JPH093113A - Production of polyolefin - Google Patents

Abstract

PURPOSE: To produce an olefin (co)polymer having excellent moldability and a low content of a low-molecular-weight component, being molded without any troubles and having a narrow compositional distribution by using a catalyst comprising specified transition metal compounds and an organoaluminumoxy compound. CONSTITUTION: Ethylene is homopolymerized or copolymerized with other (α- olefins at 0-120 deg.C under a pressure of atmospheric pressure to 50kg/cm<2> G by slurry polymerization or vapor-phase polymerization in the presence of a catalyst obtained by bringing at least one member selected from among transition metal compounds represented by formula I [wherein R<1> to R<10> are each a hydrocarbon group (e.g. a 1-20C alkyl), an alkylsilyl, an alkylgermyl or a four- to six- membered carbocyclic ring; Q is a hydrocarbon groups (a 1-20C aryl or alkyl), an alkoxyl, an aryloxy, siloxy, H or a halogen; Me is a 3-6 group transition metal; and (p) is 0 or 1] and formula II, at least one member selected from among transition compounds of formula II and an organoaluminiumoxy compound into contact with each other.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyolefin using an olefin polymerization catalyst. More specifically, the present invention relates to a method for producing a polyolefin having excellent moldability, low content of low molecular weight components, no smoke generation during molding, and a narrow composition distribution in a copolymer.

[0002]

2. Description of the Related Art It is known that in order to improve the moldability of ethylene polymers, it is necessary to increase the melt tension. Therefore, studies have been conducted to improve the melt tension of an ethylene-based copolymer obtained by using a Ziegler type titanium-based catalyst or a chromium-based catalyst. For example, JP-A-56-90810 and JP-A-60-106806 disclose a method for improving the moldability by improving the melt tension of an ethylene polymer obtained by using a Ziegler type titanium catalyst. Has been done. However, although the melt tension of ethylene-based polymers generally obtained by using titanium-based catalysts and chromium-based catalysts is improved, the molecular weight distribution is wide and there are many low-molecular-weight components such as those extracted with hexane, which causes smoke emission during molding. There was a problem that was generated. Further, the ethylene-based copolymer has a problem in that the composition distribution is wide and the molded product becomes sticky.

On the other hand, a method for producing polyethylene and ethylene-α-olefin copolymers using a metallocene catalyst composed of a metallocene compound and methylaluminoxane is known. The ethylene-based polymer obtained by this method has a narrow molecular weight distribution and a small amount of low-molecular weight components, so that smoking during molding was improved, but there was a problem in moldability because of low melt tension. In order to solve this problem, studies have been conducted to improve the melt tension by using two kinds of metallocene compounds in a metallocene catalyst system. For example, JP-A-6
-206922, JP-A-6-206923, JP-A-6-
In 206924, two transition metal compounds having at least two alkyl-substituted cyclopentadienyl ligands are combined with an aluminoxane, and if necessary, a carrier, a catalyst system using an organoaluminum compound, or a prepolymerization of this catalyst. A method for producing polyethylene and an ethylene-α-olefin copolymer using the catalyst system obtained by the above is disclosed. Since the ethylene-based copolymer obtained by this method has a narrow composition distribution and a small amount of low molecular weight components, smoking during molding was reduced and stickiness of the molded product was also improved. However, the improvement in moldability was not sufficient. Therefore, if the melt tension is high, the moldability is excellent, the low molecular weight component is small, there is no problem such as smoking during molding, and in the copolymer, if a method for producing an ethylene polymer having a narrow composition distribution can be presented, Its industrial value is extremely high.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing a polyolefin having excellent moldability, a small amount of low molecular weight components, no problems such as smoking during molding, and a narrow composition distribution in a copolymer. The purpose is to do.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors finally found a novel polyolefin production method which meets the purpose,
The present invention has been reached. That is, the method for producing a polyolefin according to the present invention comprises (A-1) the general formula (1)

[Chemical 6] [In the formula, R ^{1 to} R ¹⁰ are hydrogen or a hydrocarbon group (having 1 carbon atom).
Is an alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc. having .about.20), an alkylsilyl group, an alkylgermyl group, or a 4- to 6-membered ring having a carbon-carbon bond, which may be the same or different. , Each Q is a hydrocarbon group having 1 to 20 carbon atoms such as aryl, alkyl, alkenyl, alkylaryl, and arylalkyl, an alkoxy group, an aryloxy group, a siloxy group,
Hydrogen or halogen, which may be the same or different, Me is a transition metal of Group 3, 4, 5 or 6 of the periodic table, and p is 0 or 1. ] Or general formula (2)

[Chemical 7] [In the formula, R ^{11 to} R ¹⁸ are hydrogen or a hydrocarbon group (having 1 carbon atom).
To alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc.), alkylsilyl group, alkylgermyl group, which may be the same or different, and R ¹⁹ is an alkylene group having 1 to 20 carbon atoms. , An alkylgermylene group or an alkylsilylene group, each Q is aryl having 1 to 20 carbons, alkyl,
It is a hydrocarbon group such as alkenyl, alkylaryl, arylalkyl, etc., an alkoxy group, an allyloxy group, a siloxy group, hydrogen or halogen, which may be the same or different, and Me is a group 3, 4, 5 or 6 of the periodic table. Is a transition metal, and p is 0 or 1. ] At least one transition metal compound selected from the transition metal compounds represented by: and (A-2) the general formula (3)

Embedded image [In the formula, R ^{20 to} R ³¹ are hydrogen or a hydrocarbon group (having 1 carbon atom).
Is an alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc. having .about.20), an alkylsilyl group, an alkylgermyl group, or a 4- to 6-membered ring having a carbon-carbon bond, which may be the same or different. , R ³² is an alkylene group having 1 to 20 carbon atoms, an alkylgermylene group or an alkylsilylene group, and each Q is a hydrocarbon group having 1 to 20 carbon atoms such as aryl, alkyl, alkenyl, alkylaryl and arylalkyl, An alkoxy group, an aryloxy group, a siloxy group, hydrogen or halogen, which may be the same or different, and M
e is a transition metal of Group 3, 4, 5 or 6 of the periodic table, and p is 0 or 1], and at least one transition metal compound selected from the transition metal compounds
(B) is characterized by polymerizing or copolymerizing an olefin in the presence of a catalyst composed of an organoaluminum oxy compound.

