JPH1036424A - Polymerization catalyst and production of polyolefin by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerization catalyst which can give a polyolefin having good powder properties and a high bulk density in a high activity without encountering a problem of deposition on the wall of a reactor by mixing a specified transition metal compound with an organoaluminumoxy compound, a carrier and a specified organometallic compound. SOLUTION: This catalyst comprises at least one transition metal compound such as represented by formula I or II, an organoaluminumoxy compound, a carrier and an organometallic compound component comprising at least one member selected from among alkyllithiums and dialkylmagnesiums and at least two trialkylaluminums. In the formulas, R<1> to R<10> are each H, a 1-20C hydrocarbon group, an alkylsilyl or an alkylgermyl; R<11> is a 1-20C alkylgermylene or an alkylsiliylene; Me is a transition metal of group 3, 4, 5 or 6 in the periodic table; p is 0 or 1; and Q' is H, a 1-20C hydrocarbon group, an alkoxyl, an aryloxy, siloxy or a halogen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an olefin polymerization catalyst and a method for producing a polyolefin using the catalyst. More specifically, the present invention relates to an olefin polymerization catalyst capable of producing a polyolefin having good powder properties and a high bulk density with high activity without adhering to a reactor wall, and a method for producing a polyolefin using the same.

[0002]

2. Description of the Related Art Recently, processes for producing polyethylene or ethylene-α-olefin copolymers using a metallocene compound and methylaluminoxane as catalysts have been developed. For example, JP-A-58-19309 discloses copolymerization of ethylene and ethylene with an α-olefin having 3 to 12 carbon atoms using biscyclopentadienyl zirconium dichloride and linear or cyclic methylaluminoxane as catalysts. A method of manufacturing the united body has been proposed. Although this method is a catalyst system having high activity per transition metal and excellent in copolymerizability, it requires a large amount of expensive methylalumoxane and is problematic from an economic viewpoint.

In order to solve this problem, a catalyst system which maintains high activity even when the amount of aluminoxane used as a catalyst component is reduced has been studied. For example, JP-A-60-
JP-A-260602 proposes a method for producing a polyolefin using a catalyst characterized by using an organoaluminum compound in addition to a metallocene compound and an aluminoxane. JP-A-63-168409 discloses a metallocene compound. A method for producing a polyolefin using a solid catalyst having a metallocene compound supported on a carrier at the same time as producing a carrier by contacting the carrier with an organomagnesium compound is disclosed. However, although these catalyst systems were able to reduce the amount of aluminoxane used while maintaining high activity, there was a problem that the resulting polymer adhered to the reactor wall, and industrial stable production was difficult. there were.

[0004] In order to solve this problem, studies have been made to support a metallocene compound or methylaluminoxane on a certain solid support in the above-mentioned catalyst system coexisting with an organoaluminum compound. For example, JP-A-61-29
6008, JP-A-63-280703, JP-A-63-2280
2804, JP-A-63-51405, JP-A-63-51
407, JP-A-63-54403, JP-A-63-610
10, JP-A-63-248803, JP-A-4-1008
08, JP-A-3-74412, JP-A-3-709, JP-A-4-7306, etc., silica, alumina,
An olefin polymerization method using a solid catalyst in which a metallocene compound and methylaluminoxane are supported on a porous inorganic metal oxide such as silica alumina is disclosed.

In parallel with these, Japanese Patent Application Laid-Open No. 1-25900
4. JP-A-1-259005 discloses a method using a catalyst in which a special metallocene compound having an alkoxysilane group as a substituent of a cyclopentadienyl ligand is supported on a porous inorganic metal oxide carrier such as silica. Has been proposed. JP-A-1-207303, JP-A-61-314
04, JP-A-4-224808 describes a method in which an organoaluminum compound is brought into contact with undehydrated silica or the like, and a catalyst in which a metallocene compound is supported on a carrier thereof is used. Also, Japanese Patent Application Laid-Open Nos.
Japanese Patent No. 211405 discloses a method using a catalyst in which a metallocene compound and an aluminoxane are supported on a spherical magnesium chloride carrier.

Further, Japanese Patent Application Laid-Open Nos. Hei 3-210307 and Hei 3-
No. 66710 proposes a method using a catalyst obtained by co-milling a metallocene compound and an aluminoxane with a solid magnesium compound. Also, JP-A-63-1992
No. 06 describes a method using a catalyst in which a metallocene compound is supported on solidified methylaluminoxane. However, although the supported catalysts described in these prior arts have improved adaptability to a slurry polymerization method or a gas phase polymerization method, their effects are still insufficient for preventing the polymer from adhering to the reactor wall. Was.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a highly active polyolefin having high powder properties and high bulk density even when the amount of expensive methylaluminoxane used is small. An object of the present invention is to provide an olefin polymerization catalyst that can be produced without the adhesion of olefins, and to produce a polyolefin using this catalyst.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have finally found a olefin polymerization catalyst and a method for producing a polyolefin which meet the purpose, and have reached the present invention. . That is, the olefin polymerization catalyst according to the present invention comprises: (A) a compound represented by the general formula (1):

Embedded image General formula (2),

Embedded image General formula (3),

Embedded image General formula (4),

Embedded image General formula (5),

Embedded image General formula (6) or

Embedded image General formula (7)

Embedded image [Wherein, R ^{1 to} R ¹⁰ are hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkylsilyl group or an alkylgermyl group, which may be the same or different, and R ¹¹ has 1 to 20 carbon atoms. Wherein each X is carbon or nitrogen and may be the same or different, each Q is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, alkoxy, allyloxy, Siloxy or halogen, which may be the same or different, and Y is -O-, -S-, -NR
¹² -, - PR ¹² - a and, R ¹² is hydrogen, having from 1 to 20 carbon atoms
, A halogenated alkyl or aryl halide. ), Me is a transition metal of Group 3, 4, 5, or 6 of the periodic table, and p is 0 or 1. And (B) an organoaluminum oxy compound,
(C) a carrier and (D) an olefin polymerization catalyst comprising at least one kind of alkyllithium and dialkylmagnesium and at least two kinds of organometallic compounds of trialkylaluminum,

The olefin polymerization catalyst described in which an organoaluminum oxy compound is supported in an amount of 5 × 10 ^{−4 to} 0.05 gram atom per gram of the carrier in terms of aluminum atom, at least two kinds of organometallic compounds ( The olefin polymerization catalyst according to any one of-, wherein D) is at least two kinds of organometallic compounds (D) selected from at least one kind of normal butyllithium and butylethylmagnesium and trialkylaluminum, Component (A) Of the transition metal compound [A], the number of moles of aluminum atoms [B] in the organoaluminum oxy compound of component (B), and the number of moles of at least two kinds of organometallic compounds used in the preparation of component (D). When the sum is [D], 1/5 <[A] / [B] <1 / 10,000 1 <[A] / [D] <1 / 100,000 The olefin polymerization catalyst according to any one of-blended in a ratio of

The component (A) described above, a transition metal compound,
Developed a method for producing a polyolefin polymer in which olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst comprising component (B) an organoaluminum oxy compound, (C) a carrier and component (D) at least two kinds of organometallic compounds. By doing so, the above problem was solved.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The olefin polymerization catalyst according to the present invention and a method for producing a polyolefin using the catalyst will be specifically described below. The transition metal compound (A) used in the present invention includes the above general formula (1), general formula (2), general formula (3), general formula (4), general formula (5),
Formula (6) or Formula (7) [wherein, R ¹ to
R ¹⁰ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, such as alkyl, alkenyl, aryl, araryl, aralkyl, and alicyclic, an alkylsilyl group, or an alkylgermyl group. Often, R ¹¹ is an alkylene group having 1 to 20 carbon atoms,
Alkylgermylene or alkylsilylene, each X is carbon or nitrogen, which may be the same or different, and each Q is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, alkoxy, allyloxy, siloxy or halogen. And each may be the same or different, and Y is -O
-, - S -, - NR 12 -, - PR 12 - (R 12 is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated alkyl or halogenated aryl.) With an electron donor ligand represented by And Me is a transition metal of Groups 3, 4, 5, or 6 of the Periodic Table, and p is 0 or 1. ] It is a transition metal compound represented by these.

