JPH11166009A - Catalyst for olefin polymerization and polymerization of olefin using the catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst for olefin polymerization enabling continuous operation of a commercial plant without causing adhesion, etc., of a polymer to a reactor during polymerization by bringing a specific transition metal compound into contact with a specific active compound, a specific compound and a solid material, etc. SOLUTION: This catalyst is obtained by bringing (A) a transition metal compound having a cyclic η binding anion ligand into contact with (B) an activated compound comprising a cation capable of forming a non-coordinating anion having compatibility with a cation capable of forming a metal complex having catalyst activity by reacting with the component A and used in an amount corresponding to 0.5-10 mol based on 1 mol component A, (C) an organometal oxy compound having an unit of the formula [M<2> is a metal of the group XIII to XV of periodic table or metalloid; R is a 1-12C hydrocarbon or a substituted hydrocarbon; (n) is a valence of a metal M<2> ; (m) is >=2], (D) a solid material and (E) a necessary, an organoaluminum compound. The catalyst is especially useful for ethylene polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel catalyst for olefin polymerization and a method for olefin polymerization using the same. More specifically, it can be applied to olefin suspension polymerization (slurry polymerization) or gas phase polymerization, and can produce a polymer with high activity and excellent powder characteristics. An object of the present invention is to provide an olefin polymerization catalyst, particularly an ethylene polymerization catalyst, which does not cause adhesion of a polymer to a vessel and can realize continuous operation of a commercial plant, and a method for polymerizing ethylene using the catalyst. Is provided.

[0002]

2. Description of the Related Art As a catalyst for producing an olefin polymer or copolymer, a so-called Ziegler-Natta type catalyst comprising a titanium compound and an organoaluminum compound has been known. On the other hand, in recent years, upon homopolymerization of ethylene or copolymerization of ethylene with another α-olefin,
A technique of polymerizing with high activity by using a catalyst comprising a soluble halogen-containing transition metal compound such as bis (cyclopentadienyl) zirconium dichloride and an aluminoxane, which is one of organic aluminum oxy compounds, has been found. The details of this technique are described in Japanese Patent Publication No. 4-12283 (corresponding to DE 3127133.2).

Further, in the catalyst comprising the above transition metal compound and aluminoxane, two or more metallocenes may be mixed and used as a transition metal compound component to change the molecular weight, molecular weight distribution, copolymerizability, etc. Japanese Patent Application Laid-Open Nos. 60-35006, 60-35007, and 60-3500 disclose techniques for using metallocene.
No. 5008 proposes this.

However, since the catalyst formed from the transition metal compound and the organoaluminum oxy compound proposed in these prior arts is soluble in a solvent, when applied to a suspension polymerization method or a gas phase polymerization method, There was a problem that the properties of the polymer were extremely poor, and the polymer adhered to the wall surface of the reactor, stirring blades, and the like, and could not be used industrially as it was. Therefore, the production process is usually limited to the solution polymerization method.However, in the case of producing a polymer having a high molecular weight by the solution polymerization method, the viscosity of the solution containing the polymer becomes extremely high, and the productivity is greatly increased. However, this method is not preferable in terms of cost, and has a serious problem in industrial application.

[0005] In order to solve the above-mentioned problems, suspension weight is measured using a catalyst in which at least one component of a transition metal compound and an organoaluminum oxy compound is supported on a porous inorganic oxide carrier such as silica, alumina or silica-alumina. Attempts have been made to polymerize olefins in a liquid or gas phase polymerization process. For example, JP-A-60-10680
No. 8 and JP-A-60-106809 (both corresponding to EP0142143), a highly active catalyst component containing a titanium compound and / or a zirconium compound soluble in a hydrocarbon solvent is contacted with a filler in advance. In the presence of the resulting product and the organoaluminum compound, and also a polyolefin compatible filler,
A method for producing a composition comprising a polyethylene polymer and a filler by copolymerizing ethylene or ethylene and an α-olefin is described.

However, in this method, a highly active catalyst component cannot be firmly supported on a filler, so that the properties of the polymer are poor, the activity is low, and the polymer is not intended to be used. However, there are many problems such as the fact that a filler is always contained. On the other hand, Japanese Patent Application Laid-Open No. 61-31404 (corresponding to DE 342467.5) discloses a mixed material comprising an organoaluminum compound obtained by bringing a water-containing inorganic substance into contact with a trialkylaluminum and a transition metal compound. A method for polymerizing or copolymerizing ethylene or ethylene and an α-olefin in the presence of a catalyst is described.

However, when an inorganic substance containing water is brought into contact with a trialkylaluminum, only the water contained in the inorganic substance reacts with the trialkylaluminum, and the reaction product is converted into an inorganic substance. Could not be firmly supported. Further, the reaction between water and trialkylaluminum is a violent exothermic reaction, and it is practically difficult to selectively synthesize only an organoaluminumoxy compound having a molecular weight effective for polymerization while controlling the molecular weight. It was hard to say that it was an effective method.

JP-A-4-224808 discloses that a metallocene compound and, if necessary, an organometallic compound are added to a solid component obtained by bringing an aluminoxane into contact with an inorganic compound containing water of crystallization or absorbed water. Describes a method of polymerizing an α-olefin by using a solid catalyst component obtained by contacting an α-olefin. Further, Japanese Unexamined Patent Application Publication No.
No. 238 discloses that a transition metal compound, a solid cocatalyst component obtained by contacting and reacting an aluminoxane with an inorganic oxide having anhydrous or 10% by weight or less of adsorbed water and an organic alkylaluminum compound are polymerized immediately before polymerization. A method for polymerizing an olefin used in contact with a olefin is described.

However, in these methods, the aluminoxane cannot be firmly supported on the inorganic solid, and the aluminoxane is liberated from the inorganic solid at the time of polymerization to form a polymerization active complex with the metallocene compound at a place different from the carrier. In order to express polymerization activity, an amorphous polymer is generated instead of a powder, and such an amorphous polymer has poor fluidity and easily adheres to the reactor, and as a result, the The benefits could not be fully demonstrated. For this reason, industrial application was practically difficult.

[0010] Further, JP-A-60-35006,
JP-A-60-35007, JP-A-60-3500
No. 8 describes that a transition metal compound and an organoaluminum oxy compound can be used by being supported on a carrier such as silica, alumina, and silica-alumina. Also,
JP-A-61-108610, JP-A-61-296
008 and JP-A-5-155931 describe a method of polymerizing an olefin in the presence of a catalyst in which a transition metal compound such as zirconocene and an aluminoxane are supported on a carrier such as an inorganic oxide.

However, in any of the methods described above, the catalyst component cannot be sufficiently firmly supported on the carrier, and the catalyst component is released from the carrier during the polymerization to exhibit the polymerization activity. The polymer by the free catalyst component adheres to the inner wall surface, the stirring blade, the baffle, and the like, and has a disadvantage that industrial continuous operation cannot be performed.

