JPH10251322A - Catalyst for producing ethylene-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new catalyst composed of a solid catalyst, with a specific transition metal compound on a support, and 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, (B) a transition metal compound with a group having a conjugate π electron as the ligand, and preferably (C) an organometallic compound. 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 and a transition metal compound with a group having a conjugate π electron as the ligand on the support.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention 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-60-10680
6, 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 production method using a catalyst supported on an inorganic oxide has been proposed (JP-A-3-93804).
A method for producing a Phillips catalyst using a catalyst obtained by treating the above-mentioned chromium catalyst with an organoaluminum compound such as aluminoxane has also been proposed (JP-A-2-105806,
JP-A-2-185506, JP-T-7-503739, U.S. Patent 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, a method has been proposed in which a Philips catalyst or a Ziegler catalyst and a so-called metallocene catalyst, or a method using a catalyst in which two or more metallocene catalysts are combined are used (JP-A-1-292009, JP-A-3-203903). JP, JP-A-4-220405, JP-A-6-122719, JP-A-7-173209, JP-A-8-41118, JP-A-8-1
No. 00018, Japanese Patent Publication No. 8-13856, and Japanese Patent Application Laid-Open No. 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 use in blown 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 inventors of the present invention have conducted intensive studies in view of the above problems, and have found that a chromium compound, an aluminoxane and a transition metal compound having a group having a conjugated π electron as a ligand are supported on a carrier. The above-mentioned problems have been solved by a solid catalyst, an ethylene-based polymerization catalyst comprising a transition metal compound having a group having a conjugated π electron as a ligand, and optionally a catalyst comprising an organometallic compound. Have been obtained, and the present invention has been achieved.

Hereinafter, the catalyst for ethylene polymerization of the present invention will be specifically described. The catalyst for ethylene polymerization according to the present invention, a chromium compound (a-2) on a carrier (a-1), aluminoxane
(a-3) a solid catalyst (A) supporting a transition metal compound having a group having a conjugated π electron as a ligand, a transition metal compound (B) having a group having a conjugated π electron as a ligand, and A catalyst comprising an organometallic compound (C) if desired.

The chromium compound (a-2) used in the present invention
May be changed to chromium oxide by baking in the presence of oxygen, or may be used without baking in the presence of oxygen. The chromium compound (a-2) when converted to chromium oxide by firing in the presence of oxygen includes chromium carboxylate, chromium-1,3-diketo compound, chromate ester, chromamide compound, organic chromium compound, trioxide Any chromium compound which can be converted to chromium oxide by calcination in the presence of oxygen, such as chromium or an oxide of chromium, a halide, an oxyhalide, a nitrate, a sulfate, an acetate, an oxalate, etc., is mentioned.

After calcination in the presence of oxygen, at least some of the chromium atoms must be in the 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]

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[0011]

Embedded image In the above formula, R ^{1 to} R ⁵ may be the same or different,
Each is 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 formate (III),
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) wherein, Y is 1,3-diketo type chelate ligand, Z
¹ and Z ² may be the same or different and are each selected from a halogen atom, alkoxy, aryloxy, 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]

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[0020]

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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 atoms, L Represents a ligand such as ¹ 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, alkyl group, alkenyl group, alkylaryl group, arylalkyl group, allyl group, or silylalkyl group having 1 to 20 carbon atoms. L ² is a ligand such as ether, pyridine and THF (tetrahydrofuran). 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 chromium carboxylate, chromium-1,3-diketo compound, chromate ester, chromamide compound, organic chromium compound and the like are mentioned.

The carrier (a-1) used in the present invention may be any one of groups 2, 4, 13 or 14 of the periodic table (the group is a compound of 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, preferably 200 to 8
00 m ² / g, pore volume of 0.5 to 3.0 cm ³ / g, preferably 1.0 to 2.5 cm ³ / g, average particle size of 10 to 200 μm,
Preferably, those having a thickness of 30 to 150 μm are preferably used.

