JPH1180230A - Catalyst for olefin polymerization and production of polyolefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently produce a polyolefin having a good particle shape by using an olefin polymn. catalyst comprising an org. transition metal compd., a halogen-contg. aluminum compd. and a magnesium compd. SOLUTION: This catalyst comprises an org. transition metal compd. of the formula (wherein R<1> is H, a hydrocarbon group or a silyl group having a hydrocarbon group; R<2> is an arom. hydrocarbon group or a heterocyclic group; R<3> to R<6> are each H, a hydrocarbon group, a silyl group having a hydrocarbon group or a cyclic structure formed by bonding to each other; M is a transition metal selected from among transition metals of the groups 4, 5 and 6 of the periodic table; X is H, halogen, a hydrocarbon group or a hydrocarbon-group- contg. an alkoxy or amido group; a is 0-3; and Y is a hydrocarbon group or a hydrocarbon-group-contg. silyl group), a halogen-contg. aluminum compd. of the formula: R<7> m AlX<2> 3-m . (wherein R<7> is a 1-20C hydrocarbon group; X<2> is halogen: and 0<m<3) and a magnesium compd. of the formula: R<8> n MgX<3> 2-n (wherein R<8> is a 1-20C hydrocarbon group; X<3> is halogen; and n is 0-2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for olefin polymerization containing a half metallocene type organic transition metal complex having a crosslinked structure as a component, and a method for producing a polyolefin using the catalyst.

[0002]

2. Description of the Related Art As a complex catalyst having high polymerization activity in olefin polymerization, a metallocene compound containing a transition metal such as titanium, zirconium or hafnium as a central metal and a metallocene catalyst containing aluminoxane as a basic component have been reported. (J. Boor, "Ziegler
Natta Catalyst and Polymerization "Academic Pres
s. New York (1979); S. Sinn
And W.A. Kaminsky Adv. Organo
met. Chem. 1899 (1980)). It discloses that these catalysts have high catalytic activity for olefin polymerization and can produce a stereoregular olefin polymer by the ligand structure of the complex. However, major drawbacks that have prevented industrial use of these catalyst systems include: First, it is difficult to synthesize aluminoxane used as a co-catalyst with good reproducibility, and therefore, it is difficult to prepare a catalyst having reproducible characteristics. And in order to produce high molecular weight polymers, expensive aluminoxane must be used in a significantly higher ratio to the metallocene compound which is the main catalyst.

In order to solve this drawback, ionic metallocene compounds have been proposed, but the boron-based counter anion compound used for stabilizing the ionic metallocene compound is still as expensive as aluminoxane. It was not industrially satisfactory.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a wide reaction field without using an expensive aluminoxane or boron-based counter anion as a co-catalyst and to improve the stability against catalyst poisons. Another object of the present invention is to provide a complex catalyst for olefin polymerization comprising a novel half metallocene complex as a constituent component, and a method for producing a polyolefin using the same.

[0005]

That is, the present invention provides:
(A) The following general formula (1)

[0006]

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(Where R ¹ is hydrogen, a hydrocarbon group, a hydrocarbon group containing a hetero atom, or a silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group, and R ² is a substituted or unsubstituted aromatic group. R ³ , R ⁴ , R ⁵ or R ⁶ may be the same or different, and may be hydrogen, a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a hydrocarbon group or a heterocyclic group. A silyl group having a heteroatom-containing hydrocarbon group, wherein R ³ , R ⁴ , R ⁵ or R ⁶ may be bonded to each other to have a cyclic structure,
M is a transition metal of Group 4, 5 or 6 of the periodic table; X ¹ is hydrogen, halogen, a hydrocarbon group, a hydrocarbon group containing a hetero atom, or an alkoxy group having a hydrocarbon group or a hydrocarbon group containing a hetero atom, or An amide group, a is 0 to 3, Y is a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silyl group having a hydrocarbon group or a heteroatom-containing hydrocarbon, and a cycloalkadienyl group and a carbon atom. Is a group that crosslinks ), An olefin polymerization catalyst comprising (B) a halogen-containing aluminum compound and (C) a magnesium compound, (A) an organic transition metal compound, (B) a halogen-containing aluminum compound, and (C) magnesium. A catalyst for olefin polymerization comprising a compound and (D) an organoaluminum compound, and further comprising (E)
The present invention relates to an olefin polymerization catalyst supported on a solid carrier, and a method for producing a polyolefin using the catalyst.

