JPH0848715A - Catalyst for preparation of olefin polymer and method for polymerizing olefin - Google Patents

Abstract

PURPOSE:To prepare an olefin polymer having a good particle shape by bringing a particular inorg. oxide, an organoaluminumoxy compd., a transition metal compd., an olefin, an organometallic compd., and ionizing ionic compd. into contact with one another. CONSTITUTION:An inorg. oxide is fired in vacuo or in a gas stream at 100 to 1000 deg.C and reacted with a halogen-contg. compd. to prepare an inorg. oxide, with the hydroxyl groups on the surface thereof being partly or entirely substituted with a halogen, having an average particle diameter of 1 to 300mum, a specific surface area of 10 to 1000m<2>/g, and a pore volume of 0.1 to 3cc/g. 1g of the inorg. oxide, an organoaluminumoxy compd. in an amt. of 10 to 200mmol (in terms of Al) per mol of transition metal atom, 0.05 to 0.5mmol (in terms of transition metal atom) transition metal compd., 0.01 to 100g of an olefin, and an ionizing ionic compd. are brought into contact with one another at -50 to 100 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an olefin polymer consisting of an inorganic oxide having surface hydroxyl groups partially or wholly substituted with halogen, an organoaluminum oxy compound, a transition metal compound, an olefin, an organometallic compound and an ionized ionic compound. The present invention relates to a catalyst for combined production and a method for polymerizing olefins using this catalyst. More specifically, the present invention relates to a catalyst for producing an olefin polymer characterized by using a small amount of an organoaluminum oxy compound in combination with an ionized ionic compound, and an olefin polymerization method using this catalyst.

[0002]

2. Description of the Related Art As a method for producing a polyolefin,
It is already known to use catalyst systems which consist of a combination of transition metal compounds and organometallic compounds. Also,
It is disclosed in Kaminsky et al. That a catalyst using metallocene and methylaluminoxane exhibits high activity when producing an olefin polymer containing propylene.
It is known from, for example, Japanese Patent No. 9309.

However, in the catalyst system disclosed in the above publication, although the polymerization activity is excellent, the solution polymerization system is often used because the catalyst system is soluble in the reaction system, and the production process is limited. In addition, it is necessary to use a relatively large amount of relatively expensive methylaluminoxane in order to produce a polymer having industrially useful physical properties. Therefore, there are problems in terms of cost and a large amount of aluminum remaining in the polymer.

On the other hand, a catalyst system in which the aforementioned soluble catalyst system is supported on an inorganic oxide carrier such as silica is disclosed in JP-A-60-35.
No. 006, etc., and Japanese Patent Application Laid-Open No. 63-152608 discloses that the use of a catalyst component prepolymerized with an olefin can improve the particle properties of a polymer produced by gas phase polymerization. . However, the polymerization activity per methylaluminoxane was not sufficient even when the olefin was polymerized according to the methods described therein.

As a method for improving these, for example, JP-A-4-8704, JP-A-4-11604,
JP-A-4-213305 discloses that a gas phase polymerization using a catalyst system prepolymerized with a small amount of methylaluminoxane gives a polymer having excellent polymerization activity and good particle properties. There is. However, although the amount of methylaluminoxane used is small, the polymerization activity is still unsatisfactory, and there has been a demand for high activation of the catalyst system.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve this problem, and reduces the amount of organoaluminum oxy compound used in gas phase polymerization or suspension polymerization, and has excellent polymerization activity. And to provide a catalyst for producing an olefin polymer having a good particle shape.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that inorganic oxides, organoaluminum oxy compounds, and transition compounds in which some or all of the surface hydroxyl groups are substituted with halogens. The inventors have found that a catalyst obtained by contacting a metal compound, an olefin, an organometallic compound, and an ionized ionic compound can be used to efficiently produce a polyolefin having high activity, excellent physical properties, and processability, and completed the present invention. It was

That is, the present invention provides (a) an inorganic oxide in which a part or all of surface hydroxyl groups are substituted with halogen,
(B) organoaluminum oxy compound, (c) transition metal compound, (d) olefin, (e) organometallic compound,
(F) A catalyst for producing an olefin polymer which is brought into contact with an ionizable ionic compound, (a) an inorganic oxide in which a part or all of surface hydroxyl groups are substituted with halogen, (b) an organoaluminum oxy compound and (c) a transition An olefin polymer characterized by comprising an olefin prepolymerization catalyst formed by prepolymerizing an olefin (d) on a catalyst component composed of a metal compound, (e) an organometallic compound, and (f) an ionizable ionic compound. A method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst for producing a coalesce and a catalyst for producing these olefin polymers.

The present invention will be described in detail below.

First, the catalyst for producing an olefin polymer of the present invention will be described.

The inorganic oxide (a) used in the present invention has an average particle size of 1 to 300 μm, particularly 10 to 200 μm.
Fine-particled porous particles in the range of 10 are preferable because they are easy to handle during catalyst preparation and polymerization processes. Specific examples of the inorganic oxide include inorganic oxides of typical elements such as silica, alumina and magnesia, inorganic oxides of transition metal elements such as titania and zirconia, and mixtures of silica-alumina, silica-magnesia and the like. These inorganic oxides usually contain Na ₂ O, K ₂ C as impurities.
It contains salts of alkali metals or alkaline earth metals such as O ₃ and BaSO ₄ . The fine-particle inorganic oxide may be used in a state of containing these impurities, but it is preferable to use an inorganic oxide that has been previously subjected to an operation of removing these impurities. The properties of such a porous fine-particle inorganic oxide differ depending on the type and production method thereof, but in the present invention, the specific surface area is 10 to 1000 m ^2.
/ G, especially 50-800 m ² / g, pore volume 0.1-
Those of 3 cc / g are preferable because many supporting components such as transition metal compounds can be supported. These inorganic oxides are used by firing at 100 to 1000 ° C. under reduced pressure or under gas flow, if necessary.

