JPH10231311A - Catalyst component for polymerizing alpha-olefin, catalyst and polymerization of alpha-olefin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalyst component capable of raising the polymerization activities based on a transition metal and aluminum and producing a polymer having a high molecular weight and a narrow distribution of the molecular weight by supporting a specific metallocene-based transition metallic compound on an ion exchangeable phyllosilicate. SOLUTION: This catalyst is obtained by combining (A) a metallocene-based transition metallic compound represented by formula I [Cp is cyclopentadienyl; R<1> and R<2> are each a group, composed of a halogen, a silicon-containing group, a 1-20C (halogen-substituted)hydrocarbon group, etc., substituted at the 1- and the 3-positions of Cp; M is Ti, Zr, or Hf; X<1> and X<2> are each a halogen, a 1-20C hydrocarbon group, an alkoxy, etc.] with (B) an ion exchangeable phyllosilicate (e.g. a smectite, a vermiculite or a mica group). The resultant catalyst component can be combined with (C) a compound represented by formula II [R<3> is a 1-20C hydrocarbon group; X<3> is a halogen, H, an alkoxy, etc.; 0<(a)<=3] to prepare a catalyst suitable for the vapor-phase polymerization and slurry polymerization of an α-olefin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a catalyst component for α-olefin polymerization, a catalyst, and a method for obtaining an α-olefin polymer in a high yield by using the catalyst.
In detail, the present invention can be applied to solution polymerization, high pressure polymerization, slurry polymerization, and gas phase polymerization, and particularly when applied to slurry polymerization and gas phase polymerization, α-olefins having a high molecular weight are used. The present invention relates to a catalyst component for α-olefin polymerization, a catalyst capable of producing a polymer, and a method for obtaining an olefin polymer in a high yield by using the catalyst.

[0002]

2. Description of the Related Art In producing an olefin polymer by polymerizing an olefin, a method using a catalyst comprising (1) a metallocene compound and (2) an aluminoxane has been proposed (Japanese Patent Application Laid-Open No. 58-119309, JP-A-2-167307). A polymerization method using these catalysts is based on a conventional Ziegler-based compound comprising a titanium compound or a vanadium compound and an organoaluminum compound.
Compared with the method using a Natta catalyst, a polymer having a very high polymerization activity per transition metal and a sharp molecular weight distribution and a sharp composition distribution can be obtained.

However, in order to industrially obtain sufficient polymerization activity using these catalysts, a large amount of aluminoxane is required, so that the polymerization activity per aluminum is low, which is not only uneconomical, but also produces It was necessary to remove catalyst residues from the polymer. On the other hand, there has been proposed a method of polymerizing an olefin using a catalyst in which one or both of the above metallocene complex and aluminoxane are supported on an inorganic oxide such as silica or alumina (Japanese Patent Application Laid-Open No. 61-1986).
Nos. 108610, 60-135408, 61-296008, JP-A-3-74412, and 3-74415. Further, a method of polymerizing an olefin with a catalyst in which one or both of a metallocene compound and an organoaluminum compound are supported on an inorganic oxide or an organic substance such as silica or alumina has been proposed (JP-A-1-101303, JP-A-1-101303). 1-2073
No. 03, JP-A-3-234709 and JP-T-Hei 3-5
01869). Further, a method using a catalyst obtained by prepolymerizing these supported catalysts has also been proposed (JP-A-3-234710, etc.).

[0004] However, even in these proposed methods, the polymerization activity per aluminum was still not sufficient, and the amount of catalyst residue in the product was not negligible. As a solution to these problems,
A catalyst comprising an ion-exchangeable layered compound or an inorganic silicate, an organoaluminum and a metallocene compound and a catalyst obtained by prepolymerizing the same have been proposed (Japanese Patent Laid-Open No. 5-2 / 1993).
No. 95022).

With these catalysts, although sufficient polymerization activity per transition metal or aluminum is obtained, it has been found that hydrogen is generated during polymerization and the generated hydrogen reduces the molecular weight of the polymer. In order to obtain, it is necessary to control a very small amount of hydrogen or to take special measures such as removing generated hydrogen.

On the other hand, in a catalyst comprising a metallocene compound and an aluminoxane, when at least one of the ligands of the metallocene compound is a cyclopentadienyl ligand having two different substituents, the molecular weight is increased. A method for obtaining an olefin polymer having a narrow molecular weight distribution has been proposed (JP-A-5-148317). However, in the catalyst system composed of the metallocene compound and the aluminoxane, when at least one of the ligands of the metallocene compound is a cyclopentadienyl ligand having the same two substituents, the obtained It has been reported that the molecular weight distribution of the resulting polymer widens.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the above problems and provides a catalyst component for α-olefin polymerization capable of obtaining a polymer having a large molecular weight and a narrow molecular weight distribution, a catalyst, and the use of the catalyst. It is another object of the present invention to provide an α-olefin polymerization method.