Hereinafter, the present invention will be described in detail.

The organic transition metal compound used as the main catalyst of the olefin polymerization catalyst of the present invention is represented by the above general formula (1).

In the general formula (1), R ¹ is hydrogen, a hydrocarbon group, a hetero atom-containing hydrocarbon group, or a silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group, and R ² is an unsubstituted aromatic. Group hydrocarbon groups and heterocyclic groups,
A hydrocarbon group, a heteroatom-containing hydrocarbon group or a substituted aromatic hydrocarbon group or a substituted heterocyclic group having a silyl group having a hydrocarbon group or a heteroatom-containing hydrocarbon group as a substituent, and R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different, hydrogen, a hydrocarbon group, a silyl group having a hetero atom-containing hydrocarbon group or a hydrocarbon group or a hetero atom-containing hydrocarbon group,, R ^3,
R ⁴ , R ⁵ and R ⁶ may be bonded to each other to have a cyclic structure.

Here, the hydrocarbon groups and heteroatom-containing hydrocarbon groups described above will be described. The hetero atom specifically indicates an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a germanium atom, or the like. Examples of the hydrocarbon group and the hetero atom-containing hydrocarbon group include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, and an n-
Butyl group, sec-butyl group, t-butyl group, cyclopentyl group, cyclohexyl group, trimethylsilylmethyl group, alkyl group such as dimethylphenylsilylmethyl group,
Benzyl group, methoxybenzyl group, aralkyl group such as dimethylaminobenzyl group, phenyl group, o-tolyl group,
m-tolyl group, p-tolyl group, o-ethylphenyl group,
m-ethylphenyl group, p-ethylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group,
p-isopropylphenyl group, o-butylphenyl group,
m-butylphenyl group, p-butylphenyl group, o-
(T-butyl) phenyl group, m- (t-butyl) phenyl group, p- (t-butyl) phenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-dimethylamino Phenyl group, m-dimethylamino group, p-dimethylamino group, 2,6-dimethylphenyl group, 2,6-diethylphenyl group, 2,6-dipropylphenyl group, 2,6-diisopropylphenyl group, 2, 6-di (n-butyl) phenyl group, 2,6-di (t-butyl) phenyl group, 2,6-di (sec-butyl) phenyl group, 2,6-diphenylphenyl group, 2,
6-dimethoxyphenyl group, 2,6-bis (dimethylamino) phenyl group, 2,6-difluorophenyl group,
2,4,6-trimethylphenyl group, 2,4,6-triethylphenyl group, 2,4,6-tripropylphenyl group, 2,4,6-tri (isopropyl) phenyl group,
2,4,6-tri (n-butyl) phenyl group,
6-tri (t-butyl) phenyl group, 2,4,6-tri (sec-butyl) phenyl group, 2,4,6-triphenylphenyl group, 2,4,6-trimethoxyphenyl group, 2, 4,6-tri (dimethylamino) phenyl group,
An aryl group such as a 2,4,6-trifluorophenyl group can be mentioned. Examples of the silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group include a trimethylsilyl group, a triethylsilyl group, and a triisopropylsilyl group. , A tributylsilyl group, a triphenylsilyl group, a dimethylmethoxysilyl group, a dimethylphenylsilyl group, and the like. Preferred examples of R ¹ include a hydrocarbon group or a silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group, and particularly preferably a methyl group, an ethyl group, an isopropyl group, an n-propyl group, and an n-
Butyl group, alkyl group such as t-butyl group, phenyl group,
And aryl groups such as a tolyl group, isopropylphenyl group, t-butylphenyl group, methoxyphenyl group, dimethylaminophenyl group and trimethylsilylphenyl group, and silyl groups such as a trimethylsilyl group, triphenylsilyl group and dimethylphenylsilyl group.

Preferred examples of R ² shown in the general formula (1) include phenyl and naphthyl as aromatic hydrocarbon groups and phenyl and naphthyl having the above-mentioned hydrocarbon groups or heteroatom-containing hydrocarbon groups. Groups, and particularly preferred examples include a phenyl group, a tolyl group,
Xylyl group, cumenyl group, mesityl group, vinylphenyl group, isopropylphenyl group, t-butylphenyl group,
Examples include a methoxyphenyl group, a dimethylaminophenyl group, a trimethylsilylphenyl group, and the like, and positional isomers thereof. Furyl, pyridyl, pyrimidyl, pyridazine, indolizine, thiophenyl, or a furyl, pyridyl, pyrimidyl, or pyridazine group having a hydrocarbon group or a heteroatom-containing hydrocarbon group as described above as a heterocyclic group. , An indolizine group, a thiophenyl group and the like or a positional isomer thereof.

