JP2000302812A - CATALYST FOR MANUFACTURING alpha-OLEFIN AND MANUFACTURE OF alpha-OLEFIN - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst which expresses high oligomerization activity of ethylene and has a high yield of C6, C8 and C10 components by contacting clay, a clay mineral or a lamellar compound of ion exchangeability with a transition metal complex in groups 4 to 6. SOLUTION: Prior to contacting with a transition metal complex, chemical treatment is preferably performed to clay, a clay mineral or a lamellar compound of ion exchangeability (clay and the like). The chemical treatment is the treatment with an acid, alkali, salts, organic substance or the like. The treated clay or the like may be used itself, or the one in which water is added and adsorbed or is treated with heating and dehydration may be used. The chemically treated clay or the like is preferably treated with an organic silane compound. The clay or the like is preferably clay or a clay mineral, preferably phyllosilicates, especially smectite or montmorillonite. The transition metal complex is suitably a metallocene. Among the transition metals, a group 4 metal is preferable, especially zirconium is preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention, alpha-olefin production catalyst and to a method for producing alpha-olefins, more particularly, C _6, C _8, components yield to C ₁₀ higher alpha-olefin for the production The present invention relates to a catalyst and a method for producing an α-olefin by oligomerization of ethylene using the catalyst.

[0002]

2. Description of the Related Art Conventionally, in producing an α-olefin by oligomerizing ethylene, a transition metal complex is used as a main catalyst, and an oxygen-containing organoaluminum compound such as alumoxane or a boron such as perfluorotetraphenyl borate is used as a co-catalyst. A method using a system compound is known. However, the usual use amount of these cocatalysts is several hundred times the mol of the main catalyst, and the activity per catalyst is low and the efficiency is low. In addition, the yields of the highly demanded C ₆ , C ₈ , and C ₁₀ components are not sufficient.

[0003] The α-olefin (oligomer) referred to in the present invention refers to a polymer having a molecular weight of 10,000 or less. Different uses. Therefore, the performance required for the catalyst used for its production differs from the performance of the catalyst used for the production of ordinary polymers,
The polymer production catalyst cannot always be used as it is.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above point of view, and can exhibit a high ethylene oligomerization activity and a high yield of C ₆ , C ₈ , and C ₁₀ components. An object of the present invention is to provide a catalyst and a method for producing an α-olefin that oligomerizes ethylene using the catalyst.

[0005]

Means for Solving the Problems The present inventors use transition metal complexes of Groups 4 to 6 of the periodic table as the main catalyst and use clay, clay mineral or ion-exchangeable layered compound as the co-catalyst. As a result, the present inventors have found that the above object can be effectively achieved, and have completed the present invention.

That is, the gist of the present invention is as follows. (1) A catalyst for producing an α-olefin obtained by bringing (a) a clay, a clay mineral or an ion-exchange layered compound into contact with (b) a transition metal complex of Groups 4 to 6 of the periodic table. (2) The α-olefin production catalyst according to the above (1), wherein the ligand of the transition metal complex as the component (b) has a conjugated five-membered ring. (3) The α-olefin production catalyst according to the above (1) or (2), wherein the transition metal in the component (b) is zirconium. (4) The α-olefin production according to any one of the above (1) to (3), wherein the clay, clay mineral or ion-exchangeable layered compound as the component (a) contains an inorganic substance containing phyllosilicates. Catalyst. (5) The above (1) to (1) to wherein the clay, clay mineral or ion-exchangeable layered compound of the component (a) is montmorillonite.
The catalyst for producing an α-olefin according to any of (4). (6) The α-olefin production catalyst according to any one of the above (1) to (5), wherein the clay, clay mineral or ion-exchange layered compound as the component (a) is treated with an organic silane compound. . (7) A method for producing an α-olefin, characterized in that ethylene is oligomerized using the catalyst for producing an α-olefin according to any one of the above (1) to (6).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The catalyst for producing an α-olefin of the present invention comprises (a)
Clay, clay mineral or ion-exchangeable layered compound (hereinafter referred to as
Also called clay. And (b) contacting with a transition metal complex of Groups 4 to 6 of the periodic table. The components (a) and (b) will be described in detail.

[0008] One of the component (a) component (a), clay or clay minerals are used. Clay is an aggregate of fine hydrated silicate minerals, a material that produces plasticity when mixed with an appropriate amount of water, exhibits rigidity when dried, and sinters when baked at high temperatures. Clay minerals are hydrated silicates that are the main component of clay. For the preparation of the α-olefin production catalyst component, any of clay and clay mineral may be used, and these may be natural products or artificially synthesized products.