The method for producing a polyolefin using the olefin polymerization catalyst according to the present invention will be specifically described below. Transition metal compound (A-1) used in the present invention
Is the general formula (1)

Embedded image [In the formula, R ^{1 to} R ¹⁰ are hydrogen or a hydrocarbon group (having 1 carbon atom).
Is an alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc. having .about.20), an alkylsilyl group, an alkylgermyl group, or a 4- to 6-membered ring having a carbon-carbon bond, which may be the same or different. , Each Q is a hydrocarbon group having 1 to 20 carbon atoms such as aryl, alkyl, alkenyl, alkylaryl, and arylalkyl, an alkoxy group, an aryloxy group, a siloxy group,
Hydrogen or halogen, which may be the same or different, Me is a transition metal of Group 3, 4, 5 or 6 of the periodic table, and p is 0 or 1. ] Or general formula (2)

Embedded image [In the formula, R ^{11 to} R ¹⁸ are hydrogen or a hydrocarbon group (having 1 carbon atom).
To alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc.), alkylsilyl group, alkylgermyl group, which may be the same or different, and R ¹⁹ is an alkylene group having 1 to 20 carbon atoms. , An alkylgermylene group or an alkylsilylene group, each Q is aryl having 1 to 20 carbons, alkyl,
It is a hydrocarbon group such as alkenyl, alkylaryl, arylalkyl, etc., an alkoxy group, an allyloxy group, a siloxy group, hydrogen or halogen, which may be the same or different, and Me is a group 3, 4, 5 or 6 of the periodic table. Is a transition metal, and p is 0 or 1. ] It is a transition metal compound represented by.

In the above equation, Me is the third of the periodic table,
Although it is a transition metal element of group 4, 5 or 6 (groups are according to the 1990 rules of inorganic chemistry nomenclature), preferably a transition metal element of group 4 of the Periodic Table, ie titanium, zirconium,
It is preferably selected from hafnium, and particularly preferably zirconium and hafnium. In the above equation,
R ^{1 to} R ¹⁰ are hydrogen or a hydrocarbon group (such as an alkyl, alkenyl, aryl, alkylaryl, or arylalkyl having 1 to 20 carbon atoms) or a 4- to 6-membered ring having a carbon-carbon bond, and each is the same. But it may be different. Examples of the hydrocarbon group as described above include methyl group, ethyl group, propyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. Groups, cetyl groups, phenyl groups, etc., alkylsilyl groups include trimethylsilyl groups, and alkylgermyl groups include trimethylgermyl groups. Examples of the ligand having a substituent as described above include a cyclopentadienyl group, a methylcyclopentadienyl group,
Alkyl substitution such as ethylcyclopentadienyl group, n-butylcyclopentadienyl group, t-butylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, dimethylcyclopentadienyl group, pentamethylcyclopentadienyl group Examples thereof include a cyclopentadienyl group, an indenyl group with or without a similar substituent, and a fluorenyl group.

In the above formula, R ^{11 to} R ¹⁸ are hydrogen or a hydrocarbon group (which is alkyl, alkenyl, aryl, alkylaryl, arylalkyl having 1 to 20 carbon atoms), which may be the same or different. Good. Examples of the hydrocarbon group as described above include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group,
t-butyl group, amyl group, isoamyl group, hexyl group,
Examples thereof include a heptyl group, an octyl group, a nonyl group, a decyl group, a cetyl group, and a phenyl group, examples of the alkylsilyl group include a trimethylsilyl group, and examples of the alkylgermyl group include a trimethylgermyl group. Examples of the ligand having a substituent as described above include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n-butylcyclopentadienyl group, a t-butylcyclopentadienyl group. Examples thereof include alkyl-substituted cyclopentadienyl groups such as an enyl group, a trimethylsilylcyclopentadienyl group, a dimethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.

In the above formula, R ¹⁹ is an alkylene group having 1 to 20 carbon atoms, an alkylgermylene group or an alkylsilylene group. As the alkylene group, a methylene group,
Examples thereof include an ethylene group, a propylene group, an isopropylidene group, a cyclopentylidene group, a cyclohexylidene group, a tetrahydropyran-4-ylidene group and a diphenylmethylene group, and examples of the alkylsilylene group include a dimethylsilylene group and a diphenylsilylene group. Can be exemplified,
Examples of the alkylgermylene group include a dimethylgermylene group and a diphenylgermylene group. In the above formula, Q is a hydrocarbon group having 1 to 20 carbon atoms such as aryl, alkyl, alkenyl, alkylaryl, and arylalkyl, or halogen, which may be the same or different.

Specific examples of the transition metal compounds represented by the general formulas (1) and (2) when Me is zirconium are shown below. 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, cyclopentadienylzirconium trimethyl, pentamethylcyclopentadienylzirconium trichloride, pentamethylcyclopentadienylzirconium trichloride Chill like.

As the transition metal compound represented by the general formula (2), dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (n) -Butylcyclopentadienyl) zirconium dichloride, isopropylidene bis (methylcyclopentadienyl) zirconium dichloride, isopropylidene bis (n-butylcyclopentadienyl) zirconium dichloride and the like can be exemplified.
In the zirconium compound as described above, a transition metal compound in which zirconium is changed to hafnium or titanium can be exemplified. Among these, bis (n-
Butylcyclopentadienyl) zirconium dichloride and dimethylsilylenebis (n-butylcyclopentadienyl) zirconium dichloride are preferably used.

The transition metal compound (A-
2) is represented by the general formula (3)

Embedded image [In the formula, R ^{20 to} R ³¹ are hydrogen or a hydrocarbon group (having 1 carbon atom).
Is an alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc. having .about.20), an alkylsilyl group, an alkylgermyl group, or a 4- to 6-membered ring having a carbon-carbon bond, which may be the same or different. , R ³² is an alkylene group having 1 to 20 carbon atoms, an alkylgermylene group or an alkylsilylene group, and each Q is a hydrocarbon group having 1 to 20 carbon atoms such as aryl, alkyl, alkenyl, alkylaryl and arylalkyl, An alkoxy group, an aryloxy group, a siloxy group, hydrogen or halogen, which may be the same or different, and M
e is a transition metal of Group 3, 4, 5 or 6 of the periodic table, and p is 0 or 1].

In the above equation, Me is the third of the periodic table,
Although it is a transition metal element of group 4, 5 or 6 (groups are according to the 1990 rules of inorganic chemistry nomenclature), preferably a transition metal element of group 4 of the Periodic Table, ie titanium, zirconium,
It is preferably selected from hafnium, and particularly preferably zirconium and hafnium. In the above equation,
R ^{20 to} R ³¹ are hydrogen or a hydrocarbon group (such as an alkyl, alkenyl, aryl, alkylaryl or arylalkyl having 1 to 20 carbon atoms) or a 4 to 6 membered ring having a carbon-carbon bond, and each is the same. But it may be different. Examples of the hydrocarbon group as described above include methyl group, ethyl group, propyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. Groups, cetyl groups, phenyl groups, etc., alkylsilyl groups include trimethylsilyl groups, and alkylgermyl groups include trimethylgermyl groups. Examples of the ligand having a substituent as described above include an indenyl group, a 2-methylindenyl group, a 2-ethylindenyl group, a 2-n-butylindenyl group, a 3-t-butylindenyl group, Examples thereof include alkyl-substituted indenyl groups such as 4-isopropylindenyl group, 4-phenylindenyl group and 2-methyl-4-phenylindenyl group, and fluorenyl groups with or without similar substituents.

