JPH10251321A - Catalyst for producing ethylene-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalyst impregnated with a specific solid catalyst component pre-polymerized in the presence of an α-olefin and further impregnated with a specific transition metal compound, which gives a polymer having a wide molecular weight distribution and melt tension, and producing little gel fisheye. SOLUTION: This catalyst for producing an ethylene-based polymer suitable for blown film formation is obtained by including (A) a solid catalytic component, and (B) a transition metal compound with a group having a conjugate πelectron as the ligand. In the above, the solid catalytic component A is prepared by the following processes: a chromium compound unbaked in the presence of oxygen is borne on a support and then baked in the presence of oxygen into a chromium oxide, followed by bearing aluminoxane on the support to form a solid catalytic component; and then 0.01 to 10g, per g of the solid catalytic component, of an α-olefin is pre-polymerized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an ethylene polymerization catalyst. More specifically, the present invention relates to a novel catalyst capable of producing an ethylene-based polymer having a wide molecular weight distribution, a large melt tension, and low generation of gel fish eyes.

[0002]

2. Description of the Related Art Ethylene-based polymers are generally and widely used as resin materials for various molded articles, but required characteristics differ depending on the molding method and application. In particular, a polymer having a relatively high molecular weight, a wide molecular weight distribution, a large melt tension, and a low generation of gel fish eyes is suitable for an ethylene polymer used for blown film molding or hollow molding.

Hitherto, as a method for producing an ethylene-based polymer having the above-mentioned performance, there have been proposed many methods by a single-stage polymerization or a multi-stage polymerization using a so-called Ziegler catalyst comprising a titanium compound, a magnesium compound and a halogen (see, for example, US Pat. JP-A-56-90809, JP-A-60-1
06806, JP-A-2-123108, JP-A-4-18407, JP-A-5-230136). In addition, a method of producing a chromium trioxide on an inorganic oxide using a so-called Phillips catalyst is known, and a chromium compound such as (pentamethylcyclopentadienyl) (2-methylpentadienyl) chromium is used. A method of producing a catalyst using a catalyst supported on an inorganic oxide has been proposed (JP-A-3-93804), in which a Philips catalyst and the above-mentioned chromium catalyst are produced using a catalyst obtained by treating an organic aluminum compound such as aluminoxane. A method has also been proposed (Japanese Patent Laid-Open No. 2-1058)
No. 06, JP-A-2-185506, JP-T-7-503739, U.S. Pat. No. 4,564,660).

Further, a method has been proposed in which two-stage polymerization is carried out using a catalyst obtained by combining a Phillips catalyst with an organoaluminum compound and a Ziegler catalyst (Japanese Patent Application Laid-Open No. 62-207307, Japanese Patent Publication No. Hei 7-207307). -103177 gazette).
In recent years, there has been proposed a method for producing a catalyst using a Phillips catalyst or a Ziegler catalyst and a so-called metallocene catalyst, or a catalyst obtained by combining two or more metallocene catalysts (JP-A-1-292009, JP-A-3-203903). No.
JP-A-4-220405, JP-A-6-122719, JP-A-Hei.
JP-A-7-173209, JP-A-8-41118, JP-A-8-10001
No. 8, JP-B-8-13856, JP-A-8-259618). However, the molecular weight distribution, melt tension, and gel fisheye of the ethylene-based polymer produced using these catalysts are not at a level sufficient for inflation film molding or hollow molding.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to provide a catalyst for producing an ethylene polymer having a wide molecular weight distribution, a large melt tension and a small gel fisheye. It is in.

[0006]

Means for Solving the Problems The present inventors have made intensive studies in view of the above problems, and as a result, have found that a solid catalyst component obtained by prepolymerizing a solid catalyst component comprising a chromium compound, a carrier and an aluminoxane in the presence of an α-olefin, and The present inventors have found that an ethylene-based polymer having the above-mentioned problems solved can be obtained by using an ethylene-based polymerization catalyst comprising a transition metal compound having a group having a conjugated π electron as a ligand.

Hereinafter, the catalyst for ethylene polymerization of the present invention will be specifically described. The catalyst for ethylene polymerization according to the present invention is obtained by prepolymerizing a solid catalyst component (a) comprising a chromium compound (a-1), a carrier (a-2) and an aluminoxane (a-3) in the presence of an α-olefin. It comprises a solid catalyst (A), a transition metal compound (B) having a group having a conjugated π electron as a ligand, and, if desired, an organometallic compound (C).

The chromium compound (a-1) used in the present invention may be converted to chromium oxide by firing in the presence of oxygen, or may be used without firing in the presence of oxygen. When converted to chromium oxide by firing in the presence of oxygen, chromium compounds include chromium carboxylate, chromium-1,3-diketo compound, chromate ester, chromium amide compound, organic chromium compound, chromium trioxide or chromium oxide. Chromium compounds which can be converted to chromium oxide by calcination in the presence of oxygen, such as compounds, halides, oxyhalides, nitrates, sulfates, acetates, and oxalates.

After calcination in the presence of oxygen, at least some of the chromium atoms must be in a hexavalent state. Specifically, examples of the chromium carboxylate include compounds of chromium (II) or chromium (III) represented by the following general formula (1) or (2).

[0010]

Embedded image

[0011]

Embedded image In the above formula, R ^{1 to} R ⁵ may be the same or different and are each a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.

Specifically, chromium (II) formate, chromium (II) acetate, chromium (II) propionate, chromium butyrate (I
I), chromium pentanoate (II), chromium hexanoate (I
I), chromium (II) 2-ethylhexanoate, chromium (II) benzoate, chromium (II) naphthenate, chromium (II) oleate, chromium oxalate (II), chromium (III) formate,
Chromium (III) acetate, chromium (III) propionate, chromium (III) butyrate, chromium (III) pentanoate, chromium hexanoate (I
II), chromium (III) 2-ethylhexanoate, chromium (III) benzoate, chromium (III) naphthenate, chromium oleate (I
II), chromium (III) oxalate and the like, and preferred are chromium (II) acetate, chromium (II) 2-ethylhexanoate, chromium (III) acetate and chromium (III) 2-ethylhexanoate.

The chromium-1,3-diketo compound includes
A chromium (III) complex having one to three 1,3-diketo compounds represented by the following general formula (3) is given.

## STR3 ## ^{Cr (Y) e (Z 1} ) f (Z 2) g (3) In the formula, Y is 1,3-diketo type chelate ligand, Z ¹ and Z ² are the same May be different from each other, each halogen atom, alkoxy, aryloxy,
Selected from alkyl, aryl, and amide, e +
f + g = 3, and e is 1 to 3.

Specifically, chromium-1,3-butanedionate, chromium acetylacetonate, chromium-2,4
Hexanedionate, chromium-2,4-heptanedionate, chromium-2,4-octanedionate, chromium-3,5-octandionate, chromium benzoylacetonate, chromium-1,3-diphenyl-1, 3-propanedionate, chromium-2-methyl-1,3-butanedionate, chromium-2-ethyl-1,3-butanedionate, chromium-2-phenyl-1,3-butanedionate, chromium- Examples thereof include 1,2,3-triphenyl-1,3-propanedionate, and chromium acetylacetonate is preferred.