Further, as the component (a), an ion-exchange layered compound can be used. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces constituted by ionic bonds and the like are stacked in parallel with weak bonding force to each other, and ions contained therein can be exchanged. Some clay minerals are ion-exchangeable layered compounds.

Specific examples of the component (a) are as follows.
To show, for example, phyllosilicates can be mentioned as clay minerals.
Can be. Phyllosilicates include phyllosilicate and phyllosilicate.
There is losilicate. Philosilicate is a natural product
Montmorillonite, saponite,
Hectorite, illite, sericite and mica
And smectite and mica or mica and vermicular
And mixed layer minerals with the Ito group. Also,
Synthetic products include silicon tetrafluoride mica (TSM), Rapona
And smecton. In addition, α
-Zr (HPO _Four)_Two, Γ-Zr (HPO_Four)_Two, Α-
Ti (HPO_Four)_TwoAnd γ-Ti (HPO_Four)_TwoEtc.
Ion crystallization with a layered crystal structure that is not an earth mineral
Compounds can be used.

Clays and clay minerals that do not belong to the ion-exchange layered compound include clays called bentonite due to low montmorillonite content, Kibushi clay, montmorillonite which contains many other components in montmorillonite,
Sepiolite, palygorskite, showing fibrous form,
In addition, there are amorphous or low-crystalline allophane, imogolite, and the like. The component (a) has a pore volume of not less than 0.1 ml / g, more preferably from 0.2 to 5.5 ml / g, having a pore volume of at least 20 ° measured by a mercury intrusion method.
Are preferred.

Next, before the component (a) is brought into contact with the component (b), impurities in the clay, the clay mineral and the ion-exchangeable layered compound are removed, and the structure and function thereof are changed. It is desirable to perform a chemical treatment in order to give a more preferable form as a catalyst component by giving.
In this chemical treatment, there are a surface treatment for removing impurities adhering to the surface of clay and the like, and a treatment for affecting the crystal structure of clay and the like. Specifically, acid treatment, alkali treatment, salt treatment, Organic material treatment and the like can be mentioned.

In this acid treatment, impurities on the surface are removed, and aluminum in the crystal structure of clay or the like is removed.
By eluting cations such as iron and magnesium, the surface area can be increased. In the alkali treatment, the crystal structure of the clay can be changed to a preferable form. Furthermore, in the salt treatment or the organic substance treatment, an ionic complex, a molecular complex, an organic complex, or the like is formed, and can be changed to a preferable form in terms of a surface area, an interlayer distance, and the like. For example, by using the ion-exchange property to replace the exchangeable ions between the layers with another bulky ion, it is also possible to obtain an interlayer material in which the layers are expanded.

The component (a) can be used as it is.
It is also possible to use water that is newly added and adsorbed.
Alternatively, those subjected to heat dehydration treatment may be used. This
Clays that have been chemically treated as in
It is better to treat with organic silane compound to increase
No. As the organic silane compound, the following general formula (1)
The organic silane compound represented by these can be mentioned. R^Ten _nSix^Two _4-n ... (1) [wherein, R^TenIs the atom at the site directly bonded to the silicon atom
Is a substituent which is a carbon atom, a silicon atom or a hydrogen atom
Yes, X^TwoMeans that the atom at the site directly bonding to the silicon atom is
A substituent which is a halogen atom, an oxygen atom or a nitrogen atom
Yes, R^TenAnd X ^TwoWhen there are multiple
R^TenOr X^TwoMay be the same or different. n is
It is an integer of 1 to 3. ]

Further, the organic silane compound has the following general formula:
Formula (2) X^Three _4-nSi (CH_Two)_mSix^Three _4-n ... (2) [wherein, X^ThreeIs the atom at the site directly bonded to the silicon atom
Is a halogen atom, an oxygen atom or a nitrogen atom
X^ThreeWhen there are a plurality of ^ThreeIs
They may be the same or different. m is 1 to 10, n is 1 to
3 is represented. Bissilyl form or polynuclear policy
It may be in the form of oxane, polysilazane or the like.

Specific examples of the organic silane compound represented by the above general formula include, for example, trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride, t-butyldimethylsilyl chloride,
Trialkylsilyl chlorides such as tert-butyldiphenylsilyl chloride and phenethyldimethylsilyl chloride, dimethylsilyl dichloride, diethylsilyl dichloride, diisopropylsilyl dichloride, di-n-
Dialkylsilyl dichlorides such as hexylsilyl dichloride, dicyclohexylsilyl dichloride, docosylmethylsilyl dichloride, bis (phenethyl) silyl dichloride, methylphenethylsilyl dichloride, diphenylsilyl dichloride, dimesitylsilyl dichloride, ditolysilyl dichloride, and ditolysilyl dichloride; And alkylarylsilyl dichlorides.