In the above formula, R ³² is an alkylene group having 1 to 20 carbon atoms, an alkylgermylene group or an alkylsilylene group. As the alkylene group, a methylene group,
Examples thereof include an ethylene group, a propylene group, an isopropylidene group, a cyclopentylidene group, a cyclohexylidene group, a tetrahydropyran-4-ylidene group and a diphenylmethylene group, and examples of the alkylsilylene group include a dimethylsilylene group and a diphenylsilylene group. Can be exemplified,
Examples of the alkyl germylene group include a dimethyl germylene group and a diphenyl germylene group. In the above formula, Q is a hydrocarbon group having 1 to 20 carbon atoms such as aryl, alkyl, alkenyl, alkylaryl, and arylalkyl, or halogen, which may be the same or different.

Specific examples of the transition metal compound represented by the general formula (3) in the case where Me is zirconium are shown below. Examples of the transition metal compound represented by the general formula (3) include ethylenebis (indenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, and dimethylsilylenebis (2-methyl). -4,5-benzindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethyl Silylene bis (3-t-butylindenyl) zirconium dichloride, isopropylidene (indenyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-t-butylindenyl) (fluor ) Zirconium dichloride, dimethylsilylene (2-methyl-4
Examples thereof include-(1-naphthyl) indenyl) (fluorenyl) zirconium dichloride. In the zirconium compound as described above, a transition metal compound in which zirconium is changed to hafnium or titanium can be exemplified. Among these, dimethylsilylenebis (2-
It is preferable to use methyl-4-phenylindenyl) zirconium dichloride and dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (fluorenyl) zirconium dichloride.

In the present invention, as the transition metal compound, at least one selected from the transition metal compounds represented by the general formula (1) or (2) and the transition metal compound represented by the general formula (3) are used. It is preferable to use in combination with at least one selected. Specifically, the screw (n
-Butylcyclopentadienyl) zirconium dichloride and dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (fluorenyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride and dimethylsilylene Combination with bis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene bis (n-butylcyclopentadienyl) zirconium dichloride and dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) ( Fluorenyl) zirconium dichloride, dimethylsilylene bis (n-
A combination of butylcyclopentadienyl) zirconium dichloride and dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride is preferred.

At least one transition metal compound selected from the transition metal compounds (A-1) represented by the general formula (1) or (2), and the transition metal compound represented by the general formula (3). At least one transition metal compound selected from (A-2) is 9 in molar ratio (A-2) / (A-1).
9/1 to 10/90, preferably 95/5 to 20/8
0, more preferably 93/7 to 30/70, and most preferably 90/10 to 40/60.

The organoaluminum oxy compound (B) used in the present invention is aluminoxane,
It may be an addition reaction product of an organoaluminum oxy compound and an organic polar compound having at least one atom selected from phosphorus atom, nitrogen atom, sulfur atom and oxygen atom in the molecule and having no active hydrogen. . The aluminoxane is an organoaluminum compound represented by the general formula (4) or the general formula (5). General formula (4)

[Chemical 12] General formula (5)

Embedded image R ³³ is a methyl group, an ethyl group, a propyl group, a butyl group,
A hydrocarbon group such as an isobutyl group, preferably a methyl group or an isobutyl group. m is an integer of 1 to 100, preferably 4 or more and particularly 8 or more. The production method of this kind of compound is known, for example, a method obtained by adding an organoaluminum compound to a hydrocarbon solvent suspension of salts having crystal water (copper sulfate hydrate, aluminum sulfate hydrate) and hydrocarbons. A method in which solid, liquid or gaseous water is allowed to act on the organoaluminum compound in a solvent can be exemplified.

Further, the general formula (6) or the general formula (7)
May be used. General formula (6)

Embedded image General formula (7)

Embedded image R ³⁴ is a methyl group, an ethyl group, a propyl group, a butyl group,
A hydrocarbon group such as an isobutyl group, preferably a methyl group or an isobutyl group. R ³⁵ is a methyl group,
It is a hydrocarbon group such as an ethyl group, a propyl group, a butyl group and an isobutyl group, or a halogen or hydrogen atom such as chlorine and bromine, and a hydroxyl group, and is different from R ³⁴ .
R ³⁵ may be the same or different. m is usually 1
To an integer of 100, preferably 3 or more, m
+ N is 2 to 100, preferably 6 or more. In the general formula (6) or (7),

Embedded image It may be a block-shaped combination or a regular or irregularly connected one. The method for producing such an aluminoxane is the same as that for the aluminoxane represented by the general formula described above. Instead of one kind of trialkylaluminum, two or more kinds of trialkylaluminum are used, or one or more kinds of trialkylaluminum and one kind are used. The above dialkylaluminum monohalide or dialkylaluminum monohydride may be used. As the aluminoxane, two or more kinds of the general formulas (4), (5), (6) and (7) may be mixed and used.

The organoaluminum compound used in producing the aluminoxane is not particularly limited, but trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum. , Tri tert-
Butylaluminum, tripentylaluminum, trihexylaluminium, trioctylaluminum, trialkylaluminum such as tricyclohexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dialkylaluminum halide such as diisobutylaluminum chloride, dimethylaluminum methoxide, diethylaluminum ethoxide. And a dialkylaluminum aryloxide such as diethylaluminum phenoxide. Among them, trialkylaluminum, particularly trimethylaluminum and triisobutylaluminum are preferably selected.

As the hydrocarbon solvent used in the production of aluminoxane, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, cyclopentane, Examples thereof include alicyclic hydrocarbons such as cyclohexane. Of these solvents, aromatic hydrocarbons are preferred.

An organoaluminum oxy compound used in the present invention, and an organic polar 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. The organic polar compound used in the addition reaction product refers to a compound having a functional group containing the atom and having no active hydrogen. Active hydrogen means hydrogen directly bonded to a phosphorus atom, a nitrogen atom, a sulfur atom or an oxygen atom. The organic polar compound having at least one atom selected from the phosphorus atom, the nitrogen atom, the sulfur atom and the oxygen atom in the molecule and having no active hydrogen as described above is optional from among those satisfying this condition. However, a phosphoric acid ester is preferable. Addition reaction of an organoaluminum oxy compound used in the present invention with an organic polar compound having at least one atom selected from phosphorus atom, nitrogen atom, sulfur atom and oxygen atom in the molecule and having no active hydrogen The product can be produced by mixing and reacting an organic aluminum oxy compound, for example, an aluminoxane, with the above organic polar compound in a hydrocarbon solvent.

The organoaluminum oxy compound according to the present invention and an organic polar 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. The characteristics of the addition reaction product will be described below. Here, an organic polar compound containing a phosphorus atom will be described as an example. The addition reaction product largely differs from the organoaluminum oxy compound used in the reaction in solubility in various inert solvents. Solubility can be evaluated by carrying out Soxhlet extraction using an inert hydrocarbon solvent such as hexane or toluene and examining the amount of extraction. The specific method of Soxhlet extraction is shown below. The flask equipped with the Soxhlet extractor is thoroughly replaced with nitrogen. The addition reaction product obtained by distilling off the solvent to dryness is weighed in a predetermined amount in terms of aluminum atom, transferred to a glass fiber cylindrical filter paper under nitrogen, and extracted with a predetermined inert solvent for 8 hours. The amount of extraction is measured by measuring the aluminum concentration in the extract. When the solubility is evaluated using this method, it is found that unlike the aluminoxane used in the reaction, it becomes slightly soluble in various solvents.
The preferred range for the amount of hexane extracted is 2 for hexane.
It is preferably 0% or less, and more preferably 15% or less. Moreover, it is desirable that the amount of extracted toluene (index of activity expression) is 15% or more. Further, for heptane, it is 25% or less, more preferably 20% or less, and for benzene, it is more than 10% and 30% or more.
% Is desirable.