When the chromium compound is used without calcination in the presence of oxygen, the carrier (a-1) can be used under a flow of molecular sieves, under a dry nitrogen gas stream at 100 to 100%.
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]

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[0033]

Embedded image Wherein R ⁴⁵ is methyl, ethyl, propyl, n-butyl,
It is a hydrocarbon group such as isobutyl, and is preferably a methyl group or an isobutyl group. r is from 1 to 100,
It is 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.

Further, the following general formula (12) or (13)
May be used.

[0036]

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[0037]

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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 . Further, a plurality of Rs present in the general formula (12)
⁴⁷ may be the same or different. s is usually 1 to 10
0, preferably 3 or more, and s + t is 2 to 1
00, 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 transition metal compound ((a
The group having a conjugated π electron, which is a ligand of -4) and (B), 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, tert-butylcyclopentadienyl Group, dimethylcyclopentadienyl group, alkyl-substituted cyclopentadienyl group such as pentamethylcyclopentadienyl group,
Alkylsilyl-substituted cyclopentadienyl groups such as trimethylsilylcyclopentadienyl group, alkylgermyl-substituted cyclopentadienyl groups such as trimethylgermylcyclopentadienyl group, or indenyl groups with or without similar substituents And a fluorenyl group.

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 preferable, and zirconium and hafnium are particularly preferable.

The transition metal compound ((a-
4) and (B)) include the following general formula (14),
The transition metal compound represented by (15), (16), (17), (18), (19) or (20) is mentioned.

[0045]

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)

[0046]

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[0047]

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[0048]

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[0049]

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In the above formula, Cp ² and Cp ³ may be the same or different, each is a ligand having the aforementioned 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. The alkyl silylene group R ⁵¹ is represented, dimethylsilylene group, a diphenyl silylene group can be exemplified. Further R
Examples of the alkylgermylene group represented by ⁵¹ include a dimethylgermylene group and a diphenylgermylene group.

[0053] Y represents -NR ⁵² -, - PR ⁵² - Medium R
Specific examples of ⁵² include methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, amyl, isoamyl,
Examples include an alkyl group such as hexyl, heptyl, octyl, nonyl, decyl, and cetyl, and a phenyl group and a benzyl group. The ^{Y -NR 52 -, - PR 52} - type ligand is preferred.

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

As the transition metal compound represented by the general formula (14), bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, 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.

As the transition metal compound represented by the general formula (16), ethylene (tert-butylamide) (tetramethylcyclopentadienyl) zirconium dichloride, ethylene (methylamide) (tetramethylcyclopentadienyl) zirconium dichloride, dimethyl 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.

As the transition metal compound represented by the general formula (17), (cyclopentadienyl) (N, N'-bis (trimethylsilyl) benzamidinato) zirconium dichloride, (cyclopentadienyl) (N, N '
-Bis (n-butyl) benzamidinato) zirconium dichloride, (cyclopentadienyl) (N, N'-
Bis (phenyl) benzamidinato) zirconium dichloride, (cyclopentadienyl) (N, N′-bis (2,6-dimethylphenyl) benzamidinato) zirconium dichloride, (cyclopentadienyl)
(N, N′-bis (2,6-di-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 ((a-4) and (B)) represented by (17), (18), (19) or (20), zirconium in the above compound is replaced with hafnium or titanium. Transition metal compounds can also be exemplified. In the present invention, as the transition metal compound ((a-4) and (B)), the above-mentioned transition metal compounds can be used alone or in combination of two or more.

The solid catalyst (A) of the present invention comprises a chromium compound (a-2), an aluminoxane (a-3), a transition metal having a group having a conjugated π electron as a ligand on a carrier (a-1). It is obtained by supporting compound (a-4). When the chromium compound (a-2) is changed to chromium oxide by firing in the presence of oxygen, the chromium compound (a-2) is first supported on the carrier (a-1), and the chromium compound is oxidized by firing in the presence of oxygen. After changing to chromium, it is important to support aluminoxane (a-3) and a transition metal compound (a-4) having a group having a conjugated π electron as a ligand.