Further, silyl halides in which the chloride moiety in the above compound is replaced by another halogen element, bis (trimethylsilyl) amide, bis (triethylsilyl) amide, bis (triisopropylsilyl) amide,
Disilazanes such as bis (dimethylethylsilyl) amide, bis (diethylmethylsilyl) amide, bis (dimethylphenylsilyl) amide, bis (dimethyltolylsilyl) amide, bis (dimethylmesitylsilyl) amide, trimethylsilyl hydroxide, triethyl Silyl hydroxide, triisopropylsilyl hydroxide,
Trialkylsilyl hydroxides such as tert-butyldimethylsilyl hydroxide and phenethyldimethylsilyl hydroxide, polysilanols called by the common name of peralkylpolysiloxypolyol, bis (methyldichlorosilyl) methane, 1,2-bis Bissilyls such as (methyldichlorosilyl) ethane, bis (methyldichlorosilyl) octane and bis (triethoxysilyl) ethane; silanes having a hydride such as dimethylchlorosilane, (N, N-dimethylamino) dimethylsilane and diisobutylchlorosilane Can be mentioned. These organic silane compounds may be used alone,
Two or more kinds may be used in combination.

Of these organic silane compounds, those having at least one alkyl group directly bonded to a silicon atom are preferred, and alkylsilyl halides, particularly dialkylsilyl halides, are suitably used. And
It is more effective to carry out the treatment with these organic silane compounds in the presence of water. In that case, the water breaks down the crystal structure (especially the laminated structure) of the clays, and acts to increase the contact efficiency between the organosilane compound and the clays. That is, the water expands the interlayer of the clay crystals, It is presumed that the diffusion of the organosilane compound into the crystals in the stack is promoted. The above component (a) may be used alone or in a combination of two or more. Among these components (a), clay or clay mineral is preferred, specifically, phyllosilicic acids are preferred, smectite is more preferred, and montmorillonite is more preferred.

Component (b) Periodic Table Nos. 4 to 6 of component ( b) generally called a main catalyst
The transition metal complex of the group can be selected from a wide range of organometallic complexes, without being limited to a group of organometallic complexes of metallocene, but metallocene is preferred. Among the transition metals, metals of Group 4 of the periodic table are preferable, and zirconium is particularly preferable.

The transition metal complexes of Groups 4 to 6 of the Periodic Table
Preferred are represented by the following general formulas (3) to (5).
But can be limited to
is not. Q¹ _a(C_FiveH_5-abR¹ _b) (C_FiveH_5-acR^Two _c) MX¹Y¹... (3) Q^Two _a(C_FiveH_5-adR^Three _d) Z¹MX¹Y¹ ... (4) (C_FiveH_5-eR^Four _e) MX¹Y¹W¹ ... (5) [where Q is¹Represents two conjugated five-membered ring ligands (C_FiveH
_5-abR¹ _b) And (C_FiveH _5-acR^Two _cCrosslink)
A bonding group;^TwoIs a conjugated five-membered ring ligand (C_FiveH
_5-adR^Three _d) And Z¹Shows a binding group that crosslinks the group. (
C_FiveH_5-eR^Four _e) Represents a conjugated five-membered ring ligand. R¹,
R^Two, R^ThreeAnd R^FourRepresents a hydrocarbon group and a halogen, respectively
Atom, alkoxy group, silicon-containing hydrocarbon group, phosphorus-containing carbon
Hydrocarbon groups, nitrogen-containing hydrocarbon groups or boron-containing hydrocarbon groups
And a is 0, 1 or 2. b, c and d are a
= 0 is an integer of 0 to 5;
An integer of 0 to 4 and a = 2 when a = 2
Indicates an integer. E represents an integer of 0 to 5. M is the period
The transition metals of Groups 4 to 6 of the Table are shown. Also, X¹, Y¹,
Z¹, W¹Each represents a covalent ligand
You. Note that X¹, Y¹And W¹Are connected to each other
To form a ring structure. ]

Specific examples of Q ¹ and Q ² include an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, an isopropylene group, a methylphenylmethylene group, a diphenylmethylene group and a cyclohexylene group; Group or its side chain lower alkyl or phenyl substituent, silylene group, dimethylsilylene group, methylphenylsilylene group, diphenylsilylene group, silylene group such as disilylene group, tetramethyldisilylene group, oligosilylene group or its side chain lower alkyl Or a phenyl substituent, a (CH ₃ ) ₂ Ge group, a (C ₆ H ₅ ) ₂ Ge
Group, (CH ₃ ) ₂ P group, (C ₆ H ₅ ) ₂ P group, (C ₄ H
₉ ) N group, (C ₆ H ₅ ) N group, (CH ₃ ) B group, (C ₄
H ₉ ) B group, (C ₆ H ₅ ) B group, (C ₆ H ₅ ) Al group,
Germanium such as (CH ₃ O) Al group, phosphorus, nitrogen,
And hydrocarbon groups containing boron or aluminum [lower alkyl groups, phenyl groups, hydrocarbyloxy groups, lower alkoxy groups (preferably lower alkoxy groups), and the like]. Among these, an alkylene group and a silylene group are preferable from the viewpoint of activity.