The method of substituting the hydroxyl group of these inorganic oxides with halogen is preferably a method of reacting with a reactant having a halogen capable of exchanging with the surface hydroxyl group. Examples of the reactant include halogen such as fluorine, chlorine, bromine and iodine, hydrogen fluoride such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, phosgene, thionyl chloride, ammonium fluoride, ammonium chloride and iodine. Examples thereof include halogen-containing compounds such as ammonium chloride, carbon tetrachloride, chloroform, and freon, but are not limited thereto. These inorganic oxides are subjected to heat treatment under reduced pressure or under gas flow at 100 to 1000 ° C. for the purpose of removing by-product H ₂ O after substituting some or all of the hydroxyl groups with halogen. You may.

The inorganic oxide may be contacted with a metal compound in advance for the purpose of post-treatment of --OH residue prior to contact with other catalyst components. The metal compound used here is not particularly limited, but an organic metal compound is preferably used. The method of contacting the inorganic oxide with the above metal compound is not particularly limited, but a method of contacting in a suspension state in an organic solvent in which the oxide is insoluble and the metal compound is soluble, an organic solvent in which both are soluble Examples thereof include a method of contacting in a medium and a method of contacting with a ball mill or the like in a substantially solvent-free state.

The organoaluminum oxy compound (b) used in the present invention is a conventionally known aluminoxane or an aluminoxane further reacted with water, and may be used as a mixture of two or more kinds. The aluminum substituent of aluminoxane is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group, and preferably a methyl group. The degree of oligomer is 4 to 60. The production method of this kind of compound is known, for example, salts containing water of crystallization (copper sulfate hydrate,
An example is a method in which an aluminum compound is added to a hydrocarbon medium suspension of aluminum sulfate hydrate or the like) and reacted.

The transition metal compound (c) used in the present invention is represented by the following general formulas (1) and (2)

[0016]

[Chemical 11]

[0017]

[Chemical 12]

[In the formula, M1 is a titanium atom, a zirconium atom or a hafnium atom, and Y is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,
It is an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group, and R1 and R2 are each independently the following general formula (3), (4), (5) or (6).

[0019]

[Chemical 13]

(Wherein each R6 is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group). A ligand, the ligand forms a sandwich structure together with M1, and R4 and R5 are each independently the following general formula (7), (8), (9) or (10)

[0021]

Embedded image

(In the formula, each R7 is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group.) A ligand, the ligand forms a sandwich structure with M1, and R3 is represented by the following general formula (1
1) or (12)

[0023]

[Chemical 15]

(In the formula, each R8 is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group, and M2 is a silicon atom or germanium. Atom or tin atom), which acts to bridge R4 and R5, and p is an integer of 1 to 5. ] I represented by
The transition metal compound of group Vb or the transition metal compound (c) is represented by the following general formula (13), (14), (15) or (16).

[0025]

Embedded image

[In the formula, M3 is independently a titanium atom,
Zirconium atom or hafnium atom, Z is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group, and L is Lewis base, w is 0 ≦ w ≦ 3, JR9 _q-1 , JR
9 _q-2 is a heteroatom ligand, J is a Va group element having a coordination number of 3 or an IVa group element having a coordination number of 2, and R 9 is independently a hydrogen atom or a halogen atom. An atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group, an arylalkyl group, an arylalkoxy group, an alkylaryl group or an alkylaryloxy group, and q is an element J. R10 is a coordination number of the following general formula (17), (1
8), (19) or (20)

[0027]

[Chemical 17]

(In the formula, each R13 is independently a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. ), R12 is a ligand represented by the following general formula (21), (22), (23) or (24)

[0029]

Embedded image

(In the formula, R14 is independently a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. ), A ligand coordinated to M3, and R1
1 is the following general formula (25) or (26)

[0031]

[Chemical 19]

(In the formula, each R15 is independently a hydrogen atom,
It is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group, and M4 is a silicon atom, a germanium atom or a tin atom. ), Which acts to crosslink R12 and JR9 _q-2 , and r is an integer of 1 to 5. ] It is suitable that it is a group IVb transition metal compound represented by the following.