Examples of the chromate ester include a chromium (VI) compound represented by the following general formula (4).

Embedded image In the formula, R ^{6 to} R ¹¹ may be the same or different and are a hydrocarbon group having 1 to 18 carbon atoms, and M ¹ and M ² are a carbon atom or a silicon atom.

When M ¹ and M ² are carbon atoms, specific examples include bis (tert-butyl) chromate, bis (1,2)
1-dimethylpropyl) chromate, bis (2-phenyl-2-propyl) chromate, bis (1,1-diphenylethyl) chromate, bis (triphenylmethyl)
Chromate, bis (1,1,2,2-tetramethylpropyl) chromate, bis (1,1,2-trimethylpropyl) chromate and the like, and bis (tert-butyl)
Chromates are preferred.

Further, when M ¹ and M ² are silicon atoms, specific examples thereof include bis (trimethylsilyl) chromate, bis (triethylsilyl) chromate, bis (tributylsilyl) chromate, bis (triisopentylsilyl) chromate, Bis (tri-2-ethylhexylsilyl) chromate, bis (tridecylsilyl) chromate, bis (tri (tetradecyl) silyl) chromate,
Bis (tribenzylsilyl) chromate, bis (triphenethylsilyl) chromate, bis (triphenylsilyl) chromate, bis (tritolylsilyl) chromate, bis (trixylsilyl) chromate, bis (trinaphthylsilyl) chromate, bis ( Dimethylphenylsilyl) chromate, bis (diphenylmethylsilyl) chromate, bis (dimethyltexylsilyl) chromate, bis (dimethylisopropylsilyl) chromate, bis (tert-butyldimethylsilyl) chromate,
Bis (tri-tert-butylsilyl) chromate, bis (triethylphenylsilyl) chromate, bis (trimethylnaphthylsilyl) chromate, polydiphenylsilylchromate, polydiethylsilylchromate and the like are mentioned, and bis (triphenylsilyl) chromate is preferred.

Examples of the chromium amide compound include compounds of chromium (II) or chromium (III) represented by the following general formula (5) or (6).

[0019]

Embedded image

[0020]

Embedded image

In the formula, R ^{12 to} R ⁴¹ may be the same or different and each is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and M ^{3 to} M ¹² are carbon and / or silicon. L ¹ represents a ligand such as ether or nitrile, and h is 0 to 2.

Specifically, tris (dimethylamido) chromium (III), tris (diethylamido) chromium (III), tris (diisopropylamido) chromium (III), tris (methylphenylamido) chromium (III), tris ( Diphenylamido) chromium (III), bis (bistrimethylsilylamide) chromium (II) -THF complex, bis (bistrimethylsilylamide) chromium (II) -diethyl ether complex, bis (methyltrimethylsilylamide) chromium (II) -THF complex , Bis (methyltrimethylsilylamide) chromium (II) -diethyl ether complex, bis (te
rt-butyltrimethylsilylamido) chromium (II) -T
HF complex, bis (tert-butyltrimethylsilylamide) chromium (II) -diethyl ether complex, bis (phenyltrimethylsilylamide) chromium (II) -THF complex, bis (phenyltrimethylsilylamide) chromium (II) -diethyl ether complex, Tris (Bistrimethylsilylamide) chromium (III), tris (bistriethylsilylamide) chromium (III), tris (bistriphenylsilylamide) chromium (III) and the like, and tris (bistrimethylsilylamide) chromium (III) is preferable. .

As the organic chromium compound, chromium (I) represented by the following general formula (7), (8) or (9)
I), chromium (III) or chromium (IV) compounds.

[0024]

(Cp ¹ ) k (R ⁴² ) 2-k Cr (7)

(Cp ¹ ) (R ⁴² ) m (R ⁴³ ) 2-m Cr (L ² ) n (8)

Embedded image (R ⁴⁴ ) p Cr (9)

Wherein Cp ¹ is a cyclopentadienyl group,
Methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group, tert-
Alkyl-substituted cyclopentadienyl groups such as butylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, dimethylcyclopentadienyl group and pentamethylcyclopentadienyl group, and alkylsilyl-substituted cycloalkyl groups such as trimethylsilylcyclopentadienyl group Alkylgermyl-substituted cyclopentadienyl groups such as pentadienyl group and trimethylgermylcyclopentadienyl group,
Alternatively, it is a ligand having a cyclopentadienyl skeleton such as an indenyl group or a fluorenyl group having or not having the same substituent.

R ⁴² and R ⁴³ may be the same or different and each has an aryl group, an alkyl group,
It is an alkenyl group, an alkylaryl group, an arylalkyl group, an allyl group, a silylalkyl group, or an alkoxy group. ^R44 is an aryl group having 1 to 20 carbon atoms, an alkyl group, an alkenyl group, an alkylaryl group, an arylalkyl group, an allyl group, or a silylalkyl group. L ²
Is ether, pyridine, THF (tetrahydrofuran)
And the like. k is 1 or 2, m is 1 or 2, n is 0 or 1, and p is 2 to 4.

Specifically, bis (cyclopentadienyl) chromium (II), bis (indenyl) chromium (II),
Bis (fluorenyl) chromium (II), (pentamethylcyclopentadienyl) (cyclopentadienyl) chromium (II), (pentamethylcyclopentadienyl) (pentadienyl) chromium (II), (pentamethylcyclopentadiene) Enyl) (2-methylpentadienyl) chromium (I
I), (pentamethylcyclopentadienyl) (2,4
-Dimethylpentadienyl) chromium (II), (pentamethylcyclopentadienyl) (dimethyl) chromium (II)
I), (pentamethylcyclopentadienyl) (dimethyl) chromium (III) -THF complex, (pentamethylcyclopentadienyl) bis (trimethylsilylmethyl) chromium (III), (pentamethylcyclopentadienyl) (dimethyl ) Chromium (III) -pyridine complex, (pentamethylcyclopentadienyl) bis (trimethylsilylmethyl) chromium (III) -pyridine complex, (pentamethylcyclopentadienyl) (dibenzyl) chromium (III) -pyridine complex, (Allyl) chromium (II), tris (allyl) chromium (III), bis (benzene) chromium (II), bis (2,4-dimethylpentadienyl) chromium (II),
Octakis (trimethylsilylmethyl) tetrachrome (II), tetrakis (trimethylsilylmethyl) chromium (IV) and the like can be mentioned.

Chromium oxides, halides, oxyhalides, nitrates, sulfates, acetates and oxalates include chromium trioxide, chromium trichloride, chromyl chloride,
Examples thereof include chromium nitrate, chromium sulfate, chromium acetate, chromium oxalate, and ammonium chromate. As the chromium compound used without firing in the presence of oxygen,
The above-mentioned chromium carboxylate, chromium-1,3-diketo compound, chromate ester, chromamide compound, organic chromium compound and the like can be mentioned.