Also, (C_FiveH_5-abR¹ _b), (C_FiveH
_5-acR^Two _c), (C_FiveH_5-adR ^Three _d) And (C_FiveH
_5-eR^Four _e) Is a conjugated five-membered ring ligand;¹, R^Two,
R^ThreeAnd R^FourRepresents a hydrocarbon group, a halogen atom,
Alkoxy group, silicon-containing hydrocarbon group, phosphorus-containing hydrocarbon
Group, nitrogen-containing hydrocarbon group or boron-containing hydrocarbon group
And a is 0, 1 or 2. b, c and d are a = 0
Is an integer from 0 to 5 respectively, and when a = 1, each is
Are integers from 0 to 4; when a = 2, each is an integer from 0 to 3
Is shown. E represents an integer of 0 to 5. Where carbonization
As the hydrogen group, those having 1 to 20 carbon atoms are preferable.
And those having 1 to 12 carbon atoms are preferred. This hydrocarbon group
As a monovalent group, a conjugated 5-membered cyclopentadiene
May be bonded to the phenyl group, and
If the two are bonded to each other,
A ring structure may be formed together with a part of the enyl group. You
That is, typical examples of the conjugated five-membered ring ligand are substituted or unsubstituted.
Cyclopentadienyl, indenyl and fluoro
A enyl group. Halogen atoms include chlorine, bromine,
Examples include iodine and fluorine atoms, and as an alkoxy group
Preferably has 1 to 12 carbon atoms. silicon
As the contained hydrocarbon group, for example, -Si (R^Five)
(R⁶) (R⁷) (R^Five, R⁶And R⁷Is carbon number 1-2
4 hydrocarbon groups), and phosphorus-containing hydrocarbons.
Group, nitrogen-containing hydrocarbon group and boron-containing hydrocarbon group
Are P- (R⁸) (R⁹), -N (R⁸) (R
⁹) And -B (R ⁸) (R⁹) (R⁸And R⁹Is the carbon number
1-18 hydrocarbon groups) and the like. R¹,
R^Two, R^ThreeAnd R^FourIf there are multiple
R¹, Multiple R^Two, Multiple R^ThreeAnd multiple R^FourIs
Each may be the same or different. Ma
In the general formula (3), the conjugated five-membered ring ligand (C_FiveH
_5-abR ¹ _b) And (C_FiveH_5-acR^Two _c) Are the same
Or different.

On the other hand, M represents a transition metal element belonging to Groups 4 to 6 of the periodic table, and specific examples thereof include titanium, zirconium, hafnium, vanadium, niobium, molybdenum, tungsten and the like. Titanium, zirconium and hafnium are preferred from the aspect of activity and zirconium is particularly preferred. Z ¹ is a covalent ligand, specifically, a halogen atom, oxygen (—O—), sulfur (—S—), an alkoxy group having 1 to 20 (preferably 1 to 10) carbon atoms, A thioalkoxy group having 1 to 20 (preferably 1 to 12) carbon atoms, 1 to 4 carbon atoms
It represents 0 (preferably 1 to 18) nitrogen-containing hydrocarbon groups and 1 to 40 (preferably 1 to 18) phosphorus-containing hydrocarbon groups. X ¹ , Y ¹ and W ¹ are each a covalent ligand, specifically, a hydrogen atom, a halogen atom,
A hydrocarbon group having 1 to 20 (preferably 1 to 10) carbon atoms,
C1-C20 (preferably 1-10) alkoxy group, amino group, C1-C20 (preferably 1-12)
A phosphorus-containing hydrocarbon group (e.g., diphenylphosphine group) or a silicon-containing hydrocarbon group (e.g., trimethylsilyl group) having 1 to 20 (preferably 1 to 12) carbon atoms; To 12) hydrocarbon compounds or halogen-containing boron compounds (for example, B (C ₆
F ₅ ) ₄ , BF _4, etc.). Among these, a halogen atom and a hydrocarbon group having 1 to 20 carbon atoms are preferable. This X
¹ , Y ¹ and W ¹ may be the same or different.