Examples of the compound represented by the general formula (1) or (2) include bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) zirconium dichloride and bis (cyclopentadienyl). Hafnium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) hafnium dichloride, bis (butylcyclopentadienyl) titanium dichloride, bis (butyl) Cyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) hafnium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (pentamethyl Cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) hafnium dichloride, bis (indenyl) titanium dichloride, bis (indenyl) zirconium dichloride, bis (indenyl) hafnium dichloride, methylenebis (cyclopentadienyl)
Titanium dichloride, methylenebis (cyclopentadienyl) zirconium dichloride, methylenebis (cyclopentadienyl) hafnium dichloride, methylenebis (methylcyclopentadienyl) titanium dichloride, methylenebis (methylcyclopentadienyl) zirconium dichloride, methylenebis (methylcyclopenta) Dienyl) hafnium dichloride, methylenebis (butylcyclopentadienyl) titanium dichloride, methylenebis (butylcyclopentadienyl) zirconium dichloride, methylenebis (butylcyclopentadienyl) hafnium dichloride, methylenebis (tetramethylcyclopentadienyl) titanium dichloride , Methylenebis (tetramethylcyclopentadienyl) Ruconium dichloride, methylenebis (tetramethylcyclopentadienyl) hafnium dichloride, ethylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) hafnium dichloride, ethylenebis (tetrahydroindenyl) titanium dichloride, Ethylenebis (tetrahydroindenyl) zirconium dichloride, ethylenebis (tetrahydroindenyl) hafnium dichloride, ethylenebis (2-methyl-1-indenyl) titanium dichloride, ethylenebis (2-methyl-1)
-Indenyl) zirconium dichloride, ethylenebis (2-methyl-1-indenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-9-)
Fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-9-fluorenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-2,7)
-Dimethyl-9-fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-2,7)
-Dimethyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2,
7-dimethyl-9-fluorenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-2,
7-di-t-butyl-9-fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2, 7-di-t-butyl-9-fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopenta) Dienyl-9-fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadiene) 2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-2,7-dimethyl -9
-Fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl-2,7-di-t-butyl-9) -Fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-
2,7-di-t-butyl-9-fluorenyl) hafnium dichloride, dimethylsilanediylbis (cyclopentadienyl) titanium dichloride, dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (cyclopenta) Dienyl) hafnium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) hafnium dichloride, dimethylsilane Diylbis (butylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (butylcyclopentadienyl) zirconium di Lolide, dimethylsilanediylbis (butylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) ) Titanium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl)
Titanium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl)
Titanium dichloride, dimethylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (indenyl) titanium dichloride, dimethylsilanediylbis (2
-Methyl-indenyl) titanium dichloride, dimethylsilanediylbis (tetrahydroindenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-)
2,7-Dimethyl-9-fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, dimethylsilanediylbis (2,2
4,5-Trimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4-
Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride, dimethylsilanediyl Bis (tetramethylcyclopentadienyl)
Zirconium dichloride, dimethylsilanediylbis (indenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl-indenyl) zirconium dichloride, dimethylsilanediylbis (tetrahydroindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-9- Fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) Zirconium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis 2,4-Dimethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) hafnium dichloride Dimethylsilanediylbis (tetramethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (indenyl) hafnium dichloride, dimethylsilanediylbis (2-methyl-indenyl) hafnium dichloride, dimethylsilanediylbis (tetrahydroindenyl) hafnium Dichloride, dimethylsilanediyl (cyclopentadienyl-9
-Fluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-di-)
t-Butyl-9-fluorenyl) hafnium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diethyl Silanediylbis (3-methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (4-t
-Butyl-2-methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride,
Diethylsilanediylbis (indenyl) titanium dichloride, diethylsilanediylbis (2-methyl-
Indenyl) titanium dichloride, diethylsilanediylbis (tetrahydroindenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9- Fluorenyl) titanium dichloride,
Diethylsilanediyl (cyclopentadienyl-2,7
-Di-t-butyl-9-fluorenyl) titanium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium Dichloride, diethylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (tetramethylcyclopentadiene (Enyl) zirconium dichloride, diethylsilanediylbis (indenyl) zirconium dichloride, diethylsilanediylbis (2-methyl-indenyl) zirconium dichloride, diethyl Njiirubisu (tetrahydroindenyl) zirconium dichloride, diethyl silane diyl (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diethyl silane diyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl)
Zirconium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, diethyl Silanediylbis (3-methylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) hafnium Dichloride, diethylsilanediylbis (indenyl) hafnium dichloride, diethylsilanediylbis (2-methyl-indenyl) hafnium dichloride, diethylsilanediylbis (tetrahi Roindeniru) hafnium dichloride, diethyl silane diyl (cyclopentadienyl -
9-fluorenyl) hafnium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9- Fluorenyl) hafnium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (3- Methylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (tetramethyl Clopentadienyl) titanium dichloride, diphenylsilanediylbis (indenyl) titanium dichloride, diphenylsilanediylbis (2-methyl-indenyl) titanium dichloride, diphenylsilanediylbis (tetrahydroindenyl) titanium dichloride, diphenylsilanediyl (cyclopenta) Dienyl-9-fluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl)
Titanium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, diphenyl Silanediylbis (2,4-dimethylcyclopentadienyl)
Zirconium dichloride, diphenylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (tetramethylcyclopenta) Dienyl) zirconium dichloride, diphenylsilanediylbis (indenyl) zirconium dichloride, diphenylsilanediylbis (2
-Methyl-indenyl) zirconium dichloride, diphenylsilanediylbis (tetrahydroindenyl)
Zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) Zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl)
Zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9
-Fluorenyl) zirconium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (3-methylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (4-t -Butyl-2-methylcyclopentadienyl)
Hafnium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (indenyl)
Hafnium dichloride, diphenylsilanediylbis (2-methyl-indenyl) hafnium dichloride,
Diphenylsilanediylbis (tetrahydroindenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, Diphenyl silanes such as diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) hafnium dichloride, and dimethyl, diethyl, dihydro, diphenyl, dibenzyl of the above group IVb transition metal compounds. A body etc. can be illustrated.