[0008]

Means for Solving the Problems The present inventors have conducted studies to solve the above-mentioned problems, and as a result, the ion-exchanged layered silicate has two positions at the 1-position and the 3-position of the cyclopentadienyl group. By supporting a specific metallocene transition metal compound having a substituent, a catalyst system capable of producing a polymer having a sufficiently high polymerization activity per transition metal and aluminum, a large molecular weight, and a narrow molecular weight distribution. Found and arrived at the present invention.

That is, the present invention firstly provides an α-olefin polymerization catalyst component obtained by combining the following components [A] and [B]. [A] a metallocene transition metal compound represented by the following formula [1]

[0010]

Embedded image (CpR ¹ R ² ) ₂ MX ¹ X ² [1]

(Cp represents a cyclopentadienyl group,
R ¹ and R ² each independently represent a halogen, a silicon-containing group, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group, an alkoxy group, an aryloxy group or a cyclopentadienyl group consisting of an amino group; And M is titanium, zirconium or hafnium, and X ¹ and X ² are each independently a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, Group, aryloxy group or amide group. )

[B] Ion-exchangeable phyllosilicate Secondly, the present invention provides an α-olefin polymerization catalyst obtained by combining the above-mentioned catalyst component with the following component [C]. [C] an organoaluminum compound represented by the following formula [2]

[0013]

## STR4 ## R _{³ a} AlX ^{3 _3-a} [2]

(In the formula (2), R ³ has 1 to 2 carbon atoms.
A hydrocarbon group of 0, X ³ represents a halogen atom, a hydrogen atom, an alkoxy group, or an amide group, and a is a number satisfying 0 <a ≦ 3). Thirdly, the present invention provides a method for polymerizing α-olefins, which comprises polymerizing α-olefins in the presence of the above-mentioned catalyst.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The metallocene transition metal compound [A] used in the catalyst component of the present invention comprises a substituted cyclopentadienyl ligand having substituents at the 1- and 3-positions and titanium, zirconium or It is an organometallic compound consisting of hafnium. Preferred as such a metallocene transition metal compound is a compound represented by the following general formula [1].

[0016]

Embedded image (CpR ¹ R ² ) ₂ MX ¹ X ² [1]

In the formula (1), Cp represents a cyclopentadienyl group, and R ¹ and R ² are each independently a halogen, a silicon-containing group, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group. , An alkoxy group, an aryloxy group or an amino group at the 1- and 3-positions of the cyclopentadienyl group. Such a substituted cyclopentadienyl group is specifically represented by the following formula.

[0018]

Embedded image

M is titanium, zirconium or hafnium, and X ¹ and X ² are each independently a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
It represents an alkoxy group, an aryloxy group or an amide group.
In the above general formula [1], R ¹ and R ² may be the same or different, and specific examples of R ¹ and R ² include halogen such as fluorine, chlorine, bromine and iodine, trimethylsilyl group, triethylsilyl. Group, silicon-containing group such as triphenylsilyl group, methyl group, ethyl group, n-propyl group,
i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-nonyl group, n-decyl group, phenyl group , A 4-methylphenyl group or the like having 1 to 1 carbon atoms
20 hydrocarbon groups, or a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a pentafluorophenyl group,
1 to 1 carbon atoms such as a fluorophenyl group, a 2-fluorophenyl group, a monochloromethyl group, and a monobromomethyl group.
20 halogen-containing hydrocarbon group, methoxy group, ethoxy group, propoxy group, alkoxy group such as butoxy group, phenoxy group, 4-methylphenoxy group, aryloxy group such as pentamethylphenoxy group, dimethylamino group, diethylamino group, And amino groups such as diisopropylamino group, diphenylamino group, dicyclohexylamino group, pyridyl group and indolyl group. Of these, particularly preferred are methyl, ethyl, propyl, i
-Propyl group, n-butyl group, i-butyl group and cyclohexyl group.

Specific examples of X ¹ and X ² include a hydrogen atom, halogen such as chlorine and bromine, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
Carbon number of i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-nonyl group, n-decyl group, phenyl group, 4-methylphenyl group, etc. 1 to 20 hydrocarbon groups, methoxy group, ethoxy group, propoxy group, alkoxy group such as butoxy group, phenoxy group, 4-methylphenoxy group, aryloxy group such as pentamethylphenoxy group, dimethylamide group, diethylamide group, An amide group such as a diisopropylamide group, a diphenylamide group, and a dicyclohexylamide group, and trifluoromethanesulfonic acid can be given. Among them, chlorine, hydrogen atom, methyl group,
A dimethylamide group, a diethylamide group, and a trifluoromethanesulfonic acid group are preferred.