Preferred specific examples of the transition metal complexes represented by the general formulas (3) and (4) include the following compounds having a conjugated five-membered ring. Bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadichloride (Enyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) ) Zirconium chlorohydride, bis (cyclopentadienyl) methylzirconium chloride,
Bis (cyclopentadienyl) ethyl zirconium chloride, bis (cyclopentadienyl) phenyl zirconium chloride, bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) di Neopentyl zirconium, bis (cyclopentadienyl) dihydrozirconium, (cyclopentadienyl)
Transition metal compounds having two conjugated five-membered ring ligands without a cross-linking group, such as (indenyl) zirconium dichloride and (cyclopentadienyl) (fluorenyl) zirconium dichloride;

Methylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, methylenebis (indenyl) zirconium chlorohydride, ethylenebis (indenyl) methylzirconium chloride, ethylenebis (indenyl) methoxychlorozirconium, ethylenebis (indenyl) zirconium Diethoxide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (4
5,6,7-tetrahydroindenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, ethylenebis (2,4-dimethylindenyl) zirconium dichloride, ethylenebis (2-methyl-4-trimethylsilylindole) Nil)
Zirconium dichloride, ethylenebis (2,4-dimethyl-5,6,7-trihydroindenyl) zirconium dichloride, ethylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) ) Zirconium dichloride, ethylene (2-
Methyl-4-tert-butylcyclopentadienyl)
(3′-tert-butyl-5′-methylcyclopentadienyl) zirconium dichloride, ethylene (2,
3,5-trimethylcyclopentadienyl) (2 ′,
4 ′, 5′-trimethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (2-methylindenyl) zirconium dichloride, isopropylidenebis (indenyl) zirconium dichloride,
Isopropylidenebis (2,4-dimethylindenyl)
Zirconium dichloride, isopropylidene (2,4
-Dimethylcyclopentadienyl) (3′5′-dimethylcyclopentadienyl) zirconium dichloride,
Isopropylidene (2-methyl-4-tert-butylcyclopentadienyl) (3′-tert-butyl-
5'-methylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (3,4
-Dimethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (3,4-
Dimethylcyclopentadienyl) zirconium chlorohydride, methylene (cyclopentadienyl) (3,4-
Dimethylcyclopentadienyl) dimethylzirconium, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) diphenylzirconium,
Methylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,4-dimethylcyclo (Pentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,3,4,5-
Tetramethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl)
(3-methylindenyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (2-methylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, isopropylidene (2.5
-Dimethylcyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (3 5-dimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (2,5-diethylcyclo) Pentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,4-
Diethylcyclopentadienyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl)
(3,4-diethylcyclopentadienyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Transition metal compound having two conjugated five-membered ring ligands bridged by an alkylene group such as cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride ,

Dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4
5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, dimethylsilylenebis (2,4-dimethyl Cyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2-
Methyl-4-naphthylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, phenylmethylsilylenebis (indenyl) zirconium dichloride, phenylmethylsilylenebis (4,5,6,7
-Tetrahydroindenyl) zirconium dichloride, phenylmethylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, phenylmethylsilylene (2,4-dimethylcyclopentadienyl)
(3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, phenylmethylsilylene (2,
3,5-trimethylcyclopentadienyl) (2 ′,
4 ', 5'-trimethylcyclopentadienyl) zirconium dichloride, phenylmethylsilylenebis (tetramethylcyclopentadienyl) zirconium dichloride, diphenylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, diphenylsilylenebis (indenyl) ) Zirconium dichloride, diphenylsilylenebis (2-methylindenyl) zirconium dichloride, tetramethyldisilylenebis (indenyl) zirconium dichloride, tetramethyldisilylenebis (cyclopentadienyl) zirconium dichloride, tetramethyldisilylene (3-methyl) Cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride , Dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) ( Tetraethylcyclopentadienyl)
Zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl)
(2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium Dichloride, dimethylsilylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2-ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2,5-diethylcyclopentadienyl) ) (Fluorenyl) zirconium dichloride, diethylsilylene (2-methylcyclopentadienyl)
(2 ′, 7′-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilylene (2,5-
Dimethylcyclopentadienyl) (2 ′, 7′-di-t
tert-butylfluorenyl) zirconium dichloride, dimethylsilylene (2-ethylcyclopentadienyl) (2 ′, 7′-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilylene (diethylcyclopentadienyl) ( 2,7-di-tert
-Butylfluorenyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl) (octahydrfluorenyl) zirconium dichloride, dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene ( It has two silylene group-bridged conjugated 5-membered ligands such as ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride and dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride Transition metal compound,