Examples of the hydrocarbon group having 1 to 20 carbon atoms in these compounds include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a t-butyl group, an amyl group, an isoamyl group, a hexyl group and a heptyl group. , Octyl group, nonyl group, decyl group, alkyl group such as cetyl group,
An aryl group such as a phenyl group and a trimethylsilyl group can be exemplified as the alkylsilyl group, and a trimethylgermyl group can be exemplified as the alkylgermyl group. In the above formula, Me is a transition metal element belonging to Group 3, 4, 5, or 6 of the periodic table (according to the rules of inorganic chemical nomenclature 1990), preferably a transition metal element belonging to Group 4 of the periodic table, ie, titanium. , Zirconium and hafnium, particularly preferably zirconium and hafnium.

The ligands of the compounds having these substituents include, for example, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group,
alkyl-substituted cyclopentadienyl groups such as n-butylcyclopentadienyl group, t-butylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, dimethylcyclopentadienyl group or pentamethylcyclopentadienyl group; Examples include an indenyl group and a fluorenyl group having or not having the same substituent.

In the compound represented by the above formula, R ¹¹
Is an alkylene group having 1 to 20 carbon atoms, alkylgermylene or alkylsilylene. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylidene group, a cyclopentylidene group, a cyclohexylidene group, a tetrahydropyran-4-ylidene group, and a diphenylmethylene group. , Dimethylsilylene group, diphenylsilylene group and the like, and examples of the alkylgermylene group include
Examples thereof include a dimethylgermylene group and a diphenylgermylene group.

X is carbon or nitrogen, which may be the same or different, and Q is hydrogen, having 1 to 20 carbon atoms.
A hydrocarbon group such as alkyl, alkenyl, aryl, araryl, aralkyl, etc., alkoxy, allyloxy, siloxy or halogen, which may be the same or different. Furthermore Y is -O -, - S -, - NR 12 -, - PR
^This is an electron donor ligand represented by 12-. Where R ¹²
Is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms such as alkyl, alkenyl, aryl, araryl and aralkyl, or an alkyl halide or aryl halide. Specifically, a methyl group as a hydrocarbon group,
Ethyl group, propyl group, butyl group, isobutyl group, t-
Examples include an alkyl group such as a butyl group, an amyl group, an isoamyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a cetyl group, and a phenyl group and a benzyl group. In ^{this, -NR 12 -, - PR 12} - type ligand is preferred.

Hereinafter, general formulas (1), (2), (3), (4), (5) and (6)
Alternatively, specific examples of the transition metal compound represented by the general formula (7) when Me is zirconium will be described. As the transition metal compound represented by the general formula (1),
Bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl)
Zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) ( Methylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (n-butylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (indenyl) zirconium dichloride, (cyclopentadienyl) (fluorenyl) zirconium dichloride , Cyclopentadienyl zirconium trichloride, cyclopentadienyl zirconium trimethyl, pentamethylcyclopentadienyl zirconium trichloride, pentamethylcyclyl Cyclopentadienyl zirconium trimethyl like.

The transition metal compounds represented by the general formula (2) include dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, isopropylidenebis (methylcyclopentadienyl) zirconium dichloride, and ethylenebis (indenyl). ) Zirconium dichloride, ethylenebis (4,5,6,7, -tetrahydro-1-indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (indenyl) Zirconium dichloride, isopropylidene (t-butylcyclopentadienyl) (t-butylindenyl) zirconium dichloride, isopropylidene (t-butylcyclopentadienyl) (t-butyl Ndeniru) zirconium dimethyl and the like.

The transition metal compound represented by the general formula (3) includes ethylene (t-butylamide) (tetramethylcyclopentadienyl) zirconium dichloride and ethylene (methylamide) (tetramethylcyclopentadienyl) zirconium. Dichloride, dimethylsilylene (t-butylamide) (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (t-butylamide) (tetramethylcyclopentadienyl) zirconium dibenzyl, dimethylsilylene (benzylamide) (tetramethylcyclopenta Dienyl)
Examples thereof include zirconium dibenzyl and dimethylsilylene (phenylamide) (tetramethylcyclopentadienyl) zirconium dichloride.

The transition metal compounds represented by the general formula (4) include (cyclopentadienyl) (N, N'-bis (trimethylsilyl) benzamidinato) zirconium dichloride and (cyclopentadienyl) (N , N'-
Bis (n-butyl) benzamidinato) zirconium dichloride, (cyclopentadienyl) (N, N'-bis (phenyl) benzamidinato) zirconium dichloride, (cyclopentadienyl) (N, N'- Bis (2,6-dimethylphenyl) benzamidinato) zirconium dichloride, (cyclopentadienyl)
(N, N'-bis (2,6-di-t-butylphenyl)
(Benzamidinato) zirconium dichloride, (n-
Butylcyclopentadienyl) (N, N′-bis (trimethylsilyl) benzamidinato) zirconium dichloride, (n-butylcyclopentadienyl) (N,
N'-bis (n-butyl) benzamidinato) zirconium dichloride, (n-butylcyclopentadienyl) (N, N'-bis (phenyl) benzamidinato) zirconium dichloride, (pentamethylcyclopentadiene) Enyl) (N, N'-bis (trimethylsilyl)
(Benzamidinato) zirconium dichloride, (pentamethylcyclopentadienyl) (N, N′-bis (n
-Butyl) benzamidinato) zirconium dichloride, (pentamethylcyclopentadienyl) (N, N ′
-Bis (phenyl) benzamidinato) zirconium dichloride, (indenyl) (N, N'-bis (trimethylsilyl) benzamidinato) zirconium dichloride, (indenyl) (N, N'-bis (n-butyl)
Benzamidinato) zirconium dichloride, (indenyl) (N, N′-bis (phenyl) benzamidinato) zirconium dichloride and the like can be exemplified.

As the transition metal compound represented by the general formula (5), dimethylsilylene (cyclopentadienyl)
(N, N'-bis (trimethylsilyl) amidinate)
Zirconium dichloride, dimethylsilylene (cyclopentadienyl) (N, N'-bis (phenyl) amidinato) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (N, N'-bis (n-butyl)
Amidinato) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (N, N '
-Bis (trimethylsilyl) amidinato) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (N, N'-bis (phenyl) amidinato) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (N, N ' -Bis (n-butyl) amidinato) zirconium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (N, N'-bis (trimethylsilyl) amidinato) zirconium dichloride, dimethylsilylene (n-
Butylcyclopentadienyl) (N, N′-bis (phenyl) amidinato) zirconium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (N,
N'-bis (n-butyl)) amidinato) zirconium dichloride, dimethylsilylene (indenyl) (N,
N'-bis (trimethylsilyl) amidinato) zirconium dichloride, dimethylsilylene (indenyl)
(N, N'-bis (phenyl) amidinato) zirconium dichloride, dimethylsilylene (indenyl)
(N, N′-bis (n-butyl) amidinato) zirconium dichloride can be exemplified.

Examples of the transition metal compound represented by the general formula (6) include bis (N, N'-bis (trimethylsilyl) benzamidinato) zirconium dichloride and bis (N, N'-bis (phenyl) benzamido. Dinato) zirconium dichloride, bis (N, N′-bis (n-butyl) benzamidinato) zirconium dichloride and the like can be exemplified.