The organoaluminum oxy compound (B) used in the present invention can also be used by supporting it on a carrier. The carrier used in that case is in the form of fine particles and is not particularly limited as long as it is solid in the polymerization medium,
It is preferably selected from inorganic oxides, inorganic chlorides, inorganic carbonates, inorganic sulfates, or organic polymers. A specific example is shown below. As inorganic oxides, SiO ₂ , A
_{l 2 O 3, MgO, ZrO} 2, TiO 2, CaO _{or, SiO 2 -Al 2 O 3,} SiO 2 -MgO, SiO
_{2 -ZrO 2, SiO 2 -TiO 2} , SiO 2 -Ca
_{O, Al 2 O 3 -MgO,} Al 2 O 3 -ZrO 2, Al 2
_{O 3 -TiO 2, Al 2 O} 3 -CaO, ZrO 2 -T
iO ₂ , ZrO ₂ —CaO, ZrO ₂ —MgO, TiO ₂
Examples thereof include complex oxides such as MgO. Magnesium chloride etc. can be illustrated as an inorganic chloride. Examples of the inorganic carbonate include magnesium carbonate, calcium carbonate, strontium carbonate and the like. Examples of the inorganic sulfate include magnesium sulfate, calcium sulfate, barium sulfate and the like. As the organic polymer carrier, polyethylene,
Fine particles such as polypropylene and polystyrene can be exemplified. Among these, porous fine particles are preferable, and specifically, it is desirable that they are selected from inorganic oxides, especially SiO ₂ , Al ₂ O ₃ and their composite oxides. The porous particles according to the present invention, it is preferable that the specific surface area is in the range of 10 to 1000 m ² / g, further 100~800m ² / g
The range is preferably 200, and particularly preferably 200
The range is up to 600 m ² / g. Further, the pore volume is preferably in the range of 0.3 to 3 cc / g, more preferably 0.5 to 2.5 cc / g, and particularly preferably 1.0 to 2 It is in the range of 0.0 cc / g. SiO ₂ , which is the preferred carrier according to the invention,
The amount of adsorbed water and the amount of surface hydroxyl groups of Al ₂ O ₃ and its composite oxide differ depending on the treatment conditions. As a preferable range of these, the water content is 5% by weight or less, and the surface hydroxyl group content is 1 / (nm) ^{2 with} respect to the surface area.
That is all. The water content and the amount of surface hydroxyl groups can be controlled by the firing temperature and treatment with an organic aluminum compound or an organic boron compound.

As a method for supporting the organoaluminum oxy compound (B) used in the present invention on a carrier, a method of supporting an organoaluminum compound on the carrier and then reacting with water or an organic polar compound, an organoaluminum compound, Examples thereof include a method of supporting a reaction product with water or an organic polar compound on a carrier, and a method of impregnating the carrier with water or an organic polar compound and then adding an organoaluminum compound to generate a reaction product on the carrier. However, the organoaluminum compound used for supporting is trialkylaluminum or aluminoxane when reacting with water, and aluminoxane when reacting with an organic polar compound. Among these methods, when reacting with water, the method is preferable, and the further method is particularly preferable. When reacting with an organic polar compound,
The method of, is preferable, and the method of further 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 and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclopentane and cyclohexane can be used. Are preferably aromatic hydrocarbon solvents. 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 addition reaction product of the organoaluminum oxy compound or the organoaluminum oxy compound and the organic polar compound supported on the carrier is 5 × 10 ^{−4 to} 0.2 gram atom per 1 g of the carrier in terms of aluminum atom. It is preferably in the range, and more preferably in the range of 5 × 10 ^{−3 to} 0.05 gram atom.

The amount of an organic polar compound having at least one atom selected from the group consisting of a phosphorus atom, a nitrogen atom, a sulfur atom and an oxygen atom used in the reaction with an organoaluminum oxy compound and having no active hydrogen. Is 0.0001 to 0.5 mol, preferably 0. 0, per 1 equivalent of aluminum atom of the organoaluminum oxy compound.
001-0.3 mol, more preferably 0.005-
It is desirable to use 0.2 mol amount. Within this range, almost all of the organic polar compound reacts with the organoaluminum oxy compound to give the corresponding addition product.

The organoaluminum oxy compound supported on the carrier according to the present invention may be used as it is, but may be an inert hydrocarbon solvent such as aromatic hydrocarbons such as benzene, toluene, xylene, pentane, hexane and heptane. It is preferred to wash with an aliphatic hydrocarbon such as octane and decane, and an alicyclic hydrocarbon such as cyclopentane and cyclohexane before use. The washing temperature at that time is usually -5.
The temperature is 0 to 200 ° C, preferably 0 to 150 ° C, more preferably 50 to 150 ° C.

The contact of the organoaluminum oxy compound (B) with the transition metal compound (A-1) and the transition metal compound (A-2) according to the present invention is carried out in the presence or absence of a monomer in advance. Alternatively, they may be introduced into the polymerization system without prior contact. The order of contacting the organoaluminum oxy compound (B) with the transition metal compound (A-1) and the transition metal compound (A-2) is arbitrarily selected, but the transition metal compound (A-1) and the transition metal A method in which the compound (A-2) is mixed in advance and then contacted with the organoaluminum oxy compound (B) is preferable. When the organoaluminum oxy compound and the transition metal compound are brought into contact with each other in advance, their reactions are usually carried out in an inert solvent. Examples of the solvent used here include benzene,
Aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclopentane and cyclohexane can be used. The organoaluminum oxy compound (B) used in the present invention and the transition metal compound (A-
The contact ratio between 1) and the transition metal compound (A-2) is [B] the number of moles of the aluminum atom of the organoaluminum oxy compound (B), the number of moles of the transition metal compound (A-1) and the transition metal compound. When the sum of the number of moles of (A-2) is [A], the value of [A] / [B] is 1/5 to 1/10000,
It is preferably 1/10 to 1/2000. The contact temperature of the component (A) and the component (B) used in the present invention is usually -50 to 150 ° C, preferably 0 to 100.
° C.