R ³ , R ⁴ , R ⁵ or R ⁶ shown in the general formula (1) may be bonded to each other to form a ring. Not only the structure of the substituted cyclopentadienyl group but also the indenyl Compounds having the structure of an indenyl group or a fluorenyl group having a group, a fluorenyl group or a hydrocarbon group or a heteroatom-containing hydrocarbon group can also be mentioned. Examples include cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl Enyl group, n-butylcyclopentadienyl group, methylethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, indenyl group, methylindenyl group, t-butylindenyl group, trimethylsilylindenyl group, dimethylaminoindenyl Nyl, methoxyindenyl, methylfluorenyl, 2,7-dimethylfluorenyl, 2,7-di (t-butyl) fluorenyl, methoxyfluorenyl, 2,7-dimethoxyfluor Nyl group, dimethylaminofluorenyl group, , It may be mentioned 7-dimethylamino fluorenyl group.

M is a titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten atom, preferably a titanium, zirconium or hafnium atom.

X ¹ is hydrogen, halogen, a hydrocarbon group, a hetero atom-containing hydrocarbon group, or an alkoxy group or an amide group having a hydrocarbon group or a hetero atom-containing hydrocarbon group. Halogen is fluorine, chlorine, bromine or the like. , Iodine, and examples of the hydrocarbon group and the hetero atom-containing hydrocarbon group include methyl group, ethyl group, isopropyl group, propyl group, butyl group, sec-butyl group, t-butyl group, benzyl group, and methoxybenzyl group. Dimethylaminobenzyl group, alkyl group such as trimethylsilylmethyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-butylphenyl group Nyl group, m-butylphenyl group, p-butylphenyl group, o- (t-butyl) phenyl group, m- (t-butyl) phenyl group, p- (t-butyl) phenyl group, o-methoxyphenyl group , M-methoxyphenyl group, p-methoxyphenyl group, o-dimethylaminophenyl group, m-dimethylaminophenyl group, p
-Dimethylaminophenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenyl group, 2,6-dipropylphenyl group, 2,6-dibutylphenyl group, 2,6-
Di (t-butyl) phenyl group, 2,6-di (sec-butyl) phenyl group, 2,6-diphenylphenyl group,
2,6-dimethoxyphenyl group, 2,6-bis (dimethylamino) phenyl group, 2,6-difluorophenyl group, 2,4,6-trimethylphenyl group, 2,4,6-
Triethylphenyl group, 2,4,6-tripropylphenyl group, 2,4,6-tri (isopropyl) phenyl group, 2,4,6-tributylphenyl group, 2,4,6-
Tri (t-butyl) phenyl group, 2,4,6-tri (s
ec-butyl) phenyl group, 2,4,6-triphenylphenyl group, 2,4,6-trimethoxyphenyl group,
2,4,6-tri (dimethylamino) phenyl group, 2,
An aryl group such as a 4,6-trifluorophenyl group can be mentioned, and the alkoxy group and the amide group include those having the above-described hydrocarbon group or heteroatom-containing hydrocarbon group as a substituent.

Y is a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silyl group having a hydrocarbon group or a heteroatom-containing hydrocarbon group, which bridges a cycloalkadienyl group with carbon, and is preferable. Examples include methylene, ethylidene, isopropylidene, phenylethylidene, diphenylmethylene, dimethylsilylene, diethylsilylene, phenylmethylsilylene, and diphenylsilylene.
It is not limited to these.

Examples of the structure are described below to explain the above-mentioned organic transition metal compounds more specifically, but the compounds of the present invention are not limited thereto.

[0018]

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The halogen-containing aluminum compound (B), which is one of the components of the catalyst for olefin polymerization in the present invention, is represented by the following general formula (2).