Examples of the transition metal compound represented by the general formula (7) include dimethylsilylenebis (N, N'-bis (trimethylsilyl) amidinato) zirconium dichloride and dimethylsilylenebis (N, N'-bis (phenyl) amidinato ) Zirconium dichloride, dimethylsilylenebis (N, N′-bis (trimethylsilyl) amidinato) zirconium dichloride, isopropylidenebis (N, N′-bis (trimethylsilyl) amidinato) zirconium dichloride, isopropylidenebis (N, N′-bis) Examples thereof include (phenyl) amidinato) zirconium dichloride and isopropylidenebis (N, N′-bis (n-butyl) amidinato) zirconium dichloride.

Among the above-mentioned zirconium compounds, transition metal compounds in which zirconium is changed to hafnium or titanium can also be exemplified. The transition metal compound according to the present invention can be used alone or in combination of two or more of the above-mentioned transition metal compounds.

As the organoaluminum oxy compound as the component (B) used in the present invention, an aluminoxane compound is usually preferably used, but a modified aluminoxane can also be used as described later.

A typical example of the above aluminoxane is represented by the general formula (8) (R ¹³ ) ₂ Al- [O-Al (R ¹³ )] _m- (R ¹³ ) (8) or the general formula (9) Organoaluminum compound represented by

Embedded image It is. [However, R ¹³ is hydrogen or carbon number 1-2.
0 hydrocarbon group, halogenated alkyl group or halogenated aryl group. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group and the like, and a methyl group and an isobutyl group are preferred. However, it may optionally contain a substituent such as a different hydrocarbon group listed above even in the same formula, for example, even if a repeating unit having a different hydrocarbon group is bonded in a block manner, They may be combined regularly or irregularly. m is 1 to 100, preferably 4 or more, particularly preferably 8 or more. A method for producing this type of compound is known, and examples thereof include a method of adding an organoaluminum compound to a hydrocarbon solvent suspension of a salt having water of crystallization (copper sulfate hydrate, aluminum sulfate hydrate), and a method for preparing a carbonized solution. A method in which solid, liquid or gaseous water is allowed to act on an organoaluminum compound in a hydrogen solvent is exemplified. In this case, two or more compounds of the general formulas (8) and (9) may be used as the aluminoxane in combination.

The organoaluminum compound used for producing aluminoxane includes trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec
Dialkylaluminum halides such as trialkylaluminum such as -butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tricyclohexylaluminum, dimethylaluminum chloride, diethylaluminum chloride and diisobutylaluminum chloride, It is selected from dialkylaluminum alkoxides such as methoxide and diethylaluminum ethoxide, and dialkylaluminum aryloxides such as diethylaluminum phenoxide. Among them, it is preferable to be selected from trialkylaluminums, particularly trimethylaluminum and triisobutylaluminum.

The hydrocarbon solvents used in the production of aluminoxanes include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, cyclopentane and cyclohexane. And other alicyclic hydrocarbons. Of these solvents, aromatic hydrocarbons are preferred.

The organoaluminum oxy compound in the component (B) used in the catalyst of the present invention only needs to contain the organoaluminum oxy compound, and other components are added or modified. No problem. Examples of the organoaluminum oxy compound to which an additive is added or a modified organoaluminum oxy compound include, for example, an aluminoxane compound in which the solubility in a solvent is reduced by adding water or heating, and a terminal with an active hydrogen-containing organic polar compound. Examples thereof include a modified aluminoxane compound and an aluminoxane compound to which an organic polar compound having no active hydrogen is added.

The organic polar compound having no active hydrogen used at this time includes at least one atom selected from a phosphorus atom, a nitrogen atom, a sulfur atom and an oxygen atom in a molecule.
An organic polar compound which has no active hydrogen and has a functional group containing the atom, and has no active hydrogen. Active hydrogen is a phosphorus atom, a nitrogen atom,
Hydrogen directly bonded to a sulfur atom or an oxygen atom. At least one atom selected from the above-mentioned phosphorus, nitrogen, sulfur and oxygen atoms is present in the molecule.
The organic polar compound having no active hydrogen and having durability can be arbitrarily selected as long as this condition is satisfied, but is preferably a phosphoric ester.

The organic polar compound and the organic aluminum oxy compound having at least one atom selected from a phosphorus atom, a nitrogen atom, a sulfur atom, and an oxygen atom in the molecule and having no active hydrogen are used in the present invention. Can be produced by mixing an organic aluminum oxy compound, for example, aluminoxane, and the above-mentioned organic polar compound in a hydrocarbon solvent and then left-handing the reaction. The amount of the organic polar compound used in this reaction is 0.1 to 1 equivalent of aluminum atom of the organic aluminum oxy compound.
0001-0.5 mol, preferably 0.001-0.
It is desirable to use 3 mol, more preferably 0.005 to 0.2 mol equivalent.

The carrier used as the carrier of the component (C) is preferably in the form of porous fine particles and solid in a polymerization medium, and may be an inorganic oxide, an inorganic chloride, an inorganic carbonate, an inorganic sulfate or an organic polymer. Selected from. Examples of the inorganic oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ ,
TiO ₂ , CaO inorganic oxide, or SiO ₂ -A
l ₂ O ₃ , SiO ₂ —MgO, SiO ₂ —ZrO ₂ , S
_{iO 2 -TiO 2, SiO 2 -CaO} , Al 2 O 3 -M
gO, Al ₂ O ₃ —ZrO ₂ , Al ₂ O ₃ —TiO ₂ ,
_{Al 2 O 3 -CaO, ZrO 2} -TiO 2, ZrO 2 -
Complex oxides such as CaO, ZrO ₂ -MgO, TiO ₂ -MgO, inorganic chlorides such as magnesium chloride, inorganic carbonates such as magnesium carbonate, calcium carbonate, strontium carbonate, inorganic salts such as magnesium sulfate, calcium sulfate, barium sulfate Sulfate can be exemplified. Examples of the organic polymer carrier include fine particles such as polyethylene, polypropylene, and polystyrene. Among these, it is desirable to be selected from inorganic oxides, especially SiO ₂ , Al ₂ O ₃ and their composite oxides.

The porous fine particles according to the present invention have an average particle diameter of 1 to 300 μm, preferably 10 to 200 μm.
m, more preferably 20 to 100 μm. Also it is preferable that the specific surface area is in the range of 10 to 1000 m ² / g, more preferably in the range of more 100~800m ² / g, particularly preferably, 200~600m ² /
g. The pore volume is 0.3 to
It is preferably in the range of 3 cc / g, and more preferably 0.5 to
It is more preferably in the range of 2.5 cc / g, and particularly preferably in the range of 1.0 to 2.0 cc / g.

The preferred carrier according to the present invention is SiO.
₂ , the amount of adsorbed water and the amount of surface hydroxyl groups of Al ₂ O ₃ and its composite oxide vary depending on the treatment conditions. As a preferable range of these, the water content is 5% by weight or less, and the amount of surface hydroxyl groups is 1 / (n
m) ² or more. The water content and the amount of surface hydroxyl groups can be controlled by selecting the firing temperature and the firing time, and by treating with an organic aluminum compound, an organic boron compound, or the like.

In the present invention, component (A) or component (B) is preferably supported on the carrier of component (C), and in particular, the organoaluminum oxy compound of component (B) is supported on the carrier of component (C). It is preferable to use it after making it. The method for supporting the organic aluminum oxy compound or its modified product on the carrier used in the present invention is a method in which the organic aluminum compound is supported on the carrier and then reacted with water or an organic polar compound. A method in which a reaction product of an organic aluminum compound and water or an organic polar compound is supported on a carrier. A method in which a carrier is impregnated with water or an organic polar compound, and then an organic aluminum compound is added to generate a reactant on the carrier. Can be exemplified. However, when the organoaluminum compound used for loading is reacted with water,
Trialkylaluminum or aluminoxane, and aluminoxane when reacting with an organic polar compound. In the case of reacting with water among these methods, the method is preferable, and the method is particularly preferable. When reacting with an organic polar compound, the above method is preferable, and a particularly preferable method is preferable.

