JPH08143616A - Catalyst for polymerization of olefin and polymerization of olefin - Google Patents

Abstract

PURPOSE: To produce an olefin copolymer having low crystallization temperature and melting point by using smaller amount of comonomer than former. CONSTITUTION: This catalyst for polymerization of olefin contains a transition metal compound (A) expressed by the formula: R<1> R<2> MX2 (M is a transition metal atom, R<1> and R<2> are each a cycloalkadienyl group having an aryl group as a substituting group and further a hydrocarbon group as a substituting group and X is a halogen atom, etc.) and (B) at least one kind of compound selected from (b1) an organic aluminumoxy compound, (b2) an ionized ionic compound and (b3) an organic aluminum compound. An olefin is polymerized in the presence of this catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for olefin polymerization and a method for polymerizing olefins, and more specifically, it is possible to produce an olefin copolymer having a lower crystallization temperature and a lower melting point than conventional olefin copolymers. The present invention relates to an olefin polymerization catalyst that can be used, and an olefin polymerization method using this catalyst.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Conventionally, olefin polymers such as ethylene polymers have been widely used as materials for hollow moldings, extrusion moldings, films, sheets and the like, and such olefin polymers are produced. As a catalyst for olefin polymerization, a catalyst composed of a transition metal catalyst component such as zirconocene and an organic aluminum oxy compound (aluminoxane) is known. As a transition metal catalyst component used in this catalyst, for example, ethylenebis (indenyl) zirconium dichloride is known, and an olefin copolymer obtained by using this transition metal catalyst component has a narrow molecular weight distribution. A film made of a polymer has features such as less stickiness.

By the way, the required properties of the olefin polymer differ depending on the application, and the required properties also differ depending on the molding method. To adjust this characteristic,
Conventionally, the crystallization temperature, melting point, etc. of the copolymer have been changed by adjusting the proportion of the comonomer.

However, when the conventional catalyst is used, there is a limit in adjusting the ratio of the comonomer to change the crystallization temperature and the melting point of the copolymer.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is an olefin copolymer having a lower crystallization temperature and a lower melting point than the conventional olefin copolymer. It is an object of the present invention to provide a polymerization catalyst and a method for polymerizing olefins using this catalyst.

[0006]

SUMMARY OF THE INVENTION An olefin polymerization catalyst according to the present invention comprises (A) a transition metal compound represented by the following formula (I):¹R²MX₂ (I) (wherein M is a transition metal atom selected from Group IVB of the periodic table)
Indicates a child, R¹And R ²Coordinates to the transition metal atom M
A ligand, a cycloal having two or more substituents
It represents a cadienyl group, which may be the same or different,
One substituent on the cycloalkadienyl group is
Hydrocarbons having 1 to 12 carbon atoms which are reel groups and others
X is a hydrocarbon group having 1 to 12 carbon atoms,
Lucoxy group, aryloxy group, trialkylsilyl group
And a group or atom selected from the group consisting of halogen atoms
And may be the same or different. ) (B) (b1) organoaluminum oxy compound, (b
2) Ionized ionic compound, (b3) Organoaluminium
At least one compound selected from
It is characterized by that.

Another embodiment of the catalyst for olefin polymerization according to the present invention is a fine particle carrier, (A) a transition metal compound represented by the above formula (I), (B) (b1) an organoaluminum oxy compound, (B
2) A solid catalyst comprising an ionized ionic compound and (b3) at least one compound selected from organoaluminum compounds, wherein the component (A) and / or the component (B) is supported on a fine particle carrier. is there.

An olefin polymerization catalyst according to another aspect of the present invention is a fine particle carrier, (A) a transition metal compound represented by the following formula (I), (B) (b1) an organoaluminum oxy compound, (B
2) Ionized ionic compound, (b3) at least one compound selected from organoaluminum compounds, wherein the component (A) and / or the component (B) is supported on a fine particle carrier as a catalyst component, and an olefin is used. Is a prepolymerization catalyst obtained by prepolymerization.

The olefin polymerization method according to the present invention is characterized in that the olefin is polymerized in the presence of the olefin polymerization catalyst of any one of the above aspects. In the present invention, an organoaluminum compound may be used together with the solid catalyst or the prepolymerization catalyst.

The olefin polymerization catalyst of the present invention can obtain an olefin copolymer having a lower crystallization temperature and a lower melting point with a smaller comonomer content than conventional olefin copolymers.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst and the olefin polymerization method according to the present invention will be specifically described below.

In the present specification, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" refers to not only homopolymers but also homopolymers. In some cases, it is used in the sense of including a copolymer.

The olefin polymerization catalyst according to the present invention comprises (A) a transition metal compound represented by the following formula (I), (B) (b1) an organoaluminum oxy compound, and (b)
2) an ionized ionic compound and (b3) at least one compound selected from organoaluminum compounds.

FIG. 1 is an explanatory view showing the steps for preparing the olefin polymerization catalyst according to the present invention. The (A) transition metal compound forming the olefin polymerization catalyst of the present invention is a compound represented by the following formula (I).

R ¹ R ² MX ₂ (I) In the formula, M represents a transition metal atom selected from Group IVB of the Periodic Table, specifically titanium, zirconium or hafnium.

R ¹ and R ² are ligands coordinated to the transition metal atom M and represent a cycloalkadienyl group having two or more substituents, which may be the same or different. Specific examples of the substituted cycloalkadienyl group include a substituted cyclopentadienyl group, a substituted cyclohexadienyl group and a substituted cycloheptadienyl group. In the present invention, R ¹ and R ² are preferably substituted cyclopentadienyl groups.

The substituted cycloalkadienyl group represented by R ¹ and R ² has an aryl group (substituent (i)) as a substituent and a hydrocarbon group having 1 to 12 carbon atoms (substituent ( ii)). The substituents substituting for R ¹ and R ² may be the same or different.