The above general formulas (15), (16) and (17)
Or as the compound represented by (18), for example, pentamethylcyclopentadienyl-di-t-butylphosphinotitanium dichloride, pentamethylcyclopentadienyl-di-t-butylamido titanium dichloride, pentamethylcyclo Pentadienyl-n-butoxide titanium dichloride, pentamethylcyclopentadienyl-di-t-butylphosphino zirconium dichloride, pentamethylcyclopentadienyl-di-t-butylamide zirconium dichloride, pentamethylcyclopentadienyl- n-butoxide zirconium dichloride, pentamethylcyclopentadienyl-di-t-butylphosphinohafnium dichloride,
Pentamethylcyclopentadienyl-di-t-butylamido hafnium dichloride, pentamethylcyclopentadienyl-n-butoxide hafnium dichloride,
Dimethylsilanediyl tetramethylcyclopentadienyl-t-butylamido titanium dichloride, dimethylsilanediyl-t-butyl-cyclopentadienyl-
t-butylamido titanium dichloride, dimethylsilanediyltrimethylsilylcyclopentadienyl-t
-Butylamidotitanium dichloride, dimethylsilanediyltetramethylcyclopentadienylphenylamidotitanium dichloride, methylphenylsilanediyltetramethylcyclopentadienyl-t-butylamidotitanium dichloride, dimethylsilanediyltetramethylcyclopentadienyl-p- n-Butylphenylamido titanium dichloride, dimethylsilanediyl tetramethylcyclopentadienyl-p-methoxyphenylamido titanium dichloride, dimethylsilanediyl-t-butylcyclopentadienyl-2,5-
Di-t-butyl-phenylamido titanium dichloride, dimethylsilanediylindenyl-t-butylamido titanium dichloride, dimethylsilanediyl tetramethylcyclopentadienylcyclohexylamido titanium dichloride, dimethylsilanediylfluorenylcyclohexylamido titanium dichloride, dimethyl Silanediyltetramethylcyclopentadienylcyclododecylamide titanium dichloride, dimethylsilanediyltetramethylcyclopentadienyl-t
-Butylamide zirconium dichloride, dimethylsilanediyl-t-butyl-cyclopentadienyl-t-
Butyramide zirconium dichloride, dimethylsilyltrimethylsilanediyl cyclopentadienyl-t-
Butylamide zirconium dichloride, dimethylsilanediyl tetramethylcyclopentadienyl phenylamide zirconium dichloride, methylphenylsilanediyl tetramethylcyclopentadienyl-t-butylamide zirconium dichloride, dimethylsilanediyl tetramethylcyclopentadienyl-pn -Butylphenylamide zirconium dichloride, dimethylsilanediyl tetramethylcyclopentadienyl-p-methoxyphenylamide zirconium dichloride, dimethylsilanediyl-t-butylcyclopentadienyl-
2,5-di-t-butyl-phenylamide zirconium dichloride, dimethylsilanediylindenyl-t-
Butylamide zirconium dichloride, dimethylsilanediyl tetramethylcyclopentadienylcyclohexylamide zirconium dichloride, dimethylsilanediylfluorenylcyclohexylamide zirconium dichloride, dimethylsilanediyl tetramethylcyclopentadienyl cyclododecylamide zirconium dichloride, dimethylsilanediyl tetramethyl Cyclopentadienyl-t-butylamide hafnium dichloride, dimethylsilanediyl-t-butyl-cyclopentadienyl-t-butylamide hafnium dichloride, dimethylsilanediyltrimethylsilylcyclopentadienyl-t-butylamide hafnium dichloride, dimethylsilane Diyl tetramethyl cyclopentadienyl phenylamide Off pyridinium dichloride, methylphenyl silane diyl tetramethylcyclopentadienyl -t- butyl amide hafnium dichloride, dimethylsilanediyl tetramethylcyclopentadienyl -p
-N-butylphenylamide hafnium dichloride,
Dimethylsilanediyl tetramethylcyclopentadienyl-p-methoxyphenylamide hafnium dichloride, dimethylsilanediyl-t-butylcyclopentadienyl-2,5-di-t-butyl-phenylamide hafnium dichloride, dimethylsilanediylindenyl -T-Butylamide hafnium dichloride, dimethylsilanediyltetramethylcyclopentadienylcyclohexylamide hafnium dichloride, dimethylsilanediylfluorenylcyclohexylamide hafnium dichloride, dimethylsilanediyltetramethylcyclopentadienylcyclododecylamide dichloride, etc. And the above group IVb transition metal compounds such as dimethyl, diethyl, dihydro, diphenyl and dibenzyl It can be exemplified, and the like.

The olefin (d) used as a constituent component of the catalyst of the present invention is ethylene, propylene, butene-
1, α-olefins such as pentene-1,4-methyl-1-pentene, hexene-1, and octene-1, cyclic olefins such as norbornene and norbornadiene, and the like, but a mixture of two or more kinds of these components is polymerized. You can also

Further, the organometallic compound (e) used in the present invention is represented by the following general formula (27)

[0037]

Embedded image

[Wherein M5 is the periodic table Ia, IIa, II
It is an element of Group Ia, Sn or Zn. R18 is independently a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group, an arylalkyl group, an arylalkoxy group,
It is an alkylaryl group or an alkylaryloxy group, and at least one R18 is a hydrogen atom or a carbon number of 1 to
It is an alkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. n is equal to the oxidation number of M5. ] It is an organometallic compound represented by.

Examples of the compound represented by the general formula (27) include trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n.
-Propyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, triamyl aluminum, dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisopropyl aluminum ethoxide, di-n-propyl aluminum ethoxide, diisobutyl aluminum ethoxide, di-
n-Butyl aluminum ethoxide, dimethyl aluminum hydride, diethyl aluminum hydride, diisopropyl aluminum hydride, di-n
-Propyl aluminum hydride, diisobutyl aluminum hydride, di-n-butyl aluminum hydride, etc. can be illustrated.

Next, the ionized ionic compound (f) used as a constituent component of the catalyst of the present invention will be described.

This ionized ionic compound is represented by the following general formula (28).

[0042] ^{[C +] [A -]} (28) where a [C ^+] is cation, specifically, trimethyl ammonium as containing an active proton,
Triethylammonium, tripropylammonium,
Tributylammonium, N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4
A Bronsted acid represented by 5-pentamethylanilinium, triphenylphosphonium, tri (o-tolyl) phosphonium, tri (p-tolyl) phosphonium, tri (mesityl) phosphonium, or a carbonium containing no active proton. Examples of the oxonium or sulfonium cation include, but are not limited to, compounds represented by triphenylcarbenium, tropylium ion and the like.

[A ⁻ ] is an anion, and is not particularly limited, and examples thereof include [AlR ₄ ⁻ ], [BR ₄ ⁻ ], [PR ₆ ⁻ ] and [ClO ₄ ⁻ ].

