same or different.

In the present invention, an olefin multimer is obtained by increasing the amount of olefins in the presence of the catalyst for increasing the amount of olefins described above. The quantification can be carried out by any of a liquid phase reaction method such as a dissolution reaction and a suspension reaction, and 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, kerosene; cyclopentane, cyclohexane, methylcyclohexane, etc. Alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, xylene, trimethylbenzene and tetralin; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof. Of these, linear saturated hydrocarbons having 5 to 7 carbon atoms such as pentane, n-hexane, and n-hebutane; and alicyclic saturated hydrocarbons such as methylcyclohexane are preferable.

When 1-hexene or 1-octene is produced mainly by a 3-4 quantification reaction of ethylene using a catalyst for increasing the amount of olefin, the chromium atom in the component (A) is usually contained in 1 liter of the reaction volume. It is used in an amount such that it ^{is 10-12} to ^10-2 mol, preferably ^10-10 to ^{10-3 mol.} In the present invention, a highly active olefin multimer can be obtained even when the component (A) is used at a relatively low concentration.

The component (B) is used in an amount such that the molar ratio [(B) / M] with the chromium atom (M) in the component (A) is usually 0.1 to 10, preferably 0.5 to 2. Be done.
Of the components (C), the component (C-1) usually has a molar ratio [(C-1) / M] of the component (C-1) to the chromium atom (M) in the component (A). It is used in an amount such that it is 0.01 to 100,000, preferably 0.05 to 50,000.
The molar ratio [(C-2) / M] of the aluminum atom in the component (C-2) to the chromium atom (M) in the component (A) of the component (C-2) is usually 10 to 500,000. , Preferably used in an amount such that it is 20 to 100,000.
The molar ratio [(C-3) / M] of the component (C-3) to the chromium atom (M) in the component (A) is usually 1 to 10, preferably 1. It is used in an amount such that it becomes ~ 5.
The ratio (g / mol) of the mass (g) of the carrier (D) to the mole of the chromium atom (M) in the component (A) of the carrier (D) is usually 100 to 10000, preferably 1000 to 5000. It is used in such an amount.
When the component (C-1) is used as the component (C), the molar ratio [(E) / (C-1)] of the component (E) is usually 0.01 to 10, preferably 0.1 to 5. It is used in such an amount. When the component (C-2) is used as the component (C), the component (E) is the molar ratio of the carrier (D) to the aluminum atom in the component (C-2) [(E) / (C-2). ] Is usually used in an amount such that 0.001-2, preferably 0.005-1. When the component (C-3) is used as the component (C), the molar ratio [(E) / (C-3)] of the component (E) is usually 0.01 to 10, preferably 0.1 to 5. It is used in such an amount.

The reaction temperature for increasing the amount of olefin is usually −50 to 200 ° C., preferably 0 to 170 ° C., more preferably 40 ° C. to 150 ° C., and particularly preferably 50 ° C. to 140 ° C. The most preferable lower limit value is 60 ° C., and the most preferable upper limit value is 130 ° C. In the catalyst for mulching used in the present invention, the higher the reaction temperature, the more the by-production of high molecular weight polymers such as polyethylene is suppressed, and the target olefin multimer (especially when ethylene is reacted is 1). -Hexene and 1-octene) tend to be advantageous in terms of efficient production. In addition, the production efficiency of 1-octene tends to be high.
For example, it is known that a reaction for selectively producing 1-hexene or 1-octene from ethylene proceeds by a metallacycle mechanism. The reason why a higher reaction temperature is more effective is that the catalyst according to the present invention has a structure that easily produces 1-hexene and 1-octene, and also because it forms a metallacycle mechanism. It is presumed that the higher temperature is more advantageous, and the overall reaction activity is increased, so that the by-product of polyethylene is suppressed.

The reaction pressure is usually normal pressure to 10 MPa, preferably normal pressure to 6 MPa, and more preferably normal pressure to 5 MPa. 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. In the catalyst of the present invention, the higher the reaction pressure, the higher the production efficiency of 1-octene tends to be. It is presumed that 1-octene is obtained via metallacyclononane produced by coordination of two molecules of ethylene to metallacyclopentane and then consonant (or sequential) insertion of ethylene. The reason why a higher reaction pressure is more effective is not necessarily clear, but the structure of the catalyst of the present invention is such that the higher the pressure, the more advantageous the coordination of two ethylene molecules to metallacyclopentane. It is presumed.