R ⁷ _m AlX ² _3-m (2) (where R ⁷ may be the same or different, a hydrocarbon group having 1 to 20 carbon atoms, X ² is a halogen atom, and m is More than 0 and less than 3. As specific examples thereof, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, n-butyl aluminum dichloride, isobutyl aluminum dichloride, hexyl aluminum dichloride, amyl aluminum dichloride, octyl aluminum dichloride, Dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, di-n-butyl aluminum chloride, diisobutyl aluminum chloride, dihexyl aluminum Roraido, diamyl aluminum chloride, octyl aluminum dichloride, sesqui methyl aluminum sesquichloride, sesqui ethylaluminum sesquichloride, there may be mentioned sesqui isopropyl sesquichloride, etc., but is not limited thereto. Further, the halogen-containing aluminum compound can be used alone or as a mixture of two or more kinds.

The magnesium compound (C) is represented by the following general formula (3).

R ⁸ _n MgX ³ _2-n (3) (where R ⁸ may be the same or different, a hydrocarbon group having 1 to 20 carbon atoms, X ³ is a halogen atom, and n is Specific examples thereof include dimethyl magnesium, diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, di-n-butyl magnesium, diisobutyl magnesium, dihexyl magnesium, diamyl magnesium, dioctyl magnesium,
Methyl ethyl magnesium, methyl propyl magnesium, methyl butyl magnesium, ethyl butyl magnesium, methyl magnesium chloride, ethyl magnesium chloride, propyl magnesium chloride,
Butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, magnesium dichloride and the like can be mentioned. Further, two or more magnesium compounds may be used in combination.

(D) The organoaluminum compound is represented by the following general formula (4).

R ⁹ ₃ Al (4) (where R ⁹ may be the same or different and is a hydrocarbon group having 1 to 20 carbon atoms). Specific examples thereof include trimethylaluminum and triethyl. Examples thereof include aluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, triamylaluminum, and trioctylaluminum. Further, in the present invention, the organoaluminum compound may be used alone or as a mixture of two or more.

The amounts of the halogen-containing aluminum compound (B) and the magnesium compound (C) used in the present invention are usually the transition metal atom in the organic transition metal compound (A): the transition metal atom in the halogen-containing aluminum compound (B). The ratio of aluminum atoms: magnesium atoms in the magnesium compound (C) is 1: 0.01 to 10,000: 0.01.
10,000 to 10,000, preferably 1: 0.1 to 500
0: 0.1 to 5000, more preferably 1: 0.1 to
5000: 1 to 5000, and the aluminum atom in the halogen-containing aluminum compound (B):
The ratio of magnesium atoms in the magnesium compound (C) is in the range of 1: 0.1 to 50, preferably 1: 0.5 to 10. When the organoaluminum compound (D) is used,
As for the amount of use, the ratio of the aluminum atom in the organoaluminum compound (D) to the transition metal in the organic transition metal compound (A) is 10,000 or less, preferably 1,000 or less.

The catalyst can be prepared without solvent or using an organic solvent inert to each component as a medium. The organic solvent used here may be any commonly used organic solvent. Specifically, benzene, toluene, xylene, isobutane, pentane, hexane, heptane, octane, a hydrocarbon compound having 9 or more carbon atoms, cyclopentane , Cyclohexane, gasoline or a mixture thereof. Further, a catalyst can be prepared using propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, styrene, or the like, which are monomers for polymerization, as a medium. Then, a catalyst can be prepared using a mixture of the above-mentioned organic solvent and monomer as a medium.

The preparation of the catalyst of the present invention is usually carried out at -50 to 10
It is performed in the range of 0 ° C. In the preparation of the catalyst, there is no particular limitation on the order in which the components are brought into contact and the reaction time. Specifically, 1) using an organic solvent as a medium,
A method in which an organic transition metal compound (A) is brought into contact with a halogen-containing aluminum compound (B) and subsequently brought into contact with a magnesium compound (C) also diluted with an organic solvent;
2) A method in which an organic transition metal compound (A) and a magnesium compound (C) are brought into contact with each other using an organic solvent as a medium, followed by contact with a halogen-containing aluminum compound (B) also diluted with the organic solvent. A halogen-containing aluminum compound (B) and a magnesium compound (C) diluted with an organic solvent are brought into contact with each other in advance, and then the organic transition metal compound (A) is diluted with an organic solvent or is not diluted with an organic solvent. Examples include a method of contacting a solid substance, but the method is not limited thereto.