Specific examples of the ionized ionic compound include tri (n-butyl) ammonium tetrakis (p-tolyl) borate, tri (n-butyl) ammonium tetrakis (m-tolyl) borate and tri (n-butyl). ) Ammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N- Dimethylanilinium tetrakis (p-tolyl) borate, N, N-Dimethylanilinium tetrakis (m-tolyl) borate, N,
N-dimethylanilinium tetrakis (2,4-dimethylphenyl) borate, N, N-dimethylanilinium tetrakis (3,5-dimethylphenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (p-tolyl) borate, triphenylcarbenium tetrakis (m-tolyl) borate, triphenylcarbenium tetrakis (2,4-dimethyl) Phenyl) borate, triphenylcarbenium tetrakis (3,5-dimethylphenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tropylium tetrakis (p-tolyl) borate, tropylium tetrakis (m-tolyl) borate ,
Tropylium tetrakis (2,4-dimethylphenyl)
Borate, tropylium tetrakis (3,5-dimethylphenyl) borate, tropylium tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, lithium tetrakis (phenyl) borate, lithium tetrakis (p-tolyl) borate, Lithium tetrakis (m-tolyl) borate, lithium tetrakis (2,4-dimethylphenyl) borate, lithium tetrakis (3,5-dimethylphenyl) borate, lithium tetrafluoroborate, sodium tetrakis (pentafluorophenyl)
Borate, sodium tetrakis (phenyl) borate, sodium tetrakis (p-tolyl) borate, sodium tetrakis (m-tolyl) borate, lithium tetrakis (2,4-dimethylphenyl) borate, sodium tetrakis (3,5-dimethylphenyl) borate , Sodium tetrafluoroborate, potassium tetrakis (pentafluorophenyl) borate, potassium tetrakis (phenyl) borate, potassium tetrakis (p-tolyl) borate, sodium tetrakis (m)
-Tolyl) borate, potassium tetrakis (2,4-dimethylphenyl) borate, potassium tetrakis (3,3)
5-dimethylphenyl) borate, potassium tetrafluoroborate, tri (n-butyl) ammonium tetrakis (p-tolyl) aluminate, tri (n-butyl)
Ammonium tetrakis (m-tolyl) aluminate,
Tri (n-butyl) ammonium tetrakis (2,4-
Dimethylphenyl) aluminate, tri (n-butyl)
Ammonium tetrakis (3,5-dimethylphenyl)
Aluminate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) aluminate, N, N
-Dimethylanilinium tetrakis (p-tolyl) aluminate, N, N-dimethylanilinium tetrakis (m-tolyl) aluminate, N, N-dimethylanilinium tetrakis (2,4-dimethylphenyl) aluminate, N, N-dimethylanilinium tetrakis (3,5-dimethylphenyl) aluminate, N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) aluminate, triphenylcarbenium tetrakis (p-tolyl) aluminate, triphenylcarbenium tetrakis (m-tolyl) aluminate, triphenylcarbenium tetrakis (2,4-dimethylphenyl) ) Aluminate, triphenylcarbenium tetrakis (3,5-dimethylphenyl) aluminate, triphenylcarbenium tetrakis (pentafluorophenyl) aluminate, tropylium tetrakis (p-tolyl) aluminate, tropylium tetrakis (m- Trily) aluminate, tropylium tetrakis (2,4
-Dimethylphenyl) aluminate, tropylium tetrakis (3,5-dimethylphenyl) aluminate, tropylium tetrakis (pentafluorophenyl) aluminate, lithium tetrakis (pentafluorophenyl) aluminate, lithium tetrakis (phenyl) aluminate, Lithium tetrakis (p-tolyl) aluminate, lithium tetrakis (m-tolyl) aluminate, lithium tetrakis (2,4-dimethylphenyl)
Aluminate, lithium tetrakis (3,5-dimethylphenyl) aluminate, lithium tetrafluoroaluminate, sodium tetrakis (pentafluorophenyl) aluminate, sodium tetrakis (phenyl) aluminate, sodium tetrakis (p-tolyl) aluminate, Sodium tetrakis (m-tolyl) aluminate, lithium tetrakis (2,4-dimethylphenyl) aluminate, sodium tetrakis (3,5-dimethylphenyl) aluminate, sodium tetrafluoroaluminate, potassium tetrakis (pentafluorophenyl) aluminum Nate, potassium tetrakis (phenyl) aluminate, potassium tetrakis (p-tolyl) aluminate, sodium tetrakis (m-tolyl) aluminate Potassium tetrakis (2,4-dimethylphenyl) aluminate, potassium tetrakis (3,5-dimethylphenyl) aluminate, but potassium tetrafluoro aluminate and the like, but it is not limited thereto.

In the olefin polymerization catalyst of the present invention, the amount of the transition metal compound (c) with respect to 1 g of the inorganic oxide (a) in which a part or all of the surface hydroxyl groups is substituted with halogen is not particularly limited, but the transition metal atom 0.005-1mmo in quantity
1, preferably 0.05 to 0.5 mmol, and the amount of Al atoms contained in the organoaluminum oxy compound (b) with respect to the transition metal compound (c) is 10 to 200 mol based on 1 mol of the transition metal atom in the transition metal compound. It is preferable to use it in a ratio of 10 to obtain a better polymerization activity. It is preferable that 0.01 to 100 g of the olefin (d) is used with respect to 1 g of the inorganic oxide (a) in which a part or all of the surface hydroxyl groups are substituted with halogen, because further good polymerization activity can be obtained.

The molar ratio of the transition metal compound (c) and the ionized ionic compound (f) used in the present invention is not particularly limited, but a transition metal compound (a): ionized ionic compound (f) molar ratio is preferable. Is from 0.01 to 1: 1
000, particularly preferably 1: 0.2 to 1:
The range is 200. By using this range, a better polymerization activity can be obtained. The amount of the organometallic compound (e) used here is not particularly limited.

In the present invention, the method for contacting the catalyst component is not particularly limited, but as a preferred contact method for obtaining a catalyst having good polymerization activity, an inorganic oxide (a) in which a part or all of the surface hydroxyl groups are substituted with halogen is preferred. An olefin prepolymerization catalyst formed by prepolymerizing an olefin (d) with a catalyst component composed of an organoaluminum oxy compound (b) and a transition metal compound (c), an organometallic compound (e), and an ionized ionic compound The method of contacting (f) can be mentioned. The conditions for contacting the olefin (d) in this prepolymerization are not particularly limited, but the prepolymerization is carried out without solvent or under an inert hydrocarbon solvent. Generally, this contact treatment is -50 to 100 ° C, preferably -20 to 60.
C., more preferably in the temperature range of 0 to 50.degree. C., and can be carried out under normal pressure or under increased pressure. When the treatment is carried out in the gas phase, it is carried out under the flow condition, and when the treatment is carried out in the liquid phase. It is preferable to make sufficient contact under stirring. The monomers used in the prepolymerization may be used alone or in combination of two or more kinds, and when prepolymerizing two or more kinds, the prepolymerization may be carried out sequentially or simultaneously.

