JPH10120721A - Polymerization catalyst and production of polyolefin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a highly active polymerization catalyst composed of a specific transition metal compound and an organoaluminum oxy compound, etc., and having high activity and good powder properties even if expensive methylaluminoxane is used in a small amount. SOLUTION: This catalyst comprises (A) a transition metal compound represented by formulae I to III [R<1> to R<10> are each H, a 1-20C hydrocarbon, an alkylsilyl or an alkylgermyl; Q is H, a 1-20C hydrocarbon, an alkoxy, an aryloxy, siloxy or a hologen; Y is O, S, etc.; Me is a transition metal of the groups III to VI of the periodic table; (P) is 0 or 1], (B) an organoaluminum oxy compound, (C) a support and (D) an organometallic compound which is a reaction product obtained by mixing (i) lithium with (ii) a trialkylaluminum and/or an organic compound which is a reaction roduct obtained by mixing (iii) an alkylmagnesium halide with the component (ii). Furthermore, the component B in an amount of 5×10<-4> to 0.05 gram atom, expressed in terms of Al atom, is preferably supported on 1g support.

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 - (} . R 12 represents hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated alkyl or halogenated aryl) an electron donor ligand represented by, Me
Is a transition metal of group 3, 4, 5, or 6 of the periodic table;
p is 0 or 1. And (B) an organoaluminum oxy compound, (C) a carrier and (D) a reaction product obtained by mixing lithium and trialkylaluminum, and / or
Or an olefin polymerization catalyst comprising an organometallic compound which is a reaction product obtained by mixing an alkyl magnesium halide and a trialkyl aluminum,

The olefin polymerization catalyst according to the above, wherein the organoaluminum oxy compound is supported in an amount of 5 × 10 ^{−4 to} 0.05 gram atom per 1 gram of the carrier in terms of aluminum atom, the transition metal compound of the component (A) [A], the number of moles of aluminum atoms [B] in the organoaluminum oxy compound of the component (B) and the number of moles [D] of the organometallic compound of the component (D), 1/5> [A ] / [B]> 1 / 10,000 1> [A] / [D]> 1 / 100,000 The olefin polymerization catalyst according to any one of the above,

The component (A) described above, a transition metal compound,
Component (B) an organoaluminum oxy compound, (C) a carrier and component (D) an organometallic compound which is a reaction product obtained by mixing lithium and trialkylaluminum, and / or an alkylmagnesium halide and trialkylaluminum. In the presence of an olefin polymerization catalyst comprising an organometallic compound that is a reaction product
The above-mentioned problems have been solved by developing a method for producing a polyolefin polymer in which olefin is polymerized or copolymerized.

[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 such as alkyl having 1 to 20 carbon atoms, alkenyl, aryl, araryl, aralkyl, alicyclic, etc., an alkylsilyl group or an alkylgermyl group, each of which may be the same or different well, R ¹¹ is an alkylene group, alkylgermylene alkylene or alkyl silylene having 1-20 carbon atoms, each X
Is carbon or nitrogen, which 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 - (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 of Groups 3, 4, 5, or 6 of the periodic table (according to the inorganic chemical nomenclature 1990 rule), preferably a transition metal element of Group 4 of the periodic table;
That is, it is preferably selected from titanium, zirconium and hafnium, and particularly preferably zirconium and hafnium.

The ligands having these substituents include:
For example, a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n-butylcyclopentadienyl group, a t-butylcyclopentadienyl group, a trimethylsilylcyclopentadienyl group,
Examples thereof include an alkyl-substituted cyclopentadienyl group such as a dimethylcyclopentadienyl group and a pentamethylcyclopentadienyl group, an indenyl group having or not having a similar substituent, and a fluorenyl group.

In 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. , A dimethylsilylene group, a diphenylsilylene group, and the like. Examples of the alkylgermylene group include a dimethylgermylene group, a diphenylgermylene group, and the like.