Specific examples of the metallocene transition metal compound represented by the above formula [1] when M is zirconium include bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis ( 1-ethyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1-n-propyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1
I-propyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride,
Bis (1-i-butyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1-t-butyl-
3-methylcyclopentadienyl) zirconium dichloride, bis (1-cyclohexyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1,3
-Dimethylcyclopentadienyl) zirconium dimethyl, bis (1-ethyl-3-methylcyclopentadienyl) zirconium dimethyl, bis (1-n-propyl-
3-methylcyclopentadienyl) zirconium dimethyl, bis (1-i-propyl-3-methylcyclopentadienyl) zirconium dimethyl, bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dimethyl, bis (1-i-butyl-3-methylcyclopentadienyl) zirconium dimethyl, bis (1-t-butyl-3-methylcyclopentadienyl) zirconium dimethyl, bis (1-cyclohexyl-3-methylcyclopentadienyl) ) Zirconium dimethyl, bis (1,
3-dimethylcyclopentadienyl) zirconium methyl chloride, bis (1-ethyl-3-methylcyclopentadienyl) zirconium methyl chloride, bis (1-
n-butyl-3-methylcyclopentadienyl) zirconium methyl chloride, bis (1-i-butyl-3-methylcyclopentadienyl) zirconium methyl chloride, bis (1-t-butyl-3-methylcyclopentadiene) Enyl) zirconium methyl chloride, bis (1,3-
Dimethylcyclopentadienyl) zirconium diethyl, bis (1-ethyl-3-methylcyclopentadienyl) zirconium diethyl, bis (1-n-butyl-3)
-Methyl-cyclopentadienyl) zirconium diethyl, bis (1-i-butyl-3-methyl-cyclopentadienyl) zirconium diethyl, bis (1-t-butyl-3-methylcyclopentadienyl) zirconium diethyl, Bis (1,3-dimethylcyclopentadienyl) zirconium diisobutyl, bis (1-ethyl-3
-Methylcyclopentadienyl) zirconium diisobutyl, bis (1-n-butyl-3-methyl-cyclopentadienyl) zirconium diisobutyl, bis (1-i
-Butyl-3-methyl-cyclopentadienyl) zirconium diisobutyl, bis (1-t-butyl-3-methylcyclopentadienyl) zirconium diisobutyl,
Bis (1,3-dimethylcyclopentadienyl) zirconium chloride monohydride, bis (1-ethyl-
3-methylcyclopentadienyl) zirconium chloride monohydride, bis (1-n-butyl-3-methyl-cyclopentadienyl) zirconium chloride monohydride, bis (1-i-butyl-3-methyl-cyclopentadiene) Enyl) zirconium chloride monohydride, bis (1-t-butyl-3-methylcyclopentadienyl) zirconium chloride monohydride,
Bis (1,3-dimethylcyclopentadienyl) zirconium dihydride, bis (1-ethyl-3-methylcyclopentadienyl) zirconium dihydride,
Bis (1-n-butyl-3-methyl-cyclopentadienyl) zirconium dihydride, bis (1-i-butyl-3-methyl-cyclopentadienyl) zirconium dihydride, bis (1-t-butyl- 3-methylcyclopentadienyl) zirconium dihydride,
Bis (1,3-dimethylcyclopentadienyl) zirconium dimethoxide, bis (1-ethyl-3-methylcyclopentadienyl) zirconium dimethoxide, bis (1-n-butyl-3-methyl-cyclopentadienyl) ) Zirconium dimethoxide, bis (1-i-butyl-3-methyl-cyclopentadienyl) zirconium dimethoxide, bis (1-t-butyl-3-methylcyclopentadienyl) zirconium dimethoxide, bis (1, 3-dimethylcyclopentadienyl) zirconium bis (dimethylamide), bis (1-ethyl-3-methylcyclopentadienyl) zirconium bis (dimethylamide), bis (1-n-butyl-3-methyl-cyclopenta Dienyl) zirconium bis (dimethylamide), bis (1-i-butyl) 3-methyl - cyclopentadienyl) zirconium bis (dimethylamide), bis (1-t-butyl-3-methylcyclopentadienyl) zirconium (dimethylamide), bis (1,3
Dimethylcyclopentadienyl) zirconium bis (diethylamide), bis (1-ethyl-3-methylcyclopentadienyl) zirconium bis (diethylamide), bis (1-n-propyl-3-methylcyclopentadienyl) zirconium bis (Diethylamide), bis (1-i-propyl-3-methylcyclopentadienyl) zirconium bis (diethylamide), bis (1-
i-butyl-3-methyl-cyclopentadienyl) zirconium bis (diethylamide), bis (1-t-butyl-3-methylcyclopentadienyl) zirconium bis (diethylamide), bis (1-cyclohexyl-3)
-Methylcyclopentadienyl) zirconium bis (diethylamide), bis (1,3-dimethylcyclopentadienyl) zirconium diethylamide monochloride,
Bis (1-ethyl-3-methylcyclopentadienyl)
Zirconium diethylamide monochloride, bis (1-
n-butyl-3-methyl-cyclopentadienyl) zirconium diethylamide monochloride, bis (1-i-
Butyl-3-methyl-cyclopentadienyl) zirconium diethylamide monochloride, bis (1-t-butyl-3-methylcyclopentadienyl) zirconium diethylamide monochloride, bis (1-methyl-3-trifluoromethylcyclopenta Dienyl) zirconium dichloride, bis (1-methyl-3-trimethylsilylcyclopentadienyl) zirconium dichloride, bis (1-cyclohexyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-
Phenylcyclopentadienyl) zirconium dichloride, bis (1-benzyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1-n-butyl-3-trifluoromethylcyclopentadienyl) zirconium dichloride, bis (1 -N-butyl-3-trimethylsilylcyclopentadienyl) zirconium dichloride, bis (1-n-butyl-3-cyclohexylcyclopentadienyl) zirconium dichloride, bis (1-n-butyl-3-phenylcyclopentadienyl) ) Zirconium dichloride, bis (1-benzyl-3)
-N-butylcyclopentadienyl) zirconium dichloride, bis (di-n-butylcyclopentadienyl)
Zirconium dichloride, bis (1-n-butyl-3-
(Ethylcyclopentadienyl) zirconium dichloride.