In carrying the support, the contact between the support and the organoaluminum oxy compound can be carried out in an inert hydrocarbon solvent. Specifically, benzene, toluene, aromatic hydrocarbons such as xylene, pentane, hexane, heptane, octane, aliphatic hydrocarbons such as decane, cyclopentane,
Although an alicyclic hydrocarbon such as cyclohexane can be used, an aromatic hydrocarbon solvent is preferable. The temperature at which the organic aluminum oxy compound is brought into contact with the carrier is usually -50 to 200C, preferably -20 to 100C, more preferably 0 to 50C. The contact time is about 0.05 to 200 hours, preferably about 0.2 to 20 hours.

The amount of the organoaluminum oxy compound or the modified product of the organoaluminum oxy compound supported on the carrier is in the range of 5 × 10 ^{-4 to} 0.05 g atom per 1 g of carrier in terms of aluminum atoms. And more preferably in the range of 5 × 10 ^{−3 to} 0.01 g atom.

The organoaluminum oxy compound (B) supported on the carrier may be used as it is, but may be used as an inert hydrocarbon solvent, for example, aromatic hydrocarbons such as benzene, toluene and xylene, pentane, hexane, heptane and octane. It is preferable to wash with an aliphatic hydrocarbon such as decane or the like, or an alicyclic hydrocarbon such as cyclopentane or cyclohexane before use. The washing temperature at that time is usually -50 to 200
° C, preferably 0 to 150 ° C, more preferably 50 to 1 ° C.
50 ° C.

As the organometallic compound of the component (D) of the present invention, at least two kinds of organometallic compounds composed of at least one of alkyllithium and dialkylmagnesium and trialkylaluminum are used. Among the organometallic compounds (D), alkyllithium includes methyllithium, ethyllithium, n-propyllithium, and n-propyllithium.
It is selected from butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, isopentyllithium, and neopentyllithium. Among them, n-butyllithium, t
tert-Butyl lithium is preferred.

As the dialkylmagnesium, n
-Butylethylmagnesium, di-sec-butylmagnesium, n-butyl-sec-butylmagnesium,
It is selected from di-tert-butylmagnesium, dineopentylmagnesium, and di-n-hexylmagnesium. Of these, n-butylethylmagnesium, di-sec-butylmagnesium, and di-n-hexylmagnesium are preferred.

Further, as the trialkylaluminum, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, , Tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, and tricyclohexyl aluminum. In this, trimethyl aluminum,
Triisobutylaluminum is preferred.

The two organometallic compounds constituting the component (D) may be used in the polymerization by contacting them in advance regardless of the presence or absence of a monomer, or may be used in a reactor in the presence of a polymerization solvent. Although they may be used in contact, they are preferably used after they are brought into contact in advance. When two kinds of organometallic compounds are used in contact with each other, the mixing ratio is such that the number of moles of alkyl lithium is [L], the number of moles of dialkylmagnesium is [M], and the number of moles of trialkylaluminum is [A]. , In the case of a combination of alkyl lithium and trialkyl aluminum,
0),

Embedded image [Wherein, R ^{14 to} R ¹⁷ are a hydrocarbon group having 1 to 20 carbon atoms. It does not matter if the mixing ratio is such that an organometallic compound having the structure represented by the formula in the skeleton exists.
When the value of [L] / [A] is 1/20 to 20, preferably 1/20
10 to 10.

In the case of a combination of a dialkylmagnesium and a trialkylaluminum, the compound represented by the general formula (1)
1)

Embedded image [Wherein, R ^{14 to} R ¹⁸ are a hydrocarbon group having 1 to 20 carbon atoms. The bond between R ¹⁶ and Mg and between R ¹⁷ and Al are missing electron bonds. [M] / [A] may be 1/20 to 2 as long as the mixing ratio is such that the compound represented by
0, preferably 1/10 to 10.

The contact of at least two kinds of organometallic compounds forming the component (D) can be carried out in an inert hydrocarbon solvent. Specifically, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclopentane and cyclohexane can be used. Is preferably an aliphatic hydrocarbon solvent. The component (D) prepared by bringing at least two kinds of organometallic compounds into contact with each other in an inert hydrocarbon solvent may be used as it is as a solution or suspension for polymerization, or after the solvent is distilled off once, the solvent is removed. May be changed and used again as a solution or suspension. The temperature at which at least two kinds of organometallic compounds are brought into contact is usually -50 to 200C, preferably -20 to 100C, more preferably 0 to 50C.
Do with. The contact time is about 0.05 to 200 hours, preferably about 0.2 to 20 hours. The concentration of the component [D] used in the polymerization is 0.05 to 5 mol / liter, preferably 0.1 to 5 mol / L, where the total mol number is the sum of the mol numbers of at least two kinds of organometallic compounds. 1
Perform in mol / l.

The transition metal compound (A) used in the present invention
The contact of the organic aluminum oxy compound (B) with the carrier (C) and the at least two kinds of organometallic compounds (D) may be carried out in the presence or absence of the monomer before the polymerization, or without contact in advance. Each may be introduced into the polymerization system. A preferred embodiment is to use an organic aluminum oxy compound supported on the carrier (C). More specifically, the order of contact between the transition metal compound (A), the organoaluminum oxy compound (B) supported on the carrier (C), and the at least two kinds of organometallic compounds (D) is arbitrarily selected. A method in which the metal compound (A) and the organoaluminum oxy compound (B) supported on the carrier (C) are mixed in advance and then contacted with at least two kinds of organometallic compounds (D), or A method is preferable in which the organoaluminum oxy compound (B) supported on the carrier (C) and the two kinds of organometallic compounds (D) are mixed in advance and then brought into contact with the two kinds of organometallic compounds (D) again. Here, when the transition metal compound (A) and the organoaluminum oxy compound (B) supported on the carrier (C) are pre-contacted with at least two kinds of the organometallic compounds (4), the reaction is usually carried out on an inert carbon. Performed in a hydrogen chloride solvent.

The solvent used in this case includes, for example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane; and alicyclic hydrocarbons such as cyclopentane and cyclohexane. Hydrocarbons can be used. The contact ratio between the transition metal compound (A), the organoaluminum oxy compound (B) and at least two kinds of the organometallic compounds (D) used in the present invention is such that the number of moles of the transition metal compound (A) is [A], The number of moles of aluminum atoms in the aluminum oxy compound (B) is [B], and the sum of the number of moles of two kinds of organometallic compounds used for preparing at least two kinds of organometallic compounds (D) is [D]. Then, the value of [A] / [B] becomes 1 /
5 to 1 / 10,000, preferably 1/10 to 1/2
000, and the value of [A] / [D] is 1 to 1/100,
000, preferably 1/10 to 1 / 10,000.

The olefin monomer used in the present invention includes ethylene alone, propylene alone, ethylene and propylene, or 1-butene, 1-pentene, 1-heptene, 1-octene, 1-decene, Α-olefins such as -methyl-1-pentene; cyclic olefins such as cyclopentene and cyclohexene; and dienes such as butadiene, 1,5-hexadiene, 1,4-hexadiene and 1,4-pentadiene. Comonomers can be copolymerized. At the time of copolymerization, two or more comonomers may be mixed and used for copolymerization with ethylene or propylene.