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 (n-butyl) amidinato) zirconium dichloride, isopropylidenenebis (N, N′-bis (trimethylsilyl) amidinato)
Zirconium dichloride, isopropylidene bis (N,
N'-bis (phenyl) amidinato) zirconium dichloride, 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 aluminoxane is represented by the general formula (8) (R ¹⁹ ) ₂ Al- [O-Al (R ¹⁹ )] _m- (R ¹⁹ ) (8) or the general formula (9) Organoaluminum compound represented by

Embedded image It is. Wherein R ¹⁹ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated alkyl group or a 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 kind 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), 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 and reacting an organic aluminum oxy compound, for example, aluminoxane, with the above organic polar compound in a hydrocarbon solvent. The amount of the organic polar compound having at least one atom selected from the group consisting of phosphorus, nitrogen, sulfur and oxygen used in this reaction and having no active hydrogen is the same as the amount of aluminum in the organic aluminum oxy compound. 0.0001-0.5 mol, preferably 0.001-0.3 mol, more preferably 0.0
It is desirable to use from 0.05 to 0.2 mol.

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, it is preferable that at least one of the component (A) and the component (B) is supported on a carrier of the component (C). It is preferable to use it after being supported on the carrier of the above). As a method of supporting the organic aluminum oxy compound or its modified product used in the present invention on a carrier, a method of supporting an organic aluminum compound on a carrier and then reacting with water or an organic polar compound, Examples of the method include a method of supporting a reaction product with water or an organic polar compound on a carrier, a method of impregnating the carrier with water or an organic polar compound, adding an organoaluminum compound, and forming a reaction product on the support. 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.

The contact between the carrier and the organoaluminum oxy compound can be carried out in an inert hydrocarbon solvent. Specifically, aromatic hydrocarbons such as benzene, toluene, xylene and the like, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclopentane and cyclohexane can be used. Is preferably an aromatic hydrocarbon solvent. The temperature at which the carrier and the organoaluminum oxy compound are brought into contact is usually -50 to 2
The reaction is carried out at 00 ° C, preferably at -20 to 100 ° C, more preferably at 0 to 50 ° C. The contact time is 0.05
It is about 200 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.

The component (D) of the present invention is an organometallic compound which is a reaction product obtained by mixing lithium and trialkylaluminum, and / or a reaction product obtained by mixing alkylmagnesium halide and trialkylaluminum. It is an organometallic compound. The alkyl group in these compounds is a saturated chain hydrocarbon group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group,
Propyl, butyl, isobutyl, t-butyl,
It is an alkyl group such as 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.

The organometallic compounds obtained by mixing lithium and trialkylaluminum include those represented by the general formula (10):

Embedded image For example, lithium tetramethyl aluminate, lithium tetraethyl aluminate, lithium-n-butyl aluminate, lithium tetraisobutyl aluminate, lithium tetrapentyl aluminate, lithium tetrahexyl aluminate, lithium tetraoctyl aluminate and the like can be exemplified.

The organometallic compound obtained by mixing the alkylmagnesium halide and the trialkylaluminum includes those represented by the general formula (11):

Embedded image Many organometallic compounds are produced depending on the type of alkyl magnesium halide and trialkyl aluminum used in the reaction. Hereinafter, specific examples of the organometallic compound having the structure represented by the general formula (11) in the skeleton will be exemplified.