The carrier (a-2) used in the present invention may be a compound of the second, fourth, thirteenth, or fourteenth group of the periodic table (the group is an inorganic chemical nomenclature 19).
According to the 90-year rule. The same applies hereinafter) oxides of the elements, or 13
It is commonly used as a component of a catalyst for ethylene-based polymerization, such as a phosphate of a group III element. Examples of oxides of Group 2, 4, 13 or 14 elements and phosphates of Group 13 elements include magnesia, titania, zirconia, alumina, silica, silica-titania, silica-zirconia, silica-alumina, phosphorus Examples include aluminum acid, gallium phosphate, and mixtures thereof.
The specific surface area is 50 to 1000 m ² / g, particularly 200 to 800 m ²
/ G, pore volume of 0.5 to 3.0 cm ³ / g, especially 1.0 to 2.5 c
m ³ / g, average particle size of 10 to 200 μm, especially 30 to 1
Those having a size of 50 μm are preferably used.

When the chromium compound is used without calcination in the presence of oxygen, the carrier (a-2) can be used under a flow of molecular sieves and a dry nitrogen gas flow at 100 to
Those fired at 900 ° C. for 10 minutes to 24 hours are preferably used. It is preferable to perform calcination in a flow of solid gas in a sufficient amount of nitrogen gas flow.

Aluminoxane (a-3) used in the present invention
Examples include a compound represented by the following general formula (10) or (11).

[0032]

Embedded image

[0033]

Embedded image

Wherein R ⁴⁵ is methyl, ethyl, propyl,
It is a hydrocarbon group such as n-butyl and isobutyl, preferably a methyl group and an isobutyl group. r is 1 to 1
00, preferably 4 or more, particularly preferably 8 or more.

Processes for producing such compounds are known,
For example, a suspension of salts having water of crystallization (eg, copper sulfate hydrate, aluminum sulfate hydrate) in an inert hydrocarbon solvent such as pentane, hexane, heptane, cyclohexane, decane, benzene, and toluene is added to trialkyl aluminum. And a method in which solid, liquid or gaseous water is allowed to act on trialkylaluminum in a hydrocarbon solvent.

The following general formula (12) or (13)
May be used.

[0037]

Embedded image

[0038]

Embedded image

Wherein R ⁴⁶ is methyl, ethyl, propyl,
It is a hydrocarbon group such as n-butyl and isobutyl, preferably a methyl group and an isobutyl group. R ⁴⁷ is selected from a hydrocarbon group such as methyl, ethyl, propyl, n-butyl and isobutyl, or a halogen atom or hydrogen atom such as chlorine and bromine, and a hydroxyl group, and represents a group different from R ⁴⁶ . In addition, a plurality of R ⁴⁷ present in the general formula (12)
May be the same or different. s is usually 1 to 100
And preferably 3 or more, and s + t is 2 to 10
0, preferably 6 or more.

In the general formula (12) or (13), two units

Embedded image May be combined in blocks or may be combined regularly or irregularly at random.

The method for producing such an aluminoxane is as follows:
It is the same as the above-mentioned aluminoxane of the general formula, and instead of one kind of trialkylaluminum, two or more kinds of trialkylaluminum are used, or one or more kinds of trialkylaluminum and one or more kinds of dialkylaluminum monohalide or dialkyl. Aluminum monohydride or the like may be used.

The solid catalyst component (a) used in the present invention
Can be obtained by supporting a chromium compound (a-1) and an aluminoxane (a-3) on a carrier (a-2). When converting a chromium compound to chromium oxide by firing in the presence of oxygen, first convert the chromium compound (a-1) to a carrier.
(a-2) It is important to support aluminoxane after supporting on a and converting it to chromium oxide by firing in the presence of oxygen. If the chromium compound and the aluminoxane are supported on the carrier (a-2) and calcined in the presence of oxygen, the effects of the present invention cannot be obtained.

The method of supporting the chromium compound (a-1) on the carrier (a-2) is carried out by impregnating and supporting the chromium compound in an aqueous system or a hydrocarbon solvent such as pentane, hexane, heptane, cyclohexane, decane, benzene or toluene. Is preferably used. The supporting temperature is generally 100 ° C or lower, preferably 0 to 40 ° C. The calcination in the presence of oxygen is performed in a range of 300 to 1000 ° C. for 1 to 48 hours using a dry gas containing oxygen. Preferably, after removal of the solvent, the process is carried out in a fluidized state with a dry gas containing oxygen.

The method for supporting the aluminoxane (a-3) is as follows:
In a carrier (a-1), a chromium compound (a-1) previously converted to chromium oxide by calcination in the presence of oxygen is applied to an inert hydrocarbon solvent such as isobutane, pentane, hexane, heptane, cyclohexane, decane, benzene, and toluene. -2)
Is suspended, and then the aluminoxane (a-3) is brought into contact with the inert hydrocarbon solution. Contact temperature is 0 to 120 ° C, preferably 10 to 100 ° C, contact time is 1 minute to 10 hours,
Preferably, for 1 minute to 5 hours, the amount of the solvent per 1 g of the carrier (a-2) is 5 to 800 ml. After the contact, the solvent is removed under reduced pressure or separated by filtration to obtain a solid catalyst component (a).

When the chromium compound is used without firing in the presence of oxygen, the order of loading the chromium compound (a-1) and the aluminoxane (a-3) on the carrier (a-2) is arbitrary. The method of supporting the chromium compound (a-1) and the aluminoxane (a-3) is preliminarily isobutane, pentane, hexane,
Heptane, cyclohexane, decane, benzene, after suspending the carrier (a-2) in an inert hydrocarbon solvent such as toluene, the inert hydrocarbon of the chromium compound (a-1) and aluminoxane (a-3) Contact the solution. Contact temperature is 0-1
20 ° C, preferably 10 to 100 ° C, contact time is 1 minute to
10 hours, preferably 1 minute to 5 hours, 1 g of the carrier (a-2)
Is from 5 to 800 ml. After the contact, the solvent is removed under reduced pressure or separated by filtration to obtain a solid catalyst component (a). These chromium compounds (a-1) and carriers (a-2)
And the use ratio of the three components of the aluminoxane (a-3) are determined when the chromium compound (a-1) is converted to chromium oxide by calcination in the presence of oxygen or when the calcination is not performed in the presence of oxygen. The content of chromium atoms in the chromium compound (a-1) is 0.01 to 1 g per 1 g of (a-2).
5% by weight, preferably 0.05 to 3% by weight, based on 1 mole of chromium atoms in the chromium compound, 1 to 600 moles, preferably 5 to 5 moles of aluminum atoms in the aluminoxane (a-3)
400 moles.

The solid catalyst (A) used in the present invention comprises α
-It is obtained by prepolymerizing the solid catalyst component (a) in the presence of an olefin. The prepolymerization is usually carried out by suspending the solid catalyst component (a) in a hydrocarbon solvent. Examples of the hydrocarbon solvent include propane, butane, isobutane, hexane, cyclohexane, heptane, benzene, toluene,
Inert hydrocarbon solvents such as xylene are used alone or as a mixture. The molecular weight of the obtained prepolymer can be adjusted by controlling the polymerization temperature or by allowing hydrogen or the like to coexist in the polymerization reactor. As the α-olefin, ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like are used. These α-olefins can be used alone or in combination of two or more. The amount of prepolymerization per 1 g of the solid catalyst component (a) is 0.01 to 10 g, preferably 0.1 to 5 g. The amount of the solvent per 1 g of the solid catalyst component (a) is 10 to 100 ml. When the chromium compound is changed to chromium oxide by firing in the presence of oxygen, the prepolymerization temperature is 0 to 110 ° C, preferably 20 to 110 ° C.
When the chromium compound is used without firing in the presence of oxygen, the temperature is 0 to 110 ° C, preferably 20 to 60 ° C.