Among these, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride,
Bis (1-ethyl-3-methylcyclopentadienyl)
Zirconium dichloride, bis (1-n-propyl-3
-Methylcyclopentadienyl) zirconium dichloride, bis (1-i-propyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride, bis ( 1-i-butyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1-
Cyclohexyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dimethyl, bis (1-ethyl-3-methylcyclopentadienyl) zirconium dimethyl, bis (1-n -Propyl-3-methylcyclopentadienyl) zirconium dimethyl, bis (1-i
-Propyl-3-methylcyclopentadienyl) zirconium dimethyl, bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dimethyl, bis (1
-I-butyl-3-methylcyclopentadienyl) zirconium dimethyl, bis (1-cyclohexyl-3-methylcyclopentadienyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl) zirconium diethylamide, bis ( 1-ethyl-3-methylcyclopentadienyl) zirconium diethylamide, bis (1-n-propyl-3-methylcyclopentadienyl) zirconium diethylamide, bis (1-i-propyl-3-methylcyclopentadienyl) Zirconium diethylamide, bis (1-n-butyl-3-methylcyclopentadienyl) zirconium diethylamide, bis (1-i-butyl-3-methylcyclopentadienyl) zirconium diethylamide, bis (1-cyclohexyl-3-methyl) Cyclopentadienyl) zirconium diethylamide are preferred.

As the metallocene-based transition metal compound which is the component [A] of the present catalyst, when M in the formula [1] is titanium or hafnium, specifically, the zirconium compounds such as titanium and hafnium The body can be mentioned. As the component [B] of the present catalyst,
An ion-exchange layered silicate is used. The ion-exchangeable layered silicate is a silicate compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and the ions contained therein are exchangeable. Ion-exchanged layered silicates are naturally produced mainly as a main component of clay minerals, but these ion-exchanged layered silicates are not particularly limited to those of natural origin and may be artificially synthesized. .

Specific examples of the ion-exchangeable phyllosilicate include kaolins such as dickite, nacrite, kaolinite, anoxite, metahaloysite, halloysite, serpentine groups such as chrysotile, risaldite, antigolite, and montmorillonite. Zaukonite, beidellite, nontronite, saponite, bentonite,
Smectites such as hectorite and stevensite,
Vermiculite, vermiculite, illite,
Examples include mica tribes such as sericite and chlorite, attapulgite, sepiolite, palygorskite, pyrophyllite, talc, chlorite, allophane, and imogolite. These may form a mixed layer.

Among these, montmorillonite, saukonite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite,
Smectites such as teniolite and mica, vermiculites and mica are preferred. These may be used as they are without any particular treatment, or may be used in contact with a ball mill, sieving, an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or an organic acid such as formic acid, acetic acid or benzoic acid, or the like. It may be used after performing the processing of. Further, they may be used alone or as a mixture of two or more.

The above-mentioned ion-exchange layered silicate can replace and exchange cations between layers or the like with other cations by utilizing its ion-exchange property. Specifically, the alkali metals such as Na ⁺ and Li ⁺ existing between the layers are exchanged with salts, acids, alkalis, and organic compounds having other cations. The ion exchange method is not particularly limited, and a general method can be employed.