The catalyst used in the method for producing a polyolefin according to the present invention is formed from the above-mentioned (A-1) transition metal compound, (A-2) transition metal compound, (B) organoaluminum oxy compound, Although it can be used as it is at the time of polymerization, it is preferably used together with an organoaluminum compound. The organoaluminum compound used in the polymerization is not particularly limited, but trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec aluminum.
-Butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, trialkylaluminum such as tricyclohexylaluminum, dimethylaluminum chloride, dialkylaluminum halide such as diethylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum. It is selected from dialkylaluminum alkoxides such as methoxide and diethylaluminum ethoxide, and dialkylaluminum aryloxides such as diethylaluminum phenoxide. Among them, trialkylaluminum having at least one linear alkyl group having 4 or more carbon atoms, particularly trinormal butylaluminum,
It is preferably selected from trinormal hexyl aluminum and trinormal octyl aluminum. The amount used is the ratio ([A] / [[A] / [A ')] of the sum [A] of the transition metal compounds (A-1) and (A-2) and the number [B'] of the aluminum atoms of the organoaluminum compound. B '])
At 1/10 to 1/100000, preferably 1/10
It is in the range of 0 to 1/10000. Further, the organoaluminum compound used during the polymerization may be used in contact with the organoaluminum oxy compound (B) immediately before the polymerization, the transition metal compound, or a contact product thereof, or may be used without prior contact. May be.

By using the method of the present invention, homopolymerization of ethylene and copolymerization with other α-olefins can be carried out. The α-olefin used in the copolymerization is propylene, 1- Butene, 1-pentene, 1
-Heptene, 1-octene, 1-decene, 4-methyl-
1-pentene, cyclopentene, cyclopentadiene,
Examples thereof include olefins such as butadiene, 1,5-hexadiene, 1,4-hexadiene, and 1,4-pentadiene, cyclic olefins, and dienes. Two or more kinds of these comonomers can be mixed and used for copolymerization with ethylene.

The polymerization method used in the present invention may be any of solution polymerization, slurry polymerization and gas phase polymerization. Preferably, it is slurry polymerization or gas phase polymerization. Also, multi-stage polymerization is possible. Alternatively, it is possible to prepolymerize the olefin. Regarding the amount of the polymerization catalyst used in the method for producing a polyolefin according to the present invention, when expressed by the concentration of the transition metal compound in the polymerization reaction system, it is usually 10 ⁻⁸ to 10 ⁻² mol / l, preferably 1
It is preferably in the range of 0 ^-7 to 10 ^-3 mol / l.
The olefin pressure of the reaction system is not particularly limited, but is preferably in the range of normal pressure to 50 kg / cm ² G, and the polymerization temperature is not limited, but is preferably -30 ° C to 200.
It is in the range of ° C. Particularly preferably, it is in the range of 0 ° C to 120 ° C. More preferably, it is 50 to 90 ° C. The molecular weight at the time of polymerization can be controlled by known means, for example, selection of temperature or introduction of hydrogen.

The polymer or copolymer of the present invention has the following features. First, it has a wide range of molecular weights. That is, depending on the kind of transition metal compound, the polymerization temperature or the amount of hydrogen introduced during the polymerization, the MFR at 190 ° C. and a load of 21.6 kg is 0.0001 g / 10 min.
To 190 ° C, MFR 1000 at load 2.16kg
A range of 0 g / 10 min can be manufactured. Secondly, the polymer or copolymer of the present invention has an essentially narrow molecular weight distribution. That is, Mw / Mn calculated from gel permeation chromatography (GPC) is about 2 to 4, and since there are few low molecular weight components, there is almost no smoke during molding. Thirdly, the relationship between the value of Mw / Mn calculated by gel permeation chromatography (GPC) and Mz / Mw is Mz / Mw ≧ Mw / Mn. Fourth, Mw / Mn is a value of 2 to 4, and although the molecular weight distribution is narrow, the ratio of MFR at 190 ° C and a load of 21.6 kg and MFR at 190 ° C and a load of 2.16 kg (HLMFR / MFR) is in the range of approximately 14-80. Fifth, since the melt tension is high, the moldability is excellent. The polymer or copolymer according to the present invention is in the form of particles having an average particle size of about 200 to 800 μm, a high bulk density of 0.30 to 0.45 g / cc, and excellent powder properties.

The copolymer of the present invention is essentially excellent in randomness and has a narrow composition distribution. Therefore, the obtained resin has good properties such as excellent transparency, a small amount of extracted components, and excellent low-temperature heat sealability. For the evaluation of the composition distribution, for example, the method by classification as shown in Macromolecules 15,1150 (1982) is the most accurate,
For convenience, a method using DSC as shown in J. Applied Polymer Science, 44, 425 (1992) may be used. In this method, for example, an ethylene copolymer having a wide composition distribution, which is polymerized with a general Ziegler-Natta catalyst, has a melting point near 120 ° C, and in some cases, a plurality of melting points around 100 ° C. On the other hand, for ethylene copolymers with a narrow composition distribution,
It has a single melting point at 115 ° C. or lower depending on the number of short chain branches.

[0035]

EXAMPLES Next, the present invention will be specifically described by way of examples. The analytical instruments used for measuring the physical properties are as follows. MFR (melt flow rate) is JIS K-6
According to 760, the temperature was 190 ° C. and the load was 2.16 kg. The HLMFR (high load melt flow rate) was measured under the load of 21.6 kg. MT is
Using polymer powder as a measurement sample, using MT measuring instrument manufactured by Toyo Seiki Seisakusho, resin temperature 190 ° C, extrusion speed 1
5 mm / min, winding speed 6.5 m / min, nozzle diameter 2.0
The measurement was performed under the conditions of 95 mm and a nozzle length of 8 mm. Molecular weight (Mn, Mw, Mz) and molecular weight distribution (Mw / Mn, M
z / Mw) was measured using GPC (150C manufactured by Waters, column shodex). The melting point was measured using Perkin Elmer (DSC-7) under the condition of 10 ° C / min. The amount of n-hexane soluble component of the polymer (the lower the soluble component, the lower the low molecular weight component) was, using a Soxhlet extractor, about 5 g of the polymer was added to n-hexane 2
It is determined by extracting with 00 ml for 4 hours, measuring the weight of the n-hexane-insoluble portion, and subtracting the weight of the n-hexane-insoluble portion from the charged polymer weight.

Reference Example 1 [Preparation of aluminoxane] 200 m fully nitrogen-substituted
50 ml of dry toluene was added to the 1-flask and Al was added to it.
2.5 g of ₂ (SO ₄ ) ₃ · 14H ₂ O was suspended. After cooling to −20 ° C., 30 mmol of trimethylaluminum (1.11 m
ol / l toluene solution (27 ml) was added over 15 minutes, the temperature was raised to 80 ° C., and the mixture was stirred for 7 hours. Then, the aluminum sulfate compound was removed under a nitrogen atmosphere to give 0.35
70 ml of a mol / l aluminoxane suspension in toluene
Was recovered.

Reference Example 2 [Supporting aluminoxane on carrier] 25 ml of toluene and 1.5 g of silica (Davison 952 was calcined at 300 ° C. for 4 hours) in a 100 ml flask which was sufficiently replaced with nitrogen.
37 ml of the above methylaluminoxane (0.35 M (Al atom conversion) toluene solution, methyl group / aluminum atom = 1.32) was added to this suspension, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the solvent was distilled off under reduced pressure. 50 ml of heptane was added, and the mixture was stirred at 80 ° C. for 4 hours. Then, the solid component was obtained by washing twice with heptane at 80 ° C. The solid component obtained is 33w
t% was aluminoxane.