Such a substituted cycloalkadienyl group is a disubstituted cycloalkadienyl group, one of the substituents is a substituted or unsubstituted aryl group, and the other is a linear saturated hydrocarbon group. It is preferably a saturated hydrocarbon group selected from a branched chain hydrocarbon group, an alicyclic saturated hydrocarbon group and an alkyl-substituted alicyclic hydrocarbon group.

Examples of the aryl group include an unsubstituted aryl group and an aryl group substituted with one or more (straight or branched) alkyl groups. The alkyl group substituted with the aryl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms.

The saturated hydrocarbon group has 1 carbon atom.
It is desirable that it is a branched or straight-chain alkyl group of -12, preferably 1-5.

Specific examples of the substituent substituting the substituted cycloalkadienyl group include an aryl group such as a phenyl group, a naphthyl group, a tolyl group, a dimethylphenyl group and an ethylphenyl group.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-group.
Butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, and other alkyl groups; cyclopentyl, cyclohexyl, methylcyclopentyl, and other cycloalkyl groups; phenyl, naphthyl, tolyl, and other aryl groups Group; aralkyl groups such as benzyl and neophyll groups can be mentioned.

A group (substituent group (i) which is substituted on the cycloalkadienyl group together with these aryl groups (substituent group (i))
As i)), an alkyl group is preferable. Substituent (ii)
May have a plurality of substituents on the cycloalkadienyl group, but in the present invention, the cycloalkadienyl group has a substituent (ii) which is 1,3-substituted with respect to the aryl group (substituent (i)). It is preferably a disubstituted product which is substituted at a position having a positional relationship.

X is a hydrocarbon group having 1 to 12 carbon atoms,
It represents a group or atom selected from the group consisting of an alkoxy group, an aryloxy group, a trialkylsilyl group and a halogen atom, which may be the same or different.

Specific examples of the hydrocarbon group having 1 to 12 carbon atoms include the same hydrocarbon groups having 1 to 12 carbon atoms as described above. Examples of the alkoxy group include a methoxy group and an ethoxy group.

As the aryloxy group, a phenoxy group,
Examples thereof include a triloxy group and a dimethylphenoxy group. Examples of the trialkylsilyl group include a trimethylsilyl group and a triethylsilyl group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. The transition metal compound represented by the above formula (I) is represented by the following formula (II), for example, when R ¹ and R ² are cyclopentadienyl groups.

[0028]

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In the formula, Ar represents an aryl group. R ³ ~ R
¹⁰ represents a hydrocarbon group having 1 to 12 carbon atoms or a group or atom selected from the group consisting of hydrogen atoms, which may be the same or different. Further, a mode in which adjacent hydrocarbons such as R ³ and R ⁴ , and R ⁷ and R ⁸ are connected to each other to form a ring can be included. Examples of the hydrocarbon group having 1 to 12 carbon atoms include the same groups as described above.

M is the same as above, and X ¹ and X ² are the same as X above. Among the transition metal compounds represented by the formula (II), R ⁴ (or R ⁵ ) and R
^A compound in which ⁹ (or R ⁸ ) is an alkyl group and the other is a hydrogen atom is preferable.

Specific examples of the transition metal compound (A) include bis (1,3-methylphenylcyclopentadienyl) zirconium dichloride, bis (1,3-ethylphenylcyclopentadienyl) zirconium dichloride,
Bis (1,3-ethyl p-tolylcyclopentadienyl) zirconium dichloride, bis (1,3-methylphenylcyclopentadienyl) zirconium dimethyl, bis (1,3-ethylphenylcyclopentadienyl) zirconium dimethyl, Bis (1,3-ethyl p-tolylcyclopentadienyl) zirconium dimethyl, bis (1,3-methyl m-tolylcyclopentadienyl) zirconium dichloride, bis (1,3-methyl m-tolylcyclopentadienyl) ) Zirconium dimethyl, bis (1,3-methyl p-tolylcyclopentadienyl) zirconium dichloride, bis (1,3-methyl
p-Tolylcyclopentadienyl) zirconium dimethyl, bis (1,3-methyl o-tolylcyclopentadienyl)
Zirconium dichloride, bis (1,3-methyl o-tolylcyclopentadienyl) zirconium dimethyl, bis (1,3
3-ethyl m-tolyl cyclopentadienyl) zirconium dichloride, bis (1,3-ethyl m-tolyl cyclopentadienyl) zirconium dimethyl, bis (1,3-methylnaphthylcyclopentadienyl) zirconium dichloride,
Bis (1,3-methylnaphthylcyclopentadienyl) zirconium dimethyl, bis (1,3-ethylnaphthylcyclopentadienyl) zirconium dichloride, bis (1,3-ethylnaphthylcyclopentadienyl) zirconium dimethyl, bis [ 1,3-methyl (dimethylphenyl) cyclopentadienyl] zirconium dichloride, bis [1,3-methyl (dimethylphenyl) cyclopentadienyl] zirconium dimethyl, bis [1,3-methyl (ethylphenyl) cyclopentadi [Enyl] zirconium dichloride,
Examples thereof include bis [1,3-methyl (ethylphenyl) cyclopentadienyl] zirconium dimethyl.

In the present invention, as the transition metal compound (A), in addition to the zirconium compound, a compound in which zirconium in the zirconium compound is replaced with titanium or hafnium can be exemplified.

A first olefin polymerization catalyst according to the present invention comprises a transition metal compound (A) represented by the above formula (I),
It is formed of at least one compound (B) selected from (b1) an organoaluminum oxy compound, (b2) an ionized ionic compound, and (b3) an organoaluminum compound.

Organoaluminum oxy compound (b1)
May be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687.