The polymerization method in which the olefin polymerization catalyst of the present invention can be used can be any of solution polymerization, slurry polymerization, and gas phase polymerization, and is preferably slurry polymerization or gas phase polymerization. Multi-stage polymerization is also possible. In some cases, the polymerization reaction may be performed after preliminarily polymerizing the olefin. The amount of the polymerization catalyst used in the method for producing a polyolefin according to the present invention does not need to be limited, but is usually 10 ⁻⁸ to 10 ^{−2 in} terms of the concentration of the transition metal compound in the polymerization reaction system.
mol / l, preferably in the range of 10 ^-7 to 10 ^-3 mol / l. Although the olefin pressure of the reaction system can be used in a wide range, it is preferably in the range of normal pressure to 50 kg / cm ² , and the polymerization temperature can be used in a wide range.
30 ° C to 200 ° C, preferably 0 ° C to 120 ° C
It is in the range of ° C. The range of 50 to 90 ° C. is particularly preferable in consideration of productivity. The molecular weight at the time of polymerization can be adjusted by known means, for example, by selecting a temperature or introducing hydrogen.

The polymer or copolymer produced using the olefin polymerization catalyst of the present invention has a wide range of molecular weight. That is, JIS K is selected by selecting the metallocene species, polymerization temperature, or adjusting the amount of hydrogen introduced during polymerization.
-7210. "Flow test method for thermoplastics"
The melt flow rate under the condition 14 (190 ° C., load 21.6 kgf: hereinafter referred to as HLMFR) in Table 1 is 0.
From the high molecular weight of 0001 g / 10 min, condition 4
(190 ° C., load 2.16 kgf: hereinafter referred to as MFR) and a melt flow rate of 10,000 g / 10
Min. low molecular weight can be manufactured. Further, the polymer or copolymer according to the present invention is in the form of particles having an average particle diameter of about 200 to 800 μm, and has a bulk density of about 0.1 μm.
It is as high as 30 to 0.45 g / cc, and is characterized by excellent powder properties. Further, the polymer or copolymer produced by using the catalyst of the present invention has a low content of catalyst component residue that adversely affects practical properties. In addition, the copolymer produced using the olefin polymerization catalyst of the present invention has essentially excellent randomness and a narrow composition distribution. Therefore, the obtained copolymer resin has excellent properties such as excellent transparency, a small amount of extractable components, and excellent low-temperature heat sealability.

[0049]

【Example】

(Reference Example) A transition metal compound of the component (A) used in the present invention and an organometallic compound having a component represented by the general formula (10) or (11) in the structure as the component (D) The result of performing ethylene polymerization using this is shown.

[Table 1] Note) (n-BuCp) ₂ ZrCl ₂ : bis-n-butylcyclopentadienyl zirconium dichloride

Next, the present invention will be described specifically with reference to examples. The melt flow rate was measured according to JIS K-7210 under the condition 4 in Table 1 and the MFR was measured.
Was used to measure HLMFR.

(Example 1) [Preparation of aluminoxane] 50 liters of dry toluene was added to a 200 liter reactor sufficiently purged with nitrogen, and 2.5 k of Al ₂ (SO ₄ ) ₃ .14H ₂ O was added thereto.
g was suspended. After cooling to −20 ° C., 30 mol of trimethylaluminum (27 l of a 1.11 mol / l toluene solution) was added over 1 hour, and the mixture was heated to 80 ° C. and stirred for 12 hours. Thereafter, the aluminum sulfate compound was removed under a nitrogen atmosphere, and 70 L of a 0.35 mol / L methylaluminoxane toluene solution was recovered. Repeat this operation again to get 0.35m
ol / liter of a toluene solution of methylaluminoxane was combined to obtain 140 liter.

[Supporting of aluminoxane on carrier] Toluene was added to a 200-liter reactor purged with nitrogen.
0 liters and 1.8 kg of silica (calculated from Davison 952 at 300 ° C. for 4 hours) are added, and the above-mentioned methylaluminoxane [0.35M (in terms of Al atom) is added to the suspension.
Toluene solution, methyl group / aluminum atom = 1.3
0] and stirred at room temperature for 60 minutes. Thereafter, the solvent was distilled off under reduced pressure. 60 L of hexane was added to obtain a hexane slurry of a solid component. This operation was performed again, and the total solid component was 5.2 kg.
Obtained a hexane slurry of a solid component suspended in 120 liters of hexane.

[Polymerization] Internal volume 290 sufficiently purged with nitrogen
Isobutane was supplied to a 1 liter loop polymerization reactor, and after filling the polymerization reactor with isobutane, the temperature was raised to 70 ° C. while stirring. Then, ethylene is divided into 10 k
g / cm ^2, and a hexane solution (0.2 g / l) of bis (normal butylcyclopentadienyl) zirconium dichloride was further supplied at 330 ml / h.
r, 2.0 g / hr of the solid catalyst component prepared above, a hexane solution of a mixture of butylethylmagnesium and triisobutylaluminum (mixing molar ratio [Mg] / [Al]
= 0.2 / 1, prepared by stirring in hexane at 20 ° C for 30 minutes, total concentration 0.5 mol / l) at 142 ml / h
The polymerization was started by continuously supplying at the rate of r. While continuously supplying isobutane as a polymerization solvent at a rate of 51.5 kg / hr, the polymerization conditions of the polymerization reactor were adjusted to an ethylene partial pressure of 1
0 kg / cm ² , polymerization temperature 70 ° C., residence time 1 hour, linear velocity of polymer slurry in polymerization reactor 6 m / sec
Held. The liquid composition in the polymerization reactor was ethylene 7.7.
Mol%, isobutane 91.6 mol%.

As a result, 18.9 kg / h under the above conditions
r, polyethylene is produced, and 19
The MFR at 0 ° C. and a load of 2.16 kgf / cm ² is 0.1
8g / 10min, 190 ° C, load 21.6kg
The ratio of HLMFR to MFR at f / cm ² (HLMFR /
MFR) was 15.8 and the density was 0.9396 g / ml. The bulk density of the obtained polymer is 0.33 g / c.
c, the average particle size was 340 μm. 1 under the above polymerization conditions
After polymerization for 00 hours, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

(Example 2) Internal volume 2 sufficiently purged with nitrogen
Isobutane was supplied to a 90-liter loop polymerization reactor. After filling the polymerization reactor with isobutane, the temperature was raised to 70 ° C. while stirring. Then, ethylene was added at a partial pressure of 1
It was supplied so as to be 0 kg / cm ² . Further, 1-hexene was supplied so that the concentration of 1-hexene in the polymerization reactor was 0.35 (molar ratio) with respect to ethylene, and a hexane solution of bis (normalbutylcyclopentadienyl) zirconium dichloride was further supplied. (0.2 g / liter) was added at 330 ml / hr, and the solid catalyst component prepared above was added at 2.0 ml / hr.
g / hr, a hexane solution of a mixture of butylethylmagnesium and triisobutylaluminum (mixing molar ratio [M
g] / [Al] = 0.1 / 1, 30 in hexane at 20 ° C.
The mixture was prepared by stirring for 1 minute, and continuously supplied at a rate of 142 ml / hr (total concentration: 0.5 mol / l) to initiate polymerization. 51.1 kg / hr of isobutane as a polymerization solvent
, The polymerization conditions of the polymerization vessel were set to ethylene partial pressure of 10 kg / cm ² , polymerization temperature of 70 ° C., residence time of 1 hour, and linear velocity of the polymer slurry in the polymerization reactor to 6
m / sec. The liquid composition in the polymerization reactor was ethylene 7.4 mol%, 1-hexene 2.2 mol%, and isobutane 90.3 mol%.