The amine compound (B) used in the present invention has a site where a nitrogen atom and a hydrogen atom are bonded. The reason why the selectivity of octene is enhanced by using such an amine compound (B) is unknown at this stage, but the present inventors estimated as follows.
When the amine compound (B) coordinates with the chromium compound (A) due to the fact that the amine compound (B) has a site where a nitrogen atom and a hydrogen atom are bonded or has an asymmetric structure, the coordination space is appropriate. It is expected to have a structure with a large size. This may also be due to the fact that the two nitrogen atoms have an ethylene structure.
Since the coordination space has an appropriate size, the coordination of chillene to the metallacyclopentane is likely to occur, so that the selectivity of octene will increase.

The quantification reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type.

The olefin quantification 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, and polyoxyalkylene (for example, polyethylene glycol, polypropylene glycol, polyethylene glycol). Block copolymer (PEG-PPG-PEG)) can be mentioned. Of these, polyoxyalkylene (for example, PEG-PPG-PEG) is preferable. The antistatic agent is used in an amount such that the ratio (g / mol) of the mass (g) of the chromium atom (M) in the component (A) to the mole is usually 100 to 10000, preferably 100 to 1000. ..

The olefin quantification reaction may be carried out by adding hydrogen. The pressure of hydrogen in the reaction is usually 0.01 MPa to 5 MPa, preferably 0.01 MPa to 1 MPa.

Hereinafter, the present invention will be specifically described based on Synthesis Examples and Examples, but the present invention is not limited to these Examples.
The structure of the compound obtained in the synthesis example was constructed ^{by using an apparatus such as 270 MHz 1} H NMR (manufactured by JEOL Ltd., apparatus name GSH-270), ICP emission spectroscopic analyzer (manufactured by Agilent Technologies, apparatus name 720-ES type). Decided.

The yield of each 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).

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

[1-octene activity]
The 1-octene activity was determined by dividing the mass of 1-octene obtained per unit time by the transition metal atomic weight (mmol) in the transition metal catalyst component used for mulching.

[1-Hexene or 1-octene selectivity (distribution)]
The selectivity of 1-hexene or 1-octene was calculated according to the following formula.
S (%) = Wp / Wr × 100
S (%): Selectivity of 1-hexene or 1-octene (mass fraction)
Wr (mass): Total mass of product produced by reaction consisting of 4 or more carbon atoms Wp (mass): Synthesis of amine compound (B) below the mass of 1-hexene or 1-octene produced by reaction An example and an example of increasing the amount of ethylene are shown.

(1) Synthesis example of amine compound [Synthesis example 1]
In a fully dried 200 mL reactor, 4 mL (36.7 mmol) of N, N-dimethylethylenediamine and 70 mL of dichloromethane were charged, and 3 mL (41.7 mmol) of propionaldehyde was added to the place where the mixture was stirred at room temperature, and at room temperature. Stirred. After 2 hours, the solvent was distilled off under reduced pressure, and the mixture was diluted with 90 mL of ethanol. Then, 1.40 g (37.1 mmol) of sodium borohydride was added, and the mixture was stirred at room temperature. After 17 hours, the solvent was distilled off under reduced pressure, and a saturated aqueous solution of ammonium chloride was added to the reaction solution to quench the reaction. The soluble component was extracted with dichloromethane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate is distilled off under reduced pressure, the crude product is distilled under reduced pressure, and the target product [hereinafter referred to as compound (B-2)] represented by the following formula (B-2) is 0. .51 g (yield 11%) was obtained.
^{1 1} H-NMR (270 MHz, CD ₃ COCD ₃ ): 2.60 (2H, t, J = 6.2 Hz), 2.52 (2H, t, J = 6.2 Hz), 2.32 (2H, t) , J = 6.2Hz), 2.14 (6H, s), 1.44 (2H, sext, J = 7.3Hz), 0.89 (3H, t, J = 7.3Hz) ppm