The synthesis of the metallocene complexes used in the examples was carried out according to the procedure described in Inorg. For bis (normal butylcyclopentadienyl) zirconium dichloride. Che
m. , 30,853 (1991), bis (1,2,4-)
JP-A-63-235309 for trimethylcyclopentadienyl) zirconium dichloride, and Organom for dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride.
It was performed by the method described in et allics, 13, 954 (1994).

Reference Example 3 [Preparation of transition metal compound (A-1) dimethylsilylenebis (normal butylcyclopentadienyl) zirconium dichloride] In a 500 ml container sufficiently replaced with argon, dimethylvir (normal butylcyclopentadiene) was added. 4.9 g (16.0 mmol) of phenyl) silane was added,
It was dissolved and diluted with 200 ml of dry THF. And n
-BuLi (1.60 mol / l hexane solution) 2
0.0 ml (32.0 mmol) was added under ice cooling. After reacting for 3 hours at room temperature, THF was distilled off under reduced pressure, and the residue was washed with hexane. Further, 100 ml of dry dichloromethane was added while cooling to -78 ° C to obtain a solution.
Zirconium tetrachloride in a flask prepared separately 3.
4 g (15.0 mmol) was added and suspended in 100 ml of dry dichloromethane. This was cooled to −78 ° C., and the dichloromethane solution was added with a cannula while cooling. After stirring at −78 ° C. for 1 hour, the temperature was returned to room temperature and the reaction was performed for 12 hours. After distilling off dichloromethane, the residue was extracted with hexane, hexane was further distilled off, and an oily substance was separated. This was recrystallized by adding pentane to obtain colorless crystals.

Reference Example 4 [Preparation of transition metal compound (A-2) dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (fluorenyl) zirconium dichloride] In a 300 ml container sufficiently replaced with argon, Dimethyl (2-methyl-7- (1-naphthyl) indenyl) (fluorenyl) silane 6.5 g (13.6 mmo)
1) was added, dissolved and diluted with 100 ml of dry THF. To this, 18.7 ml (28.7 mmol) of n-BuLi (1.65 mol / l hexane solution) was added under ice cooling. After reacting for 2 hours at room temperature, THF was distilled off under reduced pressure. Further, while cooling to -78 ° C, 50 ml of dry toluene was added to obtain a greenish brown suspension solution. In a separately prepared flask, 3.2 g (1
(3.6 mmol) was added and suspended with 100 ml of dry toluene. This was cooled to −78 ° C., and the above green-brown suspension solution was added with a cannula while cooling. 1 at -78 ° C
After stirring for an hour, the mixture was returned to room temperature and reacted for 10 hours to obtain a red suspension solution. The suspension solution was centrifuged to remove the toluene solution portion and separate a red solid. This was extracted into 600 ml of dry methylene chloride with a Soxhlet extractor, and the obtained red transparent solution was concentrated to obtain red crystals.

Example 1 A hexane solution of tri-n-butylaluminum (0.5 mol / l) was placed in an autoclave made of SUS and having an internal volume of 1.5 l which had been sufficiently replaced with nitrogen.
Of 1.6 ml, and a toluene suspension of aluminoxane (0.35 mol / l) prepared in Reference Example 1 above for 3.7 m
1, a solution of 0.12 mg of bis (n-butylcyclopentadienyl) zirconium dichloride dissolved in 1 ml of hexane and 1.84 mg of dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (fluorenyl) zirconium dichloride. After introducing a mixed solution of a solution dissolved in 7 ml of toluene and 800 ml of isobutane, 70
The temperature was raised to ° C. Mixed gas of ethylene and hydrogen (H ₂ / C ₂
Polymerization was started by introducing H ₄ (molar ratio) = 4 × 10 ⁻⁵ , and the mixed gas pressure was 10 kg / cm ² and the temperature was 30 at 70 ° C.
Partial polymerization was carried out to obtain 93 g of a polymer. The activity per aluminoxane is 245 g-polymer / g-aluminoxane.hr.atm, and the activity per complex is 950.
It was 0 g-polymer / g-complex.hr.atm. The MFR of this polymer at 190 ° C. and a load of 2.16 kg is 0.21 g / 10 min, and at 190 ° C. and a load of 21.
MFR at 6kg and M at 190 ° C, load 2.16kg
The ratio of FR (HLMFR / MFR) is 48.2, and M
w / Mn is 3.62, Mz / Mw is 3.80, melt tension is 19.0 g, and hexane-soluble component amount is 0.58 w.
t%.

Example 2 Polymerization was performed in the same manner as in Example 1 except that 225 mg of aluminoxane supported on silica prepared in Reference Example 2 was used instead of the toluene suspension of aluminoxane, and 103 g of a polymer was obtained. It was The activity per aluminoxane is 275 g-polymer / g-aluminoxane.hr.atm, and the activity per complex is 10
It was 500 g-polymer / g-complex / hr / atm. M of this polymer at 190 ° C. and a load of 2.16 kg
FR is 0.17g / 10min, MFR at 190 ° C, load 21.6kg and 190 ° C, load 2.16kg.
The MFR ratio (HLMFR / MFR) was 54.5, Mw / Mn was 3.80, Mz / Mw was 4.04, the melt tension was 19.5 g, and the amount of the hexane-soluble component was 0.
It was 62 wt%.

(Example 3) A hexane solution of tri-normal-butylaluminum (0.5 mol / l) was placed in an autoclave made of SUS and having an internal volume of 1.5 l that had been sufficiently replaced with nitrogen.
1.6 ml, 225 mg of aluminoxane supported on silica prepared in Reference Example 2 above, and 0.12 m of bis (n-butylcyclopentadienyl) zirconium dichloride.
g in 1 ml of hexane and a solution of dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (fluorenyl) zirconium dichloride (1.84 mg) in 7 ml of toluene and isobutane 8
After introducing 00 ml, the temperature was raised to 70 ° C. Polymerization was initiated by introducing ethylene together with 48 g of 1-hexene, and polymerization was carried out at 70 ° C. for 30 minutes at an ethylene pressure of 10 kg / cm ² , to obtain 59 g of a polymer. The activity per aluminoxane is 158 g-polymer / g-aluminoxane.hr.atm, and the activity per complex is 6050 g.
-Polymer / g-complex / hr / atm. The MFR of this polymer at 190 ° C. and a load of 2.16 kg is 0.
03g / 10min, 190 ° C, load 21.6k
MFR in g and MFR at 190 ° C and a load of 2.16 kg
Ratio (HLMFR / MFR) is 82.7, and Mw /
Mn was 3.24, Mz / Mw was 3.35, and the hexane-soluble component amount was 0.63 wt%. Further, the melting point showed a single peak and was 102.5 ° C., and the melt tension could not be measured.