As a result, 16.6 kg / h under the above conditions
r, polyethylene is produced and the MF of this polymer is
R is 4.30 g / 10 min, HLMFR and MF
The ratio of R (HLMFR / MFR) is 15.6 and the density is 0.
It was 9290 g / ml. The bulk density of the obtained polymer was 0.33 g / cc, and the average particle size was 310 μm. After 100 hours of polymerization under the above polymerization conditions, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 3 A hexane solution of a mixture of butylethylmagnesium and triisobutylaluminum (mixing molar ratio [Mg] / [Al] = 0.4 / 1, prepared by stirring in hexane at 20 ° C. for 30 minutes) Total concentration 0.5mol
/ Liter), and the same operation as in Example 1 was performed except that the solution was continuously supplied at a rate of 142 ml / hr. As a result, polyethylene was produced at a rate of 17.6 kg / hr under the above conditions, and the MFR of this polymer was 0.18 g / hr.
10 minutes and the ratio of HLMFR to MFR (HLMF
R / MFR) is 15.7, density is 0.9395 g / ml
Met. The bulk density of the obtained polymer was 0.32 g.
/ Cc, and the average particle size was 320 μm. After polymerization for 100 hours under the above polymerization conditions, when the polymerization reactor was opened,
There was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 4 A hexane solution of a mixture of butylethylmagnesium and triisobutylaluminum (mixing molar ratio [Mg] / [Al] = 0.4 / 1, prepared by stirring in hexane at 20 ° C. for 30 minutes) Total concentration 0.5mol
/ Liter), and the same operation as in Example 2 was performed except that the solution was continuously supplied at a rate of 142 ml / hr. As a result, polyethylene was produced at a rate of 15.9 kg / hr under the above conditions, and the MFR of this polymer was 3.68 g / hr.
10 minutes and the ratio of HLMFR to MFR (HLMF
R / MFR) is 15.8, density is 0.9321 g / ml
Met. The bulk density of the obtained polymer was 0.32 g.
/ Cc, and the average particle size was 320 μm. After polymerization for 100 hours under the above polymerization conditions, when the polymerization reactor was opened,
There was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 5 A hexane solution of a mixture of butylethylmagnesium and triisobutylaluminum (mixing molar ratio [Mg] / [Al] = 1/1, prepared by stirring in hexane at 20 ° C. for 30 minutes, total concentration) 0.5 mol / l), and the same operation as in Example 1 was performed except that the solution was continuously supplied at a rate of 142 ml / hr. As a result, polyethylene was produced at a rate of 17.9 kg / hr under the above conditions, and the MFR of this polymer was 0.20 g / 1.
0 min, and the ratio of HLMFR to MFR (HLMFR
/ MFR) was 16.1 and the density was 0.9395 g / ml. The bulk density of the obtained polymer was 0.34 g /
cc, and the average particle size was 330 μm. After 100 hours of polymerization under the above polymerization conditions, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 6 A hexane suspension of a mixture of normal butyl lithium and triisobutyl aluminum (mixing molar ratio [Li] / [Al] = 0.1 / 1, stirred in hexane at 20 ° C. for 30 minutes) Preparation, total concentration 0.5mol
/ Liter), and the same operation as in Example 1 was performed except that the solution was continuously supplied at a rate of 142 ml / hr. As a result, polyethylene was produced at a rate of 18.9 kg / hr under the above conditions, and the MFR of this polymer was 0.17 g / hr.
10 minutes and the ratio of HLMFR to MFR (HLMF
R / MFR) is 16.3, density is 0.9396 g / ml
Met. The bulk density of the obtained polymer was 0.34 g.
/ Cc, and the average particle size was 340 μm. After polymerization for 100 hours under the above polymerization conditions, when the polymerization reactor was opened,
There was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 7 Hexane suspension of a mixture of normal butyl lithium and triisobutyl aluminum (mixing molar ratio [Li] / [Al] = 0.1 / 1, stirred in hexane at 20 ° C. for 30 minutes) Preparation, total concentration 0.5mol
/ Liter), and the same operation as in Example 2 was performed except that the solution was continuously supplied at a rate of 142 ml / hr. As a result, polyethylene was produced at a rate of 22.5 kg / hr under the above conditions, and the MFR of this polymer was 0.53 g / hr.
10 minutes and the ratio of HLMFR to MFR (HLMF
R / MFR) is 15.6, density is 0.9122 g / ml
Met. The bulk density of the obtained polymer was 0.34 g.
/ Cc, and the average particle size was 330 μm. After polymerization for 100 hours under the above polymerization conditions, when the polymerization reactor was opened,
There was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 8 A hexane suspension of a mixture of normal butyl lithium and triisobutyl aluminum (mixing molar ratio [Li] / [Al] = 0.2 / 1, stirred in hexane at 20 ° C. for 30 minutes) Preparation, total concentration 0.5mol
/ Liter), and the same operation as in Example 1 was performed except that the solution was continuously supplied at a rate of 142 ml / hr. As a result, polyethylene was produced at a rate of 19.2 kg / hr under the above conditions, and the MFR of this polymer was 0.13 g / hr.
10 minutes and the ratio of HLMFR to MFR (HLMF
R / MFR) is 15.5, density is 0.9388 g / ml
Met. The bulk density of the obtained polymer was 0.34 g.
/ Cc, and the average particle size was 320 μm. After polymerization for 100 hours under the above polymerization conditions, when the polymerization reactor was opened,
There was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 9 A hexane suspension of a mixture of normal butyl lithium and triisobutyl aluminum (mixing molar ratio [Li] / [Al] = 0.2 / 1, stirred in hexane at 20 ° C. for 30 minutes) Preparation, total concentration 0.5mol
/ Liter), and the same operation as in Example 2 was performed except that the solution was continuously supplied at a rate of 142 ml / hr. As a result, polyethylene was produced at a rate of 21.3 kg / hr under the above conditions, and the MFR of this polymer was 0.63 g / hr.
10 minutes and the ratio of HLMFR to MFR (HLMF
R / MFR) is 15.8, and density is 0.9177 g / ml.
Met. The bulk density of the obtained polymer was 0.34 g.
/ Cc, and the average particle size was 320 μm. After polymerization for 100 hours under the above polymerization conditions, when the polymerization reactor was opened,
There was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 10 A hexane suspension of a mixture of normal butyllithium and triisobutylaluminum (mixing molar ratio [Li] / [Al] = 0.3 / 1, stirred in hexane at 20 ° C. for 30 minutes) Preparation, total concentration 0.5mol
/ Liter), and the same operation as in Example 1 was performed except that the solution was continuously supplied at a rate of 142 ml / hr. As a result, polyethylene was produced at a rate of 16.8 kg / hr under the above conditions, and the MFR of this polymer was 0.13 g / hr.
10 minutes and the ratio of HLMFR to MFR (HLMF
R / MFR) is 15.4, density is 0.9392 g / ml
Met. The bulk density of the obtained polymer was 0.34 g.
/ Cc, and the average particle size was 330 μm. After polymerization for 100 hours under the above polymerization conditions, when the polymerization reactor was opened,
There was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 11 A hexane suspension of a mixture of normal butyllithium and triisobutylaluminum (mixing molar ratio [Li] / [Al] = 0.3 / 1, stirred in hexane at 20 ° C. for 30 minutes) Preparation, total concentration 0.5mol
/ Liter), and the same operation as in Example 2 was performed except that the solution was continuously supplied at a rate of 142 ml / hr. As a result, polyethylene was produced at a rate of 17.2 kg / hr under the above conditions, and the MFR of this polymer was 1.00 g / hr.
10 minutes and the ratio of HLMFR to MFR (HLMF
R / MFR) is 15.3, density is 0.9165 g / ml
Met. The bulk density of the obtained polymer was 0.34 g.
/ Cc, and the average particle size was 330 μm. After polymerization for 100 hours under the above polymerization conditions, when the polymerization reactor was opened,
There was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 12 A hexane suspension of a mixture of normal butyllithium and triisobutylaluminum (mixing molar ratio [Li] / [Al] = 0.7 / 1, stirred in hexane at 20 ° C. for 30 minutes) Preparation, total concentration 0.5mol
/ Liter), and the same operation as in Example 1 was performed except that the solution was continuously supplied at a rate of 142 ml / hr. As a result, polyethylene was produced at a rate of 15.4 kg / hr under the above conditions, and the MFR of this polymer was 0.21 g / hr.
10 minutes and the ratio of HLMFR to MFR (HLMF
R / MFR) is 15.8, density is 0.9390 g / ml
Met. The bulk density of the obtained polymer was 0.34 g.
/ Cc, and the average particle size was 340 μm. After polymerization for 100 hours under the above polymerization conditions, when the polymerization reactor was opened,
There was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 13 A hexane suspension of a mixture of normal butyllithium and triisobutylaluminum (mixing molar ratio [Li] / [Al] = 0.7 / 1, stirred in hexane at 20 ° C. for 30 minutes) Preparation, total concentration 0.5mol
/ Liter), and the same operation as in Example 2 was performed except that the solution was continuously supplied at a rate of 142 ml / hr. As a result, polyethylene was produced at a rate of 12.6 kg / hr under the above conditions, and the MFR of this polymer was 2.60 g / hr.
10 minutes and the ratio of HLMFR to MFR (HLMF
R / MFR) is 16.3, density is 0.9230 g / ml
Met. The bulk density of the obtained polymer was 0.35 g.
/ Cc, and the average particle size was 330 μm. After polymerization for 100 hours under the above polymerization conditions, when the polymerization reactor was opened,
There was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 14 A hexane suspension of a mixture of normal butyl lithium and triisobutyl aluminum (mixing molar ratio [Li] / [Al] = 1/1, prepared by stirring in hexane at 20 ° C. for 30 minutes, The same operation as in Example 1 was performed, except that the total concentration was 0.5 mol / liter) and the mixture was continuously supplied at a rate of 142 ml / hr. As a result, polyethylene was produced at a rate of 14.8 kg / hr under the above conditions, and the MFR of this polymer was 0.20 g / 1.
0 min, and the ratio of HLMFR to MFR (HLMFR
/ MFR) was 16.3 and the density was 0.9397 g / ml. The bulk density of the obtained polymer was 0.35 g /
cc, and the average particle size was 320 μm. After 100 hours of polymerization under the above polymerization conditions, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 15 A hexane suspension of a mixture of normal butyl lithium and triisobutyl aluminum (mixing molar ratio [Li] / [Al] = 1/1, prepared by stirring in hexane at 20 ° C. for 30 minutes, The same operation as in Example 2 was performed, except that the total concentration was 0.5 mol / liter) and the solution was continuously supplied at a rate of 142 ml / hr. As a result, polyethylene was produced at a rate of 12.8 kg / hr under the above conditions, and the MFR of this polymer was 2.50 g / 1.
0 min, and the ratio of HLMFR to MFR (HLMFR
/ MFR) was 16.1 and the density was 0.9238 g / ml. The bulk density of the obtained polymer was 0.33 g /
cc, and the average particle size was 320 μm. After 100 hours of polymerization under the above polymerization conditions, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 16 A hexane suspension of a mixture of normal butyl lithium and triethylaluminum (mixing molar ratio [Li] / [Al] = 0.2 / 1, prepared by stirring in hexane at 20 ° C. for 30 minutes) , A total concentration of 0.5 mol / l), and the same operation as in Example 1 was performed except that the solution was continuously supplied at a rate of 142 ml / hr. As a result, polyethylene was produced at a rate of 15.0 kg / hr under the above conditions, and the MFR of this polymer was 0.18 g / 1.
0 min, and the ratio of HLMFR to MFR (HLMFR
/ MFR) was 16.3 and the density was 0.9391 g / ml. The bulk density of the obtained polymer was 0.33 g /
cc, and the average particle size was 320 μm. After 100 hours of polymerization under the above polymerization conditions, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 17 A hexane suspension of a mixture of normal butyl lithium and triethylaluminum (mixing molar ratio [Li] / [Al] = 0.2 / 1, prepared by stirring in hexane at 20 ° C. for 30 minutes) , A total concentration of 0.5 mol / liter), and the same operation as in Example 2 was performed except that the solution was continuously supplied at a rate of 142 ml / hr. As a result, polyethylene was produced at a rate of 13.2 kg / hr under the above conditions, and the MFR of this polymer was 3.00 g / hr.
0 min, and the ratio of HLMFR to MFR (HLMFR
/ MFR) was 15.9 and the density was 0.9226 g / ml. The bulk density of the obtained polymer was 0.32 g /
cc, and the average particle size was 310 μm. After 100 hours of polymerization under the above polymerization conditions, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 18 Instead of bis (normalbutylcyclopentadienyl) zirconium dichloride,
The same operation as in Example 12 was performed except that bis (normal butyl cyclopentadienyl) hafnium dichloride was used. As a result, polyethylene was produced at a rate of 10.1 kg / hr under the above conditions, the MFR of this polymer was 0.06 g / 10 min, the ratio of HLMFR to MFR (HLMFR / MFR) was 15.5, and the density was 0.93
It was 95 g / ml. The bulk density of the obtained polymer was 0.33 g / cc, and the average particle size was 300 μm.
After 100 hours of polymerization under the above polymerization conditions, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