Japanese Patent Application Laid-Open No. 63-280703 (corresponding to EP 0294942) discloses an organometallic compound,
It describes a solid catalyst for olefin polymerization formed from a particulate carrier, an aluminoxane, a transition metal compound of Group 4 of the periodic table, and an olefin polymer produced by prepolymerization. Further, JP-A-5-155930 discloses that
A method of performing prepolymerization using a particulate carrier having a specific range of the amount of adsorbed water and the amount of surface hydroxyl groups is described.

These methods improve the powder properties of the polymer by performing prepolymerization, and lose the catalyst over time by protecting the catalyst formed from the transition metal compound and the organoaluminum oxy compound with the prepolymerized polymer. Although prevention of activity was expected, improvement of polymer properties had some effects, but was still insufficient. In addition, since an extra step of pre-polymerization is required, there are problems that factors for quality variation increase and that the cost is disadvantageous. As described above, in the prior art, in suspension polymerization (slurry polymerization) or gas phase polymerization of olefins, a polymer having excellent powder characteristics is polymerized without causing adhesion to a reactor or the like. There was a problem that can not be.

[0014]

Accordingly, it is desired to develop a novel catalyst system having high polymerization activity and capable of polymerizing a polymer having excellent powder properties without causing adhesion to a reactor. The present invention provides such a novel olefin polymerization catalyst and a method for polymerizing olefins using the same.

[0015]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve such problems, and as a result, it has been surprisingly found that a catalyst obtained by contacting specific components at a specific ratio is used. In addition, a polymer powder that does not cause phenomena such as adhesion to a reactor during polymerization and has extremely excellent powder properties is
They have found that they can be produced effectively and efficiently with high activity, and have completed the present invention.

That is, the present invention provides the following catalyst components (A), (B) and (C) of the present inventors and optionally component (E).
Is brought into contact with the catalyst component (D) at an appropriate ratio, whereby the catalyst components (A) and (B) are extremely strongly supported on (D).
When olefin polymerization is carried out using such a strongly supported catalyst, phenomena such as adhesion of the polymer to the reactor due to release of the catalyst component from the carrier during polymerization do not occur, and the obtained polymer It has also been found to be excellent in powder properties, and has found an excellent effect of enabling stable continuous polymerization indispensable for commercial operation, and has finally completed the present invention.

(A) a transition metal compound having a cyclic η-bonding anion ligand; (B) a non-coordinating anion compatible with a cation capable of forming a metal complex having a catalytic activity by reacting with the above transition metal compound. And (C) an organometallic oxy compound having a unit represented by the following formula:

Embedded image (Where M ² is a metal or metalloid of Groups 13 to 15 of the periodic table, R is each independently a hydrocarbon group having 1 to 12 carbon atoms or a substituted hydrocarbon group, and n is a metal M ² And m is an integer of 2 or more.) (D) Solid material (E) Organoaluminum compound

Accordingly, an object of the present invention is to provide a catalyst for olefin polymerization, particularly a catalyst for ethylene polymerization, which enables continuous operation of a commercial plant without causing a phenomenon such as polymer adhesion to a reactor during polymerization. Is to provide. Another object of the present invention is to provide a method for effectively and efficiently polymerizing ethylene using the above catalyst.

According to one aspect of the present invention, there is provided an olefin polymerization catalyst obtained by bringing at least the following components (A) to (E) into contact. (A) a transition metal compound having a cyclic η-binding anion ligand (B) a metal complex having a catalytic activity by reacting with the transition metal compound in an amount equivalent to 0.5 to 10 times the molar amount of the transition metal compound. Activating compound comprising a cation that can be formed and a compatible non-coordinating anion. (C) An organometallic oxy compound having a unit represented by the following formula in an amount equivalent to 0.05 to 20 times the molar amount of the above transition metal compound.

[0020]

Embedded image (Where M ² is a metal or metalloid of Groups 13 to 15 of the periodic table, R is each independently a hydrocarbon group having 1 to 12 carbon atoms or a substituted hydrocarbon group, and n is a metal M ² And m is an integer of 2 or more.) (D) Solid material If necessary, (E) organoaluminum compound

In such an olefin polymerization catalyst, since the catalyst component is extremely firmly supported on the solid material as the catalyst carrier, the catalyst component is not released from the carrier during the polymerization.
Therefore, a phenomenon such as adhesion of the polymer to the reactor does not occur, and the polymer obtained as a powder has excellent fluidity and excellent powder properties such as packing density. is there.

When the olefin polymerization catalyst of the present invention is used for ethylene polymerization, an ethylene polymer having excellent powder properties such as fluidity and packing density can be obtained. Thus, the heat of polymerization can be effectively removed, and an improvement in productivity can be expected. Hereinafter, the olefin polymerization catalyst and the polymerization method using the same according to the present invention will be described more specifically.

The olefin polymerization catalyst of the present invention is characterized by being obtained by contacting at least the following components (A) to (E). (A) a transition metal compound having a cyclic η-bonding anion ligand; and (B) a metal complex having catalytic activity by reacting with the transition metal compound in an amount equivalent to 0.5 to 10 times the molar amount of the transition metal compound. Activating compound consisting of a cation and a non-coordinating anion compatible with the cation.

[0024]

Embedded image (Where M ² is a metal or metalloid of Groups 13 to 15 of the periodic table, R is each independently a hydrocarbon group having 1 to 12 carbon atoms or a substituted hydrocarbon group, and n is a metal M ² And m is an integer of 2 or more.) (D) Solid material If necessary, (E) organoaluminum compound

In the present invention, (A) cyclic η is used as a catalyst component.
A transition metal compound having a binding anion ligand (hereinafter, referred to as “component (A)” in the present invention) is used. The component (A) of the present invention can be represented by, for example, the following general formula (1). L ₁ MX _p X ′ _q (1) In the formula, M is a transition metal belonging to Group 4 of the Periodic Table having an oxidation number of +2, +3 or +4, which has one or more ligands L and an η5 bond.

L is a cyclic η-bonding anion ligand, and each independently represents a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, or an octahydrofluorenyl group. A hydrocarbon group containing up to 20 non-hydrogen atoms, a halogen, a halogen-substituted hydrocarbon group, an aminohydrocarbyl group, a hydrocarbyloxy group, a dihydrocarbylamino group, a hydrocarbylphosphino group, a silyl group. , An aminosilyl group, a hydrocarbyloxysilyl group, and a halosilyl group, each independently having 1 to 8 substituents, and two hydrocarbyl groups each having L containing up to 20 non-hydrogen atoms. Diyl, halohydrocarbadiyl, hydrocarbyleneoxy, hydrocarby N'amino, siladiyl, Haroshirajiiru, may be linked by a divalent substituent of aminosilane or the like.