The catalyst for producing an olefin polymer of the present invention is obtained as described above, and a Lewis base compound may be added thereto. Specific Lewis base compounds include methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate. , Hexyl acetate, cyclohexyl acetate, benzyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 3-
Ethylhexyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isopentyl butyrate, isobutyl isobutyrate, ethyl isovalerate, isokichi Isobutyl herbate, butyl stearate, pentyl stearate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, benzyl benzoate, ethyl cinnamate, diethyl oxalate, dibutyl oxalate, oxalic acid Esters such as dipentyl, diethyl malonate, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate and triacetin, methylacetate Amine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, diisopropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, 2-ethylhexylamine, allylamine, aniline, N -Methylaniline, N, N-dimethylaniline, N, N-diethylaniline, toluidine, cyclohexylamine, dicyclohexylamine, pyrrole, piperidine, pyridine, picoline, 2,4-lutidine, 2,6-lutidine, 2,6- Amines such as di (t-butyl) pyridine, quinoline and isoquinoline, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether Ether, anisole, phenetole, butyl phenyl ether, methoxy toluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, veratrole, 1,2-epoxypropane, dioxane, trioxane, furan,
Ethers such as 2,5-dimethylfuran, tetrahydrofuran, tetrahydropyran, 1,2-diethoxyethane, 1,2-dibutoxyethane and crown ether, acetone, methyl ethyl ketone, methyl propyl ketone,
Diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methyl pentyl ketone, dipropyl ketone,
Diisobutyl ketone, cyclohexanone, methylcyclohexanone, ketones such as acetophenone, dimethyl sulfide, diethyl sulfide, thioethers such as thiophene, tetrahydrothiophene, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, Tetraisopentoxysilane, tetrahexoxysilane, tetraphenoxysilane, tetrakis (2-ethylhexoxy) silane, tetrakis (2-ethylbutoxy) silane, tetrakis (2-methoxyethoxy) silane, methyltrimethoxysilane, ethyltrimethoxysilane , Propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane , Sec-butyltrimethoxysilane, t-butyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, norbonyltrimethoxysilane, cyclohexyltrimethoxysilane, chloromethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 4-chlorotrimethoxysilane, triethoxysilane, methyltriethoxysilane,
Ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, ethyltriisopropoxysilane, isopentyltributoxysilane, methyltrihexoxysilane , Methyldimethoxysilane, dimethyldimethoxysilane, propylmethyldimethoxysilane, propylethyldimethoxysilane, dipropyldimethoxysilane, isopropylmethyldimethoxysilane, diisopropyldimethoxysilane, propylisopropyldimethoxysilane, butylmethyldimethoxysilane, butylethyldimethoxysilane, butylpropyl Dimethoxysilane, butylisopropyldimethoxysilane, dibutyldimethoxysilane, Seo-butyl methyl dimethoxy silane,
Diisobutyldimethoxysilane, sec-butylethyldimethoxysilane, di (sec-butyl) dimethoxysilane, t-butylmethyldimethoxysilane, t-butylpropyldimethoxysilane, di (t-butyl) dimethoxysilane, t-butylhexyldimethoxysilane, Diisoamyldimethoxysilane, hexylpropyldimethoxysilane, decylmethyldimethoxysilane, norbonylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, Diisopropyldiethoxysilane, sec-butylmethyldiethoxysilane, t-butylmethyldiethoxysilane, dime Distearate butoxy silane, trimethyl methoxy silane, trimethyl ethoxy silane, trimethyl tetraisopropoxysilane, trimethylpropoxysilane,
Silyl ethers such as trimethyl-t-butoxysilane, trimethylisobutoxysilane, trimethylbutoxysilane, trimethylpentoxysilane, and trimethylphenoxysilane, methylphosphine, ethylphosphine, phenylphosphine, benzylphosphine, dimethylphosphine, Diethylphosphine, diphenylphosphine, methylphenylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine, tributylphosphine, ethylbenzylphenylphosphine, ethylbenzylbutylphosphine, trimethoxyphosphine, diethylethoxyphosphine Phosphines such as fins, triphenylphosphine oxide, dimethylethoxyphosphine oxide, trieth Phosphine oxides such as cyphosphine oxide, nitriles such as acrylonitrile, cyclohexanedinitrile and benzonitrile, nitro compounds such as nitrobenzene, nitrotoluene and dinitrobenzene, acetone dimethyl acetal, acetophenone dimethyl acetal, benzophenone dimethyl acetal, cyclohexanone dimethyl acetal Examples thereof include acetals such as diethyl carbonate, diphenyl carbonate, carbonates such as ethylene carbonate, thioacetals such as 1-ethoxy-1- (methylthio) cyclopentane, and thioketones such as cyclohexanethione. It is not limited.

When a Lewis base compound is added to obtain a catalyst, the transition metal compound (c) and the Lewis base compound are in mols.
The ratio is not particularly limited, but the molar ratio of the transition metal compound (c): Lewis base compound is preferably 1: 0.01 to.
It is in the range of 1: 1000, particularly preferably 1: 0.1
˜1: 100.

In addition, in preparing the catalyst, the method of adding the Lewis base compound is not limited, but it is preferable to add the Lewis base compound after contacting (a) to (f).

In the present invention, in the presence of the catalyst for producing an olefin polymer prepared by the above method, the α-olefin or the cyclic olefin is in a solution state, a suspension state or a gas phase state at a temperature of -60 to 280 ° C. , 0.5 to 200
It can be polymerized or copolymerized to produce a polyolefin under a pressure of 0 bar.

As these olefins, ethylene,
Propylene, butene-1, pentene-1,4-methyl-
Examples thereof include α-olefins such as 1-pentene, hexene-1, and octene-1, and cyclic olefins such as norbornene and norbornadiene, but it is also possible to polymerize a mixed component of two or more kinds thereof.

When the polymerization is carried out in a solution state or a suspension state, the catalyst for producing an olefin polymer obtained by the above method may be used as it is or may be diluted with a polymerization solvent. The polymerization solvent may be any organic solvent commonly used, and specifically, halogenated hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride, and fats such as pentane, hexane, heptane, octane, nonane and decane. Examples thereof include aromatic hydrocarbons such as group hydrocarbons, benzene, toluene and xylene, or the olefin itself can be used as a solvent.