Examples of the organometallic compound having the structure represented by the general formula (11) in its skeleton include methylmagnesium tetramethylaluminate, methylmagnesium methyltriethylaluminate, methylmagnesium methyltripropylaluminate, methylmagnesium methyltriethylaluminate. -N-butyl aluminate, methyl magnesium methyl triisobutyl aluminate, methyl magnesium methyl tripentyl aluminate, methyl magnesium methyl trihexyl aluminate, methyl magnesium methyl trioctyl aluminate, ethyl magnesium ethyl trimethyl aluminate, ethyl magnesium tetraethyl Aluminate, ethyl magnesium ethyl tripropyl aluminate, ethyl magnesium ethyl tri-n
-Butyl aluminate, ethyl magnesium ethyl triisobutyl aluminate, ethyl magnesium ethyl tripentyl aluminate, ethyl magnesium ethyl trihexyl aluminate, ethyl magnesium ethyl trioctyl aluminate, propyl magnesium propyl trimethyl aluminate, propyl magnesium propyl triethyl aluminate , Propyl magnesium tetrapropyl aluminate, propyl magnesium propyl tri-n-butyl aluminate, propyl magnesium propyl triisobutyl aluminate, propyl magnesium propyl tripentyl aluminate, propyl magnesium propyl trihexyl aluminate, propyl magnesium propyl trioctyl aluminate , N-butylmag N-butyl trimethyl aluminate, n-butyl magnesium n-butyl triethyl aluminate, n-butyl magnesium-n-butyl tripropyl aluminate, n-butyl magnesium tetra-n-butyl aluminate, n-butyl Magnesium-n-butyltriisobutylaluminate, n-butylmagnesium-n-butyltripentylaluminate,
n-butylmagnesium-n-butyltrihexylaluminate, n-butylmagnesium-n-butyltrioctylaluminate, isobutylmagnesiumisobutyltrimethylaluminate, isobutylmagnesiumisobutyltriethylaluminate, isobutylmagnesiumisobutyltripropylaluminate, isobutyl Magnesium isobutyl tri-n-butyl aluminate, isobutyl magnesium tetraisobutyl aluminate,
Isobutyl magnesium isobutyl tripentyl aluminate, isobutyl magnesium isobutyl trihexyl aluminate, isobutyl magnesium isobutyl trioctyl aluminate, pentyl magnesium pentyl trimethyl aluminate, pentyl magnesium pentyl triethyl aluminate, pentyl magnesium pentyl tripropyl aluminate, pentyl magnesium pentyl tri -N-butyl aluminate, pentyl magnesium pentyl triisobutyl aluminate, pentyl magnesium tetrapentyl aluminate, pentyl magnesium pentyl trihexyl aluminate, pentyl magnesium pentyl trioctyl aluminate, hexyl magnesium hexyl trimethyl aluminate, hexyl mag Nitrosium hexyl triethyl aluminate, hexyl magnesium hexyl tripropyl aluminate, hexyl magnesium hexyl tri -n-
Butyl aluminate, hexylmagnesium hexyltriisobutylaluminate, hexylmagnesiumhexyltripentylaluminate, hexylmagnesiumtetrahexylaluminate, hexylmagnesiumhexyltrioctylaluminate, octylmagnesium octyltrimethylaluminate, octylmagnesiumoctyltriethylaluminate, octyl There are magnesium octyl tripropyl aluminate, octyl magnesium octyl tri-n-butyl aluminate, octyl magnesium octyl triisobutyl aluminate, octyl magnesium octyl tripentyl aluminate, octyl magnesium octyl trihexyl aluminate, and octyl magnesium tetraoctyl aluminate. .