The prepolymerization time is 1 minute to 5 hours, preferably 5 minutes to 2 hours when the chromium compound (a-1) is changed to chromium oxide by firing in the presence of oxygen.
When the chromium compound is used without firing in the presence of oxygen, the heating time is 1 minute to 2 hours, preferably 2 minutes to 1 hour. When the chromium compound (a-1) is changed to chromium oxide by firing in the presence of oxygen, the prepolymerization pressure is from normal pressure to 20 kg / cm ² , preferably from normal pressure to 15 kg / c.
m ² , and when the chromium compound is used without firing in the presence of oxygen, the pressure is normal pressure to 10 kg / cm ² , preferably normal pressure to 5 kg / cm ² .

The solid catalyst (A) obtained by the above method is usually purified by the following method. That is, the mixture of the solid catalyst (A) and the unreacted product is obtained by using the hydrocarbon solvent used at the time of prepolymerization or another hydrocarbon solvent, and extracting the supernatant liquid by a gradient method or a filtration method. Wash and purify using.

The group having a conjugated π electron which is a ligand of the transition metal compound (B) used in the present invention is a ligand having a cyclopentadienyl skeleton, an amidinato skeleton or an allyl skeleton. Examples of the ligand having a cyclopentadienyl skeleton include, for example, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group, te
rt-butylcyclopentadienyl group, dimethylcyclopentadienyl group, alkyl-substituted cyclopentadienyl group such as pentamethylcyclopentadienyl group, alkylsilyl-substituted cyclopentadienyl group such as trimethylsilylcyclopentadienyl group, Examples thereof include an alkylgermyl-substituted cyclopentadienyl group such as a trimethylgermylcyclopentadienyl group, or an indenyl group or a fluorenyl group having or not having the same substituent.

Examples of the ligand having an amidinato skeleton include, for example, an amidinato group, an alkyl-substituted amidinate group such as N, N'-bis (n-butyl) amidinate group, an N, N'-bis (trimethylsilyl) amidinate group, and the like. Alkylsilyl-substituted amidinato group, N, N'-
Aryl-substituted amidinate groups such as bis (phenyl) amidinate group, N, N′-bis (n-butyl) benzamidinato group, N, N′-bis (dimethylphenyl) benzamidinato group, N, N ′ Examples include an amidinato group having a plurality of substituents such as -bis (2,6-) benzamidinato group. In addition, examples of the ligand having an allyl skeleton include allyl groups having or not having the same substituent as described above.

The transition metal used in the present invention is a transition metal element belonging to Group 3, 4, 5, or 6 of the periodic table, preferably a transition metal element belonging to Group 4 of the periodic table, ie, titanium, Those selected from zirconium and hafnium are preferred, and zirconium and hafnium are particularly preferred.

The transition metal compound (B) used in the present invention
The following general formulas (14), (15), (16),
The transition metal compound represented by (17), (18), (19) or (20) is mentioned.

[0053]

Embedded image (Cp ² ) (Cp ³ ) u Me (Q ¹ ) 3-u (14)

Embedded image R ⁵¹ (Cp ² ) (Cp ³ ) Me (Q ¹ ) (Q ² ) (15)

Embedded image R ⁵¹ (Cp ² ) (Y) Me (Q ¹ ) (Q ² ) (16)

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

In the above formula, Cp ² and Cp ³ may be the same or different and each is a ligand having the above-mentioned cyclopentadienyl skeleton, and R ^{48 to} R ⁵⁰ may be the same or different; A hydrogen atom, an alkyl having 1 to 20 carbons,
A hydrocarbon group such as alkenyl, aryl, araryl, aralkyl and alicyclic, an alkylsilyl group or an alkylgermyl group, and R ⁵¹ has 1 to 20 carbon atoms.
An alkylene group, an alkylgermylene group or an alkylsilylene group,

X ¹ and X ² may be the same or different and each is a carbon atom or a nitrogen atom, and Q ¹ and Q ²
May be the same or different and each represents a hydrogen atom,
To 20 hydrocarbon groups, alkoxy groups, allyloxy groups,
A siloxy group or a halogen, and Y is -O-, -S
-, -NR ^52- , -PR ^52- (where R ⁵² is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkyl halide or an aryl halide), and Me Is a transition metal selected from zirconium, hafnium and titanium, and u is 0 or 1.

In the above general formula, examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^{48 to} R ⁵⁰ include methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, hexyl, heptyl, An alkyl group such as octyl, nonyl, decyl and cetyl can be exemplified, an aryl group can be exemplified by phenyl, an alkylsilyl group can be exemplified by trimethylsilyl, and an alkylgermyl group can be exemplified by trimethylgermyl. In the above general formula, the alkylene group having 1 to 20 carbon atoms represented by R ⁵¹ includes a methylene group, an ethylene group, a propylene group, an isopropylidene group, a cyclopentylidene group, a cyclohexylidene group, a tetrahydropyran-4-ylidene group And a diphenylmethylene group. Examples of the alkylsilylene group represented by R ⁵¹ include a dimethylsilylene group,
Examples thereof include a diphenylsilylene group. In addition, R ⁵¹
Examples of the alkylgermylene group represented by include a dimethylgermylene group and a diphenylgermylene group.

Specific examples of R ^{52 in} —NR ⁵² — and —PR ⁵² — represented by Y include methyl, ethyl, propyl,
Butyl, isobutyl, tert-butyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl,
Examples thereof include an alkyl group such as cetyl, and a phenyl group and a benzyl group. Y represents -NR ^52- , -PR ⁵²
-Type ligands are preferred.

The general formulas (14), (15), (16),
Specific examples of the transition metal compound (B) represented by (17), (18), (19) or (20) are given below when Me is zirconium.

Examples of the transition metal compound represented by the general formula (14) include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, and bis (n-propylcyclopentadienyl) zirconium dichloride. , Bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) ) Zirconium dichloride, (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (n-
(Butylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (indenyl) zirconium dichloride, (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclopentadienyl zirconium trichloride, cyclopentadienyl zirconium trimethyl, pentamethyl Examples thereof include cyclopentadienyl zirconium trichloride and pentamethylcyclopentadienyl zirconium trimethyl.

Examples of the transition metal compound represented by the general formula (15) include dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, isopropylidenebis (methylcyclopentadienyl) zirconium dichloride, and ethylenebis (indenyl) zirconium dichloride. , Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl)
Zirconium dichloride, isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride, isopropylidene (tert-butylcyclopentadienyl) (tert-butylindenyl) zirconium dichloride, isopropylidene (tert-butylcyclopentadienyl) ( (tert-butylindenyl) zirconium dimethyl and the like.

Examples of the transition metal compound represented by the general formula (16) include ethylene (tert-butylamide) (tetramethylcyclopentadienyl) zirconium dichloride, ethylene (methylamide) (tetramethylcyclopentadienyl) zirconium dichloride, Silylene (tert-butylamide) (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (tert-butylamide) (tetramethylcyclopentadienyl) zirconium dibenzyl, dimethylsilylene (benzylamide) (tetramethylcyclopentadienyl) Examples thereof include zirconium dibenzyl and dimethylsilylene (phenylamide) (tetramethylcyclopentadienyl) zirconium dichloride.