As the conventionally known aluminoxane, there may be mentioned a chain organoaluminum oxy compound represented by the following formula (i) or a cyclic organoaluminum oxy compound represented by the following formula (ii). Can
Usually it is a mixture of these.

[0036]

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In the above formulas (i) and (ii), R
^a is an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms; an alkenyl group having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms; 6 to 20 carbon atoms, preferably 6 to
12 aryl groups; hydrocarbon groups such as arylalkyl groups having 7 to 20 carbon atoms, preferably 7 to 12 carbon atoms. n represents the degree of polymerization and is usually 3 to 50, preferably 5 to
40, more preferably 7-40.

The conventionally known method for producing such aluminoxane is not particularly limited, but it can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. The method of adding an organoaluminum compound such as trialkylaluminum to the suspension of a hydrocarbon medium, and reacting the organoaluminum compound with adsorption water or crystallization water. (2) A method in which water, ice, or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organic metal component. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent or suspended in the poor solvent of the aluminoxane.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum and trisec-butyl. Aluminum, trialkyl aluminum such as tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, and tridecyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; dimethyl aluminum chloride, diethyl aluminum Chloride, diethyl aluminum bromide, diisobutyl aluminum chloride, etc. Alkylaluminum halides; diethylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide; and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. Further, as the organoaluminum compound used when preparing the aluminoxane, isoprenylaluminum represented by the following formula can also be used.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (wherein x, y and z are positive numbers, and z ≧ 2x) The above-mentioned organic aluminum The compounds may be used alone or in combination. When the organoaluminum compounds are used in combination, for example, trimethylaluminum and triisobutylaluminum are used in combination.

As the solvent used for preparing the aluminoxane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides Among these, hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

As the ionized ionic compound (b2), there are disclosed in JP-A-1-501950 and JP-A-1-502.
036, JP 3-179005, JP 3-179006, JP 3-207703, JP 3-207704, and JP 4-253.
Examples thereof include Lewis acids, ionic compounds and carborane compounds described in Japanese Patent No. 711.

As the Lewis acid, triphenylboron,
Tris (4-fluorophenyl) boron, Tris (p-tolyl) boron, Tris (o-tolyl) boron, Tris (3,5-
Dimethylphenyl) boron, Tris (pentafluorophenyl) boron, MgCl ₂ , Al ₂ O ₃ , SiO ₂ -Al ₂
Examples include O _{3 and the} like.

As the ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferroferrite Examples include cerium tetra (pentafluorophenyl) borate.

Carborane compounds include dodecaborane, 1-carbaundecaborane, bis-n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarbaundeca) borate, tri-n-butylammonium. (Trideca hydride-7-carbaundeca) borate etc. can be illustrated.

Such an ionized ionic compound (b
2) can be used as a mixture of two or more kinds. As the organoaluminum compound (b3), for example, an organoaluminum compound represented by the following formula (iii) can be exemplified.

R ^b _n AlX _3-n (iii) (wherein R ^b represents a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen atom or a hydrogen atom, and n represents 1 to 1).
It is 3. ) In the above formula (iii), R ^b is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group. Alkyl groups such as isopropyl group, isobutyl group, pentyl group, hexyl group and octyl group;
Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group.

Specific examples of such an organoaluminum compound include the following compounds. Trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri (2-ethylhexyl) aluminum, and tridecyl aluminum; alkenyl aluminum such as isoprenyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride , Diisopropyl aluminum chloride, diisobutyl aluminum chloride, dimethyl aluminum bromide and other dialkyl aluminum halides; methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide Ummesquihalide; alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide;
Alkyl aluminum hydride such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound (b3), a compound represented by the following formula (iv) can also be used. During ^{_{R b n AlL 3-n ...}} (iv) ( wherein, R ^b are as defined above, L is -OR ^c group, -
OSiR ^d ₃ group, -OAlR ^e ₂ group, -NR ^f ₂ group, -SiR
^g ₃ group or —N (R ^h ) AlR ^j ₂ group, n is 1 to 2
R ^c , R ^d , R ^e and R ^j are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ^f is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group. , Phenyl group, trimethylsilyl group and the like, and R ^g and R ^h are methyl group, ethyl group and the like. Among such organoaluminum compounds represented by the formula (iv), a compound represented by R ^b _n Al (OAlR ^e ₂ ) _3-n such as Et ₂ AlOAlEt ₂ , (iso-Bu) ₂
AlOAl (iso-Bu) _{2 and the} like are preferable.

Among the organoaluminum compounds represented by the above formulas (iii) and (iv), the compound represented by the general formula R ^b ₃ Al is preferable, and the compound in which R ^b is an isoalkyl group is particularly preferable.

The olefin polymerization catalyst according to the first aspect of the present invention may contain water as a catalyst component in addition to the components (A) and (B). Examples of the water used in the present invention include water dissolved in a polymerization solvent as described below, or adsorbed water or crystal water contained in a compound or salt used in producing the organoaluminum oxy compound (b1). You can

The olefin polymerization catalyst according to the first aspect of the present invention comprises (A) a transition metal compound [component (A)] represented by the above formula (I), and (B) (b1) an organoaluminum oxy Compound (component (b1)), (b2) ionized ionic compound [component (b2)], and (b3) at least one compound selected from organoaluminum compounds [component (b3)].

Hereinafter, at least one compound selected from the component (b1), the component (b2) and the component (b3) may be referred to as the component (B). In the present invention, the component (B)
It is desirable to use the component (b1) alone or to use the component (b1) and the component (b3) in combination.