Further, magnesium bis (tetramethylaluminate), magnesium bis (ethyltrimethylaluminate), magnesium bis (propyltrimethylaluminate), magnesium bis (n-butyltrimethylaluminate), magnesium bis (isobutyltrimethylaluminate) , Magnesium bis (bentyl trimethyl aluminate), magnesium bis (hexyl trimethyl aluminate), magnesium bis (octyl trimethyl aluminate), magnesium bis (methyl triethyl aluminate), magnesium bis (tetraethyl aluminate), magnesium bis (propyl) Triethylaluminate), magnesium bis (n-butyltriethylaluminate), magnesium bis (isobutyltriethyl) Aluminate), magnesium bis (pentyltriethylaluminate), magnesium bis (hexyltriethylaluminate), magnesium bis (octyltriethylaluminate), magnesium bis (methyltripropylaluminate), magnesium bis (ethyltripropylaluminate) , Magnesium bis (tetrapropylaluminate), magnesium bis (n-butyltripropylaluminate), magnesium bis (isobutyltripropylaluminate), magnesium bis (pentyltripropylaluminate), magnesium bis (hexyltripropylaluminate) ), Agnesium bis (octyltripropylaluminate), Magnesium bisK (Methyltri-
n-butylaluminate), magnesium bis (ethyltri-n-butylaluminate), magnesium (propyltri-n-butylaluminate), magnesium bis (tetra-n-butylaluminate), magnesium bis (isobutyltri-n) -Butyl aluminate),
Magnesium bis (pentyltri-n-butylaluminate), magnesium bis (hexyltri-n-butylaluminate), magnesium bis (octyltri-n
-Butyl aluminate), magnesium bis (methyl triisobutyl aluminate), magnesium bis (ethyl triisobutyl aluminate), magnesium bis (propyl triisobutyl aluminate), magnesium bis (n-butyl triisobutyl aluminate), magnesium bis (Tetraisobutylaluminate), magnesium bis (pentyltriisobutylaluminate), magnesium bis (hexyltriisobutylaluminate), magnesium bis (octyltriisobutylaluminate), magnesium bis (methyltripentylaluminate), magnesium bis ( Ethyl tripentyl aluminate), magnesium bis (propyl tripentyl aluminate), magnesium bis (n-butyl tripentyl aluminate) , Magnesium bis (isobutyl tripentyl aluminate), magnesium bis (tetrapentyl aluminate), magnesium bis (hexyl tripentyl aluminate), magnesium bis (octyl tripentyl aluminate), magnesium bis (methyl trihexyl aluminate) , Magnesium bis (ethyltrihexylaluminate), magnesium bis (propyltrihexylaluminate),
Magnesium bis (n-butyl trihexyl aluminate), magnesium bis (isobutyl trihexyl aluminate), magnesium bis (pentyl trihexyl aluminate), magnesium bis (tetrahexyl aluminate), magnesium bis (octyl trihexyl aluminate) , Magnesium bis (methyltrioctylaluminate), magnesium bis (ethyltrioctylaluminate), magnesium bis (propyltrioctylaluminate), magnesium bis (n-butyltrioctylaluminate), magnesium bis (isobutyloctylaluminate) ), Magnesium bis (pentyl trioctyl aluminate), magnesium bis (hexyl trioctyl aluminate), magnesium bis (tetra Chi le aluminate), magnesium bis (tetraoctyl aluminate) can be exemplified.

The component (D) of the present invention contains an organometallic compound having a structure represented by the general formula (10) or (11) in its skeleton. You may mix and use an organometallic compound. The preparation of the component (D) can be carried out by contacting the corresponding simple metal or organometallic compound with a trialkylaluminum, and this contact can be carried out in an inert hydrocarbon solvent. Specifically, benzene, toluene, aromatic hydrocarbons such as xylene, pentane, hexane, heptane,
Aliphatic hydrocarbons such as octane and decane, and alicyclic hydrocarbons such as cyclopentane and cyclohexane can be used, but aliphatic hydrocarbon solvents are preferred.
It was prepared by contacting a metal or an organometallic compound with an organometallic compound in an inert hydrocarbon. The component (D) may be used as it is as a solution or suspension in the polymerization, or may be used after once distilling off the solvent, changing the solvent and again forming a solution or suspension. The temperature at which the metal or organometallic compound is brought into contact with the organometallic compound is usually -5.
The reaction is carried out at 0 to 200 ° C, preferably at -20 to 100 ° C, more preferably at 0 to 80 ° C. The contact time is 0.0
It is about 5 to 200 hours, preferably about 0.2 to 20 hours. The concentration of the component [D] when used in polymerization is [AI], where the mole number of AI in the organometallic compound is [AI].
Is carried out at a concentration of 0.05 to 5 mol / l, preferably 0.1 to 1 mol / l.

The transition metal compound (A) used in the present invention
And the organoaluminum oxy compound (B), the carrier (C) and the organometallic compound (D) are contacted in the presence of a monomer.
Alternatively, it may be carried out before polymerization in the absence of, or may be introduced into the polymerization system without contact in advance. 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) and the organometallic compound (D) supported on the carrier (C) is arbitrarily selected. ) And the organoaluminum oxy compound (B) supported on the carrier (C) are preliminarily mixed and then brought into contact with the organometallic compound (D), or the transition metal compound (A) is supported on the carrier (C). A method is preferred in which the organoaluminum oxy compound (B) and the organometallic compound (D) are mixed in advance and then brought into contact with the organometallic compound (D) again. When the transition metal compound (A), the organoaluminum oxy compound (B) supported on the carrier (C), and the organometallic compound (D) are preliminarily contacted, the reaction is usually performed in an inert hydrocarbon solvent. Do with.

