JP2009072665A - Catalyst for olefin polymerization, and manufacturing method of ethylene polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for olefin polymerization having an excellent ethylene polymerization activity, and a manufacturing method of 1-hexene or 1-octene using the catalyst. <P>SOLUTION: The catalyst for ethylene polymerization includes [A] a transition metal complex compound represented as a general formula (I), and if required, [B] at least one compound selected from a group consisting of (b-1) an organic metallic compound, (b-2) an organoaluminum oxy compound, and (b-3) a compound reacting with [A] the transition metal complex compound to form an ion pair. Additionally, the ethylene polymerization method using the catalyst is provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to an olefin multimerization catalyst and a method for producing an ethylene multimer, and more specifically, an olefin multimerization catalyst containing a transition metal complex compound, and ethylene in the presence of an olefin multimerization catalyst to produce 1-hexene. Alternatively, it relates to a method for producing 1-octene.

Most of the industrialization of olefins that have been industrialized is carried out using organoaluminum or a transition metal compound as a catalyst. Particularly, when ethylene is used in a large quantity, a mixture of α-olefins is obtained. Among α-olefins, 1-hexene and 1-octene are particularly in demand as raw materials for polyolefins, and a method for producing 1-hexene and 1-octene with high selectivity is desired. Only the ethylene trimerization method using a chromium compound is industrialized as a method (see, for example, Patent Document 1). In this case, about 8 kg of 1-hexene is obtained per hour per millimole of chromium atoms under 100 bar ethylene pressure conditions, but the activity can be reduced at lower pressures to reduce the production pressure and the cost of the catalyst. Higher is preferable. In addition, there are very few examples of techniques for producing 1-hexene by ethylene trimerization using a transition metal compound other than a chromium compound (see, for example, Patent Documents 2 and 3 and Non-Patent Documents 1 and 2). Further, as a technique for obtaining 1-octene by tetramerization of ethylene, a technique using a chromium compound is known, but it has not been industrialized (for example, Non-Patent Document 3).
reference).
US Pat. No. 5,856,257 JP-T-2004-524959 International Publication No. 01/68572 pamphlet Journal of American Chemical Society 2001, 123, 7423-7424 Journal of Organometallic Chemistry 2004, 689, 3643-1668. Journal of American Chemical Society 2004, 126, 14712-14713

  The present invention has been made in view of the above-described problems of the prior art, and provides an olefin multimerization catalyst having excellent activity, and ethylene 3 having high selectivity in the presence of the olefin multimerization catalyst. It aims at providing the manufacturing method of 1-hexene by quantification, and the manufacturing method of 1-octene by ethylene tetramerization.

  As a result of intensive studies to solve the above problems, the present inventors have found that an olefin multimerization catalyst containing a transition metal complex compound having a specific structure has an excellent activity, and ethylene is used as a raw material in the presence of the catalyst. As a result of the multimerization reaction, it was found that the selectivity for producing 1-hexene or 1-octene is high and suitable for the production of 1-hexene or 1-octene, and the present invention was completed.

That is, the present invention relates to the following [1] to [5].
[1]
[A] An olefin multimerization catalyst comprising a transition metal complex compound represented by the following general formula (I).

(In the general formula (I), R ^{1 to} R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, or boron. A containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be linked to each other, and R ¹ is Z may be connected to R, and R ⁵ may be connected to Z.
M represents a transition metal atom of Group 4 of the periodic table.
X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing A group, a germanium-containing group, or a tin-containing group, the groups represented by X may be the same as or different from each other, and the groups represented by X may be bonded to each other to form a ring.
Y represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom.
Z represents a hydrocarbon group or a heterocyclic compound residue which may have a substituent.
In the formula, the bond connecting Y and Z may be a double bond or a triple bond, and the bond connecting Y and R ¹ may be a double bond or a triple bond.
In the formula, the dotted line indicates a coordination bond. )
[2]
[A] The number of olefins according to [1], in which the shortest number of bonds connecting Y of the transition metal complex compound represented by the general formula (I) to M and connecting Z to adjacent N is 5 or 6. Catalyst for quantification.

[3]
[A] a transition metal complex compound represented by the general formula (I), and

  [B] selected from the group consisting of (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) [A] a compound that reacts with a transition metal complex compound to form an ion pair. The olefin multimerization catalyst according to [1] or [2], comprising at least one compound.

[4]
A process for producing 1-hexene, wherein ethylene is trimerized in the presence of the olefin multimerization catalyst according to any one of [1] to [3].

[5]
A method for producing 1-octene, wherein ethylene is tetramerized in the presence of the olefin multimerization catalyst according to any one of [1] to [3].

  The present invention can provide an olefin multimerization catalyst having high activity. Furthermore, according to the ethylene multimerization technique according to the present invention, 1-hexene or 1-octene can be selectively produced with higher activity than conventional catalysts and is extremely valuable industrially.

Hereinafter, the olefin multimerization catalyst of the present invention and the method for producing 1-hexene or 1-octene using the olefin multimerization catalyst will be specifically described.
In addition, in this invention, the olefin multimerization is making an olefin into a 2-10 mer.

  The olefin multimerization catalyst of the present invention includes [A] a transition metal complex compound represented by the general formula (I). Also, the olefin multimerization catalyst usually reacts with [B] (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) [A] a transition metal complex compound to form an ion pair. At least one compound selected from the group consisting of compounds that form

In addition, the compound which reacts with (b-3) [A] transition metal complex compound to form an ion pair is also referred to as “ionized ionic compound”.
[[A] transition metal complex compound]
The [A] transition metal complex compound contained in the olefin multimerization catalyst of the present invention is a transition metal complex compound represented by the following general formula (I).