Examples of the transition metal compound represented by the general formula (17) include (cyclopentadienyl) (N, N'-bis (trimethylsilyl) benzamidinato) zirconium dichloride and (cyclopentadienyl) (N, N N '
-Bis (n-butyl) benzamidinato) zirconium dichloride, (cyclopentadienyl) (N, N'-
Bis (phenyl) benzamidinato) zirconium dichloride, (cyclopentadienyl) (N, N′-bis (2,6-dimethylphenyl) benzamidinato) zirconium dichloride, (cyclopentadienyl)
(N, N′-bis (2,6-di-tert-butylphenyl) benzamidinato) zirconium dichloride,
(N-butylcyclopentadienyl) (N, N′-bis (trimethylsilyl) benzamidinato) zirconium dichloride, (n-butylcyclopentadienyl)
(N, N'-bis (n-butyl) benzamidinato)
Zirconium dichloride, (n-butylcyclopentadienyl) (N, N'-bis (phenyl) benzamidinato) zirconium dichloride, (pentamethylcyclopentadienyl) (N, N'-bis (trimethylsilyl) benzami Dinat) zirconium dichloride,
(Pentamethylcyclopentadienyl) (N, N′-bis (n-butyl) benzamidinato) zirconium dichloride, (pentamethylcyclopentadienyl)
(N, N′-bis (phenyl) benzamidinato) zirconium dichloride, (indenyl) (N, N′-bis (trimethylsilyl) benzamidinato) zirconium dichloride, (indenyl) (N, N′-bis ( n
-Butyl) benzamidinato) zirconium dichloride, (indenyl) (N, N'-bis (phenyl) benzamidinato) zirconium dichloride, and the like.

Examples of the transition metal compound represented by the general formula (18) include dimethylsilylene (cyclopentadienyl) (N, N'-bis (trimethylsilyl) amidinato) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (N , N'-bis (phenyl) amidinato) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (N, N'-bis (n-butyl) amidinato) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (N ,
N'-bis (trimethylsilyl) amidinato) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (N, N'-bis (phenyl) amidinato) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (N, N'-
Bis (n-butyl) amidinato) zirconium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (N, N′-bis (trimethylsilyl) amidinato) zirconium dichloride, dimethylsilylene (n
-Butylcyclopentadienyl) (N, N'-bis (phenyl) amidinato) zirconium dichloride, dimethylsilylene (n-butylcyclopentadienyl)
(N, N'-bis (n-butyl) amidinato) zirconium dichloride, dimethylsilylene (indenyl)
(N, N'-bis (trimethylsilyl) amidinate)
Zirconium dichloride, dimethylsilylene (indenyl) (N, N'-bis (phenyl) amidinato) zirconium dichloride, dimethylsilylene (indenyl)
(N, N'-bis (n-butyl) amidinato) zirconium dichloride and the like can be exemplified.

Examples of the transition metal compound represented by the general formula (19) include bis (N, N′-bis (trimethylsilyl) benzamidinato) zirconium dichloride and bis (N, N′-bis (phenyl) benzamidina). G) zirconium dichloride, bis (N, N'-bis (n-butyl) benzamidinato) zirconium dichloride and the like.

Examples of the transition metal compound represented by the general formula (20) include dimethylsilylenebis (N, N'-bis (trimethylsilyl) amidinato) zirconium dichloride and dimethylsilylenebis (N, N'-bis (phenyl) amidinato) Zirconium dichloride, dimethylsilylenebis (N, N′-bis (n-butyl) amidinato) zirconium dichloride, isopropylidenebis (N, N′-bis (trimethylsilyl) amidinato) zirconium dichloride, isopropylidenebis (N, N′-) Bis (phenyl) amidinato) zirconium dichloride, isopropylidenebis (N, N′-bis (n-butyl) amidinato) zirconium dichloride and the like can be exemplified.

The general formulas (14), (15), (16),
As another specific example of the transition metal compound (B) represented by (17), (18), (19) or (20), a transition metal compound in which zirconium in the above compound is replaced with hafnium or titanium is also exemplified. You can also. In the present invention, as the transition metal compound (B), one of the above-mentioned transition metal compounds may be used alone,
More than one species can be used in combination.

The catalyst of the present invention can be obtained by bringing the solid catalyst (A) into contact with the transition metal compound (B).
Hereinafter, an example of a method for contacting the solid catalyst (A) with the transition metal compound (B) will be described.

After previously suspending the solid catalyst in an inert hydrocarbon solvent such as isobutane, pentane, hexane, heptane, cyclohexane, decane, benzene, and toluene,
The transition metal compound is contacted with the inert hydrocarbon solution. The contact temperature is 0 to 120 ° C, preferably 10 to 100
C., the contact time is 1 second to 10 hours, preferably 2 seconds to 1 hour, and the amount of the solvent per 1 g of the solid catalyst is 3 to 800 ml. The ratio of the solid catalyst (A) to the transition metal compound (B) is such that the metal atom in the transition metal compound (B) is 0.01 mmol to 10 mol per 1 mol of the chromium atom in the solid catalyst (A).
Mole, preferably 0.1 mmol to 5 mole.

In the present invention, the organometallic compound (C) can be used together with the above-mentioned catalyst. By using the organometallic compound (C), the polymerization activity is improved, and the effect of preventing the polymer from adhering to the reactor wall can be obtained. The organometallic compound (C) used in the present invention may be any of the following:
It is an organometallic compound of a Group 2 or 3 element.

Specific compounds when the metal is lithium, magnesium or aluminum are exemplified. Examples of the organometallic compound of lithium include alkyl lithium such as methyl lithium, ethyl lithium, n-propyl lithium, n-butyl lithium, isobutyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, isopentyl lithium, and the like. Can be exemplified.

The organometallic compounds of magnesium include:
Examples include dialkylmagnesium such as n-butylethylmagnesium, di-sec-butylmagnesium, n-butyl-sec-butylmagnesium, di-tert-butylmagnesium, dineopentylmagnesium, and di-n-hexylmagnesium.

The organometallic compounds of aluminum include:
Trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum,
Tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, trialkyl aluminum such as tricyclohexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, dialkyl aluminum halide such as diisobutyl aluminum chloride, dimethyl aluminum methoxide, Examples thereof include dialkyl aluminum alkoxides such as diethyl aluminum ethoxide, and dialkyl aluminum aryloxides such as diethyl aluminum phenoxide.