As one example, the ion exchange layered silicate is added to an aqueous solution of a salt, acid, alkali or organic compound, dispersed and stirred for a desired time. At this time, the ion exchange amount can be controlled to a desired value by appropriately selecting the concentration, temperature, and the like of the salts, acids, alkalis, or organic compounds. Specifically as such salts, acids, alkalis or organic compounds,
Examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as acetic acid and oxalic acid, and polyacids represented by heteropolyacid. In these cases, protons are exchanged between layers. After ion exchange with ammonium ions such as ammonium chloride and ammonium sulfate, protons can be introduced between the layers by heat treatment or the like. In addition, salts composed of a cation containing at least one kind of atom selected from the group consisting of Group 2 to 14 atoms and at least one kind of anion can be used. Examples of such salts include magnesium and aluminum. , Titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, tin, and other chlorides, bromides, iodides, lead sulfates, nitrates, chlorates, and perchlorates. In this case, a cation containing at least one atom selected from the group consisting of Group 2 to 14 atoms is introduced between the layers. Examples of the ion-exchangeable organic compound include monobutylammonium ion, dibutylammonium ion, tributylammonium ion, tetrabutylammonium ion, anilinium ion,
Organic compounds having an ammonium ion having at least one hydrocarbon group, such as a dimethylanilinium ion, a tetraphenylphosphonium ion, a tetrabutylphosphonium ion, or a phosphonium ion, may be mentioned. Further, organometallic compounds such as porphyrin and crown ether complex salts can be introduced. Further, by appropriately selecting the salt treatment conditions, the atoms in the layer structure can be exchanged.

When these ion-exchangeable layered silicates are used in the present catalyst, they may be used in any shape in accordance with the polymerization apparatus to be used, but are applicable to a gas phase polymerization method, a slurry polymerization method and the like. In this case, the average particle size is from 5 μm to 1
The use of granulated particles having a particle size of 00 μm is advantageous in terms of process operation because the bulk density of the catalyst and the resulting polyethylene can be increased. Further, it is preferable that these ion-exchange layered silicates are dried before reacting with the metallocene complex. In the present invention, a catalyst can be obtained by combining, for example, the following component [C] with the catalyst component obtained by combining the aforementioned component [A] and component [B].

[0029]

[Omitted] R _{³ a} AlX ^{3 _3-a} [2]

In the formula (2), R ³ has 1 to 20 carbon atoms.
X ³ represents a halogen atom, a hydrogen atom, an alkoxy group, or an amide group, and a is a number satisfying 0 <a ≦ 3.

Specific examples of the component [C] satisfying this formula include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum and tri-n-hexylaluminum, and diethylaluminum. Alkyl aluminum hydrides such as hydride, diisobutylaluminum hydride, etc., halogen-containing alkylaluminums such as diethylaluminum chloride and diisobutylaluminum chloride, alkylaluminum alkoxides such as diethylaluminum methoxide and diisobutylaluminum methoxide, diethylaluminum (diethylamide), diisobutylaluminum (diethylamide) ) And the like. Of these, trialkylaluminums such as triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, and tri-n-hexylaluminum are preferred.

The method for producing the catalyst is not particularly limited. For example, the catalyst can be produced by the following method. In an inert gas, a previously dried salt-treated or treated ion-exchanged layered silicate is suspended in a hydrocarbon solvent, and a hydrocarbon solution in which a metallocene complex is dissolved and, if necessary, organic aluminum are added. It is obtained by processing for a predetermined time.

In the present invention, the above-mentioned [A] and [B]
If necessary, add organoaluminum to the components and add α
-It is also possible to contact with an olefin or an aromatic vinyl monomer and use it after prepolymerization. Prepolymerization is usually
Performed with ethylene, but optionally other olefins,
For example, propylene, 1-butene, 4-methyl-1-pentene, α-olefins such as 3-methyl-1-pentene,
Aromatic vinyl monomers such as styrene and α-methylstyrene, or mixtures thereof can be used.

When the catalyst component of the present invention is used as a prepolymerized catalyst, a prepolymerized polymer is present in the catalyst.
The amount of the prepolymerized polymer present in the catalyst is 0.01 to 1000 g, preferably 0.1 g, per 1 g of the component [B] used, that is, 1 g of the ion-exchange layered silicate.
It is 1 g to 100 g, more preferably 1 g to 50 g. Solvents used for contacting the ion-exchange layered silicate with the metallocene transition metal compound include inert hydrocarbons,
Specifically, chain hydrocarbons such as pentane, hexane and heptane, benzene, toluene, xylene and the like are preferable. Although the contact temperature is not particularly limited, it is preferable to perform the contact between -20 ° C and 150 ° C.

The metallocene transition metal compound used for the component [B], which is an ion-exchange layered silicate, [A]
Although the amount of the component is appropriately selected, it is preferably used in an amount of 1 μmol to 1000 μmol per 1 g of the component [B]. The method of the preliminary polymerization is not particularly limited, but is usually performed by slurry polymerization in a hydrocarbon solvent. The hydrocarbon solvent used at this time is appropriately selected. For example, the hydrocarbon solvent used at the time of the above-mentioned contact is suitably used. The pre-polymerized catalyst may be used as a slurry after the completion of the pre-polymerization, or may be used, if necessary, after washing and drying to obtain a powder.
At this time, the drying conditions are not particularly limited, but preferably the drying is performed at 0 ° C. to 100 ° C. under reduced pressure or under a flow of a dry inert gas.