X is each independently a monovalent anionic sigma-bonded ligand having up to 60 non-hydrogen atoms, a divalent anionic sigma-bonded ligand divalently linked to M, Or a divalent anionic σ-bonded ligand that binds to M and L with a valence of one each. X ′ is a neutral Lewis base coordinating compound selected from phosphine, ether, amine, olefin, and / or conjugated diene, each independently having 4 to 40 carbon atoms. 1 is an integer of 1 or 2.

P is an integer of 0, 1 or 2;
Divalent anionic sigma-bonded ligand or 1 each for M and L
When the ligand is a divalent anionic σ-bonded ligand that binds with each valence, p is at least 1 less than the formal oxidation number of M, and X is a divalent anionic bond that binds with M divalently. When the ligand is a σ-bonded ligand, p is at least 1 + 1 less than the formal oxidation number of M. Further, q is an integer of 0, 1 or 2. In the present invention, as the component (A), in the general formula (1), l =
The case of 1 is preferred. For example, a preferred example of the component (A) of the present invention is represented by the following general formula (2).

[0029]

Embedded image In the formula, M is titanium, zirconium, or hafnium having a formal oxidation number of +2, +3, or +4.

R ³ is each independently hydrogen, a hydrocarbon group, a silyl group, a germyl group, a cyano group, a halogen, or a complex group thereof, each of which can have up to 20 non-hydrogen atoms; the hydrocarbadiyl R ³ mutually What phase俟adjacent, may be to form a divalent derivative of such siladiyl or germadiyl it the annular. X "
Is each independently a halogen, a hydrocarbon group, a hydrocarbyloxy group, a hydrocarbylamino group, or a silyl group, each having up to 20 non-hydrogen atoms, and two X ″ s having 5 to 30 carbon atoms. A conjugated diene or a divalent derivative may be formed.

Y is -O-, -S-, -NR ^* -, -PR
^* -, and, Z is _{^{SiR * 2, CR * 2,}} SiR * 2 S
iR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , CR ^*
₂ SiR ^* ₂ or GeR ^* ₂ , wherein R ^* is an alkyl or aryl group having 1 to 4 carbon atoms. N is an integer of 1 to 3. Further, more preferable examples as the component (A) of the present invention are represented by the following general formulas (3) and (4).

[0032]

Embedded image Wherein each R ³ is independently hydrogen, a hydrocarbon group, a silyl group, a germyl group, a cyano group, a halogen, or a complex thereof, and each can have up to 20 non-hydrogen atoms.

M is titanium, zirconium or hafnium. Z, Y, X and X 'are the same as defined above. p is 0, 1 or 2, and q is 0 or 1. However, when p is 2 and q is 0, the oxidation number of M is +4, and X is a halogen, hydrocarbon group, hydrocarbyloxy group, dihydrocarbylamide group, dihydrocarbyl sulfide group, hydrocarbyl sulfide group, silyl group. Or these are complex groups and have up to 20 non-hydrogen atoms.

When p is 1 and q is 0, the oxidation number of M is +3 and X is an allyl group, 2- (N, N-dimethylaminomethyl) phenyl group or 2- (N, N- A stabilized anion ligand selected from dimethyl) -aminobenzyl group, or a derivative of M having an oxidation number of +4 and X being a divalent conjugated diene, or both M and X are metallocyclopentene Forming a group.

When p is 0 and q is 1, the oxidation number of M is +2, and X 'is a neutral conjugated or non-conjugated diene, optionally substituted with one or more hydrocarbon groups. And X ′ may include up to 40 carbon atoms;
It forms a π-type complex with M. Further, in the present invention, examples most suitable as the component (A) are represented by the following general formulas (5) and (6).

[0036]

Embedded image In the formula, R ³ is each independently hydrogen or an alkyl group having 1 to 6 carbon atoms. M is titanium, and Y is -O-, -S-, -NR ^* -, -PR ^* -.

[0037] Z is ^{_{SiR * 2, CR * 2,}} SiR * 2 S
iR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , CR ^*
₂ SiR ^* ₂ or GeR ^* ₂ , wherein R ^* is each independently hydrogen, a hydrocarbon group, a hydrocarbyloxy group, a silyl group, a halogenated alkyl group, a halogenated aryl group, or a composite group thereof. , The R ^* is 20
Until the can have a non-hydrogen atoms, also making it the optionally Z ^* 2 one R ^* How or Z ^* cyclic I R ^* and is coupled with in R ^* and Y medium, medium You may.

P is 0, 1 or 2, and q is 0 or 1. However, when p is 2 and q is 0, the oxidation number of M is +
And X is each independently a methyl or benzyl group. When p is 1 and q is 0, the oxidation number of M is +3.
And X is 2- (N, N-dimethyl) aminobenzyl, or the oxidation number of M is +4 and X is 2-butene-1,4-diyl. If pp is 0 and q
Is 1, the oxidation number of M is +2 and X ′ is 1,4-
Diphenyl-1,3-butadiene or 1,3-pentadiene. The diene is an example of an asymmetric diene that forms a metal complex, and is actually a mixture of geometric isomers.

The transition metal compound of the present invention can be synthesized by a generally known method. A preferred method of synthesizing the transition metal compound is described in USSN 8/04, registered April 24, 1995.
427,378. In the present invention, the catalyst component (B) is an activating compound comprising a cation capable of forming a metal complex having a catalytic activity by reacting with a transition metal compound and a compatible non-coordinating anion (hereinafter referred to as “component” in the present invention). (B) ”).

In the present invention, a complex is formed by bringing the component (B) into contact with the component (A), and this complex exhibits high olefin polymerization activity as a catalytically active species. In the present invention, examples of the component (B) include compounds defined by the following general formula (7). [L-H] ^{d +} [M _m Q _p ] ^d- (7) In the formula, [L-H] ^{d +} is a proton-donating Bronsted acid, and L is a neutral Lewis base.

In the formula, [M _m Q _p ] ^d- is a compatible non-coordinating anion, M is a metal or metalloid selected from Groups 5 to 15 of the periodic table, and Q is Each independently a hydride, dialkylamide group, halide, alkoxide group, allyloxide group, hydrocarbon group, 20 carbon atoms
Q is a substituted hydrocarbon group up to 1 and a halide is 1 or less. M is an integer of 1 to 7;
Is an integer of 2 to 14, d is an integer of 1 to 7, and pm = d.

In the present invention, a preferable example of the component (B) is represented by the following general formula (8). _{[M m Q n (G q} (T-H) r) z] d- (8) where, M is a metal or metalloid selected from Group 5 to Group 15 of the periodic table. Q is as defined in the general formula (7), G is a polyvalent hydrocarbon group having a valence of r + 1 bonded to boron and T, and T is O, S, NR, or P
R is where R is a hydrocarbyl, trihydrocarbylsilyl group, trihydrocarbylgermanium group, or hydrogen.