As the organometallic compound composed of lithium and aluminum, lithium tetramethyl aluminate,
Lithium trimethyl ethyl aluminate, lithium trimethyl propyl aluminate, lithium trimethyl butyl aluminate, lithium trimethyl hexyl aluminate, lithium trimethyl octyl aluminate, lithium triethyl methyl aluminate, lithium tetraethyl aluminate, lithium triethyl propyl aluminate, lithium triethyl Butyl aluminate, lithium triethylhexyl aluminate, lithium triethyl octyl aluminate, lithium tributyl methyl aluminate, lithium tributyl ethyl aluminate, lithium tributyl propyl aluminate, lithium tetrabutyl aluminate, lithium tributylhexyl aluminate, lithium tributyl octyl aluminum Nate, lithium Isobutyl methyl aluminate,
Lithium triisobutyl ethyl aluminate, lithium triisobutyl propyl aluminate, lithium triisobutyl butyl aluminate, lithium triisobutyl hexyl aluminate, lithium triisobutyl octyl aluminate, lithium trihexyl methyl aluminate, lithium trihexyl ethyl aluminate, lithium Trihexyl butyl aluminate, lithium tetrahexyl aluminate, lithium trihexyl octyl aluminate, lithium trioctyl methyl aluminate, lithium trioctyl ethyl aluminate, lithium trioctyl ethyl aluminate, lithium trioctyl butyl aluminate, lithium trioctyl Examples thereof include tylhexyl aluminate and lithium tetraoctyl aluminate.

Examples of the organometallic compound consisting of magnesium and aluminum include ethyl magnesium tetramethyl aluminate, ethyl magnesium trimethyl ethyl aluminate, ethyl magnesium trimethyl propyl aluminate, ethyl magnesium trimethyl butyl aluminate, ethyl magnesium trimethyl hexyl aluminate, ethyl magnesium Magnesium trimethyl octyl aluminate, ethyl magnesium triethyl methyl aluminate, ethyl magnesium tetraethyl aluminate, ethyl magnesium triethyl propyl aluminate, ethyl magnesium triethyl butyl aluminate, ethyl magnesium triethyl hexyl aluminate, ethyl magnesium triethyl octyl aluminate, ethyl magnesium Tributyl methyl aluminate, ethylmagnesium tributyl ethyl aluminate, ethylmagnesium tetrabutyl aluminate, ethylmagnesium tributyl hexyl aluminate, ethylmagnesium tributyl octyl aluminate, ethylmagnesium triisobutyl methyl magnesium,
Ethyl magnesium triisobutyl ethyl aluminate, ethyl magnesium triisobutyl butyl aluminate, ethyl magnesium triisobutyl hexyl aluminate, ethyl magnesium triisobutyl octyl aluminate,

Butyl magnesium tetramethyl aluminate, butyl magnesium trimethyl ethyl aluminate, butyl magnesium trimethyl propyl aluminate, butyl magnesium trimethyl butyl aluminate, butyl magnesium trimethyl hexyl aluminate, butyl magnesium trimethyl octyl aluminate, butyl magnesium triethyl methyl aluminum Butyl magnesium triethyl aluminate, butyl magnesium triethyl propyl aluminate, butyl magnesium triethyl butyl aluminate, butyl magnesium triethyl hexyl aluminate, butyl magnesium triethyl octyl aluminate, butyl magnesium triisobutyl methyl aluminate, butyl magnesium triethyl Soviet-butyl ethyl aluminate,
Butylmagnesium tetraisobutylaluminate, butylmagnesiumtriisobutylhexylaluminate, butylmagnesiumtriisobutyloctylaluminate,

Hexyl magnesium tetramethyl aluminate, hexyl magnesium trimethyl ethyl aluminate, hexyl magnesium trimethyl propyl aluminate, hexyl magnesium trimethyl butyl aluminate, hexyl magnesium trimethyl hexyl aluminate, hexyl magnesium trimethyl octyl aluminate, hexyl magnesium triethyl methyl aluminum Hexyl magnesium triethyl aluminate, hexyl magnesium triethyl propyl aluminate, hexyl magnesium triethyl butyl aluminate, hexyl magnesium triethyl hexyl aluminate, hexyl magnesium triethyl octyl aluminate, hexyl magnesium tributyl methyl aluminate, Hexyl magnesium tributyl ethyl aluminate, hexyl magnesium tetrabutyl aluminate, hexyl magnesium tributyl hexyl aluminate, hexyl magnesium tributyl octyl aluminate, and

Magnesium bis (tetramethylaluminate), magnesium bis (tetraethylaluminate), magnesium bis (tetrapropylaluminate), magnesium bis (tetrabutylaluminate)
G), magnesium bis (tetraisobutylaluminate), magnesium bis (tetrahexylaluminate), magnesium bis (tetraoctylaluminate) and the like.

Among the organometallic compounds, an organometallic compound of magnesium is preferred, and n-butylethylmagnesium is more preferred.

The compound consisting of these two kinds of organometallic compounds can be obtained by contacting the corresponding two kinds of organometallic compounds. This contact involves pentane, hexane,
The reaction can be carried out in an inert hydrocarbon solvent such as heptane, octane, decane, cyclopentane, cyclohexane, benzene, toluene and xylene. Contact temperature is -50 ~
200 ° C, preferably -20 to 100 ° C, more preferably 0 to 50 ° C, and the contact time is about 0.05 to 200 hours, preferably about 0.2 to 20 hours.

In the present invention, as the organometallic compound (C), one of the above-mentioned organometallic compounds may be used alone.
Alternatively, two or more kinds can be used in combination.
The amount of the organometallic compound used is such that the total amount of metal atoms in the organometallic compound is usually 1 to 2000 mol, preferably 1 to 1500 mol, per 1 mol of the metal atom in the transition metal compound. .

The polymerization of ethylene using the catalyst of the present invention can be carried out by a liquid phase polymerization method such as slurry polymerization or solution polymerization or a gas phase polymerization method. The liquid phase polymerization method is usually performed in a hydrocarbon solvent. As the hydrocarbon solvent, propane, butane, isobutane, hexane,
Inert hydrocarbon solvents such as cyclohexane, heptane, benzene, toluene and xylene are used alone or as a mixture of two or more. The polymerization reaction can be carried out in two or more stages by changing the conditions.

The polymerization temperature is generally from 0 to 300 ° C.
Practically, it is 20 to 200 ° C. The polymerization pressure is usually from normal pressure to 50 kg / cm ² . The molecular weight and molecular weight distribution of the obtained polymer can be adjusted by controlling the polymerization temperature and / or the amount of the catalyst component, or by allowing hydrogen or the like to coexist in the polymerization reactor. Furthermore, if necessary, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, etc.
-An olefin alone or two or more types may be introduced into a polymerization reactor and copolymerized. The content of α-olefin in the ethylene polymer is preferably 20 mol% or less, more preferably 15 mol% or less.

[0087]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

I. The methods for measuring the physical properties of the polyethylene obtained in the examples and comparative examples are as follows. (1) Polymer pretreatment for physical property measurement: Toyo Seiki Co., Ltd.
0.2% by weight of C225 Geigy's B225 was added as an additive and kneaded at 190 ° C. for 7 minutes under nitrogen. (2) Molecular weight, molecular weight distribution: Number average molecular weight (Mn) measured by gel permeation chromatography (GPC) under the following conditions
And the weight average molecular weight (Mw) were determined. The molecular weight distribution is represented by the ratio of Mw to Mn (Mw / Mn),
The larger the w / Mn, the wider the molecular weight distribution. The measurement conditions are as follows. Measurement conditions : WATERS 150C model, Column: Shodex-HT806M, Solvent: 1,2,4-trichlorobenzene, Temperature: 135 ° C, Sample concentration: 2mg / 5ml, Universal rating using monodisperse polystyrene fraction.