The catalyst of the present invention is used for the polymerization of α-olefins. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene and 4-methyl. Examples thereof include vinylcycloalkanes such as -1-pentene and vinylcyclohexane, ethylidene norbornene derivatives, styrene and styrene derivatives, and include homopolymerization and copolymerization with these monomers. The polymerization method is not particularly limited, for example,
It can be used in a gas phase polymerization method, a slurry polymerization method, a solution polymerization method, a high pressure polymerization method, or the like, but when this catalyst is used, a polymer having a high bulk density and a good particle shape can be obtained. Therefore, it is suitably used for a gas phase polymerization method and a slurry polymerization method.

[0037]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited by these examples unless departing from the gist of the present invention. In the examples, the MFR is based on JIS K6760,
It measured at 2.degree. Further, the value measured by GPC was used for Mw / Mn. That is, using a standard polystyrene having a known molecular weight, the number average molecular weight Mn and the weight average molecular weight Mw are converted into Mw / M by a universal method.
The n value was determined. The measurement is ISOC-AL manufactured by Waters.
Using C / GPC, the column was AD80M /
S, three samples were dissolved in o-dichlorobenzene, and 200 μl of a 0.2% by weight solution was used.
The test was performed at 40 ° C. at a flow rate of 1 ml / min.

Example 1 (1) Preparation of Catalyst After a 200 ml flask equipped with a stirrer was purged with nitrogen,
2.0 g (average particle size: 59 μm) of a granulated zinc ion-exchange type mica previously dried under reduced pressure at 200 ° C. for 2 hours, and bis (1,3-dimethylcyclopentadienyl) zirconium dichloride as a metallocene complex; 55.
70 ml of a complex solution in which 8 mg was dissolved in toluene was added at room temperature. After stirring for 10 minutes, heptane was added to adjust the total amount of the solvent to 200 ml, thereby preparing a slurry catalyst.

(2) Polymerization In a stainless steel, 1.0 L autoclave, which had been dried at 100 ° C. for 30 minutes under a stream of nitrogen, 500 ml of heptane, 30 ml of 1-hexene at room temperature and the above (1)
8.0 ml of the slurry catalyst prepared in
(Equivalent to 0 mg), the temperature and the pressure of ethylene were increased to 65 ° C. and 7.0 kgf / cm ² -G, respectively, to stabilize the temperature and pressure in the polymerization tank. Thereto a heptane solution of triethylaluminum (triethylaluminum 5
(Equivalent to 7 mg) was added to initiate polymerization.
The polymerization was carried out for 1.5 hours while maintaining the total pressure at 7.0 kgf / cm ² -G. After the completion of the polymerization, the reaction system was cooled, and after purging ethylene, a polyethylene slurry was extracted and filtered. The obtained polymer was dried at 100 ° C. for 12 hours to obtain 29.5 g of an ethylene / 1-hexene copolymer. Using the obtained copolymer, melt flow rate (NMR), weight average molecular weight (Mw), and number average molecular weight (Mn) were measured. Table 1 shows the results.

Example 2 In Example 1, bis (1-ethyl-3-methylcyclopentadienyl) zirconium dichloride, 60.2 mg, was used in place of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride. Catalyst preparation, polymerization and post-treatment were carried out in the same manner except that
g was obtained. Table 1 shows the results.

Example 3 In Example 1, bis (1-n-butyl-3-methylcyclopentadienyl) was used instead of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride.
Except for using 69.2 mg of zirconium dichloride, the catalyst preparation, polymerization and post-treatment were carried out in the same manner to obtain polymer 1
5.2 g were obtained. Table 1 shows the results.

Example 4 In Example 1, bis (1-i-butyl-3-methylcyclopentadienyl) was used instead of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride.
Except for using 69.2 mg of zirconium dichloride, the catalyst preparation, polymerization and post-treatment were carried out in the same manner to obtain polymer 1
5.6 g were obtained. Table 1 shows the results.

Comparative Example 1 Example 1 was repeated except that bis (n-butylcyclopentadienyl) zirconium dichloride and 64.7 mg were used in place of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride. Preparation of catalyst,
After polymerization and post-treatment, 26.2 g of a polymer was obtained. Table 1 shows the results.