M is an integer of 1 to 7, and n is 0
Q is an integer of 0 or 1; r is an integer of 1 to 3; z is an integer of 1 to 8;
Is an integer of 1 to 7, and n + z−m = d. A more preferred example of the component (B) of the present invention is represented by the following general formula (9). [LH] ⁺ [BQ ₃ Q ′] ⁻ (9) wherein [LH] ⁺ is a proton-donating Bronsted acid, and L is a neutral Lewis base. Further, in the formula [BQ ₃ Q '] ^- is a non-coordinating anion compatible,
Q is a pentafluorophenyl group, and one remaining Q ′
Is a substituted aryl group having 6 to 20 carbon atoms and having one OH group as a substituent.

Specific examples of the compatible non-coordinating anion of the present invention include, for example, triphenyl (hydroxyphenyl) borate, diphenyl-di (hydroxyphenyl)
Borate, triphenyl (2,4-dihydroxyphenyl) borate, tri (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl ) Borate, tris (3,5-dimethylphenyl) (hydroxyphenyl)
Borate, tris (3,5-di-trifluoromethylphenyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxybutyl) borate, tris (Pentafluorophenyl) (4-hydroxy-cyclohexyl) borate, tris (pentafluorophenyl) (4- (4'-hydroxyphenyl) phenyl) borate, tris (pentafluorophenyl) (6-hydroxy-2-naphthyl) borate And most preferably tris (pentafluorophenyl) (4-hydroxyphenyl) borate.

Examples of other preferred compatible non-coordinating anions include the above exemplified borates wherein the hydroxy group is NH
Borates replaced with R groups. here,
R is preferably a methyl group, an ethyl group or a t-butyl group. Specific examples of the proton-providing Bronsted acid of the present invention include, for example, triethylammonium, tripropylammonium, tri (n-butyl)
Ammonium, trimethylammonium, tributylammonium, tri (n-octyl) ammonium and the like; and trialkyl group-substituted ammonium cations, and N, N-dimethylanilinium, N, N
N, N-dialkylanilinium cations such as -diethylanilinium, N, N-2,4,6-pentamethylanilinium, N, N-dimethylbenzylanilinium and the like are also suitable. Further, dialkylammonium cations such as di- (i-propyl) ammonium, dicyclohexylammonium and the like are also preferable, and triphenylphosphonium, tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium and the like can be used. A triarylphosphonium cation, such as
Alternatively, dimethylsulfonium, diethylfluphonium, diphenylsulfonium and the like are also suitable.

In the present invention, the amount of component (B) used is equivalent to 0.5 to 10 times the molar amount of component (A). In the present invention, the number of moles of the component (A) is converted to the number of moles of the transition metal element contained in the component (A), and the number of moles of the component (B) is the number of moles of the boron element contained in the component (B). It is a number conversion. For example, when 1 mole of the transition metal is contained in the component (A), the number of moles of the component (A) is 1 mole. The same applies to the component (B). In the present invention, the amount of component (B) used is preferably 0.8 to 5 times the molar equivalent of component (A), and more preferably 1 to 2 times the molar equivalent. In the present invention, (C) an organometallic oxy compound having a unit represented by the following formula (hereinafter referred to as “component (C)” in the present invention) is used as a catalyst component.

[0047]

Embedded image (Where M ² is a metal or metalloid of Groups 13 to 15 of the periodic table, R is each independently a hydrocarbon group having 1 to 12 carbon atoms or a substituted hydrocarbon group, and n is a metal M ² And m is an integer of 2 or more.)

A preferred example of the component (C) of the present invention is, for example, an organic aluminum oxy compound containing a unit represented by the following formula.

Embedded image (However, R is an alkyl group having 1 to 8 carbon atoms, and m is an integer of 2 to 60.)

The most preferred example of the component (C) of the present invention is
For example, methylalumoxane containing a unit represented by the following formula.

Embedded image (However, m is an integer of 2 to 60.)

In the present invention, the amount of component (C) used is equivalent to 0.05 to 20 times the molar amount of component (A). In the present invention, the number of moles of the component (C) is converted into the number of moles of the metal or metalloid contained in the component (C). For example, when the component (C) contains one mole of a metal or metalloid, the number of moles of the component (C) is one mole. At this time,
Naturally, the number of moles of the metal or metalloid of the component (C) does not indicate the number of moles contained in one molecule of the component (C), but the number of moles contained in the entire molecular assembly. Say.

In the present invention, the amount of component (C) used is
Preferably it is 0.1 to 5 times the molar equivalent of component (A), more preferably 0.5 to 2 times the molar equivalent. In the present invention, by bringing the component (C) into contact with the components (A) and (B) at an appropriate ratio, the components (A) and (B) can be firmly supported on the component (D). . In the present invention, a solid material (D) (hereinafter, referred to as “component (D)” in the present invention) is used as a catalyst component. The component (D) of the present invention is used for supporting components (A) and (B) which form a catalytically active species.

As such a component (D), for example,
A porous polymer material such as a copolymer of polyethylene, polypropylene or styrene divinylbenzene, or, for example, silica, alumina, magnesia, magnesium chloride, zirconia, titania, boron oxide, calcium oxide, zinc oxide, barium oxide, vanadium pentoxide, oxide Periodic Tables 2, 3, such as chromium and thorium oxide,
At least one inorganic solid oxide selected from the inorganic solid oxides of Group 4, 13, and 14 elements, and mixtures thereof, and double oxides thereof are included. Examples of the double oxide of silica include a double oxide of silica and an element of Group 2 or 13 of the periodic table, such as silica magnesia and silica alumina. In the present invention, silica, alumina, and silica are referred to as Group 2 or 13 of the periodic table.
A double oxide with a group III element is preferred, and silica is particularly preferred.

When silica is used as the carrier, its shape is not particularly limited, and may be granular, spherical, aggregated, fume-shaped, or the like. Specific examples of suitable silica include Grace Devison's SD3216.30, S
P-9-10046, Davison Thyroid ^™ 245, Davison 948 and Davison 952, Aerosil 812 from Degussa AG, ES70X from Crossfield, P-6 and P-10 from Fuji Silysia.

The preferred component (D) of the present invention is T. E
Has a specific surface area of 10 to 1000 m ² / g, preferably 100 to 60 m ² / g, determined by a nitrogen gas adsorption method using
0 m ² / g. The pore volume determined by the nitrogen gas adsorption method is 5 cm ³ / g or less, preferably 0.1 to 3
cm ³ / g, more preferably 0.2 to 2 cm ³
/ G. In the present invention, the average particle size of the component (D) is not particularly limited, but is usually 0.5 to 500 μm,
Preferably it is 1 to 200 μm, most preferably 5 to 200 μm.
To 100 μm.