[0054]

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

The polymerization operation, reaction and solvent purification were all carried out under an inert gas atmosphere. Further, as the solvent and the like used in the reaction, those which were previously purified, dried and deoxidized by a known method were used. The compounds used in the reaction were those synthesized and identified by known methods. The melting index (MI) described in the examples was measured by a method according to ASTM D1238 condition E.

Example 1 [Preparation of prepolymerization catalyst] A 500 ml glass flask was subjected to fluorination treatment with NH ₄ F (200
1.01 g and 15 ml of decane were added to make a suspension. To this was added 5.6 ml of a toluene solution of methylaluminoxane (2.98 mol / l), and the mixture was stirred at room temperature for 1 hour.
Stirred for hours. Then, a toluene solution of bis (indenyl) zirconium dichloride (0.0024 mol /
l) 70 ml was added, and the mixture was stirred at room temperature for 1 hour. Then
Add 35 ml of decane, introduce ethylene at atmospheric pressure, and
The mixture was stirred at 0 ° C. for 3 hours under an ethylene gas atmosphere. After the completion of prepolymerization, remove the solvent with a bridge filter,
Washing was performed 4 times with 200 ml of hexane. As a result, zirconium was 0.084 per 1 g of the ash content of the prepolymerization catalyst.
A prepolymerization catalyst containing 1 mmol of polyethylene and 10 g of polyethylene was obtained.

[Polymerization] The interior of the stainless steel magnetic stirring type autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 150 g of sodium chloride was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Then, a mixture of the prepolymerized catalyst prepared above (corresponding to 2.4 μmol of zirconium), 1.5 mmol of triisobutylaluminum and 5 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was inserted into an autoclave. Immediately, ethylene gas was introduced, and polymerization was carried out at 80 ° C. for 30 minutes while continuously adding ethylene gas so that the internal pressure of the autoclave became 8 kg / cm ² G. After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, and a mixture of the produced polymer and sodium chloride was taken out. This mixture was washed with pure water, dissolved in sodium chloride, and then dried. As a result, MI is 1.1g
/ 10 minutes, the polymer having a bulk density of 0.30 g / cm ³ is 82
g was obtained.

Example 2 [Preparation of pre-polymerization catalyst] 1.0 g of silica magnetically treated with NH ₄ F (calcined at 200 ° C. for 5 hours) and 30 ml of hexane were placed in a 1 l glass electromagnetic stirring autoclave.
Was added to make a suspension. 7.0 ml of a toluene solution of methylaluminoxane (2.39 mol / l) was added thereto,
Stirred at room temperature for 1 hour. Then, a toluene solution of bis (indenyl) zirconium dichloride (0.0024
(mol / l) 70 ml was added, and the mixture was stirred at room temperature for 1 hour.
Then, 40 ml of hexane was added, and prepolymerization was carried out at 30 ° C. for 3 hours while continuously adding ethylene gas so that the internal pressure of the autoclave became 0.5 kg / cm ² G. After the completion of the preliminary polymerization, the solvent was removed, and the mixture was washed with 200 ml of hexane four times. As a result, 1 g of silica as a prepolymerization catalyst
Thus, a prepolymerization catalyst containing 0.052 mmol of zirconium and 8 g of polyethylene was obtained.

[Polymerization] The interior of the stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 150 g of sodium chloride was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Then, a mixture of the prepolymerized catalyst prepared above (corresponding to 2.5 μmol of zirconium), 1.5 mmol of triisobutylaluminum and 5 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was inserted into an autoclave. Immediately, ethylene gas was introduced, and polymerization was carried out at 80 ° C. for 35 minutes while continuously adding ethylene gas so that the internal pressure of the autoclave became 8 kg / cm ² G. After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, and a mixture of the produced polymer and sodium chloride was taken out. This mixture was washed with pure water, dissolved in sodium chloride, and then dried. As a result, MI is 1.6g
/ 10 minutes, the polymer having a bulk density of 0.38 g / cm ³ is 10
1 g was obtained.

Example 3 [Polymerization] The interior of a stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 150 g of sodium chloride was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Next, the prepolymerized catalyst obtained in Example 2 (corresponding to zirconium 2.5 μmol), triisobutylaluminum 1.5 mmol, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 5 μmol
Then, a mixture of 1.25 μmol of diphenyldimethoxysilane and 1.25 μmol of diphenyldimethoxysilane was inserted into the autoclave. Immediately introduce ethylene gas and the internal pressure of the autoclave is 8 kg / cm
8 while continuously adding ethylene gas to ² G
Polymerization was carried out at 0 ° C. for 35 minutes. After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, and a mixture of the produced polymer and sodium chloride was taken out. This mixture was washed with pure water, dissolved in sodium chloride, and then dried. As a result, MI was 1.9 g / 10 minutes, and 110 g of a polymer having a bulk density of 0.36 g / cm ³ was obtained.

Example 4 [Polymerization] The interior of a stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 150 g of sodium chloride was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Then, the prepolymerized catalyst obtained in Example 2 (corresponding to 2.5 μmol of zirconium), 1.5 mmol of triisobutylaluminum and 5 μm of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.
The mixture of ol was inserted into the autoclave. Immediately mixed gas of ethylene / butene-1 (butene-1 content 2
9 mol%) was introduced, and the internal pressure of the autoclave was 8 kg /
8 while continuously adding the mixed gas so as to obtain cm ² G
Polymerization was carried out at 0 ° C. for 35 minutes. After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, and a mixture of the produced polymer and sodium chloride was taken out. This mixture was washed with pure water, dissolved in sodium chloride, and then dried. As a result, MI was 40 g / 10 minutes and melting point was 1.
73 g of polymer with a bulk density of 0.41 g / cm ³ at 26 ° C.
Obtained.

Example 5 [Polymerization] 500 ml of hexane and 0.5 mmol of triisobutylaluminum were added to a stainless steel electromagnetic stirring autoclave having an internal volume of 2 l, and the mixture was stirred for 10 minutes. An autoclave was prepared by mixing the solution with the prepolymerized catalyst obtained in Example 2 (corresponding to 1.0 μmol of zirconium), 0.3 mmol of triisobutylaluminum and 2 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. Inserted into. 4 kg / cm ² inside the autoclave with ethylene
While maintaining at G, polymerization was carried out at 80 ° C. for 30 minutes. As a result, MI was 0.83 g / 10 minutes and bulk density was 0.06 g / c.
29 g of m ³ polymer was obtained.