In the general formula (I), R ^{1 to} R ⁵ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, or boron. A containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other. R ¹ may be linked to Z, and R ⁵ may be linked to Z.

More specifically, R ^{1 to} R ⁵ are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, Arylthio group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group
, A nitro group, a carboxyl group, a sulfo group, a mercapto group, an aluminum-containing group or a hydroxy group.

Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.
Specifically, the hydrocarbon group has 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, preferably 1-20, more preferably 1-10, most preferably 2-10 linear or branched alkyl groups; vinyl, allyl,
A linear or branched alkenyl group having 2 to 30, preferably 2 to 20 carbon atoms such as isopropenyl; a linear or branched alkenyl group such as ethynyl and propargyl having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms; A branched alkynyl group; a cyclic saturated hydrocarbon group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl; carbon atoms such as cyclopentadienyl, indenyl and fluorenyl A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl; tolyl, isopropylphenyl , T-butylphenyl, dimethylphenyl, di-t-butylphenyl Examples include alkyl-substituted aryl groups such as benzyl; alkylidene groups having 1 to 30, preferably 5 to 10 carbon atoms such as benzylidene, methylidene, and ethylidene.

  In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen. For example, a halogenated hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl, chlorophenyl and the like. Can be mentioned.

  In the hydrocarbon group, a hydrogen atom may be substituted with another hydrocarbon group, and examples thereof include aryl group-substituted alkyl groups such as benzyl, cumyl, diphenylethyl, and trityl.

  Further, the hydrocarbon group is a heterocyclic compound residue; oxygen such as alkoxy group, aryloxy group, ester group, ether group, acyl group, carboxyl group, carbonate group, hydroxy group, peroxy group, carboxylic anhydride group, etc. Containing group; amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group and ammonium salt Nitrogen-containing groups such as those; boron-containing groups such as boranediyl group, boranetriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate group, Isothiocyanate group, sulfone ester Groups, sulfonamido groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups and other sulfur-containing groups; phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphorous-containing groups such as phosphato groups, It may have a silicon-containing group, a germanium-containing group, or a tin-containing group.

Among these, in particular, 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, adamantyl, etc. 20, more preferably 1-10, more preferably 2-10 linear or branched alkyl groups; phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc. 6-30, preferably 6. An aryl group having ˜20; a halogen atom, an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an aryl group or aryloxy having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms; A substituted aryl group substituted with 1 to 5 substituents such as a group is preferred.

  Heterocyclic compound residues include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and heterocyclic groups thereof. Examples thereof include a group further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, in the compound residue.

Examples of the oxygen-containing group, nitrogen-containing group, sulfur-containing group, and phosphorus-containing group are the same as those exemplified as the substituent that may be contained in the hydrocarbon group.
Examples of the boron-containing group include those similar to those exemplified as the substituent which may be contained in the hydrocarbon group, alkyl group-substituted boron, aryl group-substituted boron, boron halide, alkyl group-substituted boron halide, etc. The group of is mentioned. As the alkyl group-substituted boron, (Et) ₂ B-, (iPr) ₂ B-, (iBu) ₂ B-, (Et) ₃ B, (iPr) ₃ B
, (IBu) ₃ B; As the aryl group-substituted boron, (C ₆ H ₅ ) ₂ B-, (C ₆ H ₅ ) ₃ B
, (C ₆ F ₅ ) ₃ B, (3,5- (CF ₃ ) ₂ C ₆ H ₃ ) ₃ B; As a boron halide, BCl _2- , BCl ₃ ; As an alkyl group-substituted boron halide, (Et) BCl -, (iBu ) BCl -, and the like _{(C 6 H 5) 2 BCl} . Of these, trisubstituted boron may be in a coordinated state. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

Examples of the aluminum-containing group include groups such as alkyl group-substituted aluminum, aryl group-substituted aluminum, aluminum halide, and alkyl group-substituted aluminum halide. Examples of the alkyl group-substituted aluminum include (Et) ₂ Al-, (iPr) ₂ Al-, (iBu) ₂ Al-, (Et) ₃ Al, (iPr) ₃ Al, (iBu) ₃ Al; (C ₆ H ₅ ) ₂ Al-; As the aluminum halide, A
lCl _2- , AlCl ₃ ; Examples of the alkyl group-substituted aluminum halide include (Et) AlCl-, (iBu) AlCl-, and the like. Of these, trisubstituted aluminum may be in a coordinated state. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. Specific examples of the hydrocarbon-substituted silyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluoro Phenyl) silyl and the like.
Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. In particular, trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are preferable. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy and the like.

Examples of the germanium-containing group and tin-containing group include those obtained by substituting silicon of the silicon-containing group with germanium and tin.
Of the nitrogen-containing groups, the amide group includes acetamide, N-methylacetamide, N-
Methylbenzamide, etc., amino groups include dimethylamino, ethylmethylamino, diphenylamino, etc., imide groups include acetamido, benzimide, etc., and imino groups include methylimino, ethylimino, propylimino, butylimino, phenylimino, etc. Is preferably exemplified.

  Among the sulfur-containing groups, the alkylthio group includes methylthio, ethylthio and the like, the arylthio group includes phenylthio, methylphenylthio, naphthylthio and the like, and the thioester group includes acetylthio, benzoylthio, methylthiocarbonyl, phenylthiocarbonyl and the like. Preferred examples of the sulfone ester group include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate, and examples of the sulfonamide group include phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide. It is done.

Two or more of R ^{1 to} R ⁵ may be linked to each other. Preferably, adjacent groups may be linked to each other to form an alicyclic ring, an aromatic ring, or a hydrocarbon ring containing a different atom such as a nitrogen atom, and these rings may further have a substituent. .