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 of the transition metal compound (A), the organoaluminum oxy compound (B), and the organometallic compound (D) used in the present invention was such that the number of moles of the transition metal compound (A) was [A], and the transition metal compound (A) was supported on a carrier. If the number of moles of aluminum atoms in the organoaluminum oxy compound (B) is [B] and the number of moles of Al in the organometallic compound (D) is [D], the value of [A] / [B] is 1 / 5
１ ／ 1 / 10,000, preferably 1 / 10１０〜1 / 2,0
00 and the value of [A] / [D] is 1 to 1 / 100,0
00, 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 / liter, preferably 10 ^-7 to 10 ^-3 mol
/ Liter range. Although the olefin pressure of the reaction system can be used in a wide range, it is preferably from normal pressure to 50 kg / c.
m ² , and the polymerization temperature can be used in a wide range, and is in the range of −30 ° C. to 200 ° C., preferably 0 ° C.
C. to 120.degree. Considering productivity, 50
A range of -90 ° C is particularly preferred. 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 7 in Table 1 (190 ° C., load 21.6 kgf: hereinafter referred to as HLMFR) is 0.0.
From high molecular weight of 001 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) An organometallic compound or a trialkylaluminum having a structure represented by the general formula (8) or (9), which is the component (D) used in the present invention, in the skeleton and the component (A) Table 1 shows the results of ethylene polymerization using the above.

[0050]

[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. The ¹ H-NMR measurement was performed using EX-400 manufactured by JEOL Ltd.

(Example 1) [Preparation of aluminoxane] 55 liters of dry toluene was added to a 200 liter reactor which had been sufficiently purged with nitrogen, and 2.8 k of Al ₂ (SO ₄ ) ₃ .14H ₂ O was added thereto.
g was suspended. After cooling to −20 ° C., 33 mol of trimethylaluminum (30 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 75 liters of a 0.35 mol / l methylaluminoxane toluene solution was recovered.

[Support of aluminoxane on carrier] Toluene 3 was placed in a 200-liter reactor sufficiently purged with nitrogen.
5 liters and 2.1 kg of silica (calculated from Davison 952 at 300 ° C. for 4 hours) were added, and the above-mentioned methylaluminoxane [0.35M (in terms of Al atom) was 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 to obtain a solid catalyst component. To this, 70 liters of hexane was added to obtain a hexane slurry of the solid catalyst component.

[Preparation of Component D]
15 liters of an isobutylmagnesium chloride ether solution (2 mol / l) was added to a 0 liter reactor, and triisobutylaluminum 15mo was added thereto.
1 (30 L of a 0.5 mol / L hexane solution) was added over 1 hour, and the mixture was stirred at 30 ° C. for 8 hours. Thereafter, by-product magnesium chloride was filtered off in a nitrogen atmosphere, the solvent was distilled off from the filtrate under reduced pressure, hexane was newly added, and 75 liters of a 0.2 mol / l hexane solution of isobutylmagnesium tetraisobutylaluminate was added. Collected. A small amount of this solution was taken out, and the solvent was distilled off and solidified. Then, ¹ H-NMR was measured using C ₆ D ₆ as a solvent. The result is shown in FIG. On the other hand, FIG. 2 shows the results of ¹ H-NMR of components prepared by mixing diisobutylmagnesium and triisobutylaluminum at a molar ratio of 1: 1 similarly using C ₆ D ₆ as a solvent. The comparison clearly shows that they are different substances.

[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, and 355 ml of a hexane solution of isobutylmagnesium tetraisobutylaluminate (concentration: 0.2 mol / l)
/ Hr was continuously supplied to initiate polymerization. While continuously supplying isobutane as a polymerization solvent at a rate of 51.5 kg / hr, the polymerization conditions of the polymerization reactor were changed to an ethylene partial pressure of 10 kg / cm ² , a polymerization temperature of 70 ° C., a residence time of 1 hour, and a The linear velocity of the polymer slurry of 6m /
sec. The liquid composition in the polymerization reactor was 7.7 mol% of ethylene and 91.6 mol% of isobutane.