(Example 19) Propylene was supplied to a loop polymerization reactor having an inner volume of 290 liters which had been sufficiently purged with nitrogen, and the polymerization reactor was filled with propylene. Thereafter, the temperature was raised to 50 ° C while stirring. Next, 330 ml / h of a toluene solution of dimethylsilylenebis (2-methylindenyl) zirconium dichloride (0.4 g / liter) was added.
r, 4.0 g / hr of the solid catalyst component prepared above, a hexane suspension of a mixture of normal butyl lithium and triisobutyl aluminum (mixing molar ratio [Li] / [Al]
= 0.3 / 1, prepared by stirring in hexane at 20 ° C for 30 minutes, total concentration 0.5 mol / l) at 142 ml / h
The polymerization was started by continuously supplying at the rate of r. The polymerization temperature was kept at 50 ° C., the residence time was 1 hour, and the linear velocity of the polymer slurry in the polymerization reactor was kept at 6 m / sec while propylene as a monomer was continuously supplied at a rate of 12.0 kg / hr. As a result, polypropylene was produced at a rate of 11.6 kg / hr under the above conditions, and 230% of this polymer was produced.
MFR at 2.16 kgf / cm ² and 2.16 kgf / cm ²
g / 10 min. The bulk density of the obtained polymer was 0.40 g / cc, and the average particle size was 320 μm. After 100 hours of polymerization under the above polymerization conditions, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 20 After 140 kg of polyethylene as a seed polymer was charged into a gas-phase reactor having an inner volume of 3900 liters which had been sufficiently purged with nitrogen, the temperature was raised to 70 ° C. while flowing nitrogen. Then, the total pressure in the reactor was 21
11. Ethylene was supplied so as to be 0.1 kg / cm ^2, and 194 ml / hr of a hexane solution (0.3 g / liter) of bis (normalphthylcyclopentadienyl) zirconium dichloride was added. 5g
/ Hr, hexane suspension of a mixture of normal butyl lithium and triisobutyl aluminum (mixing molar ratio [L
i] / [Al] = 0.3 / 1, 30 in hexane at 20 ° C.
(Total concentration 0.5 mol / l)
The polymerization was started by continuously feeding at a rate of 40 ml / hr. While supplying ethylene at a rate of 30 kg / hr, the polymerization conditions of the reactor were adjusted to a total pressure of 21 kg / cm ² and a polymerization temperature of 7
It was kept at 0 ° C. and a residence time of 5 hours. As a result, polyethylene was produced at a rate of 32.5 kg / hr under the above conditions, the MFR of this polymer was 0.25 g / 10 min, and the ratio to HLMFR (HLMFR / MFR) was 1
6.5, the density was 0.941 g / ml. The bulk density of the obtained polymer was 0.35 g / cc, and the average particle size was 340 μm. After the polymerization under the above polymerization conditions for 100 hours, when the reactor polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Example 21 Isobutane was supplied to a loop polymerization reactor having an internal volume of 2901, which had been sufficiently purged with nitrogen, and the polymerization reactor was filled with isobutane. Thereafter, the temperature was raised to 70 ° C. with stirring. Then, ethylene was added at a partial pressure of 10
Kg / cm ^2, and hydrogen was supplied at a concentration of 5.5 × 10
^-4 (polymerization ratio). Further, a hexane solution (0.2 g / 1) of bis (normalbutylcyclopentadienyl) zirconium dichloride was added to 330 ml /
hr, 2.0 g / hr of the solid catalyst component prepared above, a hexane suspension of a mixture of normal butyl lithium and triisobutyl aluminum (molar ratio [Li] / [Al]
= 0.3 / 1, prepared by stirring for 30 minutes at 20 ° C in hexane, total concentration 0.5 mol / l) at 142 ml / h
The polymerization was started by continuously supplying at the rate of r. While continuously supplying isobutane as a polymerization solvent at a rate of 51.5 kg / hr, the polymerization conditions of the polymerization vessel were adjusted to an ethylene partial pressure of 10K.
g / cm ² , the polymerization temperature was 70 ° C., the residence time was 1 hour, and the linear velocity of the polymer slurry in the polymerization vessel was kept at 6 m / sec. As a result, polyethylene was produced at a rate of 14.0 kg / hr under the above conditions, and the MFR of the polymer at 190 ° C. under a load of 2.16 kg was 1240.0 g / 10 mi.
n, the MFR at 190 ° C. and the load of 21.6 kg was 1
MFR ratio at 90 ° C. under a load of 2.16 kg (HLMFR
/ MFR) was 17.8 and the density was 0.9702 g / ml. The bulk density of the obtained polymer was 0.34 g /
cc, and the average particle size was 340 μm. After 100 hours of polymerization under the above polymerization conditions, when the polymerization reactor was started, there was no adhesion of the polymer to the polymerization reactor wall and the stirring impeller.