(3) Melt flow rate: Measured at a temperature of 190 ° C. and a load of 21.6 kg according to JIS-K-6760 by HL
Shown as MFR. (4) Density: Measured according to JIS K6760. (5) Fish eye: Using a biaxial stretching device manufactured by Toyo Seiki Co., Ltd., under the following conditions, the thickness obtained by pressing was 0.5 m.
m, heat and stretch a 90 mm × 90 mm press plate,
Observe the presence of gel fisheye by forming into a film,
Evaluation was made according to the following criteria. Conditions Stretching temperature: 128 ° C, Preheating time: 3 minutes and 30 seconds, Stretching speed: 3 m / min, Stretching ratio: Maximum (vertical) 5 times × (horizontal) 5 times. Evaluation criteria ○: no gel / fish eye, ×: gel / fish eye. (6) Melt tension: using a melt tension tester manufactured by Toyo Seiki Co., Ltd., resin temperature 190 ° C., orifice diameter 2.1 m
m, orifice length 8 mm, extrusion speed 15 mm / min, and winding speed 6.5 mm / min.

II. The compounds used in the examples and comparative examples are as follows. Chromium compound (a-1) (1) Bis (tert-butyl) chromate (a-1-1) Synthesized by the method described in Synth. Commun., 10 , 905 (1980). (2) Tris (bistrimethylsilylamide) chromium (a-1-
2) It was synthesized by the method described in J. Chem. Soc. (A), 1433 (1971). (3) Chromium acetate (a-1-3) A commercially available product (manufactured by Wako Pure Chemical Industries, Ltd.) was used. Support (a-2 ) (1) Silica (a-2-1) manufactured by DAVISON: grade 952, specific surface area: 283 m ² / g, pore volume: 1.67
cm ³ / g, average particle size: 138 μm. (2) Silica (a-2-2) manufactured by Fuji Silysia Chemical Ltd .: Grade CARi
ACT P-3, specific surface area: 722 m ² / g, pore volume: 1.21 c
m ³ / g, average particle size: 34 μm. Aluminoxane (a-3) (1) Methylaluminoxane (a-3-1) Toluene solution of methylaluminoxane manufactured by Tosoh Akzo.

Transition using a group having a conjugated π electron as a ligand
Metal compound (B) (1) Dimethylsilylene (tert-butylamide) (tetramethylcyclopentadienyl) titanium dichloride (B-
1) It was synthesized by the method described in JP-A-3-63088. (2) Ethylene bis (indenyl) zirconium dichloride (B-2) and bis (n-butylcyclopentadienyl) zirconium dichloride (B-3) Commercial products (manufactured by Kanto Chemical Co., Ltd.) were used.

Organometallic compound (C) n-Butylethylmagnesium (n-BuEtMg) (C
-1), triethylaluminum _{(Et 3 Al) (C-} 2), and triisobutylaluminum _{(Bu 3 Al) (C-} 3) should be designed manufactured by Tosoh Akzo Co., n- butyl lithium (n- (BuLi) (C-4) used was manufactured by Aldrich.

[0093]

EXAMPLE Preparation of solid catalyst component (a1) 15 g of silica (a-2-1) manufactured by DAVISON was placed in a flask, and chromium acetate (a-1 manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 100 ml of distilled water was used. -3) was added so that the amount of chromium atoms supported was as shown in Table 1, and the mixture was stirred at room temperature for 30 minutes. Distilled water was removed from the obtained slurry at 110 ° C. The obtained powder was subjected to a cylindrical firing electric furnace (diameter 38 mm,
First, the temperature was increased at a linear velocity of 4 cm / sec at a flow rate of 60 ° C./hr using nitrogen gas. After reaching 350 ° C., nitrogen was switched to air, and calcination was performed at this temperature for 18 hours while flowing at the same linear velocity. Then, the atmosphere was switched to nitrogen, and the temperature was lowered to room temperature. A carrier supporting the changed chromium compound was obtained. 3 g of the carrier supporting the chromium compound and 30 ml of hexane were added to a flask purged with nitrogen to form a slurry. To this slurry was added a toluene solution of 2.8 mol / l methylaluminoxane (a-3-1) manufactured by Tosoh Akzo Co., Ltd., and the molar ratio of the aluminum atom in methylaluminoxane to the chromium atom in the carrier supporting the chromium compound was as shown in Table 1. And stirred at 40 ° C. for 1 hour. The solvent was removed under vacuum to obtain a solid catalyst component (a1).

Preparation of Solid Catalyst Component (a2) In a nitrogen-purged flask, 3 g of silica (a-2-2) manufactured by Fuji Silysia Chemical Ltd. calcined in nitrogen at 400 ° C. for 8 hours and 30 ml of hexane were added to form a slurry. . To this slurry was added 0.1 mol / l of a hexane solution of a chromium compound shown in Table 1 so that the amount of chromium carried was as shown in Table 1, and the mixture was stirred at 40 ° C. for 1 hour. To this slurry was added a toluene solution of 2.8 mol / l methylaluminoxane (a-3-1) manufactured by Tosoh Akzo Co., Ltd. so that the molar ratio of aluminum atoms to chromium atoms in methylaluminoxane would be as shown in Table 1. Then, the mixture was stirred at 40 ° C. for 1 hour. The solvent was removed under vacuum to obtain a solid catalyst component (a2).

Preparation of Solid Catalyst Component (a3 ) 3 g of silica (a-2-2) manufactured by Fuji Silysia Chemical Ltd. and calcined in nitrogen at 400 ° C. for 8 hours and 30 ml of hexane were added to a nitrogen-purged flask to form a slurry. In this slurry,
The molar ratio of aluminum atoms and chromium atoms in methylaluminoxane when a 2.8 mol / l toluene solution of methylaluminoxane (a-3-1) manufactured by Tosoh Akzo Co., Ltd. was adjusted to the amount shown in Table 1 for the amount of chromium atoms carried. The mixture was added so that the ratio became the value shown in Table 1, and the mixture was stirred at 40 ° C. for 1 hour. To this slurry, 0.1 mol / l of a hexane solution of a chromium compound shown in Table 1 was added such that the amount of chromium atoms carried became the amount shown in Table 1, and the mixture was stirred at 40 ° C. for 1 hour. The solvent was removed under vacuum to obtain a solid catalyst component (a3).

Preparation of Solid Catalyst (A1) In a 1.5-liter autoclave purged with nitrogen, 600 ml of hexane as a solid catalyst component shown in Table 1 was previously charged.
The temperature was raised to the temperature shown in Table 1. Then, ethylene was added at a partial pressure as shown in Table 1 to perform prepolymerization. After stopping the supply of ethylene, the reaction system was cooled, and the supernatant was taken out and hexane was added. This operation was repeated three times.
A part of the obtained slurry containing the solid catalyst was extracted, the solvent was removed under reduced pressure, and the solid catalyst was analyzed. The prepolymerization amount was as shown in Table 1 per 1 g of the solid catalyst component.

