JPH1180231A - Olefin polymerization catalyst and method for producing polyolefin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a complex catalyst which has a high catalytic activity and an enhanced stability to catalyst poison by using an org. transition metal compd., a halogen-contg. aluminum compd. and a magnesium compd. SOLUTION: An org. transition metal compd. of formula I, a halogen-contg. aluminum compd. of formula II and a magnesium compd. of formula III are used. In the formulas, R<4> to R<4> are each H, a hydrocarbon group, a heteroatom- contg. hydrocarbon group or a silyl group having a hydrocarbon group or a heteroatom-contg. hydrocarbon group provided each of them may form a ring: R<5> is cycloalkadienyl; M is a transition metal selected from among transition metals of the groups 4-6; X<1> is H, halogen, a hydrocarbon group, a heteroatom- contg. hydrocarbon group or an alkoxy or amido group having a hydrocarbon group or a heteroatom-contg. hydrocarbon group; a is 1-2; b is 0-1; c is 1-3 provided a+b+c=4; R<6> and R<7> are each a 1-20C hydrocarbon group; X<2> and X<3> are each halogen; 0<=m<3; and n is 0-2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for olefin polymerization containing a non-metallocene type organic transition metal complex as a constituent 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 It is an object of the present invention to provide a catalyst having high catalytic performance and high stability against catalyst poisons without using expensive aluminoxane or boron-based counter anion as a co-catalyst. Another object of the present invention is to provide a novel complex catalyst for olefin polymerization and a method for producing a polyolefin using the same.

[0005]

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

[0006]

Embedded image

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, a hydrocarbon group, a heteroatom-containing hydrocarbon group,
Or a silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group, R ¹ , R ² , R ³ and R ⁴ may each form a ring, and R ⁵ is a cycloalkadienyl group , M is a transition metal atom of the periodic table group 4, 5 or 6, X ¹ is alkoxy of hydrogen, halogen, hydrocarbon group, a hetero atom-containing hydrocarbon group or a hydrocarbon group or a hetero atom-containing hydrocarbon group, A is 1 or 2, b is 0 or 1, c is 1 to 3, and the sum of a, b and c is 4. ), An olefin polymerization catalyst comprising (B) a halogen-containing aluminum compound and (C) a magnesium compound, (A) an organic transition metal compound,
(B) an olefin polymerization catalyst comprising a halogen-containing aluminum compound, (C) a magnesium compound and (D) an organoaluminum compound; and (E) an olefin polymerization catalyst comprising the above-mentioned olefin polymerization catalyst supported on a (E) solid carrier. The present invention relates to a catalyst 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 , R ² , R ³ and R ⁴ each independently represent hydrogen, a hydrocarbon group, a hetero atom-containing hydrocarbon group, or a hydrocarbon group or a hetero atom-containing hydrocarbon group. R ¹ , R ² , R ³
And R ⁴ may combine with 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-diisopropylpropyl 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,
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,
Aryl groups such as a 2,4,6-trifluorophenyl group and a naphthyl group can be mentioned. Examples of the hetero atom-containing hydrocarbon group include the above-mentioned alkoxy group having a hydrocarbon group and an amide group. Examples of the heteroatom-containing hydrocarbon group also include a heterocyclic group, and specific examples thereof include a furyl group, a pyridyl group, a pyrimidyl group,
Examples include a pyridazine group, an indolizine group, a thiophenyl group, or a furyl group, a pyridyl group, a pyrimidyl group, a pyridazine group, a pyridazine group, an indolizine group, and a thiophenyl group each having a hydrocarbon group or a heteroatom-containing hydrocarbon group.
Further, examples of the silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group include a trimethylsilyl group,
Examples thereof include a triethylsilyl group, a triisopropylsilyl group, a tributylsilyl group, a triphenylsilyl group, a dimethylmethoxysilyl group, and a dimethylphenylsilyl group. Further, R ¹ , R ² , R ³ and R ⁴ may form a ring structure such as a benzo ring, and may have a phosphadenyl skeleton, a phosphafluorenyl skeleton or the like. Preferred examples of R ¹ , R ² , R ³ and R ⁴ include:
A silyl group having a hydrocarbon group or a hydrocarbon group or a heteroatom-containing hydrocarbon group, particularly preferably a methyl group, an ethyl group, an isopropyl group, an n-propyl group, and n
-Butyl group, t-butyl group, trimethylsilyl group, phenyl group, naphthyl group, tolyl group, xylyl group, cumenyl group, mesityl group, vinylphenyl group, isopropylphenyl group, t-butylphenyl group, methoxyphenyl group,
Examples thereof include a dimethylaminophenyl group, a trimethylsilylphenyl group, and the like, and positional isomers thereof.