As a result, 16.4 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
6g / 10min, 190 ° C, load 21.6kg
The ratio of HLMFR to MFR at f / cm ² (HLMFR /
MFR) was 15.4 and the density was 0.9392 g / ml. The bulk density of the obtained polymer is 0.35 g / c.
c, average particle size is 340 μm, fine powder polymer (particle size 50 μm)
m or less) was 2.5% by weight. 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 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 isobutylmagnesium tetraisobutylaluminate (concentration: 0.2 mol / l) was continuously supplied at a rate of 355 ml / hr to initiate polymerization. 51.1 kg of isobutane as a polymerization solvent
The polymerization conditions of the polymerization reactor were 10 kg / cm ² of ethylene partial pressure, the polymerization temperature was 70 ° C., the residence time was 1 hour, and the linear velocity of the polymer slurry in the polymerization reactor was 6 m / sec. Held. 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, 17.5 kg / h under the above conditions
r, polyethylene is produced and the MF of this polymer is
R is 0.85 g / 10 min, HLMFR and MF
The ratio of R (HLMFR / MFR) is 15.5 and the density is 0.5.
It was 9256 g / ml. The bulk density of the obtained polymer was 0.36 g / cc, the average particle size was 340 μm, and the weight fraction of the finely divided polymer (particles having a particle size of 50 μm or less) was 2.1% by weight. 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) [Preparation of component D] 80 L of dry hexane was added to a 200 L reactor which was sufficiently purged with nitrogen, and 243 g of lithium was suspended therein. To this suspension, 47 mol of triisobutylaluminum (94 l of a 0.5 mol / l hexane solution) was added over 1 hour, and the mixture was heated to 60 ° C. and stirred for 8 hours. Thereafter, metal aluminum was removed under a nitrogen atmosphere, and 0.2 mol /
170 liters of a liter suspension of lithium tetraisobutylaluminate in hexane was recovered. After the suspension was taken out a small amount of, solidified by removing the solvent, ¹ H-N
MR was measured using C ₆ D ₆ as a solvent. The result is shown in FIG. On the other hand, a component prepared by mixing isobutyllithium and triisobutylaluminum at a molar ratio of 1: 1
FIG. 4 shows the results of ¹ H-NMR similarly measured using C ₆ D ₆ as a solvent. The comparison clearly shows that they are different substances.

[Polymerization] Instead of the hexane solution of isobutylmagnesium tetraisobutylaluminate, the hexane suspension (0.2 mol / l) of lithium tetrabutylaluminate prepared above was used.
The same operation as in Example 1 was performed except that the mixture was continuously supplied at a rate of 1 / hr. As a result, 15.9k under the above conditions
g / hr, polyethylene was produced, and the MFR of this polymer was 0.20 g / 10 min.
And the MFR (HLMFR / MFR) were 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.
m, the weight fraction of the finely divided polymer (particles having a particle size of 50 μm or less) was 2.7% by weight. 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 4 Instead of a hexane solution of isobutylmagnesium tetraisobutylaluminate,
Using the hexane suspension of lithium tetrabutyl aluminate prepared above (0.2 mol / l), 35
Example 2 except that it was continuously supplied at a rate of 5 ml / hr.
The same operation as described above was performed. As a result, under the above conditions, 1
Polyethylene was produced at a rate of 7.9 kg / hr, and the MFR of this polymer was 0.92 g / 10 min.
The ratio of LMFR to MFR (HLMFR / MFR) is 15.
7. The density was 0.9237 g / ml. The bulk density of the obtained polymer was 0.34 g / cc and the average particle size was 3
The weight fraction of 30 μm and the finely divided polymer (particles having a particle size of 50 μm or less) was 3.7% by weight. Under the above polymerization conditions, 10
After polymerization for 0 hours, when the polymerization reactor was opened, there was no adhesion of the polymer to the polymerization reactor wall and the impeller for stirring.