Dimethylgermylene bis (indenyl)
Zirconium dichloride, dimethylgermylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, methylaluminenebis (indenyl) zirconium dichloride, phenylamylenebis (indenyl) zirconium dichloride, phenylphosphylenebis (indenyl) zirconium dichloride, ethylborenebis ( Indenyl) zirconium dichloride,
Phenylamylene bis (indenyl) zirconium dichloride, phenylamylene (cyclopentadienyl)
A transition metal compound having two conjugated five-membered ligands bridged by a hydrocarbon group containing germanium, aluminum, boron, phosphorus or nitrogen, such as (fluorenyl) zirconium dichloride;

Pentamethylcyclopentadienyl-bis (phenyl) aminozirconium dichloride, indenyl-bis (phenyl) aminozirconium dichloride, pentamethylcyclopentadienyl-bis (trimethylsilyl) aminozirconium dichloride, pentamethylcyclopentadienylphenoxy Zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) tert-butylamino zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) phenylamino zirconium dichloride, dimethylsilylene (tetrahydroindenyl) decylaminozirconium dichloride, dimethylsilylene ( Tetrahydroindenyl) [bis (trimethylsilyl) amino] zirco Umujikuroraido, dimethyl gel Mi (tetramethylcyclopentadienyl) phenylamino zirconium dichloride, pentamethylcyclopentadienyl zirconium trichloride transition metal compound having one conjugated five-membered cyclic ligand, such as,

(1,1′-dimethylsilylene) (2,
2′-isopropylidene) -bis (cyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) -bis (cyclopentadienyl) zirconium dichloride,
(1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadienyl) dimethylzirconium, (1,1′-dimethylsilylene) (2
2′-isopropylidene) -bis (cyclopentadienyl) dibenzylzirconium, (1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadienyl) bis (trimethylsilyl) zirconium, (1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadienyl) bis (trimethylsilylmethyl) zirconium, (1,2 ′
-Dimethylsilylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,1 ′
-Dimethylsilylene) (2,2′-ethylene) -bis (indenyl) zirconium dichloride, (1,1 ′
-Ethylene) (2,2'-dimethylsilylene) -bis (indenyl) zirconium dichloride, (1,1 '
Transition metal compounds having two conjugated five-membered ring ligands in which ligands are double-bridged, such as -dimethylsilylene) (2,2′-cyclohexylidene) -bis (indenyl) zirconium dichloride,

Further, in the compounds described in (1) to (4) above, the chlorine atom of these compounds is replaced with a bromine atom, iodine atom, hydrogen atom, methyl group, phenyl group, benzyl group,
Those substituted with a methoxy group, a dimethylamino group and the like can be mentioned. Further, there can be mentioned those in which zirconium as the central metal of the above transition metal compound is replaced with a metal such as titanium, hafnium, chromium, niobium, and tungsten.

Finally, examples of the transition metal compound represented by the general formula (5) include the following compounds. Cyclopentadienyl zirconium trichloride, methylcyclopentadienyl zirconium trichloride, dimethylcyclopentadienyl zirconium trichloride, trimethylcyclopentadienyl zirconium trichloride, tetramethylcyclopentadienyl zirconium trichloride, pentamethylcyclopentadi Enyl zirconium trichloride, n-butylcyclopentadienyl zirconium trichloride,
Transition metal compounds having a conjugated five-membered ring ligand such as indenyl zirconium trichloride, fluorenyl zirconium trichloride, tetrahydroindenyl zirconium trichloride, octahydrofluorenyl zirconium trichloride, and the like. Examples thereof include those in which an element atom is replaced with another halide, hydrogen, an alkyl group, an alkoxy group, or the like, and those in which zirconium as a central metal is replaced with titanium or hafnium.

Other complexes that cannot be represented by the above general formula include chelate complexes, and specific examples of transition metal complexes of Groups 4 to 6 of the periodic table include 2,2'-methylene-
4,4 ', 6,6'-tetra-tert-butyldiphenoxyzirconium dichloride; 2,2'-thio-
4,4'-dimethyl-6,6'-di-tert-butyldiphenoxyzirconium dichloride; 2,2-isobutylidene-4,4 ', 6,6'-tetramethyldiphenoxyzirconium dichloride; Further, there can be mentioned those obtained by replacing zirconium as a central metal in these compounds with titanium or hafnium. The above component (b) may be used alone,
Two or more kinds may be used in combination.

Next, a method for preparing a catalyst for producing an α-olefin by bringing the component (a) into contact with the component (b) will be described. The contact treatment of these two components may be performed in the air, but is preferably performed in an inert gas stream such as argon or nitrogen. Pentane, hexane, heptane,
It is preferably carried out in a hydrocarbon such as toluene or xylene. Furthermore, it is more preferable to carry out the reaction in a system free of compounds having active hydrogen such as water, hydroxyl groups, amino groups, etc. which are harmful to the catalyst. For this purpose, it is preferable to remove water and a compound having active hydrogen from the system in advance by using an alkylating agent of the component (c) described later. That is, (a) and (b)
It is better to use the catalyst obtained by contacting (c) with (c) as a catalyst. The component (c) is not necessarily used at the time of preparing the catalyst, but may be used in the reaction system at the time of producing the α-olefin.