Comparative Example 1 [Preparation of Preliminary Polymerization Catalyst] In [Preparation of Prepolymerization Catalyst] of Example 2, untreated silica (calcined at 200 ° C. for 5 hours) was used instead of silica treated with fluorine by NH ₄ F. A catalyst was prepared in the same manner as in Example 2 except that was used. As a result, a prepolymerized catalyst containing 0.087 mmol of zirconium and 10 g of polyethylene per 1 g of silica of the prepolymerized catalyst was obtained.

[Polymerization] 500 ml of hexane and 0.5 mmol of triisobutylaluminum were added to a stainless steel magnetic stirring type autoclave having an internal volume of 2 liters, and 1
Stir for 0 minutes. This solution was mixed with the prepolymerized catalyst prepared above (corresponding to 1.0 μmol of zirconium), 0.3 mmol of triisobutylaluminum and 2 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and inserted into an autoclave. did. 4 inside the autoclave with ethylene
Polymerization was carried out at 80 ° C. for 30 minutes while keeping it at kg / cm ² G. As a result, 13 g of a polymer having an MI of 0.76 g / 10 minutes and a bulk density of 0.04 g / cm ³ was obtained.

[0065]

EFFECT OF THE INVENTION By using the catalyst for producing an olefin polymer of the present invention, an olefin polymer having an excellent polymerization activity and a good particle shape can be obtained.

Claims (6)

[Claims] 1. An inorganic oxide in which part or all of surface hydroxyl groups are substituted with halogen, (b) an organoaluminum oxy compound, (c) a transition metal compound, (d) an olefin, and (e) an organometallic compound. (F) A catalyst for producing an olefin polymer, which is obtained by contacting an ionized ionic compound. 2. A catalyst component comprising (a) an inorganic oxide in which some or all of the surface hydroxyl groups are substituted with halogen, (b) an organoaluminum oxy compound, and (c) a transition metal compound, and an olefin (d) is preliminarily prepared. An olefin prepolymerization catalyst formed by polymerization and (e) an organometallic compound,
(F) A catalyst for producing an olefin polymer, which comprises an ionized ionic compound. 3. The transition metal compound (c) according to claim 1 or 2 is represented by the following general formula (1): Or the following general formula (2) [In the formula, M1 is a titanium atom, a zirconium atom or a hafnium atom, and Y is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 6 to 2 carbon atoms.
0 is an aryl group, an arylalkyl group or an alkylaryl group, and R 1 and R 2 are each independently the following general formula (3), (4), (5) or (6) (In the formula, each R6 is independently a hydrogen atom and a carbon number of 1 to 20.
Is an alkyl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. ), The ligand forms a sandwich structure together with M1, and R4 and R5 are independently the following general formulas (7), (8), (9) or ( 10) [Chemical 4] (In the formula, each R7 is independently a hydrogen atom and a carbon number of 1 to 20.
Is an alkyl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. ), The ligand forms a sandwich structure together with M1, and R3 is represented by the following general formula (11) or (1
2) [Chemical 5] (In the formula, each R8 is independently a hydrogen atom and a carbon number of 1 to 20.
Is an alkyl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group, and M2 is a silicon atom, a germanium atom or a tin atom. ), Acting to crosslink R4 and R5,
p is an integer of 1 to 5. ] It is a group IVb transition metal compound represented by these, The catalyst for olefin polymer manufacture characterized by the above-mentioned. 4. The transition metal compound (c) according to claim 1 or claim 2, which is represented by the following general formulas (13), (14) and (1):
5) or (16) [In the formula, M3 is independently a titanium atom, a zirconium atom or a hafnium atom, and Z is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,
An aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group, L is a Lewis base,
w is 0 ≦ w ≦ 3, JR9 _q-1 and JR9 _q-2 are heteroatom ligands, and J is a Va group element having a coordination number of 3 or a IVa group having a coordination number of 2 R9 are each independently a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group, an arylalkyl group, an arylalkoxy group, An alkylaryl group or an alkylaryloxy group, q is the coordination number of the element J,
R10 is represented by the following general formula (17), (18), (19) or (20): (In the formula, each R13 independently represents a hydrogen atom or a carbon number of 1-2.
An alkyl group of 0, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. ), R12 is a ligand represented by the following general formula (21),
(22), (23) or (24) (In the formula, each R14 is independently a hydrogen atom and a carbon number of 1-2.
An alkyl group of 0, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. ), Which is a ligand coordinated to M3, and R11 is represented by the following general formula (25) or (26): (In the formula, each R15 is independently a hydrogen atom and a carbon number of 1-2.
It is an alkyl group of 0, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group, and M4 is a silicon atom, a germanium atom or a tin atom. ), Which acts to crosslink R12 and JR9 _q-2 , and r is an integer of 1 to 5. ] IV
A catalyst for producing an olefin polymer, which is a group b transition metal compound. 5. The organometallic compound (e) according to claim 1 or 2 is represented by the following general formula (27): [Wherein, M5 is a periodic table group Ia, IIa, IIIa, Sn
Alternatively, it is an element of Zn. R18 is independently a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms,
An aryl group having 6 to 20 carbon atoms, an aryloxy group, an arylalkyl group, an arylalkoxy group, an alkylaryl group or an alkylaryloxy group, wherein at least one R18 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon atom. It is an aryl group, an arylalkyl group or an alkylaryl group of the number 6 to 20. n is equal to the oxidation number of M5. ] It is an organometallic compound represented by these, The catalyst for olefin polymer manufacture characterized by the above-mentioned. 6. In the presence of the catalyst for producing an olefin polymer according to claim 1, α-olefin or cyclic olefin in a solution state, a suspension state or a gas phase state, -60 to 2
A method for producing an olefin polymer, which comprises polymerizing or copolymerizing at a temperature of 80 ° C. and a pressure of 0.5 to 2000 bar.