Example 4 A hexane solution of tri-n-butylaluminum (0.5 mol / l) was placed in an autoclave made of SUS and having an internal volume of 1.5 l which had been sufficiently replaced with nitrogen.
1.6 ml, 225 mg of aluminoxane supported on silica prepared in Reference Example 2 above, 0.22 m of bis (n-butylcyclopentadienyl) zirconium dichloride.
a solution of 1 g of hexane dissolved in 1 ml of hexane and 1.69 mg of dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (fluorenyl) zirconium dichloride dissolved in 7 ml of toluene, and isobutane 8
After introducing 00 ml, the temperature was raised to 70 ° C. Mixed gas of ethylene and hydrogen (H ₂ / C ₂ H ₄ (molar ratio) = 4 × 10
^-5 ) is introduced to start the polymerization, and the mixed gas pressure is 10k.
performs 30 minutes of polymerization at ^{g / cm 2, 70 ℃,} 142g
Was obtained. 380 activity per aluminoxane
g-polymer / g-aluminoxane.hr.atm, activity per complex is 14900 g-polymer / g-
Complex · hr · atm. 190 of this polymer
MFR at ℃, load 2.16kg is 0.62g / 10m
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 25.5 and Mw / Mn is 2.7.
9, Mz / Mw is 3.23, melt tension is 12.5
The amount of g and hexane-soluble component was 0.55 wt%.

Example 5 A hexane solution of tri-n-butylaluminum (0.5 mol / l) was placed in an autoclave made of SUS and having an internal volume of 1.5 l that had been sufficiently replaced with nitrogen.
Of dimethylsilylene bis (n-butylcyclopentadienyl) zirconium dichloride 0.25 mg in hexane 1 ml and dimethylsilylene (2- Methyl-4- (1-naphthyl)
After introducing 1.72 mg of indenyl) (fluorenyl) zirconium dichloride in 7 ml of toluene and 800 ml of isobutane, the temperature was raised to 70 ° C. Polymerization was started by introducing ethylene, and the polymerization was carried out at 70 ° C. for 30 minutes at an ethylene pressure of 10 kg / cm ² to obtain 79 g of a polymer. The activity per aluminoxane is 210 g-polymer / g-aluminoxane.hr.
The activity per complex was 8050 g-polymer / g-complex · hr · atm. The MFR of this polymer at 190 ° C. and a load of 2.16 kg is 0.92 g /
10 min, M at 190 ° C, load 21.6 kg
Ratio of FR and MFR at 190 ° C and load 2.16 kg (H
LMFR / MFR) is 44.7, Mw / Mn is 3.74, Mz / Mw is 5.02, and melt tension is 1
0.2 g, and the amount of hexane-soluble components was 0.58 wt%.

(Example 6) A hexane solution of trinormal butyl aluminum (0.5 mol / l) was placed in an autoclave made of SUS and having an internal volume of 1.5 l which had been sufficiently replaced with nitrogen.
1.6 ml, 225 mg of aluminoxane supported on silica prepared in Reference Example 2 above, 0.25 m of bis (n-butylcyclopentadienyl) zirconium dichloride.
g was dissolved in 1 ml of hexane, a mixed solution of a solution of 1.94 mg of dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride in 8 ml of toluene and 800 ml of isobutane were introduced, and then the temperature was raised to 70 ° C. Warmed. Mixed gas of ethylene and hydrogen (H
₂ / C ₂ H ₄ (molar ratio) = 4 × 10 ⁻⁵ ) was introduced to initiate polymerization, and mixed gas pressure was 10 kg / cm ² , 70 ° C.
Polymerization was carried out for 30 minutes to obtain 163 g of polymer.
The activity per aluminoxane is 435 g-polymer / g-
Aluminoxane.hr.atm, activity per complex is 14900 g-polymer / g-complex.hr.atm
Met. 190 ° C of this polymer, load 2.16 kg
MFR at 0.47g / 10min, 190
MFR at 190 ° C., load 21.6 kg and 190 ° C., load 2.
The ratio of MFR at 16kg (HLMFR / MFR) is 3
8.3, Mw / Mn was 3.11, Mz / Mw was 3.52, the melt tension was 14.5 g, and the hexane-soluble component amount was 0.61 wt%.

Comparative Example 1 A hexane solution of tri-n-butylaluminum (0.5 mol / l) was placed in an autoclave made of SUS and having an internal volume of 1.5 l which had been sufficiently replaced with nitrogen.
1.6 ml, 74 mg of aluminoxane supported on silica prepared in Reference Example 2 above, and 0.40 mg of bis (n-butylcyclopentadienyl) zirconium dichloride.
Solution of 2 in hexane and isobutane 800
After introducing ml, the temperature was raised to 70 ° C. Polymerization is started by introducing ethylene, and ethylene pressure is 10 kg / cm
^2. Polymerization was carried out at 70 ° C. for 30 minutes to obtain 112 g of polymer. The activity per aluminoxane was 1820 g-polymer / g-aluminoxane.hr.atm, and the activity per complex was 112000 g-polymer / g-complex.hr.atm. The MFR of this polymer at 190 ° C. and a load of 2.16 kg is 0.13 g / 10 min, and the MFR at 190 ° C. and a load of 21.6 kg and 190
Ratio of MFR at ℃ and load of 2.16 kg (HLMFR / M
FR) is 15.8, Mw / Mn is 2.31, Mz
/ Mw was 1.98, the melt tension was 4.8 g, and the amount of hexane-soluble components was 0.54 wt%.

(Comparative Example 2) A hexane solution of tri-n-butylaluminum (0.5 mol / l) was placed in an autoclave made of SUS and having an internal volume of 1.5 l which had been sufficiently replaced with nitrogen.
1.6 ml, 225 mg of aluminoxane supported on silica prepared in Reference Example 2 above, and dimethylsilylene (2
After introducing a solution of 2.02 mg of -methyl-4- (1-naphthyl) indenyl) (fluorenyl) zirconium dichloride in 8 ml of toluene and 800 ml of isobutane, the temperature was raised to 70 ° C. Polymerization was started by introducing ethylene, ethylene pressure was 10 kg / cm ² , 70 ° C.
Polymerization was carried out for 30 minutes to obtain 26 g of a polymer. The activity per aluminoxane was 70 g-polymer / g-aluminoxane.hr.atm, and the activity per complex was 2500 g-polymer / g-complex.hr.atm. M of this polymer at 190 ° C. and a load of 21.6 kg
FR is 0.02, Mw / Mn is 3.94, Mz /
Mw is 2.65, and the amount of hexane-soluble components is 1.24.
wt%. The melt tension could not be measured.