Examples of the cycloalkadienyl group of R ⁵ shown in the general formula (1) include a cyclopentadienyl group and a substituted cyclopentadienyl group. May form a ring, and examples thereof include compounds having an indenyl group, a fluorenyl group, or an indenyl group or a fluorenyl group having a hydrocarbon group or a heteroatom-containing hydrocarbon group. Specifically, cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group,
Tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, n-butylcyclopentadienyl group, methylethylcyclopentadienyl group, trimethylsilylcyclopenta Dienyl group,
Indenyl group, methylindenyl group, t-butylindenyl group, trimethylsilylindenyl group, dimethylaminoindenyl group, methoxyindenyl group, methylfluorenyl group, 2,7-dimethylfluorenyl group, 2,7 −
Examples thereof include a di (t-butyl) fluorenyl group, a methoxyfluorenyl group, a 2,7-dimethoxyfluorenyl group, a dimethylaminofluorenyl group, and a 2,7-dimethylaminofluorenyl group. Further, the cycloalkadienyl group represented by R ⁵ may be bonded to R ¹ , R ² , R ³ or R ⁴ .

M is a transition metal atom belonging to Group 4, 5 or 6 of the periodic table, preferably a titanium atom, a zirconium atom,
A hafnium atom, a vanadium atom, a niobium atom, a tantalum atom, a chromium atom, a molybdenum atom or a tungsten atom, more preferably a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom or a chromium atom.

X ¹ is hydrogen, halogen, a hydrocarbon group, a heteroatom-containing hydrocarbon group, or an alkoxy group or an amide group having a hydrocarbon group or a heteroatom-containing hydrocarbon group. Halogen is fluorine, chlorine, bromine. , 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.

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 ⁶ _m AlX ² _3-m (2) (where R ⁶ 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 ⁷ _n MgX ³ _2-n (3) (where R ⁷ 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).

[0020] (wherein, R ⁸ may be the same or different and each is a hydrocarbon group having 1 to 20 carbon _{^{atoms.) R 8 3 Al (4}} ) As a specific example, trimethyl aluminum, 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 in the absence of a 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 in the range of -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 shape of the solid carrier used in the present invention is not limited, but the particle size is 1 to 300 micrometers, preferably 1 to 200 micrometers.

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, polymerization means not only homopolymerization but also copolymerization, and the polyolefin obtained by these polymerizations is used in the sense of including not only homopolymers but also copolymers.

Further, the present invention relates to a method for stably producing a polyolefin using the novel catalyst system 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, the polymerization can be carried out 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 the polymerization is carried out in a gas phase, an olefin polymer having a uniform particle shape can be efficiently and stably produced. . 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.

[0037]

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 under 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.

Example 1 An organic transition metal compound (2,3,4,5-Me ₄ C ₄ P) TiCl ₃ was placed in a 500 ml Schlenk tube purged with nitrogen.
Was dissolved in 100 ml of toluene. To the solution was added diethylaluminum chloride.
10 ml of a 5 mol / l toluene solution was added and stirred for 10 minutes. To the obtained yellow homogeneous solution, 5 ml of a heptane solution of 1.89 mol / l of ethylbutylmagnesium was slowly added dropwise with vigorous stirring. Stirring was performed for 1 hour to obtain a pale yellow catalyst component 1.

Example 2 1200 ml of hexane was introduced into a 2 liter autoclave, and then the partial pressure of ethylene was adjusted to 8 kg / cm ² , and the internal temperature was raised to 70 ° C. Example 1 here
The catalyst component 1 obtained in the above was fractionated so as to be 2 μmol in terms of Ti atom, diluted with 10 ml of toluene, and then pressurized with nitrogen. Polymerization was carried out at 80 ° C. for 60 minutes while continuously supplying ethylene to obtain 63.5 g of a polymer. The obtained polymer was a powder having good flowability, and no wall polymer was observed. The HLMI was 0.03 g / 10 min and the bulk density (BD) was 0.19 g / ml.