As the alkylating agent of the above component (c),
An organozinc compound or an organomagnesium compound can be used, but an inexpensive organoaluminum compound is preferable. Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-tert-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum methoxide, diethylaluminum ethoxide, etc. Halogen or alkoxy group-containing alkyl aluminum, alumoxanes such as methylalumoxane, ethylalumoxane, isobutylalumoxane and the like can be mentioned. Among them, trialkylaluminum is preferable, and triisobutylaluminum is particularly preferable.

The proportion of the component (a) to the component (b) is based on the unit weight (g) of the component (a) such as clay.
(B) 0.01 to 100 mmol of the transition metal complex of the component,
Preferably it is in the range of 0.1 to 50 mmol. (C)
The amount of the alkylating agent used as the component is usually 0.1 to 1,0 of the component (c) per unit weight (g) of the clay or the like as the component (a).
The amount is in the range of 00 mmol, preferably 10 to 500 mmol, but even when used in excess, the suspended slurry of clay or the like can be washed out with a solvent and removed from the system.

The contact treatment of these catalyst components may be performed in a catalyst preparation tank or may be performed in a reactor. The conditions such as temperature, pressure, and time of the contact treatment are not particularly limited. Can be achieved. Lastly, the method for producing an α-olefin of the present invention will be described. In the method for producing an α-olefin of the present invention, an ethylene oligomerization reaction is carried out using the catalyst prepared as described above, if necessary, in the presence of the component (c). The method for performing this reaction is not particularly limited, and may be any method such as a solution reaction method using a solvent, a liquid phase solventless reaction method using substantially no solvent, a gas phase reaction method, Further, any of a continuous reaction and a batch reaction may be used. When a solvent is used, examples of the solvent include hydrocarbon solvents such as pentane, hexane, heptane, cyclohexane, benzene, and toluene. These solvents may be used alone or as a mixture of two or more. You may use it. When a solvent is used, the amount of the catalyst used is
It is advantageous from the viewpoint of reaction activity that the component (b) is used usually in the range of 0.1 to 1,000 micromol, preferably 1 to 500 micromol.

The reaction conditions are not particularly limited.
The reaction temperature is usually -78 to 200 ° C, preferably normal temperature to
It is in the range of 150 ° C. The ethylene pressure of the reaction system is usually from normal pressure to 15 MPa, preferably from normal pressure to 5 MPa.
Range. In addition, the adjustment of the molecular weight during the reaction
It can be performed by known means, for example, selection of temperature and pressure, or introduction of hydrogen.

[0038]

[Example 1]

(1) Chemically treated clay A 40 g of commercially available montmorillonite (Kunimine F, manufactured by Kunimine Industries Co., Ltd.) was pulverized by a pulverizer for 4 hours. 20 g of crushed montmorillonite was placed in a 500 ml three-neck separable flask, and magnesium chloride hexahydrate 2
0 g was dispersed in 100 ml of dissolved deionized water, and treated with stirring at 90 ° C. for 0.5 hour. After treatment,
The solid component was washed with water. The treatment with magnesium chloride and washing with water were repeated once again to obtain montmorillonite treated with magnesium chloride. Next, this was dispersed in 160 ml of a 6% aqueous hydrochloric acid solution, and treated under reflux with stirring for 2 hours. After the treatment, washing with water was repeated until the filtrate became neutral, and the obtained clay slurry was filtered under pressure. The filtrate was dried at room temperature under vacuum for 18 hours to obtain chemically treated clay A. The water content of the chemically treated clay A was 15% by weight.
However, the moisture content was calculated from the weight loss of the clay obtained by placing the dried chemically treated clay in a muffle furnace, raising the temperature to 150 ° C. in 30 minutes, and holding at that temperature for 1 hour.

(2) Modified clay slurry B 1.0 g of chemically treated clay A (water content: 15% by weight) and 50 ml of toluene were added to a 300 ml Schlenk tube to obtain a clay slurry. While stirring the clay slurry solution, 0.96 g (3.6 mmol) of di-n-hexylsilyl dichloride was slowly added dropwise thereto over 15 minutes. After the dropwise addition, the mixture was stirred at room temperature under a nitrogen stream for 3 days. Then, heat at 100 ° C for 1 hour,
Washed twice with 00 ml toluene. And
The obtained slurry is added with 25 ml of a 0.5 mol / l toluene solution of tributylaluminum, heated at 100 ° C. for 1 hour, washed twice with 200 ml of toluene, and adjusted to 50 ml with toluene. In this way, a modified clay slurry B was prepared.