The component (D) may be subjected to a heat treatment and / or a chemical treatment, if necessary, in order to remove water and surface hydroxyl groups present on the surface. In the present invention, as the component (D), either a solid material from which water or surface hydroxyl groups have been removed or a solid material containing a small amount of water or surface hydroxyl groups can be used, but a solid material from which water or surface hydroxyl groups have been removed is more preferable. preferable. The heat treatment of the component (D) can be performed by heating at 30 ° C. to 1000 ° C. for 10 minutes to 50 hours in an inert atmosphere or a reducing atmosphere. In a typical component (D), the amount of surface hydroxyl groups is at least 0.1 micromolar, preferably at least 5 micromolar, more preferably at least 50 micromolar per gram of component (D), and 10 mmol Or less, preferably 5 mmol or less. Most preferably, it is 0.5 to 2 mmol per gram.

The amount of such surface hydroxyl groups can be determined by a known method such as an infrared absorption spectrum method, a titration method using metal alkyl or metal hydride. For example, the amount of surface hydroxyl groups can be determined by adding an excess of dialkylmagnesium to a slurry of component (D) dispersed in a solvent and determining the amount of dialkylmagnesium remaining in the solvent based on a known method. it can. Such a method is based on the following reaction. S—OH + MgR ₂ → S—OMgR + RH Here, S is (D) a solid material.

(D) As another method for measuring the amount of surface hydroxyl groups of the solid material, the following method is exemplified. That is,
(D) The solid material is dried at 250 ° C. for 10 hours under a nitrogen atmosphere and weighed to obtain an initial weight W ₁ (unit: g). Thereafter, the dried solid is heated to 1000 ° C., cooled to room temperature and weighed to determine the weight W ₂ . The amount of surface hydroxyl groups can be determined by substituting the difference ΔW between W ₁ and W ₂ into the following equation. Amount of surface hydroxyl groups = 1000 × △ W / (18 × W ₁ ) mm
ol / g The component (D) of the present invention preferably does not contain water of crystallization, water of adsorption, and the like. Such moisture can be removed by heating at 250 ° C. for 1 hour or more under an inert atmosphere or a reducing atmosphere.

In the present invention, in order to remove water and surface hydroxyl groups present on the surface of the component (D), the composition is heated at 250 ° C. for 1 hour or more under an inert atmosphere or a reducing atmosphere, and then subjected to a chemical treatment. Is preferred. As such a chemical treatment, it is recommended to contact the component (D) with an organometallic compound. Examples of such organometallic compounds include compounds of Group 2 to Group 13 elements of the periodic table, and particularly preferred are organoaluminum and organomagnesium. Specific examples of the organic aluminum include, for example, trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, and mixtures thereof.

In the present invention, an organoaluminum compound (E) (hereinafter referred to as “component (E)” in the present invention) is used as a catalyst component, if necessary. By using the component (E) as required in the present invention, the effect of the component (C) for firmly supporting the components (A) and (B) on the component (D) can be further increased. The component (E) of the present invention is, for example, a compound represented by the following formula. AlR _n X _3-n (where R is each independently an alkyl group having 1 to 12 carbon atoms, each is independently an aryl group having 6 to 20 carbon atoms, X is halogen, hydrogen or an alkoxy group, The group is linear, branched or cyclic, and n is an integer of 1 to 3.)

In the present invention, examples of the component (E) include, in the above general formula, R is a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a phenyl group, a tolyl group, and the like. And X include a methoxy group, an ethoxy group, a butoxy group, and chloro. Specific examples of the component (E) of the present invention include trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, dimethylmethoxyaluminum, diethylethoxyaluminum, dibutylbutoxyaluminum and the like. No. Of these,
Particularly preferred are trimethylaluminum, triethylaluminum, dimethylmethoxyaluminum, and diethylethoxyaluminum.

When alumoxane is used as the component (C) in the present invention, the unreacted alkylaluminum is usually contained in the commercially available alumoxane, so that the component (E) may not be used in some cases. For example, commercially available methylalumoxane often contains 10% or more of trimethylaluminum, and when such a methylalumoxane is used, use of the component (E) can sometimes be omitted.

In the present invention, the method of combining the component (A), the component (B), the component (C), the component (D), and optionally the component (E) is not particularly limited. For example, a method in which the components (A), (B), (C) and, if necessary, the component (E) are brought into contact with each other, and then the component (D) is brought into contact with the component (B) and the component (C). If necessary, a method of bringing the component (E) into contact with the component (D), then contacting the component (A), and the like can be employed. It is possible to stably maintain such high activity for a long period of time.

At the time of such contact of the respective components, the contact of the components (A), (B) and (C) and, if necessary, (E) is preferably carried out in a good solvent of the respective components. In particular, when the component (B) or the component (C) is used in the present invention, it is recommended to use these good solvents. When the component (D) is brought into contact with the other components (A), (B) and (C), it is preferably carried out in a poor solvent for the components (A), (B) and (C). Examples of the good solvent for the components (A), (B) and (C) include aromatic compounds such as benzene, toluene and xylene. (A),
Examples of the poor solvent of (B) and (C) include linear or branched hydrocarbon compounds such as isobutane, pentane, isopentane, hexane, heptane, octane, decane, dodecane and kerosene.

Next, a specific embodiment in which ethylene is polymerized in the presence of the catalyst of the present invention will be described. Ethylene is homopolymerized using the olefin polymerization catalyst of the present invention, or ethylene and an α-olefin having 3 to 20 carbon atoms, a cyclic olefin having 3 to 20 carbon atoms, a compound represented by the formula CH ₂
ＣＨCHR (where R is an aryl group having 6 to 20 carbon atoms) and at least one selected from the group consisting of a linear, branched or cyclic diene having 4 to 20 carbon atoms. Olefins can be copolymerized.

In the present invention, the α-olefin having 3 to 20 carbon atoms is, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, The cyclic olefin having 3 to 20 carbon atoms selected from the group consisting of 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene is, for example, cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl -2
-Norbornene, tetracyclododecene, and 2-methyl-1.4,5.8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene selected from the group consisting of a general formula CH ₂ ＣＨCHR (where R is 6 carbon atoms)
To 20 aryl groups. ) Is, for example, styrene, vinylcyclohexane,
The linear, branched or cyclic diene having 4 to 20 carbon atoms is, for example, a group consisting of 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, and cyclohexadiene Selected from.

The density and physical properties of the ethylene polymer can be controlled by copolymerizing ethylene with the above-mentioned olefin (comonomer). The olefin polymerization according to the present invention can be carried out by either a suspension polymerization method or a gas phase polymerization method. In the suspension polymerization method, an inert hydrocarbon medium can be used as a medium for suspension polymerization, and olefin itself can be used as a solvent.