[Synthesis Example 2]
2.1 mL (19.2 mmol) of N, N-dimethylethylenediamine and 35 mL of dichloromethane were charged in a fully dried 100 mL reactor, and 2.5 mL (20.4 mmol) of hexanal was added to the place where the mixture was stirred at room temperature. , Stirred at room temperature. After 4 hours, the solvent was distilled off under reduced pressure, and the mixture was diluted with 46 mL of ethanol. Then, 0.75 g (19.7 mmol) of sodium borohydride was added, and the mixture was stirred at room temperature. After 21 hours, the solvent was distilled off under reduced pressure, and a saturated aqueous solution of ammonium chloride was added to the reaction solution to quench the reaction. After neutralizing the reaction solution with an aqueous potassium carbonate solution, the soluble component was extracted with dichloromethane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate is distilled off under reduced pressure, and the crude product is distilled under reduced pressure to obtain the target product (hereinafter referred to as compound (B-3)) represented by the following formula (B-3). 48 g (44% yield) was obtained.
^{1 1} H-NMR (270 MHz, CD ₃ COCD ₃ ): 2.60 (2H, t, J = 6.2 Hz), 2.55 (2H, t, J = 6.2 Hz), 2.32 (2H, t) , J = 6.2Hz), 2.14 (6H, s), 1.47-1.29 (8H, m), 0.89 (3H, t, J = 7.0Hz) ppm

[Synthesis Example 3]
Put 2.1 mL (19.2 mmol) of N, N-dimethylethylenediamine and 35 mL of dichloromethane in a fully dried 100 mL reactor, and add 3.2 mL (20.5 mmol) of 1-octanal to the mixture while stirring at room temperature. It was added and stirred at room temperature. After 4 hours, the solvent was distilled off under reduced pressure, and the mixture was diluted with 46 mL of ethanol. Then, 0.75 g (19.7 mmol) of sodium borohydride was added, and the mixture was stirred at room temperature. After 21 hours, the solvent was distilled off under reduced pressure, and a saturated aqueous solution of ammonium chloride was added to the reaction solution to quench the reaction. After neutralizing the reaction solution with an aqueous potassium carbonate solution, the soluble component was extracted with dichloromethane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate is distilled off under reduced pressure, and the crude product is distilled under reduced pressure to obtain the target product (hereinafter referred to as compound (B-4)) represented by the following formula (B-4). 18 g (yield 31%) was obtained.
^{1 1} H-NMR (270 MHz, CD ₃ COCD ₃ ): 2.60 (2H, t, J = 6.2 Hz), 2.55 (2H, t, J = 6.5 Hz), 2.32 (2H, t) , J = 6.5Hz), 2.14 (6H, s), 1.47-1.38 (2H, m), 1.30 (10H, brs), 0.88 (3H, t, J = 6) .5Hz) ppm

[Synthesis Example 4]
2.1 mL (19.2 mmol) of N, N-dimethylethylenediamine and 35 mL of dichloromethane were charged in a fully dried 100 mL reactor, and 4.5 mL (20.4 mmol) of dodecanal was added to the mixture while stirring at room temperature. , Stirred at room temperature. After 4 hours, the solvent was distilled off under reduced pressure, and the mixture was diluted with 46 mL of ethanol. Then, 0.74 g (19.5 mmol) of sodium borohydride was added, and the mixture was stirred at room temperature. After 16 hours, the solvent was distilled off under reduced pressure, and a saturated aqueous solution of ammonium chloride was added to the reaction solution to quench the reaction. After neutralizing the reaction solution with an aqueous potassium carbonate solution, the soluble component was extracted with dichloromethane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate is distilled off under reduced pressure, and the crude product is distilled under reduced pressure to obtain the target product (hereinafter referred to as compound (B-5)) represented by the following formula (B-5). 13 g (yield 23%) was obtained.
^{1 1} H-NMR (270 MHz, CD ₃ COCD ₃ ): 2.59 (2H, t, J = 6.5 Hz), 2.54 (2H, t, J = 6.5 Hz), 2.32 (2H, t) , J = 6.2Hz), 2.14 (6H, s), 1.47-1.38 (2H, m), 1.30 (18H, brs), 0.88 (3H, t, J = 6) .5Hz) ppm