R ¹ may be linked to Z, and R ⁵ may be linked to Z. When R ¹ or R ⁵ is connected to Z, a hydrocarbon ring containing a hetero atom such as an aromatic ring, an aliphatic ring, or a nitrogen atom may be formed by connecting R ¹ or R ⁵ and Z; These rings may further have a substituent.

In the general formula (I), M represents a transition metal atom of Group 4 of the periodic table, preferably zirconium, titanium or hafnium, and more preferably titanium.

In the general formula (I), X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, or a heterocyclic ring. A formula compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group is shown. The groups represented by X may be the same as or different from each other, and the groups represented by X may be bonded to each other to form a ring.

Here, the halogen atom is usually fluorine, chlorine, bromine or iodine.
As a hydrocarbon group, the thing similar to what was illustrated by R < ¹ > -R < ⁵ > of the said general formula (I) is mentioned.

  Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, eicosyl; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, adamantyl; vinyl, Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, phenanthryl, and the like Examples include, but are not limited to, an aryl group. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 30 carbon atoms is substituted with halogen. Of these, those having 1 to 20 carbon atoms are preferred.

As the heterocyclic compound residue include the same ones as exemplified for R ¹ to R ⁵ in the general formula (I).
Examples of the oxygen-containing group include the same groups as those exemplified for R ^{1 to} R ⁵ in the general formula (I). Specifically, hydroxy groups; alkoxy groups such as methoxy, ethoxy, propoxy, butoxy; Examples include, but are not limited to, aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; carbonyl groups and the like.

Examples of the sulfur-containing group include the same groups as those exemplified for R ^{1 to} R ⁵ in the general formula (I), and specifically, methyl sulfonate, trifluoromethane sulfonate, and phenyl sulfonate. Sulfonate groups such as benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate, triisobutyl benzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methyl sulfinate; Sulfinate groups such as phenyl sulfinate, benzyl sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene sulfinate; alkylthio group; arylthio group and the like are limited thereto. With things No.

Specific examples of the nitrogen-containing group include the same groups as those exemplified for R ^{1 to} R ⁵ in the general formula (I). Specific examples include amino groups; methylamino, dimethylamino, diethylamino, di- Alkylamino groups such as propylamino, dibutylamino, dicyclohexylamino; arylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino, or alkylarylamino groups; It is not a thing.

Specific examples of the boron-containing group include BR ₄ other than tetraphenylborate (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).
Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methyl phosphite, ethyl phosphite, and phenyl phosphite Phosphite groups (phosphide groups); phosphonic acid groups; phosphinic acid groups and the like, but are not limited thereto.

Specific examples of the silicon-containing group include those exemplified for R ^{1 to} R ⁵ in the general formula (I). Specific examples include phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, Hydrocarbon-substituted silyl groups such as propylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tolylsilylsilyl, trinaphthylsilyl; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; Examples include silicon-substituted aryl groups such as trimethylsilylphenyl.

Specific examples of the germanium-containing group include the same groups as those exemplified for R ^{1 to} R ⁵ in the general formula (I), specifically, a group in which silicon in the silicon-containing group is substituted with germanium. Is mentioned.

Examples of the tin-containing group include those exemplified as R ^{1 to} R ⁵ in the general formula (I), and more specifically, a group in which silicon in the silicon-containing group is substituted with tin. It is done.
Specific examples of the halogen-containing group include fluorine-containing groups such as PF ₆ and BF ₄ , ClO ₄ , and Sb.
Examples include, but are not limited to, chlorine-containing groups such as Cl ₆ and iodine-containing groups such as IO ₄ .

Specific examples of the aluminum-containing group include, but are not limited to, AlR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

In these, a halogen atom and an alkyl group are preferable, and also chlorine, bromine, and a methyl group are preferable.
In the general formula (I), Y represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom, and is an atom constituting an ether structure, a ketone structure, an amine structure, an imine structure or the like.

In the general formula (I), Z represents a hydrocarbon group or heterocyclic compound residue which may have a substituent.
In the general formula (I), the coordinate between Y and M, and the distance between Z and adjacent N is appropriate for Y to coordinate to the metal atom M, so that [A] transition metal complex The olefin multimerization catalyst containing a compound can produce 1-hexene and 1-octene with high selectivity. It is preferable that the shortest number of bonds connecting Y and N is 5 or 6, since 1-hexene and 1-octene can be produced with higher selectivity.

  In addition, the shortest number of bonds that coordinate Y and M and connect Z and adjacent N can be counted as in the following (A) and (B). In the case of (B), it is 5.

Z is a group that coordinates to M and connects N adjacent to Z and the Y. Specific examples include structures shown in Chemical Formulas 5 to 10, but are not limited thereto. In the structures of Chemical Formulas 5 to 10, hydrogen atoms may be substituted with the substituents exemplified for R ^{1 to} R ⁶ .

  In the following specific examples, the wavy line bonded to the carbon-carbon double bond means a cis isomer or a trans isomer.

In the general formula (I), the bond connecting Y and Z may be a double bond or a triple bond, and the bond connecting Y and R ¹ may be a double bond or a triple bond.
Moreover, in general formula (I), a dotted line display shows a coordinate bond. Specific structures of the general formula (I) are listed below.

  [A] The transition metal complex compound represented by the general formula (I) can be synthesized in accordance with, for example, the method described in Journal of Organometallic Chemistry 2003, 678, pages 134-141.

  The reaction product obtained by the method described in the above document can be used as an olefin multimerization catalyst without any purification operation after the reaction, but it should be used after purification by a refining operation such as recrystallization. Is preferred.

The olefin multimerization catalyst of the present invention is usually [B] (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) in addition to the above [A] transition metal complex compound.
[A] It contains at least one compound selected from the group consisting of compounds that react with transition metal complex compounds to form ion pairs.