Specific examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, methylcyclopentane and the like. Alicyclic hydrocarbons; benzene, toluene,
Aromatic hydrocarbons such as xylene; and ethyl chloride;
Examples thereof include halogenated hydrocarbons such as chlorobenzene and dichloromethane, and mixtures thereof.

The amount of catalyst feed in the polymerization of ethylene using the olefin polymerization catalyst of the present invention is as follows:
For example, it is desirable to adjust the catalyst concentration in the polymerization system so that the amount of the catalyst is 1 wt% to 0.001 wt% with respect to the weight of the polymer obtained per hour. The polymerization temperature is usually 0 ° C. or higher, preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and is 150 ° C. or lower, preferably 110 ° C. or lower, more preferably 100 ° C. or lower. The polymerization pressure is usually from normal pressure to 100 kg / c.
m ² , preferably 2 to 50 kg / cm ² , more preferably 5 to 30 kg / cm ² , and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. . It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

Furthermore, for example, DE 3127133.2
As described in, the molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.
In the present invention, the catalyst for olefin polymerization can contain other components useful for olefin polymerization in addition to the above components. Hereinafter, the present invention will be described more specifically based on Examples and the like, but the present invention is not limited to these Examples and the like.

[0070]

EXAMPLES Example 1 One gram of silica (P-10, manufactured by Fuji Silysia Ltd.) was calcined at 500 ° C. for 6 hours in a nitrogen atmosphere, dehydrated, and dispersed in 20 ml of a hexane solution to form a slurry. To this slurry, 5 ml of a hexane solution of triethylaluminum (concentration 1 M) was added, and 2
After stirring for an hour, the hydroxyl groups on the silica surface were crushed. Triethylaluminum remaining in the solution was removed by decantation and the volume was adjusted to obtain 50 ml of triethylaluminum-treated silica slurry.

On the other hand, bis (hydrogenated tallowalkyl) methylammonium-tris (pentafluorophenyl)
1.14 g of (4-hydroxyphenyl) borate was dissolved in 10 ml of toluene to obtain a 100 mM toluene solution of the borate. Methyl alumoxane (MMAO3A manufactured by Tosoh Akzo Co., Ltd.)
0.5 ml of a 1.96 mM toluene solution) was added, and toluene was further added, so that the borate concentration was 8 in terms of borate.
After adjusting the concentration to 0 mM, the mixture was stirred at room temperature for 30 minutes and further at 70 ° C. for 1 hour to obtain a borate-MAO mixed solution.

1 ml of this borate-MAO mixed solution was added to 50 ml of a silica slurry, and the mixture was stirred for 0.5 hour to carry the borate on the silica. In addition, 10mmo
1 of titanium (N-1,1-dimethylethyl) dimethyl [1- (1,2,3,4,5-eta) -2,3,4
5-tetramethyl-2,4-cyclopentadiene-1-
Il] silanaminato [(2-) N]-(η4-1,3-
Pentadiene (hereinafter referred to as "titanium complex" in the present invention) was dissolved in 100 ml of Isopar E solution.
0.8 ml is taken out from the 1M solution, and the mixture is stirred for 3 hours to react the titanium complex with the borate to form a catalytically active species. Then, the slurry is decanted, and a light green solid catalyst slurry carrying the catalytically active species is added. 50 ml were obtained.

Hexane 800 in a 1.8 liter reactor
After adding 50 ml of 1-butene and pressurizing with ethylene to an internal pressure of 10 kgG at an internal temperature of 70 ° C., the slurry of the solid catalyst was taken out to 15 mg in terms of solid catalyst and added to the reactor. , Ethylene and 1-
Copolymerization of butene was started. Ethylene was added so that the internal pressure was maintained at 10 kgG during the polymerization, and polymerization was performed for 30 minutes. After the completion of the polymerization, a polymer slurry was extracted from the reactor, the catalyst was deactivated with methanol, and then filtered, washed and dried to obtain a dry powder of the polymer. At this time, no deposit of the polymer was observed in the reactor used. By the above polymerization, about 85 g of a polymer powder was obtained. The polymer powder has an average particle size of 300 μm and a bulk density of 0.3.
0 g / cm ³ , showing excellent powder properties with very good fluidity.

(Embodiment 2) The borate-MAO of Embodiment 1
In preparing the mixed solution, a solid catalyst was obtained with exactly the same formulation, except that methylalumoxane (MMAO, type 4 manufactured by Tosoh Akzo) was used. The polymerization was also carried out under the same conditions. By the above polymerization, about 80 g of a polymer powder was obtained. The polymer powder has an average particle size of 300 μm, a bulk density of 0.30 g / cm ³ , and has extremely good fluidity.
It showed excellent powder properties.

Example 3 One gram of silica (P-10 manufactured by Fuji Silysia Ltd.) was calcined at 500 ° C. for 6 hours in a nitrogen atmosphere, dehydrated, and dispersed in 20 ml of hexane to form a slurry. To this slurry, 5 ml of a hexane solution of triethylaluminum (concentration: 1 M) was added, followed by stirring for 2 hours to crush the hydroxyl groups on the silica surface. Triethylaluminum remaining in the solution was removed by decantation and the volume was adjusted to obtain 50 ml of triethylaluminum-treated silica slurry.

On the other hand, bis (hydrogenated tallowalkyl) methylammonium-tris (pentafluorophenyl)
1.14 g of (4-hydroxyphenyl) borate was dissolved in toluene to obtain a 12 ml (approximately 83 mM) toluene solution. This borate-toluene solution was cooled to −5 ° C., and methylalumoxane (RMA manufactured by Albemarle) was
O, 1M toluene solution), 0.5 ml, stirred for 0.5 hour, and further stirred at room temperature (about 23 ° C.) for 1 hour to obtain a mixed solution of borate and MAO (concentration in terms of borate: 80 mM).
I got

1 ml of this mixed solution of borate and MAO was added to 50 ml of a slurry of silica, and the mixture was stirred for 0.5 hour to carry the borate on silica. Hereinafter, similarly to Example 1,
Polymerization was carried out by continuously supporting the titanium complex. By the above polymerization, about 90 g of a polymer powder was obtained. The polymer powder had an average particle size of 300 μm, a bulk density of 0.30 g / cm ³ , and exhibited excellent fluidity and excellent powder properties.