The order in which the aluminoxane (a-3) and the transition metal compound (a-4) having a group having a conjugated π electron as a ligand are supported is not limited. Aluminoxane (a-3) together with chromium compound (a-2) and / or a transition metal compound (a-4) having a group having a conjugated π electron as a ligand are supported on a carrier (a-1), and oxygen is present. If the lower firing is performed, the effect of the present invention cannot be obtained.

The method of supporting the chromium compound (a-2) on the carrier (a-1) 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 300 to 1000
It is carried out in the range of ° C. for 1 to 48 hours with a dry gas containing oxygen. Preferably, it is carried out in a state fluidized by a dry gas containing oxygen after removing the solvent.

The method of supporting the aluminoxane (a-3) and the transition metal compound (a-4) having a group having a conjugated π electron as a ligand is carried out in advance by isobutane, pentane, hexane, heptane, cyclohexane, decane and benzene. After suspending the carrier (a-1) supporting the chromium compound (a-2) converted to chromium oxide by baking in the presence of oxygen in an inert hydrocarbon solvent such as toluene, the aluminoxane (a-3 ) And a transition metal compound having a group having a conjugated π electron as a ligand (a
-4) The inert hydrocarbon solution is brought into contact with the solution. The contact temperature is 0 to 120 ° C, preferably 10 to 100 ° C, and the contact time is 1 minute to 10 hours, preferably 1 minute to 5 hours.
The amount of the solvent per 1 g of 1) is 5 to 800 ml. After the contact, the solvent is removed under reduced pressure or separated by filtration to obtain a solid catalyst.

When the chromium compound is used without firing in the presence of oxygen, the chromium compound (a-
2) The loading order of the aluminoxane (a-3) and the transition metal compound (a-4) having a group having a conjugated π electron as a ligand is arbitrary.

Chromium compound (a-2), aluminoxane (a-3)
A method of supporting a transition metal compound (a-4) having a group having a conjugated π electron as a ligand is preliminarily isobutane, pentane, hexane, heptane, cyclohexane, decane,
Benzene, after suspending the carrier in an inert hydrocarbon solvent such as toluene, chromium compound (a-2), aluminoxane (a-3)
And the above-mentioned inert hydrocarbon solution of a transition metal compound (a-4) having a group having a conjugated π electron as a ligand. The contact temperature is 0 to 120 ° C., preferably 10 to 100 ° C., the contact time is 1 minute to 10 hours, preferably 1 minute to 5 hours, and the amount of the solvent per 1 g of the carrier is 5 to 800 ml. After the contact, the solvent is removed under reduced pressure or separated by filtration to obtain a solid catalyst (A).

The carrier (a-1), the chromium compound (a-2), the aluminoxane (a-3), and the transition metal compound (a-4) having a group having a conjugated π electron as a ligand The usage rate is
When the chromium compound (a-2) is changed to chromium oxide by calcination in the presence of oxygen, and when calcination is not performed in the presence of oxygen, the carrier (a-1) 1 g
The chromium compound (a-2) has a chromium atom content in the chromium compound (a-2) of 0.01 to 5% by weight, preferably 0.05 to 3% by weight.
Aluminoxane (a-3) per mole of chromium atom
1 to 600 moles, preferably 5 moles of aluminum atoms therein
A metal atom in the transition metal compound (a-4) having a group having a conjugated π electron as a ligand is 1 mmol to 10 mol per 1 mol of a chromium atom in the solid catalyst (A); It is preferably from 10 mmol to 1 mol.

The catalyst of the present invention is formed by bringing the solid catalyst (A) into contact with a transition metal compound (B) having a group having a conjugated π electron as a ligand. Here, the used transition metal compound (B) having a group having a conjugated π electron as a ligand is the same as that described for the transition metal compound (a-4), and the solid catalyst (A) May be the same as or different from the transition metal compound (a-4) used in the preparation of the compound, and one type may be used alone, or two or more types may be used in combination.