The solid carrier (E) used in the present invention comprises:
An inorganic or organic carrier, specifically CaCl 2
_{2 and the} like, SiO ₂ , Al ₂ O ₃ , ZrO, B ₂ O ₃ , Ca
Oxides represented by O, ZnO, SiO ₂ —Al ₂ O _3, zeolite, and the like, clay minerals, and clay minerals modified with organic or inorganic salts can be used. The organic carrier may be a polyolefin such as polyethylene, polypropylene, poly 1-butene, or polystyrene, or a mixture of these polyolefins and a polar polymer such as polyethyl methacrylate, polyester, or polyimide, or a copolymer of the organic carrier. You may. Further, a combination of some of the above-mentioned inorganic carriers and organic carriers can also be used.

The method for preparing a solid catalyst for olefin polymerization from the solid support (E) described above and the catalyst for olefin polymerization containing the above-mentioned organic transition metal compound (A) as a main component is not particularly limited. Examples of the method include a method of mixing the components in a solvent inert to each component or using a monomer to be polymerized as a solvent. Also,
There are no particular restrictions on the order in which these components are reacted, and there are no particular restrictions on the temperature or the processing time for this treatment.

The catalyst in the present invention can be prepared by a usual polymerization method,
That is, it can be used for any of slurry polymerization, gas phase polymerization, high pressure polymerization, solution polymerization and bulk polymerization.

In the present invention, the term "polymerization" means not only homopolymerization but also copolymerization, and the polyolefin obtained by these polymerizations is used to include not only homopolymers but also copolymers.

Further, the present invention relates to a method for stably producing a polyolefin using these novel catalyst systems while substantially forming polymer particles.

When a polyolefin is produced in the presence of a solid catalyst for olefin polymerization obtained by prepolymerizing an olefin using the catalyst for olefin polymerization or the solid catalyst for olefin polymerization of the present invention, the resulting polyolefin has a high bulk density. In addition, adhesion of the polyolefin to the reactor wall hardly occurs, and stable production is realized particularly by gas phase polymerization or slurry polymerization.

The olefin used in the prepolymerization is not particularly limited, but is preferably an α-olefin having 2 to 16 carbon atoms or a cyclic olefin, and specifically, ethylene, propylene, 1-butene, 4-methyl-1 -Pentene, 1
Α-olefins such as -hexene, 1-octene, styrene, butadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 4-methyl-1,4-hexadiene, 7-methyl-1, Examples thereof include conjugated and non-conjugated dienes such as 6-octadiene, and cyclic olefins such as cyclobutene. These may be used alone or as a mixture of two or more. When pre-polymerization is performed using two or more olefins, the pre-polymerization can be carried out sequentially or simultaneously by adding them to the reaction system.

The method for performing the prepolymerization using the olefin polymerization catalyst of the present invention is not particularly limited as long as the olefin polymerization catalyst and the above-mentioned olefin for prepolymerization can be polymerized. Generally, -50 to 100
° C, preferably -20 to 60 ° C, more preferably -10.
It can be carried out under normal pressure or under pressure in a temperature range of ４０40 ° C., and is sufficiently contacted under flow conditions when treating in a gas phase and under stirring conditions when treating in a liquid phase. Preferably.

In the present invention, it is possible to carry out polymerization using two or more kinds of organic transition metal compounds.

The polymerization of the olefin in the present invention can be carried out in a gas phase or a liquid phase. In particular, when it is carried out in a gas phase, an olefin polymer having a uniform particle shape can be produced efficiently and stably. . When the polymerization is carried out in the liquid phase, the solvent used may be any organic solvent generally used, and specifically, benzene, toluene, xylene, propane, isobutane, pentane, hexane, heptane, gasoline, saturated hydrocarbon Compounds and the like,
An olefin itself such as propylene, 1-butene, 1-hexene, 1-octene can be used as a solvent.

The olefin used for the polymerization in the present invention is ethylene, propylene, 1-butene, 4-methyl-
Α-olefins such as 1-pentene, 1-hexene, 1-octene and styrene, butadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 4-methyl-1,4-hexadiene, 7 Conjugated and non-conjugated dienes such as -methyl-1,6-octadiene; cyclic olefins such as cyclobutene; and ethylene and propylene and styrene;
It is also possible to carry out polymerization by mixing three or more kinds of components such as hexene and styrene, ethylene, propylene and ethylidene norbornene.