The olefin polymerization catalyst according to the first aspect of the present invention is prepared by mixing, for example, the component (A), the component (B) and optionally water as a catalyst component in an inert hydrocarbon solvent or an olefin solvent. It can be prepared by

Specific examples of the inert hydrocarbon solvent used for preparing the catalyst include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methyl. Examples thereof include alicyclic hydrocarbons such as cyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

Next, an example of the proportion of each component used in preparing the olefin polymerization catalyst of the first aspect of the present invention will be described. When the components (A) and (B) are mixed and contacted with each other, the concentration of the component (A) is usually 10 ^-8 to 10 ^-1 mol / liter (solvent), preferably 10 ^-7 , in terms of transition metal atoms. The range is from 5 × 10 ^-2 mol / liter (solvent).

When the organoaluminum oxy compound (b1) is used as the component (B), the atomic ratio of the aluminum in the component (b1) to the transition metal in the component (A) (Al /
(Transition metal) is usually 10 to 10,000, preferably 20.
~ 5000.

When the ionized ionic compound (b2) is used as the component (B), the molar ratio of the component (A) to the component (b2) (component (A) / component (b2)) is usually 0.01.
It is in the range of -10, preferably 0.1-5.

When the organoaluminum oxy compound (b1) and the organoaluminum compound (b3) are used as the component (B), the amount of the component (b1) used is in the same range as described above, and the component (b3) is used. Aluminum atom (Al-b3) and aluminum atom (Al- in the component (b1))
The atomic ratio (Al-b3 / Al-b1) with b1) is usually 0.02 to
The range is 20, preferably 0.2 to 10.

The olefin polymerization catalyst according to the second aspect of the present invention comprises a fine particle carrier, (A) a transition metal compound represented by the above formula (I), and (B) (b1) an organoaluminum oxy compound. , (B
2) A solid catalyst comprising an ionized ionic compound and (b3) at least one compound selected from organoaluminum compounds, wherein the component (A) and / or the component (B) is supported on a fine particle carrier. .

In the olefin polymerization catalyst of the present invention, the component (A) and / or the component (B) is supported on a fine particle carrier to increase the melt tension of the obtained olefin (co) polymer. And moldability can be improved.

In the present invention, the component (b) is used as the component (b
It is desirable to use 1) alone or to use the components (b1) and (b3) in combination. The particulate carrier used in the present invention is an inorganic or organic compound and has a particle size of 10 to 300 μm, preferably 2
A granular or fine particle solid of 0 to 200 μm is used.

Of these, the inorganic compound is preferably a porous oxide, and specifically, SiO ₂ , Al ₂ O ₃ , MgO,
ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO,
ThO ₂ or the like, or a mixture thereof such as SiO _{2
-MgO, SiO 2 -Al 2 O 3} , SiO 2 -TiO 2, S
_{iO 2 -V 2 O 5, SiO} 2 -Cr 2 O 3, SiO 2 -TiO 2
-MgO etc. can be illustrated. Among these S
It is preferable that the main component is at least one component selected from iO ₂ and Al ₂ O ₃ .

The inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ )
_It does not matter if it contains a carbonate, a sulfate, a nitrate or an oxide component such as ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O.

The properties of such a fine particle carrier vary depending on the type and production method, but the fine particle carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² /
g, preferably 100 to 700 m ² / g, and the pore volume is 0.3 to 2.5 cm ³ / g.
The particulate carrier may be 100 to 1000 ° C., if necessary.
Preferably, it is used by firing at 150 to 700 ° C.

In such a fine particle carrier, it is desirable that the amount of adsorbed water is less than 1.0% by weight, preferably less than 0.5% by weight, and the surface hydroxyl group is 1.0% by weight or more, preferably 1.5%. ~ 4.0% by weight, particularly preferably 2.0 ~
It is preferably 3.5% by weight.

Here, the amount of adsorbed water (% by weight) and the amount of surface hydroxyl groups (% by weight) of the particulate carrier are determined as follows. [Amount of adsorbed water] The particulate carrier was heated at a temperature of 200 ° C. under normal pressure,
The weight loss when dried under nitrogen flow for 4 hours was calculated and expressed as a percentage of the weight before drying. [Amount of surface hydroxyl group] X is the weight of the fine particle carrier obtained by drying at a temperature of 200 ° C. under normal pressure and nitrogen flow for 4 hours.
(G), and further add the particulate carrier at 1000 ° C. to 20
The weight of the calcined product obtained by calcining for a time in which the surface hydroxyl groups have disappeared is defined as Y (g) and calculated by the following formula.

Surface hydroxyl group amount (wt%) = {(X−Y) / X} × 100 Further, as a fine particle carrier that can be used in the present invention, an organic compound having a particle size in the range of 10 to 300 μm is used. Granular or particulate solids can be mentioned.
These organic compounds include ethylene, propylene, 1-
(Co) polymer produced mainly from α-olefin having 2 to 14 carbon atoms such as butene and 4-methyl-1-pentene, or polymer or copolymer produced mainly from vinylcyclohexane and styrene Can be illustrated.

The olefin polymerization catalyst of the second aspect according to the present invention may contain the same water as the catalyst component of the first olefin polymerization catalyst. The olefin polymerization catalyst according to the second aspect of the present invention comprises the fine particle carrier, the component (A) and the component (B), and the component (A) and / or the component (B) is supported on the fine particle carrier. Is a solid catalyst. To support the component (A) and / or the component (B) on the particulate carrier, the particulate carrier and the component (A) and / or the component (B) are brought into contact with each other, for example, in an inert hydrocarbon solvent. Examples of the inert hydrocarbon solvent used here include the same ones as described above.