Example 5 A hexane suspension of lithium tetraethylaluminate (lithium and triethylaluminum in hexane at 60 ° C.) prepared in the same manner as in Example 3 instead of the hexane solution of isobutylmagnesium tetraisobutylaluminate Prepared for 8 hours with stirring at a concentration of 0.02 mol / liter).
The same operation as in Example 1 was performed except that the mixture was continuously supplied at a rate of 1 / hr. As a result, 12.9k under the above conditions
g / hr, polyethylene was produced, and the MFR of this polymer was 0.18 g / 10 min.
And the MFR ratio (HLMFR / MFR) was 15.5, and the density was 0.9394 g / ml. The bulk density of the obtained polymer was 0.34 g / cc, and the average particle size was 320 μm.
m, the weight fraction of the finely divided polymer (particles having a particle size of 50 μm or less) was 2.3% by weight. 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 lithium tetraethyl aluminate (lithium and tri-n) was prepared in the same manner as in Example 3 in place of the hexane solution of isobutylmagnesium tetraisobutylaluminate.
Prepared by stirring butyl aluminum in hexane at 60 ° C. for 8 hours, at a concentration of 0.2 mol / L),
The same operation as in Example 1 was performed except that the solution was continuously supplied at a rate of 5 ml / h. As a result, 15.6 under the above conditions
Polyethylene is produced at a rate of kg / hr, and the MFR of this polymer is 0.16 g / 10 min.
The ratio of R to MFR (HLMFR / MFR) was 15.8, and the density was 0.9399 g / ml. The bulk density of the obtained polymer was 0.33 g / cc, and the average particle size was 320 μm.
m, the weight fraction of the finely divided polymer (particles having a particle size of 50 μm or less) was 2.5% by weight. 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 7) Internal volume 2 sufficiently purged with nitrogen
After supplying propylene to a 90-liter loop polymerization reactor, filling the polymerization reactor with propylene, 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, the solid catalyst component prepared above was 4.0 g / hr, and the hexane suspension of lithium tetraisobutylaluminate prepared in Example 3 (concentration: 0.2 mol / l) was 3 parts.
The polymerization was started by continuously supplying the mixture at a rate of 55 ml / hr. While continuously supplying the monomer propylene at a rate of 12.0 kg / hr, the polymerization temperature was 50 ° C., the residence time was 1 hour, and the linear velocity of the polymer slurry in the polymerization vessel was 6 m / sec.
c. As a result, 11.8 kg /
The resulting polymer has an MFR of 2.40 g / 230 ° C. under a load of 2.16 kg.
It was 10 minutes. The bulk density of the obtained polymer was 0.38 g / cc, the average particle size was 300 μm, and the weight fraction of the finely divided polymer (particles having a particle size of 50 μm or less) was 2.2% by weight. 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.

(Embodiment 8) Internal volume 3 sufficiently purged with nitrogen
After putting 140 kg of seed polymer polyethylene into a 900-liter gas-phase reactor, nitrogen was blown into the reactor.
The temperature was raised to 0 ° C. Then, the total pressure in the reactor was 21
kg / cm ² , ethylene was supplied, and a hexane solution (0.3 g / liter) of bis (normal butylcyclopentadienyl) zirconium dichloride was further added to 1 kg / cm ^2.
94 ml / hr, the solid catalyst component prepared above was mixed with 12.5
g / hr, a hexane suspension of lithium tetrabutyl aluminate (concentration: 0.2 mol / l) prepared in Example 3 was continuously supplied at a rate of 600 ml / hr to initiate polymerization. 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. The} polymerization temperature was kept at 70 ° C. and the residence time was kept at 5 hours.