Comparative Example 2 A catalyst was prepared in the same manner as in Example 1 except that bis (1,2-dimethylcyclopentadienyl) zirconium dichloride was used instead of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride. Preparation, polymerization and post-treatment were performed to obtain 14.9 g of a polymer. Table 1 shows the results
Shown in

[0045]

[Table 1]

Example 5 (1) [Preparation of prepolymerized catalyst]
0.700 L of heptane was added to a 1.5 L autoclave dried at 2 ° C. for 2 hours, and the temperature was controlled at 30 ° C. while stirring. 10.0 g of a granulated zinc ion-exchange type synthetic mica previously dried under reduced pressure at 200 ° C. for 2 hours (average particle size 55
Micron), and bis (1,3
-Dimethylcyclopentadienyl) zirconium dichloride, 0.28 g of a 96 ml toluene solution was added, and the pressure was increased to about 0.5 kg-G (gauge pressure), followed by contact at that temperature for 10 minutes. After the contact, a solution of triethylaluminum in heptane (triethylaluminum, 1.1 g
), The temperature was raised to 60 ° C., and contact was continued at that temperature for another 10 minutes. After contact, internal pressure is 0.2kg-G
After purging with nitrogen until it reaches 0.45 L
/ Min. When the integrated ethylene feed amount became about 7 times the amount of ethylene charged with respect to the charged synthetic mica, the feed of ethylene was stopped, and then the inside ethylene was purged while cooling the autoclave to stop the polymerization. After purging, the contents were withdrawn from a withdrawal line at the bottom of the autoclave into a flask with a 2 L internal volume sufficiently purged with nitrogen. After standing and decanting the solvent, drying was performed at 70 ° C. for 2 hours under reduced pressure to obtain a prepolymerized catalyst. (2) [Polymerization] 500 ml of heptane at room temperature in a 1.0 L autoclave dried at 100 ° C. for 30 minutes under a stream of nitrogen at room temperature, and 0.03 g of the prepolymerized catalyst produced in the above (1) as a clay mineral Considerable amount (0.2
4 g) and 60 ml of 1-butene were introduced. Temperature and pressure of ethylene were 65 ° C and 22.0kgf /
cm ² -G. When the temperature and pressure were stabilized, a heptane solution of triethylaluminum (equivalent to 57 mg of triethylaluminum) was added to the polymerization system to initiate polymerization. The polymerization was conducted under an ethylene pressure of 22.0 kgf / cm ^2.
Performed for 1.5 hours while maintaining -G. After the completion of the polymerization, the reaction system was cooled, and after purging ethylene, a polyethylene slurry was extracted and filtered. The obtained polymer is 1
After drying at 00 ° C. for 12 hours, 38.4 g of ethylene / 1
-A butene copolymer was obtained. Table 2 shows the results.

Example 6 (1) [Preparation of Preliminary Polymerization Catalyst] The procedure was the same as in Example 5 (1) except that trivalent chromium ion exchange type synthetic mica was used instead of zinc ion exchange type synthetic mica. Was. (2) [Polymerization] Polymerization was carried out in the same manner as in (5) of Example 5, using the prepolymerized catalyst produced in (1) above. Table 2 summarizes the results.

Example 7 (1) [Preparation of prepolymerized catalyst] Instead of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1-ethyl-3-methylcyclopentadienyl) zirconium dichloride was used. The procedure was performed in the same manner as in Example 6, (1) except that 0.30 g was used. (2) [Polymerization] Polymerization was carried out in the same manner as in (5) of Example 5, using the prepolymerized catalyst produced in (1) above. Table 2 summarizes the results.

Example 8 (1) [Preparation of prepolymerized catalyst] Instead of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1-n-butyl-3-methylcyclopentadienyl) zirconium The procedure was carried out in the same manner as in Example 5, (1) except that 0.35 g of dichloride was used. (2) [Polymerization] Polymerization was carried out in the same manner as in (5) of Example 5, using the prepolymerized catalyst produced in (1) above. Table 2 summarizes the results.

Example 9 (1) [Preparation of prepolymerized catalyst] Instead of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1-n-butyl-3-methylcyclopentadienyl) zirconium was used. The procedure was performed in the same manner as in Example 6, (1) except that 0.35 g of dichloride was used. (2) [Polymerization] Polymerization was carried out in the same manner as in (5) of Example 5, using the prepolymerized catalyst produced in (1) above. Table 2 summarizes the results.

Example 10 (1) [Preparation of prepolymerized catalyst] Instead of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1-i-butyl-3-methylcyclopentadienyl) zirconium The procedure was performed in the same manner as in Example 6, (1) except that 0.35 g of dichloride was used. (2) [Polymerization] Polymerization was carried out in the same manner as in (5) of Example 5, using the prepolymerized catalyst produced in (1) above. Table 2 summarizes the results.

Comparative Example 3 (1) [Preparation of Prepolymerized Catalyst] Bis (n-butylcyclopentadienyl) zirconium dichloride was used instead of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride. It carried out similarly to (1) of Example 5. (2) [Polymerization] Polymerization was carried out in the same manner as in (5) of Example 5, using the prepolymerized catalyst produced in (1) above. Table 2 summarizes the results.