An example of a method for contacting the solid catalyst (A) with a transition metal compound (B) having a group having a conjugated π electron as a ligand will be described below. The solid catalyst (A) is previously suspended in an inert hydrocarbon solvent such as isobutane, pentane, hexane, heptane, cyclohexane, decane, benzene, and toluene, and then the above-mentioned inert hydrocarbon solution of the transition metal compound (B) is added to the suspension. Make contact. Contact temperature is 0-120 ° C,
The temperature is preferably 10 to 100 ° C., the contact time is 2 seconds to 10 hours, preferably 5 seconds to 1 hour, and the amount of the solvent per 1 g of the solid catalyst is 3 to 800 ml. The metal atom in the transition metal compound is 0.01 to 1 mole of the chromium atom in the solid catalyst.
The amount is from 10 to 10 mol, preferably from 0.1 to 5 mol.

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 is an organometallic compound of an element belonging to Group 1, 2 or 3 of the periodic table, and specific compounds in the case where the metal is lithium, magnesium or aluminum are exemplified.

As the organometallic compound of lithium, methyl lithium, ethyl lithium, n-propyl lithium,
Examples thereof include alkyl lithiums such as n-butyl lithium, isobutyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, and isopentyl lithium.

The organometallic compounds of magnesium include:
Examples thereof 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 with pentane, hexane, heptane, octane, decane, cyclopentane and cyclohexane. , Benzene, toluene, xylene and the like. Contact temperature is -50 to 2
00 ° C, preferably -20 to 100 ° C, more preferably 0 to 50 ° C, and the contact time is 0.05 to 200 hours, preferably
It is about 0.2 to 20 hours.

In the present invention, as the organometallic compound (C), the above-mentioned organometallic compounds can be used alone or in combination of two or more. The amount used when using the organometallic compound 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. Used in appropriate amounts.

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, xylene, etc. each alone or
Used as a mixture of more than one species. 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., and practically from 20 to 200 ° C. The polymerization pressure is usually from normal pressure to 50 kg / cm ² . Polymerization temperature and / or
Alternatively, the molecular weight and the molecular weight distribution of the obtained polymer can be adjusted by controlling the amount of the catalyst component or by allowing hydrogen or the like to coexist in the polymerization reactor. further,
Propylene, 1-butene, 1-hexene,
Α-olefins such as 4-methyl-1-pentene and 1-octene may be copolymerized by introducing one or more of them into a polymerization reactor. Α- in ethylene-based polymer
The olefin content is preferably at most 20 mol%, particularly preferably at most 15 mol%.

[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.
Using a plastograph made by Ciba Geigy, 0.2 wt% of 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 Apparatus: WATERS 150C model, Column: Shodex-HT806M, Solvent: 1,2,4-trichlorobenzene, Temperature: 135 ° C, Sample concentration: 2mg / 5ml, Universal evaluation 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 Examples and Comparative Examples were obtained as follows. Support (a-1) (1) Silica (a-1-1) 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-1-2) 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. Chromium compound (a-2) (1) Bis (tert-butyl) chromate (a-2-1) Synthesized by the method described in Synth. Commun., 10 , 905 (1980). (2) Tris (bistrimethylsilylamide) chromium (a-2-
2) It was synthesized by the method described in J. Chem. Soc. (A), 1433 (1971). (3) Chromium acetate (a-2-3) A commercially available product (manufactured by Wako Pure Chemical Industries, Ltd.) was used. 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 compounds ((a-4) and (B)) (1) Dimethylsilylene (tert-butylamide) (tetramethylcyclopentadienyl) titanium dichloride ((a-4
-1) and (B1)) It was synthesized by the method described in JP-A-3-63088. (2) Ethylene bis (indenyl) zirconium dichloride ((a-4-2) and (B2)) A commercially available product (manufactured by Kanto Chemical Co., Ltd.) was used. (3) Bis (n-butylcyclopentadienyl) zirconium dichloride (a-4-3) and (B3)) A commercially available product (manufactured by Kanto Chemical Co., Ltd.) was 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 (A1) 15 g of silica (a-1-1) manufactured by DAVISON was placed in a flask, and chromium acetate (a-2- manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 100 ml of distilled water was used. 3) was added so that the amount of supported chromium atoms became the amount shown in Table 1, and the mixture was stirred at room temperature for 30 minutes. At 110 ° C., distilled water was removed from the obtained slurry. The obtained powder was placed in a cylindrical firing electric furnace (diameter 38 m).
m, with a perforated plate) and first heated with nitrogen gas at a linear velocity of 4 cm / sec at a rate of 60 ° C./hr. After reaching 350 ° C., the nitrogen is switched to air and at this temperature one flow while flowing at the same linear velocity.
After calcining for 8 hours, the atmosphere was switched to nitrogen, the temperature was lowered to room temperature, and a carrier supporting a chromium compound changed to chromium oxide by calcining in the presence of oxygen was obtained. Carrier 3 supporting the above chromium compound in a nitrogen-purged flask
g and 30 ml of hexane were added 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. Next, 0.5 mol / l of a hexane solution of a transition metal compound shown in Table 1 was added to the slurry, and the mixture was stirred at room temperature for 10 minutes. The solvent was removed under vacuum to obtain a solid catalyst (A1).