  Hereinafter, compounds that react with (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) [A] a transition metal complex compound to form an ion pair will be described.

[(B-1) Organometallic compound]
Specific examples of the organometallic compound (b-1) used as necessary in the present invention include the following organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table. Examples thereof include (b-1a), (b-1b), and (b-1c) described below. In the present invention, the (b-1) organometallic compound of [B] does not include the (b-2) organoaluminum oxy compound described later.

(B-1a) General formula R ^a _m Al (OR ^b ) _n H _p X _q (wherein R ^a and R ^b have 1 to 15 carbon atoms which may be the same or different from each other, preferably 1 -4 represents a hydrocarbon group, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is a number 0 ≦ q <3. And m + n + p + q = 3).

(B-1b) General formula M ² AlR ^a ₄ (wherein M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) A complex alkylated product of a group 1 metal and aluminum in the periodic table represented by:

(B-1c) General formula R ^a R ^b M ³ (wherein R ^a and R ^b represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms which may be the same or different from each other); M ³ is Mg, Zn
Or Cd). A dialkyl compound of a metal of Group 2 or Group 12 of the periodic table.

Examples of the organoaluminum compound belonging to (b-1a) include the following compounds. General formula R ^a _m Al (OR ^b ) _3-m (wherein R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other. M is preferably a number of 1.5 ≦ m ≦ 3.), An organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein R ^a is 1 to 1 carbon atoms) 15, preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, and m is preferably 0 <m <3.) An organoaluminum compound represented by the general formula R ^a _m AlH _{3− m} (wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3), a general formula during _{^{R a m Al (oR b)}} n X q ( wherein, R ^a and R ^b are optionally carbon atoms be the same or different from each other 1 15, preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <33, q is a number 0 ≦ q <3, and m + n + q = 3).

More specifically, as the organoaluminum compound belonging to (b-1a), trimethylaluminum, triethylaluminum, tri (n-butyl) aluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecyl Tri (n-alkyl) aluminum such as aluminum; triisopropylaluminum, triisobutylaluminum, tri (sec-butyl) aluminum, tri (tert-butyl) aluminum, tri (2-methylbutyl) aluminum, tri (3-methylbutyl) aluminum , Tri (2-methylpentyl) aluminum, tri (3-methylpentyl) aluminum, tri (4-methylpentyl) aluminum, tri (2-methylhexyl) Tri-branched alkyl aluminums such as aluminum, tri (3-methylhexyl) aluminum, tri (2-ethylhexyl) aluminum;
Tricyclohexyl aluminum, tri-cycloalkyl aluminum such as tri-cyclooctyl aluminum; triphenyl aluminum, triaryl aluminum such as tri-tolyl aluminum, diethyl aluminum hydride, dialkylaluminum hydride such as diisobutylaluminum _{hydride; (iC 4 H 9) x} Al y (C ₅ H ₁₀ ) _z (wherein x, y and z are positive numbers and z ≧ 2x. IC ₄ H ₉ represents an isobutyl group) Alkenyl aluminum;
Alkyl aluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide and isobutylaluminum isopropoxide; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; Ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide R ^a _2.5 Al (OR ^b ) _0.5 (wherein R ^a and R ^b are carbon atoms having 1 to 15 carbon atoms, which may be the same as or different from each other, preferably 1 to 4 carbon atoms). A partially alkoxylated alkylaluminum having an average composition represented by, for example: diethylaluminum phenoxide, diethylal Ni (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl) -4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide) and the like; dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, Dialkylaluminum halides such as diisobutylaluminum chloride; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; Partially halogenated alkylaluminums such as alkylaluminum dihalides such as aluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride; Ethylaluminum dihydride, propylaluminum dihydride Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as hydride; partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxycycloride, ethylaluminum ethoxybromide, etc. Can be mentioned.

Moreover, the compound similar to (b-1a) can also be used, for example, the organoaluminum compound which two or more aluminum compounds couple | bonded through the nitrogen atom is mentioned. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

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

  As (b-1) organometallic compounds other than the above (b-1a) to (b-1c), methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethyl Magnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride and the like can also be used.

A compound that can form the organoaluminum compound in the multimerization reaction system, such as a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium, can also be used.

(B-1) Among organometallic compounds, organoaluminum compounds are preferred. The above (b-1) organometallic compounds are used singly or in combination of two or more.
[(B-2) Organoaluminum oxy compound]
The (b-2) organoaluminum oxy compound used as necessary in the present invention may be a conventionally known aluminoxane, or a benzene insoluble organoaluminum as exemplified in JP-A-2-78687. It may be an oxy compound.

A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon medium. (2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (b-1a).

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
The organoaluminum compounds as described above are used singly or in combination of two or more.

  Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromide and bromide. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, those which are insoluble or hardly soluble in benzene are preferred.

  Examples of the organoaluminum oxy compound used in the present invention also include an organoaluminum oxy compound containing boron represented by the following general formula (i).

In the formula, R ⁶ represents a hydrocarbon group having 1 to 10 carbon atoms. R ⁷ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different.
The organoaluminum oxy compound containing boron represented by the general formula (i) includes an alkyl boronic acid represented by the following general formula (ii) and an organoaluminum compound in an inert solvent under an inert gas atmosphere. In particular, it can be produced by reacting at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.

R ⁶ —B (OH) ₂ (ii)
(Wherein R ⁶ represents the same group as described above)
Specific examples of the alkyl boronic acid represented by the general formula (ii) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, and n-hexyl boronic acid. Cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid, and the like. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable.