Preparation of solid catalyst (A2) A solid catalyst component, 1-hexene, hexane 600
ml, and the temperature was raised to the temperature shown in Table 1 to perform prepolymerization. After cooling the reaction system, the supernatant was taken out and hexane was added. This operation was repeated three times. A part of the obtained slurry containing the solid catalyst was extracted, the solvent was removed under reduced pressure, and the solid catalyst was analyzed. The prepolymerization amount was as shown in Table 1 per 1 g of the solid catalyst component.

Examples 1 and 2: Table 1 shows the conditions for the type of ethylene polymerization catalyst, the amount of catalyst, the polymerization temperature, the hydrogen / ethylene weight ratio and the like. 1.5 L of isobutane was previously charged into a 3 L autoclave purged with nitrogen, and the temperature was raised to the polymerization temperature. Then, hydrogen / hydrogen at the mixing ratio shown in Table 1
Ethylene mixed gas was injected until the partial pressure became 10 kg / cm ^2, and contacted for further 20 seconds.
A 0.5 mmol / l transition metal compound in hexane solution was added to initiate polymerization. Polymerization was performed for 60 minutes while maintaining the mixed gas partial pressure at 10 kg / cm ² . Then, the polymerization was terminated by discharging the content gas out of the system. The results (polymer yield (g), HLMFR (dg /
Min), weight average molecular weight (Mw), molecular weight distribution (Mw / M
n), density (g / cm ³ ), melt tension (g), and gel fisheye state) are shown in Table 1.

Examples 3 to 7: Table 1 shows the conditions for the type of ethylene polymerization catalyst, the amount of the catalyst, the polymerization temperature and the hydrogen / ethylene weight ratio. Into a 3-liter autoclave purged with nitrogen, 3 ml (1.5 mmol) of a 0.5 mol / l hexane solution of an organometallic compound shown in Table 1 and 1.5 liter of isobutane were charged in advance, and the temperature was raised to the polymerization temperature. Then, a mixed gas of hydrogen / ethylene having a mixing ratio shown in Table 1 was injected until the partial pressure became 10 kg / cm ² , and further contacted with the solid catalyst shown in Table 1 for 20 seconds and 0.5 mmol / cm ^2.
1 hexane solution of a transition metal compound was added to initiate polymerization. Polymerization was performed for 60 minutes while maintaining the mixed gas partial pressure at 10 kg / cm ² . Then, the polymerization was terminated by discharging the content gas out of the system. Table 1 shows the results.
Shown in

Examples 8 and 9: ethylene and 1-hexe
Table 1 shows conditions such as the type of copolymerization catalyst, the amount of catalyst, the polymerization temperature, and the hydrogen / ethylene weight ratio. Into a 3-liter autoclave purged with nitrogen, 3 ml (1.5 mmol) of a 0.5 mol / l hexane solution of an organometallic compound shown in Table 1, 1.5 liter of isobutane, and 1-hexene were charged in advance, and the temperature was raised to the polymerization temperature. Then, a hydrogen / ethylene mixed gas having a mixing ratio shown in Table 1 was injected until the partial pressure became 10 kg / cm ² , and further contacted with the solid catalyst shown in Table 1 for 20 seconds.
A 0.5 mmol / l transition metal compound in hexane solution was added to initiate polymerization. Polymerization was performed for 60 minutes while maintaining the mixed gas partial pressure at 10 kg / cm ² . Then, the polymerization was terminated by discharging the content gas out of the system. Table 1 shows the results.

Comparative Example 1 Polymerization of Ethylene Polymerization of ethylene was carried out in the same manner as in Example 1, except that a solid catalyst containing no chromium was used. Table 1 shows the results.

Comparative Example 2 Polymerization of Ethylene In Example 1, except that no transition metal compound was used.
Ethylene was polymerized in the same manner. Table 1 shows the results.

Comparative Example 3: Preparation of solid catalyst component (a4 ) 15 g of silica (a-2-1) manufactured by DAVISON was placed in a flask, and chromium acetate manufactured by Wako Pure Chemical Industries, Ltd. dissolved in 100 ml of distilled water was used. The amount of chromium atoms supported was adjusted to the amount shown in Table 1, and the mixture was stirred at room temperature for 30 minutes.
Distilled water was removed from the resulting slurry at 110 ° C.
The obtained powder was placed in a cylindrical firing electric furnace (diameter 38 mm, with a perforated plate), and first, a linear velocity of 4 c using nitrogen gas.
The temperature was raised at a flow rate of m / sec at a rate of 60 ° C./hr. When it reaches 350 ° C, switch nitrogen to air,
After sintering at this temperature for 18 hours while flowing at the same linear speed, the atmosphere was switched to nitrogen and the temperature was lowered to room temperature.
A solid catalyst component (a4) was obtained.

Table 1 shows the conditions for the type of the ethylene polymerization catalyst, the amount of the catalyst, the polymerization temperature, the hydrogen / ethylene weight ratio, and the like. In a 3-liter autoclave purged with nitrogen, the solid catalyst component (a4) 253 shown in Table 1 was previously added.
mg, a 2.8 mol / l toluene solution of methylaluminoxane, manufactured by Tosoh Akzo Co., Ltd., having a molar ratio of aluminum atoms in methylalumoxane to chromium atoms in the solid catalyst component (a4) shown in Table 1, 0.5 mmol / Table 1 of l
Hexane solution of transition metal compound shown in isobutane 1.5
Liter was charged and the temperature was raised to the polymerization temperature. Subsequently, a hydrogen / ethylene mixed gas was injected until the partial pressure reached 14.0 kg / cm ² to initiate polymerization. 14.0 kg of mixed gas partial pressure
/ Cm ² and polymerization was carried out for 60 minutes. Then, the polymerization was terminated by discharging the content gas out of the system. Table 1 shows the results.

[0105]

[Table 1]

[0106]

[Table 2]

[0107]

Industrial Applicability By using the catalyst of the present invention, it is possible to industrially produce an ethylene polymer having a wide molecular weight distribution, a large melt tension, and a low gel fisheye, and particularly suitable for blown film molding and hollow molding. It can be manufactured efficiently.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a step of preparing an ethylene-based polymerization catalyst of the present invention.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shintaro Inazawa Oita City, Oita Pref.

Claims (5)

[Claims] 1. A solid catalyst component (a) comprising a chromium compound (a-1), a carrier (a-2) and an aluminoxane (a-3) is α-
An ethylene polymerization catalyst comprising a solid catalyst (A) prepolymerized in the presence of an olefin and a transition metal compound (B) having a group having a conjugated π electron as a ligand. 2. The amount of the solid catalyst component (a) is from 0.01 to 1 per gram.
The catalyst for ethylene-based polymerization according to claim 1, wherein a solid catalyst (A) obtained by prepolymerizing 0 g of an α-olefin is used. 3. An ethylene-based polymerization catalyst obtained by adding an organometallic compound (C) to the catalyst according to claim 1 or 2. 4. After supporting the chromium compound (a-1) on the carrier (a-2) and converting it to chromium oxide by firing in the presence of oxygen, aluminoxane (a-3) is added to the carrier (a-2). 2. The catalyst for ethylene-based polymerization according to claim 1, wherein the solid catalyst component (a) supported on (1) is used. 5. The catalyst for ethylene polymerization according to claim 1, wherein a chromium compound (a-1) which is not calcined in the presence of oxygen is used.