Example 4 2 kg of a solid catalyst was produced with exactly the same formulation as in Example 1 except that the ratio was increased.
Using this catalyst, continuous polymerization was performed in a pilot plant. Conditions for continuous polymerization are ethylene pressure 10 K / G, temperature 7
0 ° C., so as to control the polymerization rate 10 kg / hr, The density of the resulting polymer is 0.950 g / cm ³ 1
-Hexene is continuously added, and the MFR of the polymer is further added.
Hydrogen gas was continuously fed so that the value became MI = 3, and a copolymer of ethylene and 1-hexene was continuously obtained. The catalyst activity at this time was about 5000 g-PE / g-catalyst. After about 7 days of continuous operation, open the polymerization reactor,
When the inside of the reactor was examined, no deposit of polymer was observed inside the reactor. The resulting polymer powder has an extremely high bulk density of 0.38 g / cm ³ and an average particle size of about 250 μm.
m, and the fluidity of the powder was practically no problem.

Example 5 Continuous polymerization was carried out in a pilot plant in exactly the same manner as in Example 4. However, the conditions of the continuous polymerization were controlled such that the ethylene pressure was 10 K / G, the temperature was 70 ° C., the polymerization rate was 10 kg / hr, and 1-butene was continuously fed so that the density of the obtained polymer was 0.935 g / cm ^3. Hydrogen gas was continuously fed so that the MFR value of the polymer was MI = 1, and ethylene and 1 were continuously fed.
-A butene copolymer was obtained. The catalytic activity at this time is about 60
It was 00 g-PE / g-catalyst. After the continuous operation for about 7 days was completed in the same manner as in Example 2, the polymerization reactor was opened, and the inside of the reactor was examined. As a result, no deposit of the polymer was found inside the reactor. The resulting polymer powder has a high bulk density of 0.39 g / cm ³ and an average particle size of about 250 μm.
The fluidity of the powder was practically no problem.

Comparative Example 1 In exactly the same manner as in Example 1, 50 l of a slurry corresponding to 1 kg of silica treated with triethylaluminum was obtained. Also, 50 mol of triethylaluminum was added to 10 l of a 100 mM solution of bis (hydrogenated tallowalkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate obtained by the same procedure as in Example 1, and toluene was further added. The concentration of borate was adjusted to 50 mM, and the mixture was stirred and mixed. 1.6 l of this mixed solution was taken out,
The mixture was added to 50 l of the above silica slurry and stirred for 1 hour.

Further, titanium (N-1,1-
Dimethylethyl) dimethyl [1- (1,2,3,4,5
-Eta) -2,3,4,5-tetramethyl-2,4-cyclopentadien-1-yl] silanaminato [(2-)
0.8 l of a solution obtained by dissolving 10 mol of N]-(η4-1,3-pentadiene) in 100 l of Isopar E solution is added, and the mixture is stirred for 3 hours to react the titanium complex with borate to form a catalytically active species. Decant and slurry of light green solid catalyst carrying catalytically active species about 50
1 was obtained.

Using this catalyst slurry, continuous polymerization was carried out in exactly the same manner as in Example 4 to obtain a copolymer of ethylene and 1-hexene. The catalyst activity at this time is about 5500 g
-PE / g-catalyst. After the end of the continuous operation, the polymerization reactor was opened, and the inside was examined. As a result, a deposit of a polymer was found inside. The resulting polymer powder has an average particle size of 20.
It was 0 μm and the bulk density was 0.23 g / cm ³ .

[0083]

Industrial Applicability The olefin polymerization catalyst of the present invention can be applied to olefin suspension polymerization (slurry polymerization) and gas-phase polymerization, and has high activity and powder character (powder character).
An olefin polymerization catalyst, particularly an ethylene polymerization catalyst, which can polymerize a polymer having excellent istics and does not cause adhesion of the polymer to the reactor during the polymerization, thus realizing continuous operation of a commercial plant. To provide.

Claims (12)