In producing an olefin polymer using the method of the present invention, polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure and monomer concentration are not particularly limited, but the polymerization temperature is -100 to 300 ° C. The polymerization time is preferably from 10 seconds to 20 hours, and the polymerization pressure is preferably from normal pressure to 3000 kg / cm ² G. It is also possible to adjust the molecular weight using hydrogen or the like during polymerization. The polymerization can be carried out by any of a batch system, a semi-continuous system, and a continuous system, and can be carried out in two or more stages by changing the polymerization conditions. Further, the polyolefin obtained after the completion of the polymerization can be separated and recovered from the polymerization solvent by a conventionally known method, and can be obtained by drying.

[0040]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

All reactions are performed in an inert gas atmosphere.
All solvents used in the reaction were purified, dried or deoxygenated by a known method in advance. The identification of the organic transition metal compound was performed using ¹ H-NMR (GPX-400 type NMR measuring apparatus manufactured by JEOL Ltd.). MI and HLMI were measured according to ASTM D-1238, and MI was 2.1
6 kg load and HLMI were performed with a 21.6 kg load. The N value represents the ratio of HLMI / MI.

Reference Example 1 ((CH ₃ ) ₃ Si (C) (2-C ₅ H ₄ N))-((CH
_{3) 2 Si) - (2,3,4,5-} (CH 3) 4 C 5) T
Synthesis of iCl ₂ 2-picoline 4.9 ml (50 mmol) in 65 ml
Dissolved in tetrahydrofuran (THF) at -78 ° C
And cooled. To this solution, 31 ml (50 mmol) of a hexane solution of n-BuLi (1.63 N) was slowly dropped.

The temperature of the reaction solution was raised to room temperature overnight, and after the reaction was completed, it was cooled again to 0 ° C. 6.3 ml (50 mmol) of trimethylsilyl chloride was slowly added dropwise thereto, and the mixture was stirred overnight. Red yellow solution obtained here was solvent removed under reduced pressure to give 7.1g by extraction with hexane _{(CH 3) 3 (2-} CH 2 -C 5 H 4 N) Si as a yellow oil.

Take 2.2 g of this yellow oil and add THF3
The solution was diluted to 0 ml, cooled to -78 ° C, and 9.0 ml (14.6 mmol) of a hexane solution of n-BuLi was slowly added dropwise. The solution was allowed to warm to room temperature. 2.7 g (13.3 mmol) of tetramethylcyclopentadienyldimethylsilyl chloride was added to the reaction solution.
20 ml of the THF solution of 1) was added and stirred overnight. After completion of the reaction, the solvent was removed from the reaction solution under vacuum, and the ligand ((C
_{H 3) 3 Si-CH- (} 2-C 5 H 4 N)) - ((CH 3) 2
1.1 g of Si)-(2,3,4,5- (CH ₃ ) ₄ C ₅ H) was obtained.

1.1 g of the ligand described above was added to 40 ml of THF.
And cooled to -78 ° C. To this, 4.4 ml (7.2 mmol) of a hexane solution of n-BuLi was slowly dropped, and the temperature was raised to room temperature by natural temperature rise. In another container, 508 mg (3.3 mmol) of titanium trichloride was suspended in 40 ml of toluene, and cooled to -78 ° C. Here, the ligand solution prepared above was slowly dropped.
The reaction solution was warmed to room temperature by natural temperature rise to complete the reaction. After the reaction solution was cooled again to −78 ° C., 1 ml of dichloromethane was added, and the mixture was stirred for 1 hour, returned to room temperature, the solvent was removed in vacuo, extracted with toluene and recrystallized to remove some impurities. The obtained organic transition metal compound was obtained in an amount of 406 mg.

¹ H-NMR (ppm, CDCl ₃ solvent):
0.04 (s), 0.15 (s), 0.84 (s),
1.51 (s), 2.17 (s), 2.29 (s),
2.47 (s), 7.00 (t), 7.20 (t),
7.58 (t), 8.31 (d) Example 1 Into a 50 ml Schlenk tube purged with nitrogen, the organic transition metal compound ((CH ₃ ) ₃ Si (C) (2-
_{C 5 H 4 N)) -} ((CH 3) 2 Si) - (2,3,4,
₂₀ μmol of 5- (CH ₃ ) ₄ C ₅ ) TiCl ₂ was collected and
Dissolved in 10 ml of toluene. 1 ml of a 1.5 mol / l solution of diethylaluminum chloride in toluene was added to the solution, and the mixture was stirred for 10 minutes. Ethylbutylmagnesium 1.89 was added to the obtained yellow homogeneous solution.
0.5 ml of a mol / l heptane solution was slowly added dropwise with vigorous stirring. Stirring was performed for 1 hour to obtain catalyst component 1.