Comparative Example 1 Instead of a hexane solution of a mixture of butylethylmagnesium and triisobutylaluminum, a hexane solution of triisobutylaluminum (0.5 mol / l) was used and continuously supplied at a rate of 142 ml / hr. The same operation as in Example 1 was performed except for the above. As a result, polyethylene was produced at a rate of 15.6 kg / hr under the above conditions, and the MFR of this polymer at 190 ° C. under a load of 2.16 Kg was 0.18 g / 10 min, and at 190 ° C. under a load of 21.6 kg. MFR of 190
° C, the ratio of MFR at a load of 2.16 kg (HLMFR / M
FR) was 16.2 and the density was 0.9392 g / ml. The bulk density of the obtained polymer is 0.25 g / c.
c, the average particle size was 200 μm. Under the above polymerization conditions, a load was applied to the stirring pump after 30 hours, and the temperature control of the polymerization reactor became impossible, so the polymerization was stopped. When the polymerization reactor was opened, adhesion of a polymer having a thickness of 2 to 3 mm was observed on the polymerization reactor wall and the stirring impeller.

Comparative Example 2 Instead of a hexane solution of a mixture of butylethylmagnesium and triisobutylaluminum, a hexane solution of trinormal butylaluminum (0.5 mol / l) was continuously used at a rate of 142 ml / hr. The same operation as in Example 1 was performed except that the supply was performed. As a result, polyethylene was produced at a rate of 15.8 kg / hr under the above conditions, and 190
0.17g / 10m in MFR at 2.16Kg
and the ratio of the MFR at 190 ° C. and a load of 21.6 Kg to the MFR at 190 ° C. and a load of 2.16 Kg (HLMF
R / MFR) is 16.3, density is 0.9406 g / ml
Met. The bulk density of the obtained polymer was 0.27 g.
/ Cc, and the average particle size was 220 μm. Under the above polymerization conditions, after the polymerization was performed for 100 hours, when the polymerization reactor was released, a thickness of 0.3 to 0.3 mm was applied to the polymerization reactor wall and the stirring impeller.
Adhesion of the polymer of about 0.5 mm was observed.

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

The present invention provides a novel olefin polymerization catalyst comprising a metallocene compound, an organoaluminum oxy compound, a carrier, at least one kind of alkyllithium and dialkylmagnesium and at least two kinds of organometallic compounds of trialkylaluminum. The present invention relates to a method for producing an olefin polymer used, which has sufficient polymerization activity by using a low amount of expensive methylaluminoxane and produces a polyolefin having an extremely wide range of molecular weight depending on the amount of hydrogen introduced during polymerization. Has the ability to do. The catalyst of the present invention can be used in any of solution polymerization, slurry polymerization, and gas phase polymerization, but the most important feature is that a conventional high-performance metallocene catalyst is problematic when used in a slurry method. Adhesion to the reactor wall can be greatly reduced while maintaining the ability to produce a polymer having a high polymerization activity and a wide range of molecular weights. The metallocene catalyst can be economically applied to slurry polymerization, and industrially stable production has become possible.

[Brief description of the drawings]

FIG. 1 is a flow chart of the catalyst of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroyuki Ohira, Oita, Oita City, Oita Prefecture, Japan 2 Oita Research Laboratory, Japan Polyolefin Co., Ltd. (72) Inventor, Shintaro Inazawa Oita City, Oita City, Oita City, 2 Onaka, Japan Oita Research Laboratory, Polyolefin Co., Ltd.

Claims (5)

[Claims] (A) a compound represented by the following general formula (1): General formula (2), General formula (3), General formula (4), General formula (5), Formula (6) or General formula (7) [Wherein, R ^{1 to} R ¹⁰ are hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkylsilyl group or an alkylgermyl group, which may be the same or different, and R ¹¹ has 1 to 20 carbon atoms. Wherein each X is carbon or nitrogen and may be the same or different, each Q is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, alkoxy, allyloxy, Siloxy or halogen, which may be the same or different, and Y is -O-, -S-, -NR
¹² -, - PR ¹² - a and, R ¹² is hydrogen, having from 1 to 20 carbon atoms
, A halogenated alkyl or aryl halide. ), Me is a transition metal of Group 3, 4, 5, or 6 of the periodic table, and p is 0 or 1. And (B) an organoaluminum oxy compound,
An olefin polymerization catalyst comprising (C) a carrier and (D) at least one kind of alkyllithium and dialkylmagnesium and at least two kinds of organometallic compounds of trialkylaluminum. 2. The olefin polymerization catalyst according to claim 1, wherein 5 × 10 ^{−4 to} 0.05 g atom of the organic aluminum oxy compound is supported per 1 g of the carrier in terms of aluminum atoms. 3. At least two kinds of organometallic compounds (D)
Is an at least two kinds of organometallic compounds (D) selected from normal butyllithium and butylethylmagnesium and trialkylaluminum, the olefin polymerization catalyst according to any one of claims 1 to 2. 4. The mole number [A] of the transition metal compound of the component (A), the mole number [B] of the aluminum atom in the organoaluminum oxy compound of the component (B), and at least 2 used in preparing the component (D). When the sum [D] of the number of moles of the kinds of organometallic compounds is defined as: 1 / 10,000 <[A] / [B] <1/5 1 / 100,000 <[A] / [D] <1 The olefin polymerization catalyst according to any one of claims 1 to 3, which is blended in a ratio. 5. The component (A) according to claim 1, a component (B) an organoaluminum oxy compound,
A method for producing a polyolefin-based polymer, comprising polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst comprising (C) a carrier and component (D) at least two kinds of organometallic compounds.