[Synthesis Example 5]
1.25 mL (10.4 mmol) of cyclohexanecarboxyaldehyde, 1.2 mL (11.0 mmol) of N, N-dimethylethylenediamine, and 30 mL of toluene were charged into a fully dried 100 mL reactor, and the mixture was stirred at room temperature. After 17 hours, the reaction solution was distilled off under reduced pressure to obtain 1.84 g (yield 98%) of the target product represented by the following formula (6) (hereinafter referred to as compound (6)).
GC-Mass Spectrometry (M +): 182
^{1 1} H-NMR (270 MHz, CDCl ₃ ): 7.54 (1H, d, J = 5.1 Hz), 3.47 (2H, t, J = 7.0 Hz), 2.50 (2H, t, J) = 7.0Hz), 2.26 (6H, s), 2.21-2.13 (1H, m), 1.82-1.64 (5H, m), 1.37-1.15 (5H) , M) ppm

[Synthesis Example 6]
1.84 g (10.1 mmol) of compound (6) and 32 mL of ethanol were charged into a fully dried 200 mL reactor and cooled to 0 ° C. Then, 0.46 g (12.1 mmol) of sodium borohydride was added at 0 ° C., the mixture was stirred at 0 ° C. for 30 minutes, and then further stirred at room temperature. After 2 hours, the reaction solution was cooled to 0 ° C. and the reaction was quenched with saturated aqueous ammonium chloride solution. The soluble component was extracted with dichloromethane, and the obtained fraction was washed with 1 M aqueous potassium carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate was distilled off under reduced pressure, and 1.62 g (yield 87%) of the target product [hereinafter referred to as compound (B-6)] represented by the following formula (B-6) was obtained. Obtained.
GC-Mass Spectrometry (M +): 184
^{1 1} H-NMR (270 MHz, CDCl ₃ ): 2.66 (2H, t, J = 6.2 Hz), 2.44 (2H, d, J = 7.0 Hz), 2.40 (2H, t, J) = 6.2Hz), 2.22 (6H, s), 1.78-1.68 (5H, m), 1.53-1.39 (1H, m), 1.32-1.12 (3H) , M), 0.96-0.82 (2H, m) ppm

[Synthesis Example 7]
Hexanal 2.0 mL (16.3 mmol) was charged in a sufficiently dried 100 mL reactor with 2.0 mL (15.9 mmol) of 1- (2-aminoethyl) pyrrolidine and 30 mL of dichloromethane, and stirred at room temperature. Was added, and the mixture was stirred at room temperature. After 4 hours, the solvent was distilled off under reduced pressure, and the mixture was diluted with 40 mL of ethanol. Then, 0.62 g (16.3 mmol) of sodium borohydride was added, and the mixture was stirred at room temperature. After 19 hours, the solvent was distilled off under reduced pressure, and a saturated aqueous solution of ammonium chloride was added to the reaction solution to quench the reaction. After neutralizing the reaction solution with an aqueous potassium carbonate solution, the soluble component was extracted with dichloromethane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate is distilled off under reduced pressure, and the crude product is distilled under reduced pressure to obtain the target product (hereinafter referred to as compound (B-7)) represented by the following formula (B-7). 63 g (yield 52%) was obtained.
^{1 1} H-NMR (270 MHz, CD ₃ COCD ₃ ): 2.63 (2H, t, J = 6.5 Hz), 2.55 (2H, t, J = 6.5 Hz), 2.53 (2H, t) , J = 6.5Hz), 2.49-2.40 (4H, m), 1.75-1.65 (4H, m), 1.46-1.25 (8H, m), 0.89 (3H, t, J = 6.5Hz) ppm

[Synthesis Example 8]
Hexanal 1.9 mL (15.5 mmol) was charged in a sufficiently dried 100 mL reactor with 2.1 mL (14.8 mmol) of 1- (2-aminoethyl) piperidine and 30 mL of dichloromethane, and stirred at room temperature. Was added, and the mixture was stirred at room temperature. After 4 hours, the solvent was distilled off under reduced pressure, and the mixture was diluted with 40 mL of ethanol. Then, 0.56 g (14.9 mmol) of sodium borohydride was added, and the mixture was stirred at room temperature. After 17 hours, the solvent was distilled off under reduced pressure, and a saturated aqueous solution of ammonium chloride was added to the reaction solution to quench the reaction. After neutralizing the reaction solution with an aqueous potassium carbonate solution, the soluble component was extracted with dichloromethane, and the obtained fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate is distilled off under reduced pressure, and the crude product is distilled under reduced pressure to obtain the target product (hereinafter referred to as compound (B-8)) represented by the following formula (B-8). 40 g (yield 45%) was obtained.
^{1 1} H-NMR (270 MHz, CD ₃ COCD ₃ ): 2.60 (2H, t, J = 6.2 Hz), 2.55 (2H, t, J = 6.8 Hz), 2.38-2.30 (6H, m), 1.56-1.46 (4H, m), 1.46-1.36 (4H, m), 1.36-1.25 (6H, m), 0.89 (3H) , T, J = 6.8Hz) ppm