Example 11 [Polymerization] In a 1.0 L autoclave, previously dried at 100 ° C. for 30 minutes under a nitrogen stream, 500 ml of heptane was added at room temperature to a prepolymerized catalyst prepared in (1) of Example 5. An amount equivalent to 0.05 g (0.3
5 g) were introduced. Temperature and ethylene pressure were 9
The temperature was raised to 0 ° C. and 7.0 kgf / cm ² -G. temperature,
When the pressure was stabilized, a solution of triethylaluminum in heptane (equivalent to 57 mg of triethylaluminum) was added to the polymerization system to initiate polymerization. The polymerization was carried out at 90 ° C. for 1.5 hours while maintaining the ethylene pressure at 7.0 kgf / cm ² -G. After the completion of the polymerization, the reaction system was cooled, and after purging ethylene, a polyethylene slurry was extracted and filtered. The obtained polymer was dried at 100 ° C. for 12 hours to obtain 30.0 g of polyethylene. Table 2 shows the results.

Comparative Example 4 [Polymerization] The procedure of Example 11 was repeated, except that the prepolymerized catalyst prepared in (1) of Comparative Example 3 was used instead of the prepolymerized catalyst prepared in (1) of Example 5. Polymerization was performed. Table 2 summarizes the results.

Example 12 [Polymerization] 100 g of dried sodium chloride was introduced into a 1.5 L autoclave made of stainless steel which had been sufficiently purged with nitrogen, and the temperature was raised to 50 ° C. When the temperature was stabilized, a solution of triethylaluminum in heptane (corresponding to 100 mg of triethylaluminum) was obtained.
After introducing 0.08 g (0.64 g) of the prepolymerized catalyst as a clay mineral, the system was replaced with ethylene, and the temperature and ethylene pressure were increased to 80 ° C. and 7.0 kgf / cm ² , respectively. -G was raised in 5 minutes to initiate polymerization. The polymerization was carried out at 80 ° C. for 2 hours while maintaining the ethylene pressure at 7.0 kgf / cm ² -G. After the polymerization was completed, the polymer obtained by removing sodium chloride by washing with water was dried at 50 ° C. for 6 hours under normal pressure and further at 80 ° C. for 3 hours under reduced pressure to obtain 75.7 g of polyethylene. Table 2 shows the results.

Comparative Example 5 [Polymerization] The procedure of Example 12 was repeated, except that the prepolymerized catalyst prepared in (1) of Comparative Example 3 was used instead of the prepolymerized catalyst prepared in (1) of Example 5. Polymerization was performed. Table 2 summarizes the results.

[0057]

[Table 2]

[0058]

According to the present invention, the polymerization activity of the catalyst is high, and therefore, α has a high molecular weight and a narrow molecular weight distribution.
-Olefin polymers can be produced.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping an understanding of the present invention.

Claims (6)

[Claims] 1. An α-olefin polymerization catalyst component obtained by combining the following component [A] and component [B]. [A] a metallocene transition metal compound represented by the following formula [1]: (CpR ¹ R ² ) ₂ MX ¹ X ² [1] (Cp represents a cyclopentadienyl group, and R ¹ and R ^Two
Are each independently a halogen, a silicon-containing group, a carbon number of 1 to
20 substituents substituted at the 1- and 3-positions of a cyclopentadienyl group consisting of 20 hydrocarbon groups or halogen-containing hydrocarbon groups, alkoxy groups, aryloxy groups or amino groups, M is titanium, zirconium or hafnium And X ¹ and X ² each independently represent a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group or an amide group. [B] Ion-exchangeable layered silicate 2. A compound represented by the formula [1]¹And R
^TwoAre each independently a straight-chain having 1 to 20 carbon atoms,
A branched or cyclic aliphatic hydrocarbon group; ¹And X^Two
Are each independently a halogen atom, having 1 to 20 carbon atoms.
The α-ole according to claim 1, which is a hydrocarbon group or an amide group.
Catalyst component for fin polymerization. 3. The compound represented by the formula [1], wherein R ¹ is a methyl group, R ² is a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms; ^2. The α-olefin polymerization catalyst component according to claim 1, wherein ¹ and X ² are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or an amide group. 4. An α-olefin in an amount of 0.01 to 1000 g per 1 g of the component (B) in the presence of the catalyst component for polymerization of an α-olefin according to any one of claims 1 to 3 and an organic aluminum compound optionally added. Α obtained by pre-polymerizing
-A catalyst component for olefin polymerization. 5. An α-olefin polymerization catalyst obtained by combining the α-olefin polymerization catalyst component according to claim 1 with the following component [C]. (C) an organoaluminum compound represented by the following formula (2) ## STR2 ## R _{³ a} AlX ^{3 _3-a} [2] (R ³ is a hydrocarbon group having 1 to 20 carbon atoms, X ³ is a halogen atom, A hydrogen atom, an alkoxy group or an amide group;
Is 0 <a ≦ 3) 6. A method for polymerizing an α-olefin, comprising polymerizing an α-olefin in the presence of the catalyst according to claim 5.