[Claims] 1. At least the following components (A) to (E)
A catalyst for olefin polymerization, which is obtained by contacting olefin. (A) a transition metal compound having a cyclic η-binding anion ligand (B) a metal complex having a catalytic activity by reacting with the transition metal compound in an amount equivalent to 0.5 to 10 times the molar amount of the transition metal compound. Activating compound comprising a cation that can be formed and a compatible non-coordinating anion. (C) An organometallic oxy compound having a unit represented by the following formula in an amount equivalent to 0.05 to 20 times the molar amount of the above transition metal compound. Embedded image (However, M ² is a metal or metalloid of Groups 13 to 15 of the periodic table, and Rs each independently have 1 to 1 carbon atoms.)
2 is a hydrocarbon group or a substituted hydrocarbon group, and n is a metal M
Is a valence of ² , and m is an integer of 2 or more. (D) Solid material If necessary (E) Organoaluminum compound 2. The olefin polymerization catalyst according to claim 1, wherein the transition metal compound is a transition metal compound represented by the following formula. L _l MX _p X ′ _q (wherein M is a transition metal belonging to Group 4 of the Periodic Table having an oxidation number of +2, +3, or +4 having an η5 bond with one or more ligands L; L is A cyclic η-bonding anion ligand, each independently being a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, or an octahydrofluorenyl group; The group is a hydrocarbon group containing up to 20 non-hydrogen atoms, halogen, halogen-substituted hydrocarbon group, aminohydrocarbyl group, hydrocarbyloxy group, dihydrocarbylamino group, hydrocarbylphosphino group, silyl group, aminosilyl group, hydrocarbyloxysilyl. May optionally have 1 to 8 substituents each independently selected from a group and a halosilyl group. May be linked by a divalent substituent such as hydrocarbadiyl, halohydrocarbadiyl, hydrocarbyleneoxy, hydrocarbyleneamino, siladiyl, halosiladiyl, aminosilane, etc. containing up to non-hydrogen atoms; Independently, monovalent anionic sigma-bonded ligands having up to 60 non-hydrogen atoms, divalent anionic sigma-bonded ligands divalently linked to M, or each of M and L X ′ is a divalent anionic σ-bonded ligand which binds with a valence of 1; each X ′ independently has 4 to 40 carbon atoms;
A neutral Lewis base coordinating compound selected from phosphines, ethers, amines, olefins, and / or conjugated dienes; L is an integer of 1 or 2, p is an integer of 0, 1 or 2 When X is a monovalent anionic σ-bonded ligand or a divalent anionic σ-bonded ligand bonded to M and L with a monovalent valence, p is a formal oxidation of M When X is a divalent anionic σ-bonded ligand that binds divalently to M, p is at least l + 1 less than the formal oxidation number of M, and q is 0, 1 or 2 It is. ) 3. The olefin polymerization catalyst according to claim 1, wherein the transition metal compound is a transition metal compound represented by the following formula. Embedded image (Wherein, M is titanium, zirconium, hafnium having a formal oxidation number of +2, +3 or +4; each R ³ is independently hydrogen, a hydrocarbon group, a silyl group, a germyl group, a cyano group, a halogen, or a these composite groups, and each can have a non-hydrogen atoms up to 20, also hydrocarbadiyl I adjacent R ³ each other phases俟, to form a divalent derivative of such siladiyl or germadiyl cyclic X "is each independently a halogen, a hydrocarbon group, a hydrocarbyloxy group, a hydrocarbylamino group, or a silyl group, each having up to 20 non-hydrogen atoms, and two X May form a neutral conjugated diene or divalent derivative having 5 to 30 carbon atoms; Y is -O-, -S-, -NR ^* -, -P
R ^* -, and Z is SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂
SiR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , CR
^* ₂ SiR ^* ₂ or GeR ^* ₂ , wherein R ^* is an alkyl or aryl group having 1 to 4 carbon atoms,
n is an integer of 1 to 3. ) 4. The olefin polymerization catalyst according to claim 1, wherein the transition metal compound is a transition metal compound represented by the following formula. Embedded image (Wherein, R ³ is each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, M is titanium, and Y is —O—, —S—, —NR ^* —, —PR ^* — And Z is SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ SiR ^* ₂ , CR ^*
₂ CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR ^* ₂ or GeR ^* ₂ , wherein R ^{* is} each independently hydrogen, a hydrocarbon group, a hydrocarbyloxy group, a silyl group, a halogenated alkyl group, a halogen An aryl group or a complex thereof, wherein R ^* can have up to 20 non-hydrogen atoms and optionally two R ^{* s in} Z ^*
Or Z ^* Medium of R ^* and Y in the R ^* and may have a ring - together, p is 0, 1 or 2, q is 0 or 1, Here, p is 2 , Q is 0, the oxidation number of M is +4 and X is each independently a methyl or benzyl group; when p is 1, q is 0, the oxidation number of M is +3 and X is 2- (N, N-dimethyl) aminobenzyl, or the oxidation number of M is +4 and X is 2-butene-1,4-diyl, and when p is 0 and q is 1, M
Has an oxidation number of +2 and X ′ is 1,4-diphenyl-
1,3-butadiene or 1,3-pentadiene. ) 5. An activating compound comprising a cation capable of reacting with a transition metal compound to form a metal complex having catalytic activity and a compatible non-coordinating anion is an activating compound defined by the following formula: The olefin polymerization catalyst according to any one of claims 1 to 4, wherein: [L-H] ^{d +} [M _m Q _p ] ^d- (wherein [L-H] ^{d +} is a proton-donating Bronsted acid, L is a neutral Lewis base, and _m Q _p ] ^d- is a compatible non-coordinating anion;
Is a metal or metalloid selected from Groups 5 to 15 of the periodic table, and Q is each independently a hydride, a dialkylamide group, a halide, an alkoxide group, an allyloxide group, a hydrocarbon group, or a substituted carbon having up to 20 carbon atoms. Q is a hydrogen group and a halide is 1 or less, and m is 1
And p is an integer of 2 to 14, and d is an integer of 2 to 14.
Is an integer of 1 to 7, and pm = d. ) 6. The olefin polymerization catalyst according to claim 5, wherein [M _m Q _p ] ^d- is a compatible non-coordinating anion defined by the following formula. _{[M m Q n (G q} (T-H) r) z] d- ( where, M is a metal or metalloid selected from Group 5 to Group 15 of the periodic table, Q is as defined above, G
Is a polyvalent hydrocarbon group having a valence of r + 1 bonded to boron and T, and t is O, S, NR, or PR, wherein R is a hydrocarbyl, trihydrocarbylsilyl group,
A trihydrocarbylgermanium group or hydrogen, m is an integer of 1 to 7, n is an integer of 0 to 7, q is an integer of 0 or 1, r is an integer of 1 to 3, z is an integer of 1 to 8, d is an integer of 1 to 7, and n + z−m = d. ) 7. The method according to claim 1, wherein [LH] ^{d +} [M _m Q _p ] ^d- is a compatible non-coordinating anion containing boron defined by the following formula: 5. The catalyst for olefin polymerization according to 5. [LH] ⁺ [BQ ₃ Q ′] ⁻ (wherein [LH] ⁺ is a proton-donating Bronsted acid, L is a neutral Lewis base, and [BQ ₃ Q '] ^- is a non-coordinating anion compatible,
Q is a pentafluorophenyl group, and one remaining Q ′
Is a substituted aryl group having 6 to 20 carbon atoms and having one OH group as a substituent. ) 8. The olefin polymerization catalyst according to claim 1, wherein the organometallic oxy compound is an organoaluminum oxy compound containing a unit represented by the following formula. Embedded image (However, R is an alkyl group having 1 to 8 carbon atoms, and m is an integer of 2 to 60.) 9. The olefin polymerization catalyst according to claim 1, wherein the organometallic oxy compound is methylalumoxane containing a unit represented by the following formula. Embedded image (However, m is an integer of 2 to 60.) 10. The olefin polymerization catalyst according to claim 1, wherein the organoaluminum compound used as required is a compound defined by the following formula. AlR _n X _3-n (where R is each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, X is a halogen, hydrogen or an alkoxy group, and the alkyl group is It is chain-like, branched or cyclic, and n is an integer of 1 to 3.) 11. The solid material is silica, alumina, magnesia, magnesium chloride, zirconia, titania, boron oxide, calcium oxide, zinc oxide, barium oxide, vanadium pentoxide, chromium oxide and thorium oxide, mixtures thereof, and the like. The olefin polymerization catalyst according to any one of claims 1 to 10, wherein the catalyst is at least one member selected from the group consisting of: 12. Ethylene is homopolymerized using an olefin polymerization catalyst component obtained by contacting at least the following components (A) to (E), or ethylene and an α-olefin having 3 to 20 carbon atoms. , Having 3 to 2 carbon atoms
A cyclic olefin of 0, a compound represented by the formula CH ₂ ＲCHR (where R is an aryl group having 6 to 20 carbon atoms), and a linear, branched or cyclic diene having 4 to 20 carbon atoms. A method for polymerizing ethylene, comprising copolymerizing at least one olefin selected from the group consisting of: (A) a transition metal compound having a cyclic η-binding anion ligand (B) a metal complex having a catalytic activity by reacting with the transition metal compound in an amount equivalent to 0.5 to 10 times the molar amount of the transition metal compound. Activating compound comprising a cation that can be formed and a compatible non-coordinating anion. (C) An organometallic oxy compound having a unit represented by the following formula in an amount equivalent to 0.05 to 20 times the molar amount of the above transition metal compound. Embedded image (Where M ² is a metal or metalloid of Groups 13 to 15 of the periodic table, R is each independently a hydrocarbon group having 1 to 12 carbon atoms or a substituted hydrocarbon group, and n is a metal M ² And m is an integer of 2 or more.) (D) Solid material If necessary, (E) organoaluminum compound