In the present invention, a catalyst in which the component (A) and the component (B) are supported on a fine particle carrier is preferable. The order of contacting the fine particle carrier, the component (A) and the component (B) when preparing such a catalyst is arbitrarily selected, but preferably the fine particle carrier and the component (B) are mixed and contacted, and then the component (A) is mixed and brought into contact. When the organoaluminum oxy compound (b1) and the organoaluminum compound (b3) are used as the component (B), the fine particle carrier and the component (b1) are mixed and contacted, then the component (A) is mixed and contacted, and the component (B) is further added. b
3) is mixed and contacted.

Next, an example of the use ratio of each component when the component (A) and / or the component (B) is supported on the particulate carrier will be described. When the particulate carrier, the component (A) and the component (B) are mixed and contacted, the component (A) is
It is usually 5 in terms of transition metal atoms per 1 g of the particulate carrier.
× 10 ^{-6 to} 5 × 10 ^-4 mol, preferably 10 ^-5 to 2 × 1
It is used in an amount of 0 ^-4 mol and the concentration of component (A) is about 10
^{-4 to} 2 × 10 ^-2 mol / liter (solvent), preferably 2
It is in the range of × 10 ^-4 to 10 ^-2 mol / liter (solvent).

When the organoaluminum oxy compound (b1) is used as the component (B), the atomic ratio of aluminum in the component (b1) to the transition metal in the component (A) (Al /
(Transition metal) is usually 10 to 10,000, preferably 20.
~ 5000.

When the ionized ionic compound (b2) is used as the component (B), the molar ratio [component (A) / component (b2)] between the component (A) and the component (b2) is usually 0.01.
It is in the range of -10, preferably 0.1-5.

When the organoaluminum oxy compound (b1) and the organoaluminum compound (b3) are used as the component (B), the amount of the component (b1) used is in the same range as described above, and the aluminum of the component (b3) is used. Atom (Al-b3) and aluminum atom (Al-b) of component (b1)
The atomic ratio (Al-b3 / Al-b1) of 1) is usually 0.02 to 2
The range is 0, preferably 0.2 to 10.

The mixing temperature for mixing and contacting the particulate carrier, the component (A) and the component (B) is usually -50 to 1.
The temperature is 50 ° C., preferably −20 to 120 ° C., and the contact time is 1 minute to 50 hours, preferably 10 minutes to 25 hours.

Solid catalyst (component) thus obtained
Is, for example, the component (b1) and the component as the component (B)
In the case of using (b3), the solid catalyst is fine particles.
The transition metal atom derived from the component (A) is contained per 1 g of the child carrier.
5 × 10^-6~ 5 × 10^-FourGram atom, preferably 10^-Five
~ 2 x 10^-FourSupported in the amount of gram atom, particulate carrier
Per gram of component (b1) and component (b3)
10 aluminum atoms ^-3~ 5 × 10^-2Gram atom, preferred
2 × 10^-3~ 2 x 10^-2Supported in the amount of grams atom
It is desirable that

The olefin polymerization catalyst according to the third aspect of the present invention comprises a fine particle carrier, (A) a transition metal compound represented by the above formula (I), and (B) (b1) an organoaluminum oxy compound. , (B
2) A solid catalyst component comprising an ionized ionic compound and (b3) at least one compound selected from organoaluminum compounds, wherein the component (A) and / or the component (B) is supported on a fine particle carrier. It is a prepolymerization catalyst in which olefin is prepolymerized.

The olefin polymerization catalyst of the present invention is capable of further increasing the melt tension value of the olefin (co) polymer obtained by supporting each component on a fine particle carrier and preliminarily polymerizing it. The property can be further improved.

In the present invention, the component (b) is used as the component (B).
It is desirable to use 1) alone or to use the components (b1) and (b3) in combination. The third olefin polymerization catalyst according to the present invention may contain the same water as the first olefin polymerization catalyst as a catalyst component.

The prepolymerization can be carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the above-mentioned particulate carrier, the component (A) and the component (B). When carrying out the prepolymerization, the fine particle carrier, the component (A)
It is preferable that the solid catalyst component is formed from component (B) and component (B). In this case, in addition to the solid catalyst component,
Further, component (b1), component (b2) and component (b3)
At least one compound selected from the above may be further added.

The olefins used in the prepolymerization include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 3-methyl-1-butene, cyclopentene, 1-pentene and 4-methyl. -1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene,
Examples thereof include 1-tetradecene. Among these, ethylene or a combination of ethylene and an olefin used in the polymerization is particularly preferable.

As the inert hydrocarbon solvent used in the prepolymerization, the same ones as mentioned above can be mentioned.
Next, an example of the use ratio of each component when preparing the prepolymerization catalyst will be described.

When the olefin is prepolymerized in the presence of the fine particle carrier, the component (A) and the component (B), the component (A) is usually converted to a transition metal atom per 1 g of the fine particle carrier. The component (A) is used in an amount of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ mol.
The concentration is about 10 ⁻⁴ to 2 × 10 ⁻² mol / liter (solvent), preferably 2 × 10 ⁻⁴ to 10 ⁻² mol / liter (solvent).

When the organoaluminum oxy compound (b1) is used as the component (B), the atomic ratio of the aluminum in the component (b1) to the transition metal in the component (A) (Al /
(Transition metal) is usually 10 to 10,000, preferably 20.
~ 5000.

When the ionized ionic compound (b2) is used as the component (B), the molar ratio [component (A) / component (b2)] between the component (A) and the component (b2) is usually 0.01.
It is in the range of -10, preferably 0.1-5.

When the organoaluminum oxy compound (b1) and the organoaluminum compound (b3) are used as the component (B), the amount of the component (b1) used is in the same range as described above, and the aluminum of the component (b3) is used. Atom (Al-b3) and aluminum atom (Al-b) of component (b1)
The atomic ratio (Al-b3 / Al-b1) of 1) is usually 0.02 to 2
The range is 0, preferably 0.2 to 10.