(2) Ethylene quantification [Example 1]
In a fully dried 100 mL Schlenk tube, 0.137 g (1.179 mmol) of N'-ethyl-N, N-dimethylethylenediamine [Compound (B-1)], 0.390 g (1.041 mmol) of chromium trichloride tetrahydrofuran ), 20 mL of dichloromethane was added, and the mixture was stirred under an argon atmosphere for 20 hours. After adding 30 mL of n-hexane to the reaction solution and concentrating to about 1/2 under reduced pressure, the insoluble matter was collected by filtration through a glass filter, washed with 8 mL of n-hexane, and dried under reduced pressure to obtain 0.160 g of a chromium compound. Got From this chromium compound, a methylcyclohexane solution (catalyst solution) of 0.001 mmol / mL in terms of chromium atoms was prepared.

29.6 mL of methylcyclohexane was placed in a fully nitrogen-substituted autoclave with an internal volume of 100 mL, and then 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 catalytic solution was added, and ethylene (0.8 M) was added.
The reaction was started by pressurizing with Pa-G). After reacting at 60 ° C. for 60 minutes while supplying ethylene at the same pressure, the reaction was stopped by adding a small amount of isopropanol. After completion of the reaction, the reaction solution was washed with 0.1N hydrochloric acid water and pure water, and the low boiling point component (component with 10 or less carbon atoms) was separated from the high boiling point component and polyethylene using a liquid nitrogen trap under reduced pressure. , Gas chromatography was used for analysis. The production amount of the low boiling point component (the production amount of the α-olefin component having 10 or less carbon atoms) is 114 mg, the production amount of polyethylene is 10 mg, and the catalytic activity calculated from the total amount of these products is 1240 g-product / (. It was mmol-Cr · hr). Among the low boiling point components, the selectivity of 1-hexene was 13.2% by mass, the selectivity of 1-octene was 66.1% by mass, and the catalytic activity of 1-octene was 754 g-product / (mmol-Cr · hr). )Met. The results are shown in Table 1.

[Examples 2 to 8]
Compounds (B-2), (B-3), (B-4), (B-5), (B-6), (B-7) and (B-8) instead of compound (B-1) ) Was used individually, but the ethylene quantification reaction was carried out in the same manner as in Example 1. The results are shown in Table 1.

[Examples 9 to 16]
The ethylene quantification reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 90 ° C. The results are shown in Table 2.

[Comparative Examples 1 to 4]
Compounds (O-1) and (O-2) represented by the following formulas (O-1), (O-2), (P-1) and (P-2) instead of compound (B-1). , (P-1) and (P-2) (both of which were purified by a conventional method) were individually used, and the ethylene quantification reaction was carried out in the same manner as in Example 1. .. The results are shown in Table 3.

The catalyst for increasing the amount of olefins of the present invention has excellent activity, and particularly has high selectivity and production efficiency of olefin multimers such as 1-octene, and is extremely useful in the production of olefin multimers. Therefore, the present invention is of extremely high industrial value.

Claims (6)

A method for producing an olefin multimer, which carries out an olefin quantification reaction in the presence of an olefin quantification catalyst containing the following components (A) to (C).
(A) Chromium compound,
(B) The amine compound represented by the following general formula (1),

(In the general formula (1), R ^{1 to} R ³ are independently hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, and 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 R ¹ to R ³ may be linked to each other.
(C) (C-1) Organometallic compound,
(C-2) Organoaluminium 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. The method for producing an olefin multimer according to claim 1, wherein in the general formula (1), R ¹ uses an ^{amine compound (B) that is not linked to R 2} and R ^3. The method for producing an olefin multimer according to claim 1 or 2, which comprises the following carrier (D) in addition to the 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 any one of claims 1 to 3, wherein the olefin quantification reaction is carried out in the presence of an antistatic agent. The method for producing an olefin multimer according to any one of claims 1 to 4, wherein the olefin is ethylene. The method for producing an olefin multimer according to any one of claims 1 to 5, wherein the olefin multimer is 1-octene.