Example 2 In a 2 l autoclave, 1200 ml of hexane, 1 ml
-Hexene (50 ml) was introduced, and then the ethylene partial pressure was adjusted to 8 kg / cm ² , and the internal temperature was raised to 70 ° C. Here, the catalyst component 1 obtained in Example 1 was converted to an organic transition metal compound ((CH ₃ ) ₃ Si (C) (2-C ₅ H ₄ N)).
_{- ((CH 3) 2 Si} ) - (2,3,4,5- (CH 3) 4
C ₅ ) The solution was fractionated so as to be 2 μmol in terms of TiCl ₂ , diluted with 10 ml of toluene, and then pressurized with nitrogen. Polymerization was carried out at 80 ° C. for 90 minutes while continuously supplying ethylene to obtain 93 g of a polymer. The obtained polymer was a powder having good flowability, and no wall polymer was observed.

Comparative Example 1 20 μmol of the organic transition metal compound used in Example 1 was dispensed into a 50 ml Schlenk tube purged with nitrogen.
Dissolved in ml of toluene. To the solution, 20 mmol of a toluene solution of 10 wt% methylaluminoxane (manufactured by Tosoh Akzo) was added in terms of aluminum atoms, and the mixture was stirred for 1 hour to obtain a catalyst component 2. The catalyst component 2 was fractionated in an amount of 10 μmol in terms of an organic transition metal compound, and polymerized under the same conditions as in Example 2 except that the catalyst component 1 was used instead of the catalyst component 1, to obtain 17 g of a polymer. This polymer was clumpy and mostly adhered to the stirring blade or the wall, and could not be obtained as a powder.

Example 3 In a 2 liter autoclave, 1200 ml of hexane, 1
-Hexene 50 ml was introduced and the partial pressure of hydrogen was 4 kg /
cm ² . Subsequently, the partial pressure of ethylene was adjusted to 8 kg / cm ² , and the internal temperature was raised to 70 ° C. Here Example 1 in an organic transition metal compound catalyst component obtained _{((CH 3) 3 Si (} C) (2-C 5 H 4 N)) -
((CH ₃ ) ₂ Si)-(2,3,4,5- (CH ₃ ) ₄ C
₅ ) Separate to ₂ μmol in terms of TiCl ₂ ,
After dilution with 10 ml of toluene, it was pressurized with nitrogen. Polymerization was carried out at 80 ° C. for 90 minutes while continuously supplying ethylene to obtain 84 g of a polymer. The obtained polymer was a powder having good flowability, and no wall polymer was observed.
The MI of this polymer was 0.70 g / 10 min, and the N value was 30. The melting point by DSC was observed at 131 ° C.

Example 4 In a 50 ml Schlenk tube purged with nitrogen, 50 mg of MgCl ₂ was fractionated and suspended in 10 ml of toluene. Here, 1.5 mol of diethylaluminum chloride
1 ml of a 1 / l toluene solution was added and stirred for 1 hour.
The organic transition metal compound used in Example 1 to the suspension _{((CH 3) 3 Si (} C) (2-C 5 H 4 N)) - ((CH
_{3) 2 Si) - (2,3,4,5-} (CH 3) 4 C 5) Ti
₂₀ μmol of Cl ₂ was added, and the mixture was further stirred for 1 hour to obtain a catalyst component 3. Polymerization was carried out under the same conditions as in Example 3 except that this catalyst component 3 was used in place of the catalyst component 1, and 90 g of a polymer was obtained. The obtained polymer was a powder having good flowability, and no wall polymer was observed. The MI of this polymer is 0.50 g / 10 min and the N value is 32
Met. Further, the melting point by DSC was observed at 129 ° C.

Example 5 Polymerization was carried out under the same conditions as in Example 3 except that 1-hexene was not added, to obtain 72 g of a polymer. The obtained polymer was a powder having good flowability, and no wall polymer was observed. The MI of this polymer is 0.01 g / 10
Min and N value was 29.

Example 6 The amount of the catalyst component 1 was 1 μm in terms of an organic transition metal compound.
The polymerization was carried out under the same conditions as in Example 3 except that the amount was changed to ol. As a result, 54 g of a polymer was obtained. The obtained polymer was a powder having good flowability, and no wall polymer was observed. The MI of this polymer was 0.60 g / 10 min, and the N value was 32. The melting point by DSC was observed at 130 ° C.