The prepolymerization temperature is -20 to 80 ° C, preferably 0 to 60 ° C, and the prepolymerization time is 0.5 to 10 ° C.
It is 0 hours, preferably about 1 to 50 hours. The olefin (co) polymer produced by the prepolymerization is the fine particle carrier 1.
0.1-500 g per g, preferably 0.2-300
It is desirable that the amount is g, more preferably 0.5 to 200 g.

When the thus prepared prepolymerized catalyst is, for example, the one in which the component (b1) and the component (b3) are used as the component (B), the prepolymerized catalyst is
The component (A) is present as a transition metal atom in an amount of about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atom, preferably 10 per 1 g of the particulate carrier.
^{-5 to} 2 × 10 ^-4 g-atoms supported on the component (b
1) and the aluminum atom (Al) derived from the component (b3) are transition metal atoms (M) derived from the component (A).
It is desirable that the carrier is supported in an amount in the range of 5 to 200, preferably 10 to 150 in terms of molar ratio (Al / M).

The prepolymerization can be carried out batchwise or continuously, and can be carried out under reduced pressure, normal pressure or under pressure. In the prepolymerization,
Producing a prepolymer having an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.2 to 7 dl / g, preferably 0.5 to 5 dl / g, in the presence of hydrogen. Is desirable.

The olefin polymerization catalyst of the present invention can be used for olefin polymerization or copolymerization of two or more olefins, and is particularly preferably used for copolymerization of two or more olefins. When two or more kinds of olefins are copolymerized by using the olefin polymerization catalyst according to the present invention, the crystallization temperature and the melting point are higher than those of conventionally known olefin copolymers even when the amount of the comonomer supplied during the polymerization is small. A low olefin copolymer is obtained.

Examples of olefins which can be polymerized using the olefin polymerization catalyst of the present invention include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1
-Tetradecene, 1-hexadecene, 1-octadecene, 1-
An α-olefin having 2 to 20 carbon atoms such as eicosene can be mentioned.

The olefin polymerization catalyst of the present invention comprises a copolymerization of ethylene with an α-olefin having 3 to 20 carbon atoms, a copolymerization of propylene with an α-olefin having 4 to 20 carbon atoms such as butene, It is preferably used for copolymerization of propylene, ethylene and butene.

In particular, an ethylene copolymer containing ethylene as a main component and a comonomer selected from α-olefins having 4 to 12 carbon atoms in a proportion of, for example, 1 to 15 mol%, preferably 1 to 10 mol%. It is preferably used for the copolymerization of

Polymerization of an olefin or copolymerization of two or more kinds of olefins is carried out in a gas phase or a liquid phase such as slurry or solution. In the slurry polymerization or solution polymerization, an inert hydrocarbon may be used as the solvent, or the olefin itself may be used as the solvent.

Specific examples of the inert hydrocarbon solvent used in the slurry polymerization and the solution polymerization include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; cyclo. Alicyclic hydrocarbons such as pentane, methylcyclopentane, cyclohexane, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, and xylene; petroleum fractions such as gasoline, kerosene, and light oil. Of these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferable.

When carrying out the polymerization, the above-mentioned catalyst usually has a concentration of transition metal atoms of 1 or less in the polymerization reaction system.
0 ^-8 to 10 ^-3 gram atom / liter, preferably 10 ^-7
It is preferably used in an amount of ^{-10 -4} gram atom / liter.

In the polymerization, in addition to the organoaluminum oxy compound (component (b1)) and the organoaluminum compound (component (b3)) supported on the carrier, an unsupported organoaluminum oxy compound and / or organic An aluminum compound may be used.
In this case, the atomic ratio of the aluminum atom (Al) derived from the unsupported organoaluminum oxy compound and / or the organoaluminum compound to the transition metal atom (M) derived from the transition metal compound (A) (Al / M )
Is in the range of 5 to 300, preferably 10 to 200, and more preferably 15 to 150.

In the present invention, when carrying out the slurry polymerization method, the polymerization temperature is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C, and when carrying out the solution polymerization method, the polymerization is carried out. The temperature is usually in the range of -50 to 500 ° C, preferably 0 to 400 ° C, and when carrying out the gas phase polymerization method, the polymerization temperature is usually 0 to 120 ° C, preferably 20 to 40 ° C.
It is in the range of 100 ° C.

The polymerization pressure is usually normal pressure to 100 kg /
It is under a pressure condition of cm ² , preferably ² to 50 kg / cm ² , and the polymerization can be carried out in any of batch system, semi-continuous system and continuous system.

It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

[0103]

INDUSTRIAL APPLICABILITY The catalyst for olefin polymerization of the present invention can produce an olefin copolymer having a lower crystallization temperature and a lower melting point with a smaller amount of comonomer supply than ever before.

According to the method for polymerizing an olefin copolymer of the present invention, an olefin copolymer having a lower crystallization temperature and a lower melting point can be produced with a smaller comonomer supply amount than in the conventional case.

In the olefin polymerization catalyst of the present invention, the component (A) and / or the component (B) are supported on a fine particle carrier to increase the melt tension of the obtained olefin (co) polymer. It is possible to improve moldability. Further, the component (A) and / or the component (B) are supported on a fine particle carrier and prepolymerized, whereby the melt tension value of the olefin (co) polymer obtained can be further increased,
The moldability can be further improved.

[0106]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

[0107]

Example 1 Toluene was charged into a 1 liter glass reactor sufficiently purged with nitrogen so that the total amount was 500 ml, and the temperature in the system was raised to 50 ° C. After that, ethylene was passed through at a rate of 100 N-liter / hr, 35 ml of 1-octene, 0.5 mmol of methylaluminoxane in terms of Al atom, and bis (1,3-methylphenylcyclopentadienyl) zirconium dichloride in terms of zirconium atom. Then 0.005 mmol was added to initiate polymerization.
After polymerizing at 50 ° C. for 15 minutes, isopropanol was added to terminate the polymerization, the solution was precipitated in 2 liters of methanol, the produced polymer was filtered, and then dried at 80 ° C. for 6 hours.