As a result, 30.3 kg / h under the above conditions
r, polyethylene is produced, and 19
The MFR at 0 ° C. and a load of 2.16 kg is 0.22 g / 10
min and the ratio to HLMFR (HLMFR / MF
R) was 16.3 and the density was 0.9406 g / ml. The bulk density of the obtained polymer is 0.35 g / c.
c, average particle size is 300 μm, fine polymer (particle size 50 μm)
m or less) was 2.8% by weight. 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 isobutylmagnesium tetraisobutylaluminate,
Triisobutylaluminum hexane solution (0.5m
ol / liter), and the same operation as in Example 1 was performed except that the water was continuously supplied at a rate of 142 ml / hr.
As a result, polyethylene was produced at a rate of 26.3 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 16.1 and the density was 0.9400 g / ml. The bulk density of the obtained polymer is 0.29 g / c.
c, average particle size is 200 μm, fine polymer (particle size 50 μm)
m or less) was 32.4% by weight.
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 isobutylmagnesium tetraisobutylaluminate,
Hexane solution of tri-n-butylaluminum (0.5
mol / 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 26.9 kg / hr under the above conditions, and the MFR of this polymer at 190 ° C. under a load of 2.16 Kg was 0.17 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 16.3 and the density was 0.9398 g / ml. The bulk density of the obtained polymer is 0.32 g / c.
c, average particle size is 180 μm, fine powder polymer (particle size 50 μm)
m or less) was 30.7% by weight.
Under the above polymerization conditions, when the polymerization reactor was opened after polymerization for 100 hours, adhesion of a polymer having a thickness of about 0.2 to 0.5 mm was observed on the polymerization reactor wall and the stirring impeller.

[0069]

[Table 2]

[0070]

[Table 3]

[0071]

The present invention relates to a novel olefin polymerization catalyst comprising a metallocene compound, an organoaluminum oxy compound and a binuclear organometallic compound and a process for producing an olefin polymer using the same. It has sufficient polymerization activity even if the amount of aluminoxane used is small, and in particular has the ability to produce polyolefins having an extremely wide range of molecular weights depending on the amount of hydrogen introduced during polymerization. The catalyst of the present invention can be used in any of solution polymerization, slurry polymerization or gas phase polymerization,
The main feature is that the conventional high performance metallocene-based catalyst adheres to the reactor wall, which has been the most problematic when used in the slurry method, because it has the ability to produce polymers with high polymerization activity and a wide range of molecular weights. The catalyst of the present invention has been developed, so that the metallocene catalyst can be economically applied to slurry polymerization and industrially stable production is possible. It became.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum of an organometallic compound having a structure represented by the general formula (11) of the present invention.

FIG. 2 is a ¹ H-NMR spectrum of a product obtained by mixing a dialkylmagnesium and a trialkylaluminum.

FIG. 3 is a ¹ H-NMR spectrum of an organometallic compound having a structure represented by the general formula (10) of the present invention.

FIG. 4 is a ¹ H-NMR spectrum of a product obtained by mixing an alkyl lithium and a trialkyl aluminum.

FIG. 5 is a flow chart of the catalyst of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tetsuya Maki No. 2 Onaka-no-Osu, Oita-shi, Oita Japan Polyolefin Co., Ltd. Oita Research Laboratory (72) Inventor Shintaro Inazawa No. 2 Onaka-no-Osu, Oita-shi, Oita Japan Polyolefin Co., Ltd. Oita Research Laboratory

Claims (4)

[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 - (} . R 12 represents hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated alkyl or halogenated aryl) an electron donor ligand represented by, Me
Is a transition metal of group 3, 4, 5, or 6 of the periodic table;
p is 0 or 1. And (B) an organoaluminum oxy compound, (C) a carrier and (D) a reaction product obtained by mixing lithium and trialkylaluminum, and / or
Or an olefin polymerization catalyst comprising an organometallic compound which is a reaction product obtained by mixing an alkyl magnesium halide and a trialkyl aluminum. 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. 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 the mole of the organometallic compound of the component (D). The number 1 [D], wherein 1 / 10,000 <[A] / [B] <1/5 1 / 100,000 <[A] / [D] <1 3. The olefin polymerization catalyst according to any one of 2. 4. The component (A) according to claim 1, wherein the component (A) is a transition metal compound, and the component (B) is an organoaluminum oxy compound.
(C) a carrier and components and (D) an organometallic compound which is a reaction product obtained by mixing lithium and trialkylaluminum and / or an organic metal which is a reaction product obtained by mixing alkylmagnesium halide and trialkylaluminum. A method for producing a polyolefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst comprising a compound.