These may be used alone or in combination of two or more.
Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (b-1a). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

The above (b-2) organoaluminum oxy compounds are used singly or in combination of two or more.
[(B-3) Ionized ionic compound]
(B-3) The compound that reacts with the [A] transition metal complex compound to form an ion pair, which is used as necessary in the present invention, reacts with the [A] transition metal complex compound to form an ion pair. A compound. Therefore, what forms an ion pair by making it contact with a [A] transition metal complex compound at least is contained in this compound.

Examples of such compounds include JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, and JP-A-3-179.
Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in Japanese Patent No. 207703, JP-A-3-307704, US Pat. No. 5,321,106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group or trifluoromethyl group) can be mentioned. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (P-Tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like can be mentioned.

Examples of the ionic compound include compounds represented by the following general formula (III).

In the formula, ^examples of R ⁸⁺ include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R ^{9 to} R ¹² are organic groups which may be the same as or different from each other, preferably an aryl group or a substituted aryl group.
Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cations, N, N-dialkylanilinium cations such as N, N, 2,4,6-pentamethylanilinium cations; dialkylammonium cations such as di (isopropyl) ammonium cations and dicyclohexylammonium cations Etc.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ⁸⁺ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

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

  Specific examples of the N, N-dialkylanilinium salt include, for example, N, N-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N, 2,4,6-pentamethylaniline. Examples thereof include nium tetraphenylborate.

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

Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Examples thereof include cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, and boron compounds represented by the following formula (IV) or (V).

Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undeca Salts of anions such as borate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate Metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) And the like.

Specific examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecarborane (14), dodecahydride-1-phenyl-1, 3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane (13), 2,7-dicarbaound decaborane (13), undecahydride-7,8-dimethyl-7,8-dicarbaound decaborane, dodecahydride-11-methyl-2,7-dicarbound decaborane , Tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri (n Butyl) ammonium 1-carba dodecaborate, tri (n- butyl) ammonium 1-trimethylsilyl-1-carba deca borate, tri (n
-Butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) Ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium 7,8-dicarbaundecaborate (12), tri (n-butyl) ammonium 2,9-dicarbaundecaborate (12), tri ( n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri (
n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n- (Butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-
Butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate and other anionic salts; tri (n-butyl) ammonium bis (nonahydride-
1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelate ( III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicar Bound Decaborate) Goldate (III), Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-di Carbaundecaborate) ferrate (III)
, Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-
Dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (I
II), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7) -Carbaundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) And salts of metal carborane anions such as) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV).

  The heteropoly compound is composed of atoms composed of silicon, phosphorus, titanium, germanium, arsenic or tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdo tungstovanadate, phosphomolybdo Tungstic acid, phosphomolybniobic acid, salts of these acids, such as metals of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium , With barium etc. Salts, and organic salts such as triphenylethyl salt, and isopoly compound can be used but not limited thereto.

The heteropoly compound and the isopoly compound are not limited to one of the above compounds, and two or more of them can be used.
The above (b-3) ionized ionic compounds are used singly or in combination of two or more.

  When the olefin multimerization catalyst of the present invention is used, an olefin multimer can be obtained with high activity. Particularly when ethylene is used as the olefin, the selectivity of 1-hexene or 1-octene is high.

  For example, when an organoaluminum oxy compound (b-2) such as methylaluminoxane is used in combination as a co-catalyst component, it exhibits very high trimerization activity or tetramerization activity with respect to ethylene to produce 1-hexene or 1-octene. Can do. Further, even when an ionized ionic compound (b-3) such as triphenylcarbonium tetrakis (pentafluorophenyl) borate is used as a co-catalyst component, 1-hexene or 1-hexene is obtained from ethylene with good activity and very high selectivity. Octene is obtained.

  The olefin multimerization catalyst according to the present invention includes [A] a transition metal complex compound, and if necessary, [B] (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (B-3) It contains at least one compound selected from ionized ionic compounds, and may further contain a [C] carrier as described later, if necessary.

[[C] carrier]
The [C] carrier used as necessary in the present invention is an inorganic or organic compound, and is a granular or particulate solid. Among these, as the inorganic compound, porous oxides, inorganic chlorides, clays, clay minerals or ion-exchangeable layered compounds are preferable.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ and B _2.
O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or composites or mixtures containing these are used, eg natural or synthetic zeolite, 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, etc. can be used SiO ₂ -TiO ₂ -MgO. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred.

The inorganic oxide is composed of a small amount 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 , Al (NO ₃ ) ₃ , N
It may contain carbonates, sulfates, nitrates and oxide components such as a ₂ O, K ₂ O and Li ₂ O.

Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m. ² / g, preferably in the range of 100 to 700 m ² / g, and the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic chloride, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic chloride may be used as it is or after being pulverized by a ball mill or a vibration mill. In addition, an inorganic chloride dissolved in a solvent such as alcohol and then precipitated in a fine particle form by a precipitating agent may be used.

  The clay used as a carrier in the present invention is usually composed mainly of a clay mineral. Further, the ion-exchangeable layered compound used as a carrier in the present invention is a compound having a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with a weak binding force, and the ions contained can be exchanged It is. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

Further, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And halloysite, and the ion-exchangeable layered compounds include 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 Examples thereof include crystalline acidic salts of polyvalent metals such as PO ₄ ) ₂ .H ₂ O.

Such a clay, clay mineral or ion-exchange layered compound preferably has a pore volume of not less than 0.1 cc / g and not less than 0.3 cc / g, as measured by mercury porosimetry. Is particularly preferred. Here, the pore volume is measured in a pore radius range of 20 to ³ × 10 ⁴ angstroms by mercury porosimetry using a mercury porosimeter. When a carrier having a pore volume with a radius of 20 angstroms or more and smaller than 0.1 cc / g is used as a carrier, high dimerization activity tends to be hardly obtained.