As a result, ethylene / 1-octene copolymer 6 having a density of 0.88 g / cm ³ , a melt flow rate (MFR) of 1.8 g / 10 minutes, a melting point of 78 ° C. and a crystallization temperature of 47 ° C. 0.3 g was obtained.

[0109]

Example 2 In Example 1, the amount of 1-octene was changed to 20.
Polymerization of ethylene and 1-octene was carried out in the same manner as in Example 1 except that the amount was changed to ml.

As a result, the density was 0.90 g / cm ³ , M
As a result, 5.9 g of an ethylene / 1-octene copolymer having an FR of 0.96 g / 10 minutes, a melting point of 93 ° C. and a crystallization temperature of 69 ° C. was obtained.

[0111]

Comparative Example 1 Except that bis (1,3-methyln-butylcyclopentadienyl) zirconium dichloride was used in place of bis (1,3-methylphenylcyclopentadienyl) zirconium dichloride in Example 1. Was polymerized with ethylene and 1-octene in the same manner as in Example 1.

As a result, the density was 0.90 g / cm ³ , M
11.5 g of an ethylene / 1-octene copolymer having an FR of 0.98 g / 10 minutes, a melting point of 97 ° C. and a crystallization temperature of 73 ° C. was obtained.

[0113]

Example 3 900 ml of hexane was charged into a 2 liter autoclave that had been sufficiently replaced with nitrogen, and the temperature inside the system was adjusted to 8
The temperature was raised to 0 ° C. After charging 24 N-liter of propylene, ethylene was charged at a total pressure of 8 kg / cm ² -G, and triisobutylaluminum 0.9 mmol,
0.1 mmo of methylaluminoxane converted to Al atom
l, bis (1,3-methylphenylcyclopentadienyl)
Zirconium dichloride was converted to zirconium atom to be 0.1.
Polymerization was initiated by adding 001 mmol. 60 at 80 ° C
After partial polymerization, the pressure was released, the solution was completely precipitated in 2 liters of methanol, the produced polymer was filtered, and then dried at 80 ° C. for 6 hours.

As a result, an ethylene / propylene copolymer 5 having an ethylene content of 86.0 mol% and an MFR of 0.10 g / 10 min as measured by infrared spectrophotometry (IR) was obtained.
2.1 g was obtained.

[0115]

[Example 4] [Preparation of solid catalyst component]
Silica dried at 250 ° C for 10 hours (average particle size 43μ
m, specific surface area 278 m ² / g, pore volume 1.1 cm ³ /
g) 8.4 g was charged and suspended in 130 ml of toluene, and then the system was cooled to 0 ° C. Then, 41.7 ml of a toluene solution of methylaluminoxane (Al: 1.54 mol / liter) was added dropwise over 20 minutes. On this occasion,
The temperature in the system was kept at 0 ° C. Subsequently, the mixture was reacted at 0 ° C. for 30 minutes, then heated to 95 ° C. over 1 hour, and reacted at that temperature for 4 hours. Then, the temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method. After washing the solid component thus obtained twice with toluene,
Resuspend in toluene (150 ml total volume).

50 ml of the obtained suspension was transferred to another reactor, and 10 ml of toluene and a toluene solution of bis (1,3-methylphenylcyclopentadienyl) zirconium dichloride (Zr: 35.4 mmol) were introduced into this system. 3.5 liter / liter) was added. Then, the temperature was raised to 80 ° C., and the reaction was further performed at 80 ° C. for 2 hours. Then, the supernatant liquid was removed, and the solid catalyst component containing 3.0 mg of zirconium per 1 g was obtained by washing twice with hexane.

[Preliminary Polymerization] The obtained solid catalyst component was resuspended in hexane (total amount: 125 ml), and 6.2 ml of a decane solution of triisobutylaluminum (Al: 1 mol / liter) and 1-hexene (0.1 ml) were added thereto. 5 ml was added at room temperature. Then, while continuously supplying ethylene into the system, prepolymerization was carried out at 35 ° C. for 3.5 hours under normal pressure. Then, the catalyst was preliminarily polymerized by washing twice with hexane. At that time, no adhesion of the prepolymerization catalyst to the reactor wall was observed.

[Polymerization] 1 liter of hexane and 4 parts of 1-hexene were placed in a 2 liter autoclave which had been sufficiently replaced with nitrogen.
0 ml and 0.75 ml of a decane solution of triisobutylaluminum (Al: 1 mol / liter) were charged, and the temperature in the system was raised to 70 ° C. Next, 0.005 milligram atom of zirconium atom in terms of zirconium atom was introduced together with ethylene to initiate the polymerization. The temperature in the system immediately rose to 80 ° C. Then, while continuously feeding ethylene, keep the total pressure at 8 kg / cm ² -G and
Polymerization was carried out at ℃ for 3 hours. As a result, the density was 0.93 g / cm ³ and the MFR was 0.0.
289 g of an ethylene / 1-hexene copolymer having a melting point of 115 ° C. and a crystallization temperature of 99 ° C. was obtained.

[0119]

Comparative Example 2 In Example 4, except that bis (1,3-methyl n-butylcyclopentadienyl) zirconium dichloride was used instead of bis (1,3-methylphenylcyclopentadienyl) zirconium dichloride. In the same manner as in Example 4, the solid catalyst component was prepared, prepolymerized, and polymerized with ethylene and 1-hexene.

As a result, the density was 0.93 g / cm ³ , M
218 g of an ethylene / 1-hexene copolymer having an FR of 0.18 g / 10 min, a melting point of 118 ° C. and a crystallization temperature of 101 ° C. was obtained.