(Comparative Example 3) A hexane solution of tri-normal-butylaluminum (0.5 mol / l) was placed in an SUS autoclave having an internal volume of 1.5 l which had been sufficiently replaced with nitrogen.
1.6 ml, 90 mg of aluminoxane supported on silica prepared in Reference Example 2 above, and 0.09 mg of bis (n-butylcyclopentadienyl) zirconium dichloride.
Was dissolved in 1 ml of hexane and bis (1,2,4-
After introducing a mixed solution of a solution of 0.40 mg of trimethylcyclopentadienyl) zirconium dichloride in 2 ml of toluene and 800 ml of isobutane, the temperature was raised to 70 ° C. Polymerization was started by introducing ethylene, and the polymerization was carried out at 70 ° C. for 30 minutes at an ethylene pressure of 10 kg / cm ² to obtain 74 g of a polymer. The activity per aluminoxane is 490 g-polymer / g-aluminoxane.hr
-Atm, and the activity per complex was 35700 g-polymer / g-complex-hr-atm. The MFR of this polymer at 190 ° C and a load of 2.16 kg is 0.04.
g / 10 min, the ratio of MFR at 190 ° C., load 21.6 kg and MFR at 190 ° C., load 2.16 kg (HLMFR / MFR) is 34.5, and Mw / Mn
Was 2.67, Mz / Mw was 2.24, the melt tension was 15.6 g, and the hexane-soluble component amount was 0.75 wt%.

(Comparative Example 4) A hexane solution of tri-n-butylaluminum (0.5 mol / l) was placed in an autoclave made of SUS and having an internal volume of 1.5 l which had been sufficiently replaced with nitrogen.
1.6 mg, 45 mg of aluminoxane supported on silica prepared in Reference Example 2 above, and 0.09 mg of bis (n-butylcyclopentadienyl) zirconium dichloride.
Was dissolved in 1 ml of hexane, a mixed solution of a solution of 0.23 mg of dimethylsilylenebis (n-butylcyclopentadienyl) zirconium dichloride in 3 ml of toluene and 800 ml of isobutane were introduced, and then 70
The temperature was raised to ° C. Polymerization was initiated by introducing ethylene, and the polymerization was carried out at 70 ° C. for 30 minutes at an ethylene pressure of 10 kg / cm ² to obtain 124 g of a polymer. The activity per aluminoxane is 1650 g-polymer / g-aluminoxane.hr.atm, and the activity per complex is 775.
It was 00 g-polymer / g-complex.hr.atm.
MFR of this polymer at 190 ° C and a load of 2.16 kg
Is 4.40 g / 10 min and Mw / Mn is 2.3.
1, Mz / Mw was 2.04, and the melt tension was 0.1.
The amount of g and hexane-soluble component was 0.78 wt%.

[0051]

EFFECTS OF THE INVENTION According to the present invention, it is possible to produce a polyolefin having excellent moldability, a small amount of low molecular weight components, no problems such as smoking during molding, and a narrow composition distribution in the copolymer.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shintaro Inazawa, Oita City, Oita Prefecture, No. 2 Nakasu, Showa Denko K.K.

Claims (4)

[Claims] 1. (A-1) General formula (1): [In the formula, R ^{1 to} R ¹⁰ are hydrogen or a hydrocarbon group (having 1 carbon atom).
Is an alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc. having .about.20), an alkylsilyl group, an alkylgermyl group, or a 4- to 6-membered ring having a carbon-carbon bond, which may be the same or different. , Each Q is a hydrocarbon group having 1 to 20 carbon atoms such as aryl, alkyl, alkenyl, alkylaryl, and arylalkyl, an alkoxy group, an aryloxy group, a siloxy group,
Hydrogen or halogen, which may be the same or different, Me is a transition metal of Group 3, 4, 5 or 6 of the periodic table, and p is 0 or 1. ] Or general formula (2) [In the formula, R ^{11 to} R ¹⁸ are hydrogen or a hydrocarbon group (having 1 carbon atom).
To alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc.), alkylsilyl group, alkylgermyl group, which may be the same or different, and R ¹⁹ is an alkylene group having 1 to 20 carbon atoms. , An alkylgermylene group or an alkylsilylene group, each Q is aryl having 1 to 20 carbons, alkyl,
It is a hydrocarbon group such as alkenyl, alkylaryl, arylalkyl, etc., an alkoxy group, an allyloxy group, a siloxy group, hydrogen or halogen, which may be the same or different, and Me is a group 3, 4, 5 or 6 of the periodic table. Of the transition metal of formula (3) and p is 0 or 1], and (A-2) a general formula (3): [In the formula, R ^{20 to} R ³¹ are hydrogen or a hydrocarbon group (having 1 carbon atom).
Is an alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc. having .about.20), an alkylsilyl group, an alkylgermyl group, or a 4- to 6-membered ring having a carbon-carbon bond, which may be the same or different. , R ³² is an alkylene group having 1 to 20 carbon atoms, an alkylgermylene group or an alkylsilylene group, and each Q is a hydrocarbon group having 1 to 20 carbon atoms such as aryl, alkyl, alkenyl, alkylaryl and arylalkyl, An alkoxy group, an aryloxy group, a siloxy group, hydrogen or halogen, which may be the same or different, and M
e is a transition metal of Group 3, 4, 5 or 6 of the periodic table, and p is 0 or 1. ] At least one transition metal compound selected from the transition metal compounds represented by,
(B) A method for producing a polyolefin using a catalyst composed of an organoaluminum oxy compound. 2. (A-1) General formula (1): [In the formula, R ^{1 to} R ¹⁰ are hydrogen or a hydrocarbon group (having 1 carbon atom).
Is an alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc. having .about.20), an alkylsilyl group, an alkylgermyl group, or a 4- to 6-membered ring having a carbon-carbon bond, which may be the same or different. , Each Q is a hydrocarbon group having 1 to 20 carbon atoms such as aryl, alkyl, alkenyl, alkylaryl, and arylalkyl, an alkoxy group, an aryloxy group, a siloxy group,
Hydrogen or halogen, which may be the same or different, Me is a transition metal of Group 3, 4, 5 or 6 of the periodic table, and p is 0 or 1. ] At least one transition metal compound selected from the transition metal compounds represented by the formula (A-2) and the general formula (3): [In the formula, R ^{20 to} R ³¹ are hydrogen or a hydrocarbon group (having 1 carbon atom).
Is an alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc. having .about.20), an alkylsilyl group, an alkylgermyl group, or a 4- to 6-membered ring having a carbon-carbon bond, which may be the same or different. , R ³² is an alkylene group having 1 to 20 carbon atoms, an alkylgermylene group or an alkylsilylene group, and each Q is a hydrocarbon group having 1 to 20 carbon atoms such as aryl, alkyl, alkenyl, alkylaryl and arylalkyl, An alkoxy group, an aryloxy group, a siloxy group, hydrogen or halogen, which may be the same or different, and M
e is a transition metal of Group 3, 4, 5 or 6 of the periodic table, and p is 0 or 1. ] At least 1 sort (s) of transition metal compound selected from the transition metal compounds represented by these, and the manufacturing method of the polyolefin which uses the catalyst which consists of (B) organoaluminum oxy compound. 3. The transition metal compound represented by the general formula (3) is dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride or dimethylsilylene (2-methyl-4- (1-naphthyl)). Indenyl) (fluorenyl) zirconium dichloride, The manufacturing method of the polyolefin of Claim 1 or Claim 2 characterized by the above-mentioned. 4. The method for producing a polyolefin according to claim 1, wherein the organoaluminum oxy compound is supported on a carrier.