COMPARATIVE EXAMPLE 1 In a 2-liter autoclave, 1200 ml of hexane, 1
-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. Where (2,3,4,5-Me ₄ C ₄ P) Ti
10 μmol of Cl ₃ and 10 mmol of methylaluminoxane (manufactured by Tosoh Akzo) in terms of aluminum atom
1 was diluted with 10 ml of toluene and pressurized with nitrogen. 90 ° C at 80 ° C with continuous ethylene supply
Polymerization was carried out to obtain 5 g of a polymer. However, the polymer was agglomerated and stuck to the reactor wall, and almost no powder was recovered.

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, the catalyst component 1 obtained in Example 1 was fractionated so as to be 2 μmol in terms of Ti atom, diluted with 10 ml of toluene, and then pressurized with nitrogen. Polymerization was carried out at 80 ° C. for 60 minutes while ethylene was continuously supplied to obtain 53 g of a polymer. The obtained polymer was a powder having good flowability, and no wall polymer was observed. MI of this polymer
Was 0.68 g / 10 min, and the N value was 24. The melting point by DSC was observed at 131 ° C.

Example 4 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.
Of heptane was added and stirred for 1 hour. To this, 10 ml of a 1.5 mol / l toluene solution of diethylaluminum chloride was added, followed by stirring for 1 hour. This suspension was used in Example 1 (2,3,4,5-Me ₄ C ₄ P)
50 μmol of TiCl ₃ was added, and the mixture was further stirred for 1 hour to obtain a catalyst component 2. Polymerization was carried out under the same conditions as in Example 2 except that this catalyst component 2 was used in place of the catalyst component 1, and 20 g of a polymer was obtained. The obtained polymer was a powder having good flowability, and no wall polymer was observed. The HLMI of this polymer was 0.09 g / 10 min.

Example 5 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 22.5 ml of a 1 / l heptane solution was used, and a catalyst component 3 was obtained. When polymerization was carried out under the same conditions as in Example 2 using this catalyst component 3, 80 g of a polymer was obtained. The obtained polymer was a powder having good flowability, and no wall polymer was observed.

COMPARATIVE EXAMPLE 2 Instead of diethylaluminum chloride, a toluene solution of 1.0 mol / l triethylaluminum was added to 15
A catalyst was prepared in the same manner as in Example 1, except for using ml. Then, polymerization was carried out according to Example 2 using this catalyst component. As a result, 2.5 g of a thread-like polymer was obtained.

[0046]

The present invention is a catalyst for olefin polymerization using an organic transition metal complex as a main catalyst and an inexpensive co-catalyst. By using this catalyst, a polyolefin having a good particle shape can be efficiently produced. It is possible to

Claims (4)

[Claims] (A) The following general formula (1): (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently 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, wherein R ¹ , R ² , R ³ and R ⁴ may each form a ring; , R ⁵ is a cycloalkadienyl group, M is a transition metal atom of Group 4, 5 or 6 of the periodic table, and X ¹ is hydrogen, halogen, a hydrocarbon group, a hydrocarbon group containing a hetero atom, or a hydrocarbon. A or 1 or 2, b is 0 or 1, c is 1-3, and the sum of a, b and c is 4. . Organic transition metal compounds represented by), (B) the following general formula (2 halogen-containing aluminum compound R ⁶ _m AlX ² _3-m (2) (here represented by), with or different R ⁶ are respectively the same And a hydrocarbon group having 1 to 20 carbon atoms, X ² is a halogen atom, and m is greater than 0 and less than 3.) and (C) a magnesium compound R ⁷ _n represented by the following general formula (3). MgX ³ _2-n (3) (wherein, R ⁷ may be the same or different, a hydrocarbon group having 1 to 20 carbon atoms, X ³ is a halogen atom, and n is an integer of 0 to 2) The catalyst for olefin polymerization characterized by the above. 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). ⁸ ₃ Al (4) (wherein R ⁸ 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.