The clay and clay mineral used in the present invention are preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchange property. . Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , and [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Etc.

These compounds are used alone or in combination of two or more.
Further, when intercalating these compounds, Si (OR) ₄ , Al (OR
₃ ), metal alkoxides such as Ge (OR) ₄ (R is a hydrocarbon group, etc.) and the like, dimerization products obtained by hydrolysis, colloidal inorganic compounds such as SiO _2, etc. can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

  The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, teniolite and synthetic mica.
Examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) dimer or vinylcyclohexane produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, Examples thereof include (co) dimers produced with styrene as a main component, and modified products thereof.

  The olefin multimerization catalyst according to the present invention contains the [A] transition metal complex compound, and if necessary, the [B] (b-1) organometallic compound, (b-2) organoaluminum oxy compound, and (B-3) includes at least one compound selected from ionized ionic compounds, and further includes a carrier [C] as necessary, and further includes a [D] organic compound component as described later as necessary. You can also.

[[D] Organic compound component]
In the present invention, the [D] organic compound component is used for the purpose of improving the multimerization performance, if necessary. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

As alcohols and phenolic compounds, those represented by R ¹³ —OH are usually used (where R ¹³ is a hydrocarbon group having 1 to 50 carbon atoms or a halogenated group having 1 to 50 carbon atoms). As the alcohol, a hydrocarbon group is preferable, and R ¹³ is preferably a halogenated hydrocarbon.

Moreover, as a phenolic compound, what substituted the (alpha) and (alpha) '-position of the hydroxyl group with the C1-C20 hydrocarbon is preferable.
As the carboxylic acid, one represented by R ¹⁴ —COOH is usually used. R ¹⁴ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable.

  As the phosphorus compound, phosphoric acid having P—O—H bond, P—OR, phosphate having P═O bond, and phosphine oxide compound are preferably used.

  As the sulfonate, those represented by the following general formula (VI) are used.

In formula (VI), M ⁴ is an element of Groups 1 to 14 of the periodic table. R ¹⁵ is hydrogen, 1 carbon atom
-20 hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms. X 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. m is an integer of 1 to 7, n is a valence of M, and 1 ≦ n ≦ 7.

  The olefin multimerization catalyst of the present invention can be used for olefin multimerization, but ethylene multimerization can be particularly suitably performed. Hereinafter, the method for increasing the amount of olefin will be described using ethylene as an example.

[Method for increasing the amount of ethylene]
The ethylene multimerization method will be described.
The ethylene multimerization method according to the present invention comprises a large amount, preferably trimerization or tetramerization of ethylene in the presence of the above catalyst.

The ethylene trimerization method is a method for producing 1-hexene from ethylene, and the ethylene tetramerization method is a method for producing 1-octene from ethylene.
The method of adding the component [A] to the reactor, the method of using each component, the method of addition, and the order of addition are arbitrarily selected during the multimerization, and the following methods are exemplified.

(1) A method in which only component [A] is added to the reactor.
(2) Component [A] and at least one component [B] selected from (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound and (b-3) an ionized ionic compound And simply adding “component [B]”) to the reactor in any order.

(3) A method in which a catalyst in which the component [A] and the component [B] are contacted in advance is added to the reactor.
(4) A method in which the component [A] and the component [B] are contacted in advance, and the component [B] is added to the reactor in any order. In this case, component [B] may be the same or different.

(5) A method in which only the catalyst component having component [A] supported on carrier [C] is added to the reactor.
(6) A method in which the catalyst component having component [A] supported on carrier [C] and component [B] are added to the reactor in any order.

(7) A method in which a catalyst in which the component [A] and the component [B] are supported on the carrier [C] is added to the reactor.
(8) A method in which the catalyst component having the component [A] and the component [B] supported on the carrier [C] and the component [B] are added to the reactor in an arbitrary order. In this case, component [B] may be the same or different.

(9) A method in which the catalyst component having component [B] supported on support [C] and component [A] are added to the reactor in any order.
(10) A method in which the catalyst component having component [B] supported on support [C], component [A], and component [B] are added to the reactor in any order. In this case, component [B] may be the same or different.

(11) A method of adding the component [A] supported on the carrier [C] and the component [B] supported on the carrier [C] to the reactor in any order.
(12) A method of adding the component [A] supported on the carrier [C], the component [B] supported on the carrier [C], and the component [B] to the reactor in any order. In this case, component [B] may be the same or different.

(13) A method of adding the component [A] and the component [D] to the reactor in an arbitrary order.
(14) A method in which component [A], component [B], and organic compound component [D] are added to the reactor in any order.

(15) A method in which component [B] and component [D] are contacted in advance, and component [A] are added to the reactor in any order.
(16) A method in which the component [D] supported on the carrier [C] and the component [A] are added to the reactor in any order.

(17) A method of adding the component [B] and the component [D] supported on the carrier [C], and the component [A] to the reactor in an arbitrary order.
(18) A method in which component [A] and component [B] are contacted in advance, and component [D] is added to the reactor in any order.

(19) A method in which the component [A] and the component [B] are contacted in advance, and the component [B] and the component [D] are added to the reactor in any order.
(20) A method in which the catalyst component in which the component [A] and the component [B] are contacted in advance and the component in which the component [B] and the component [D] are contacted in advance are added to the reactor in an arbitrary order.

(21) A method of adding the component [A] supported on the carrier [C], the component [B], and the component [D] to the reactor in any order.
(22) A method of adding the component [A] supported on the carrier [C] and the component [D] to the reactor in an arbitrary order.

(23) A method in which the component [A] supported on the carrier [C] and the component [B] and the component [D] previously contacted are added to the reactor in any order.
(24) A method in which a catalyst component in which the components [A] and [D] are contacted in advance is added to the reactor.