The above results are shown in Table 1.

[0122]

[Table 1]

[0123]

Example 5 Ethylene and 1-hexene were prepared in the same manner as in Example 4 except that ethylene gas containing 0.1 mol% hydrogen gas was used as the ethylene gas supplied during the polymerization. Was copolymerized.

As a result, the density was 0.94 g / cm ³ , the MFR was 1.53 g / 10 min, and the melting point was 119 ° C.
And the crystallization temperature is 105 ° C. and the MT is 2.5 g.
An ethylene / 1-hexene copolymer was obtained.

The melt tension (MT (g)) is determined by measuring the stress when the molten polymer is stretched at a constant speed. That is, the produced polymer powder is melted by a usual method and then pelletized to obtain a measurement sample, using an MT measuring device manufactured by Toyo Seiki Seisakusho, and a resin temperature of 1
90 ° C, extrusion speed 15 mm / min, winding speed 10-
20m / min, nozzle diameter 2.09mmφ, nozzle length 8m
m conditions.

[0126]

Example 6 Instead of bis (1,3-methylphenylcyclopentadienyl) zirconium dichloride as the transition metal compound in Example 4, bis (1,3-methyl-p-tolylphenylcyclopentadienyl) was used. Using zirconium dichloride, as ethylene gas supplied during polymerization,
Copolymerization of ethylene and 1-hexene was carried out in the same manner as in Example 4 except that ethylene gas containing 0.1 mol% hydrogen gas was used.

As a result, the density was 0.94 g / cm ³ , the MFR was 1.22 g / 10 min, and the melting point was 121 ° C.
And the crystallization temperature is 106 ° C. and the MT is 3.0 g.
An ethylene / 1-hexene copolymer was obtained.

[0128]

Comparative Example 3 In Example 4, instead of bis (1,3-methylphenylcyclopentadienyl) zirconium dichloride as the transition metal compound, bis (1,3-methyl-n-butylcyclopentadienyl) zirconium was used. Using dichloride, as the ethylene gas supplied during the polymerization, 0.05
Copolymerization of ethylene and 1-hexene was carried out in the same manner as in Example 4 except that ethylene gas containing mol% of hydrogen gas was used.

As a result, the density was 0.94 g / cm ³ , the MFR was 1.44 g / 10 min, and the melting point was 123 ° C.
And the crystallization temperature is 108 ° C. and the MT is 1.0 g.
An ethylene / 1-hexene copolymer was obtained.

The above results are shown in Table 2.

[0131]

[Table 2]

As can be seen from Table 2 above, according to the present invention, an olefin (co) polymer having a large melt tension value and good moldability can be obtained.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

Claims (5)

[Claims] 1. A transition metallization represented by the following formula (I):
Compound and R¹R²MX₂ (I) (wherein M is a transition metal atom selected from Group IVB of the periodic table)
Indicates a child, R¹And R ²Coordinates to the transition metal atom M
A ligand, a cycloal having two or more substituents
It represents a cadienyl group, which may be the same or different,
One substituent on the cycloalkadienyl group is
Hydrocarbons having 1 to 12 carbon atoms which are reel groups and others
X is a hydrocarbon group having 1 to 12 carbon atoms,
Lucoxy group, aryloxy group, trialkylsilyl group
And a group or atom selected from the group consisting of halogen atoms
And may be the same or different. ) (B) (b1) organoaluminum oxy compound, (b
2) Ionized ionic compound, (b3) Organoaluminium
At least one compound selected from
An olefin polymerization catalyst characterized by the following. 2. A particulate carrier, (A) a transition metal compound represented by the following formula (I), and R:¹R²MX₂ (I) (wherein M is a transition metal atom selected from Group IVB of the periodic table)
Indicates a child, R¹And R ²Coordinates to the transition metal atom M
A ligand, a cycloal having two or more substituents
It represents a cadienyl group, which may be the same or different,
One substituent on the cycloalkadienyl group is
Hydrocarbons having 1 to 12 carbon atoms which are reel groups and others
X is a hydrocarbon group having 1 to 12 carbon atoms,
Lucoxy group, aryloxy group, trialkylsilyl group
And a group or atom selected from the group consisting of halogen atoms
And may be the same or different. ) (B) (b1) organoaluminum oxy compound, (b
2) Ionized ionic compound, (b3) Organoaluminium
At least one compound selected from
The component (A) and / or the component (B)
Olephy characterized in that it is supported on a particulate carrier.
Polymerization catalyst. 3. A particulate support, (A) a transition metal compound represented by the following formula (I), and R:¹R²MX₂ (I) (wherein M is a transition metal atom selected from Group IVB of the periodic table)
Indicates a child, R¹And R ²Coordinates to the transition metal atom M
A ligand, a cycloal having two or more substituents
It represents a cadienyl group, which may be the same or different,
One substituent on the cycloalkadienyl group is
Hydrocarbons having 1 to 12 carbon atoms which are reel groups and others
X is a hydrocarbon group having 1 to 12 carbon atoms,
Lucoxy group, aryloxy group, trialkylsilyl group
And a group or atom selected from the group consisting of halogen atoms
And may be the same or different. ) (B) (b1) organoaluminum oxy compound, (b
2) Ionized ionic compound, (b3) Organoaluminium
At least one compound selected from
The component (A) and / or the component (B)
Olefin is preliminarily added to the catalyst component supported on the particulate carrier.
Olefin polymerization catalyst characterized by being prepared and polymerized
Medium. 4. A method for polymerizing an olefin, which comprises polymerizing an olefin in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 3. 5. A method for polymerizing an olefin, which comprises polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 2 or 3 and an organoaluminum compound.