(3) Preparation of Transition Metal Catalyst Bis (cyclopentadienyl) zirconium dichloride (29 mg) was added to 0.5 ml of the modified clay slurry B at room temperature and stirred at room temperature for 0.5 hour.
Thus, 0.5 ml of the catalyst preparation liquid C (1
A catalyst containing 0 mg clay) was prepared.

(4) Ethylene oligomerization reaction 400 ml of toluene and 1.0 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum were added to a 1 liter autoclave, and the temperature was raised to 115 ° C. Therefore, 0.5 ml of the catalyst preparation liquid C (10 mg) prepared in (3) of Example 1 was used.
Catalyst containing clay) and ethylene pressure of 3.5MPa
The reaction was carried out for 60 minutes while continuously supplying such that a was maintained. Thereafter, the reaction was stopped by adding a 1.0 mol / liter aqueous solution of sodium hydroxide. Unreacted ethylene and a part of the produced 1-butene and 1-hexene were weighed with a wet flow meter, and then subjected to gas chromatography for component analysis and quantification. Α- in the reaction solution
The olefin was determined by gas chromatography using n-undecane as an internal standard. The polymer was separated by filtration, dried at 120 ° C. for 12 hours, and quantified. as a result,
Total product weight was 4.04 g. The oligomerization activity per zirconium metal is 432 kg / g-Zr /
h. The results of the distribution of α-olefins produced
It is shown in the table.

[Comparative Example 1] (1) Preparation of transition metal catalyst In Example 1 (3), 29 mg of bis (cyclopentadienyl) zirconium dichloride was added to 0.5 ml of the modified clay slurry B at room temperature. In place of the addition, 60 mg of bis (cyclopentadienyl) zirconium dichloride was used as it was.

(2) Ethylene Oligomerization Reaction To a 1 liter autoclave, 400 ml of toluene and a concentration of 1.0 mmol / milliliter (-Al
1.0 mL of a toluene solution of (CH ₃ ) O— as converted to 1 unit) of polymethylalumoxane was added,
The temperature was raised to 115 ° C. Therefore, bis (cyclopentadienyl) zirconium dichloride 6 of Comparative Example 1 (1) was used.
0 mg was charged, and the reaction was carried out for 60 minutes while continuously supplying ethylene pressure to maintain 3.5 MPa. Thereafter, the reaction was stopped by adding a 1.0 mol / liter aqueous solution of sodium hydroxide. Unreacted ethylene and a part of the produced 1-butene and 1-hexene were weighed with a wet flow meter, and then subjected to gas chromatography for component analysis and quantification. The α-olefin in the reaction solution was determined by gas chromatography using n-undecane as an internal standard. Further, the polymer was separated by filtration, and 120
It dried at 12 degreeC for 12 hours, and quantified. As a result, the total product weight was 111.93 g. The oligomerization activity per zirconium metal was 1,218 kg / g-Zr / h. Table 1 shows the results of the α-olefin distribution.

[0044]

[Table 1]

[0045]

The catalyst for producing an α-olefin of the present invention comprises:
High ethylene oligomerization activity and C ₆ , C ₈ ,
Due to the high component of the yield of C _10, it can be used to manufacture industrially advantageously α- olefins.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Haruhito Sato 1-1, Anesaki Beach, Ichihara-shi, Chiba

Claims (7)

[Claims] 1. Production of α-olefin by oligomerization of ethylene obtained by contacting (a) a clay, a clay mineral or an ion-exchangeable layered compound with (b) a transition metal complex of Groups 4 to 6 of the periodic table. Catalyst. 2. The ligand of the transition metal complex of component (b) is:
The catalyst according to claim 1, which has a conjugated five-membered ring. 3. The catalyst for producing an α-olefin according to claim 1, wherein the transition metal in the component (b) is zirconium. 4. The α- according to any one of claims 1 to 3, wherein the clay, clay mineral or ion-exchangeable layered compound as the component (a) contains an inorganic substance containing phyllosilicates.
Catalyst for olefin production. 5. The catalyst for producing an α-olefin according to claim 1, wherein the clay, clay mineral or ion-exchange layered compound as the component (a) is montmorillonite. 6. The catalyst for producing an α-olefin according to claim 1, wherein the clay, clay mineral or ion-exchangeable layered compound as the component (a) is treated with an organic silane compound. 7. A process for producing α-olefins, comprising subjecting ethylene to oligomerization using the catalyst for producing α-olefins according to claim 1.