(25) A method in which a catalyst component obtained by previously contacting component [A], component [B], and component [D] in any order is added to the reactor.
(26) A method in which component [A], component [B], and component [D] are contacted in advance, and component [B] is added to the reactor in any order. In this case, component [B] may be the same or different.

(27) A method in which a catalyst in which the component [A] and the component [D] are supported on the carrier [C] is added to the reactor.
(28) A method in which a catalyst in which the component [A], the component [B], and the component [D] are supported on the carrier [C] is added to the reactor.

  (29) A method in which component [A], component [B] and component [D] are supported on a carrier [C] and a catalyst component and component [B] are added to the reactor in any order. In this case, component [B] may be the same or different.

In the method for producing 1-hexene or 1-octene according to the present invention, 1-hexene or 1-octene is obtained by increasing the amount of ethylene in the presence of the above-mentioned catalyst for increasing the number of olefins. In the present invention, multimerization can be carried out in any of liquid phase reaction methods such as dissolution reaction and suspension reaction, or gas phase reaction methods.

  In the liquid phase trimerization or tetramerization method, an inert hydrocarbon medium is used. Specific examples of the inert hydrocarbon medium used include propane, butane, pentane, hexane, heptane, octane, decane, and dodecane. Aliphatic hydrocarbons such as kerosene; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenations such as ethylene chloride, chlorobenzene, and dichloromethane There may be mentioned hydrocarbons or mixtures thereof.

In the production of 1-hexene or 1-octene using the olefin multimerization catalyst as described above, the component [A] is usually 10 ⁻¹² to 10 ⁻² mol per liter of reaction volume, preferably The amount used is 10 ⁻¹⁰ to 10 ⁻³ mol. In the present invention, the component [
Even when A] is used at a relatively low concentration, ethylene can be trimerized or tetramerized with high multimerization activity.

  In addition, when component [B] is used, component (b-1) is obtained by converting the molar ratio of component (b-1) to the transition metal complex atom (M) in component [A] [(b-1) / M] is usually 0.01 to 100,000, preferably 0.05 to 50,000.

  Component (b-2) has a molar ratio [(b-2) / M] of the aluminum atom in component (b-2) and the transition metal atom (M) in component [A] usually 10 to 10. The amount used is 500,000, preferably 20 to 100,000.

Component (b-3) has a molar ratio [(b-3) / M] of component (b-3) and transition metal atom (M) in component [A] usually from 1 to 10, preferably It is used in such an amount as to be 1-5.
Component [C] is an amount such that the ratio (g / mmol) of component [C] to moles of transition metal atom (M) in component [A] is usually 100 to 10,000, preferably 1000 to 5000. Used.

  In the case of component (b-1), component [D] has a molar ratio [(D) / (b-1)] of usually 0.01 to 10, preferably 0.1 to component [B-1]. In the case of component (b-2), the molar ratio [(D) / (b-2)] between component [D] and the aluminum atom in component (b-2) is usually 0. 0.001 to 2, preferably 0.005 to 1 and in the case of component (b-3), the molar ratio [(D) / (b-3)] is usually 0.01 to 10, preferably Is used in an amount of 0.1-5.

The ethylene multimerization temperature using such an olefin multimerization catalyst is usually in the range of −50 to 200 ° C., preferably 0 to 170 ° C. The reaction pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the multimerization reaction is performed in any of batch, semi-continuous and continuous methods. Can do.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

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

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

[Selectivity of 1-hexene or 1-octene]
The selectivity of 1-hexene or 1-octene was determined according to the following formula.
S (%) = Wp / Wr × 100
S (%): 1-hexene or 1-octene selectivity (weight fraction)
Wr (weight): total weight of products having 4 or more carbon atoms generated by the reaction Wp (weight): weight of 1-hexene or 1-octene generated by the reaction The transition metal compound according to the present invention is shown below. While showing a specific synthesis example, the specific Example and comparative example of ethylene multimerization are shown.

[Synthesis Example 1]
(Synthesis of Compound 1)

In a well-dried 200 mL two-necked eggplant flask (condenser with three-way cock, with magnetic stirrer), 3.44 g (20 mmol) of 2-methoxyphenylboronic acid, 3.19 g (21 mmol) of 2-bromobenzenamine, and 0.21 of palladium chloride. 355 g (2.0 mmol), 1.05 g (4.0 mmol) of triphenylphosphine and potassium carbonate (30 mmol) were added, suspended in 50 mL of toluene, and reacted at 100 ° C. for 9.5 hours. 50 mL of water was added to the reaction solution, and the mixture was extracted with toluene. The organic layer was dried over MgSO ₄ and concentrated to obtain 6.3 g of a crude product. The crude product was purified using silica gel column chromatography (eluent: hexane / ethyl acetate = 3/1) to obtain 1.76 g (yield 44%, yellow solid) of Compound 1.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.38-6.98 (m, 6H, Ar-H), 6.85-6.75 (m, 2H, Ar-H), 3.80 (s, 3
H, CH ₃ ), 3.67 (br, 2H, NH ₂ ).
(Synthesis of Compound 2)

  Add 996 mg (5.0 mmol) of Compound 1 and 475 mg (5.0 mmol) of pyrrole-2-carboxaldehyde to a well-dried 100 mL eggplant flask (with three-way cock and magnetic stirrer), dissolve in 20 mL of ethanol, and add 2 mg of acetic acid. And reacted at room temperature for 48 hours. The solvent was distilled off from the reaction solution under reduced pressure to obtain 1.38 g of Compound 2 (yield 99%, orange viscous oil).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.35 (s, 1H), 7.39-7.26 (m, 3H), 7.25-7.21 (m, 2H,), 7.05-6.95 (m, 2H), 6.89-6.83 (m , 2H), 6.60-6.58 (m, 1H), 6.24-6.22 (m, 1H), 3.60 (s, 3H). Pyrrole-NH is missing.
(Synthesis of Compound 3)