Example 7 In a 50 ml Schlenk tube purged with nitrogen, 50 mg of SiO ₂ calcined at 500 ° C. was suspended in 10 ml of toluene, and 1.89 mol / l of ethylbutylmagnesium was added.
Was added and the mixture was stirred for 1 hour. Here, 1.5 mol / l of diethyl aluminum chloride
Was added and stirred for 1 hour. The organic transition metal compound used in Example 1 ((C
_{H 3) 3 Si (C)} (2-C 5 H 4 N)) - ((CH 3) 2 S
_{i) - (2,3,4,5- (CH 3} ) 4 C 5) TiCl 2
20 μmol was added, and the mixture was further stirred for 1 hour to obtain a catalyst component 4. Polymerization was carried out under the same conditions as in Example 3 except that this catalyst component 4 was used in place of the catalyst component 1, to obtain 28 g of a polymer. The obtained polymer was a powder having good flowability, and no wall polymer was observed. The MI of this polymer is 0.09 g / 10 min and the N value is 30
Met. Further, the melting point by DSC was observed at 129 ° C.

Example 8 Instead of ethylbutylmagnesium, dibutylmagnesium: triethylaluminum = 7.5 mol: 1.
0mol mixed solution, 0.42mo per magnesium atom
A catalyst was prepared in the same manner as in Example 1, except that 2.25 ml of a 1 / l heptane solution was used, to obtain a catalyst component 5. Polymerization was carried out using this catalyst component 5 under the same conditions as in Example 2 to obtain 88 g of a polymer. The obtained polymer was a powder having good flowability, and no wall polymer was observed.

[0055]

According to the present invention, it is possible to efficiently produce a polyolefin having a good particle shape by using an olefin polymerization catalyst mainly comprising an organic transition metal compound having a novel structure.

Claims (4)

[Claims] (A) The following general formula (1): (Where R ¹ is hydrogen, a hydrocarbon group, a hetero atom-containing hydrocarbon group, or a silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group, and R ² is a substituted or unsubstituted aromatic hydrocarbon Group or heterocyclic group,
R ³ , R ⁴ , R ⁵ or R ⁶ may be the same or different, and each represents a hydrogen, a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silyl group having a hydrocarbon group or a heteroatom-containing hydrocarbon group. R ³ , R ⁴ , R ⁵ or R ⁶ may be bonded to each other to form a cyclic structure, M is a transition metal of Group 4, 5 or 6 of the periodic table, and X ¹ is hydrogen, halogen, A hydrocarbon group, a hetero atom-containing hydrocarbon group, or an alkoxy group or an amide group having a hydrocarbon group or a hetero atom-containing hydrocarbon group, a is 0 to 3, Y is a hydrocarbon group or a hetero atom-containing hydrocarbon group; A hydrogen group, or a silyl group having a hydrocarbon group or a heteroatom-containing hydrocarbon, and a group that bridges a cycloalkadienyl group with carbon. ) Organic transition metal compound represented by
(B) the following general formula (2) halogen-containing aluminum compound R ⁷ _m AlX ² _3-m (2) (here represented by, or different R ⁷ are respectively the same, carbide having 1 to 20 carbon atoms A hydrogen group, X ² is a halogen atom, and m is greater than 0 and less than 3.) and (C) a magnesium compound represented by the following general formula (3): R ⁸ _n MgX ³ _2-n (3) Wherein R ⁸ may be the same or different, and each is a hydrocarbon group having 1 to 20 carbon atoms, X ³ is a halogen atom, and n is an integer of 0 to 2). Olefin polymerization catalyst. 2. The organic transition metal compound (A) according to claim 1, (B) a halogen-containing aluminum compound, (C) a magnesium compound, and (D) an organic aluminum compound R represented by the following general formula (4). ^9. An olefin polymerization catalyst comprising: ⁹ ₃ Al (4) wherein R ⁹ may be the same or different and is a hydrocarbon group having 1 to 20 carbon atoms. 3. An olefin polymerization catalyst comprising the olefin polymerization catalyst according to claim 1 supported on a solid carrier (E). 4. A method for producing a polyolefin, comprising polymerizing an olefin using the catalyst for olefin polymerization according to any one of claims 1 to 3.