96 mg (4.0 mmol) of sodium hydride and 20 mL of tetrahydrofuran were added to a well-dried 50 mL two-necked eggplant flask (with a three-way cock, with a magnetic stirrer) and stirred, and 8.0 mL of a solution of compound 2 in tetrahydrofuran while cooling with ice ( 0.5M, 4.0 mmol) was added dropwise, and the mixture was allowed to react for 1 hour while gradually rising to room temperature. After adding 1.0 mL (8.0 mmol) of trimethylsilyl chloride to the reaction solution and reacting at room temperature for 2 hours, the solvent was distilled off and 20 mL of hexane was added. This was filtered through a glass filter and the solvent was distilled off to obtain a yellow oil.
¹ H NMR (δ, CDCl ₃ ): 8.13 (s, 1H), 7.38-6.58, m, 10H), 6.41-6.38 (m, 1H), 3.51 (s, 3H), 0.13 (s, 9H).
This oil was dissolved in 10 mL of dichloromethane, and 4.0 mL (4.0 mmol) of a 1.0 mol / L dichloromethane solution of titanium tetrachloride was added to a well-dried 50 mL two-necked eggplant flask (with a three-way cock and with a magnetic stirrer). It was dripped at -78 degreeC to what added 20 mL of dichloromethane. The reaction solution was allowed to react for 8 hours while gradually warming to room temperature, then concentrated to about 2 mL, and 20 mL of hexane was added to precipitate a solid. This solid was collected by filtration and washed with hexane to obtain 893 mg of Compound 3 (yield 52%, green solid).

The result of analyzing the obtained product was as follows. The measurement result of ¹ H NMR spectrum is shown in FIG.
¹ H NMR (δ, CDCl ₃ ): 7.75-6.99 (m, 10H), 6.14-6.12 (m, 1H), 6.46-6.45 (m, 1H), 4.01 (s, 3H).

  28 mL of toluene was placed in an autoclave having an internal volume of 100 mL that was sufficiently purged with nitrogen, and then 1.0 mmol of methylaluminoxane (MAO, 1M toluene solution) was added in terms of aluminum atoms. Subsequently, the compound 3 (0.001 mmol) was added together with 1.0 mL of toluene, and the reaction was started by pressurizing with ethylene (0.8 MPa-G). The reaction was stopped at 25-28 ° C. for 30 minutes while supplying ethylene at the same pressure, and then the reaction was stopped by adding a small amount of isopropanol. After completion of the reaction, the reaction solution is washed with 0.1 N hydrochloric acid and pure water, and a low boiling point component (10 or less carbon atoms) is separated from the high boiling point component and polyethylene using a liquid nitrogen trap under reduced pressure. Analysis was performed using chromatography. Among the products, the selectivity for 1-hexene was 40%. The selectivity of polyethylene was 60%, and the catalytic activity calculated from the total amount of these products was 0.17 kg-product / (mmol-Ti · h).

[Comparative Example 1]
28 mL of toluene was placed in an autoclave having an internal volume of 100 mL that was sufficiently purged with nitrogen, and then 1.0 mmol of methylaluminoxane (MAO, 1M toluene solution) was added in terms of aluminum atoms. Subsequently, 0.001 mmol of the following compound 4 (1 mM toluene solution) described in Organometallics 2001, Vol. 20, pp. 4793-4799 was added, and the reaction was started by pressurizing with ethylene (0.8 MPa-G). The reaction was stopped at 25-35 ° C. for 10 minutes while supplying ethylene at the same pressure, and then the reaction was stopped by adding a small amount of isopropanol. After completion of the reaction, the reaction solution is washed with 0.1N hydrochloric acid and pure water, and a low-boiling component (10 or less carbon atoms) is separated from polyethylene using a liquid nitrogen trap under reduced pressure, and gas chromatography is used. Analysis. 2.03 g of polyethylene was obtained as a product, but 1-hexene was not detected.

3 is a diagram showing the measurement result of ¹ H NMR spectrum of Compound 3. FIG.

Claims (5)

[A] An olefin multimerization catalyst comprising a transition metal complex compound represented by the following general formula (I).

(In the general formula (I), R ^{1 to} R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, or boron. A containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be linked to each other, and R ¹ is Z may be connected to R, and R ⁵ may be connected to Z.
M represents a transition metal atom of Group 4 of the periodic table.
X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing A group, a germanium-containing group, or a tin-containing group, the groups represented by X may be the same as or different from each other, and the groups represented by X may be bonded to each other to form a ring.
Y represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom.
Z represents a hydrocarbon group or a heterocyclic compound residue which may have a substituent.
In the formula, the bond connecting Y and Z may be a double bond or a triple bond, and the bond connecting Y and R ¹ may be a double bond or a triple bond.
In the formula, the dotted line indicates a coordination bond. ) [A] The olefin according to claim 1, wherein the shortest number of bonds connecting Y of the transition metal complex compound represented by the general formula (I) to M and linking Z to adjacent N is 5 or 6. Catalyst for multimerization. [A] a transition metal complex compound represented by the general formula (I), and
[B] selected from the group consisting of (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) [A] a compound that reacts with a transition metal complex compound to form an ion pair. The olefin multimerization catalyst according to claim 1 or 2, comprising at least one compound.   A process for producing 1-hexene, wherein ethylene is trimerized in the presence of the olefin multimerization catalyst according to any one of claims 1 to 3.   The manufacturing method of 1-octene which tetramerizes ethylene in presence of the catalyst for olefin multiplication of any one of Claims 1-3.

Images