Preparation of Solid Catalyst (A2 ) 3 g of silica (a-1-2) 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. 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. Next, 0.5 mmol / l of a hexane solution of a transition metal compound shown in Table 1 was added to the slurry, followed by stirring at room temperature for 10 minutes. The solvent was removed under vacuum to obtain a solid catalyst (A2).

Preparation of Solid Catalyst (A3 ) 3 g of silica (a-1-2) 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,
When a 2.8 mol / l toluene solution of methylaluminoxane (a-3-1) manufactured by Tosoh Akzo Co., Ltd. was used and the supported amount of chromium atoms was adjusted to the amount shown in Table 1, the moles of aluminum and chromium atoms in methylaluminoxane were measured. 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. Next, 0.5 mmol / l of a hexane solution of a transition metal compound shown in Table 1 was added to the slurry, followed by stirring at room temperature for 10 minutes. The solvent was removed under vacuum to obtain a solid catalyst (A3).

Preparation of Solid Catalyst (A4 ) 3 g of silica (a-1-2) 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,
0.1 mol / l of a hexane solution of a chromium compound shown in Table 1 was added so that the amount of supported chromium atoms became the amount shown in Table 1, and the mixture was stirred at 40 ° C. for 1 hour. Then 0.5mm
1 / l of a hexane solution of a transition metal compound shown in Table 1 was added, and the mixture was stirred at room temperature for 10 minutes. Further, a toluene solution of 2.8 mol / l methylaluminoxane (a-3-1) manufactured by Tosoh Akzo Co., Ltd. was added so that the molar ratio between aluminum atoms and chromium atoms in methylaluminoxane would be as shown in Table 1. And stirred at 40 ° C. for 1 hour. The solvent was removed under vacuum to obtain a solid catalyst (A4).

Examples 1 and 2: Table 1 shows conditions for the type of ethylene polymerization catalyst, amount of catalyst, polymerization temperature, hydrogen / ethylene weight ratio and the like. 1.5 liters of isobutane was previously charged into a 3 liter autoclave purged with nitrogen, 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 for 20 seconds with the solid catalyst shown in Table 1 and 0.5 mmol / l of transition metal. A hexane solution of the compound was added to initiate polymerization. 10kg /
cm ² and polymerization was carried out for 60 minutes. Then, the polymerization was terminated by discharging the content gas out of the system. The results (polymer yield (g), HLMFR (d
g / min), weight average molecular weight (Mw), molecular weight distribution (Mw)
/ Mn), density (g / cm ³ ), melt tension (g) and gel fisheye state) are shown in Table 1.

Examples 3-6: Table 1 shows the conditions for the type of ethylene polymerization catalyst, the amount of the catalyst, the polymerization temperature, the hydrogen / ethylene weight ratio, and the like. 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 7 to 9: Ethylene and 1-hexene
Table 1 shows conditions such as the type of the copolymerization 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, 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. The partial pressure of the mixed gas was maintained at 10 kg / 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.

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 Polymerization of ethylene was carried out in the same manner as in Example 1, except that the transition metal compound (B) was not used. Table 1 shows the results.

Comparative Example 3: Preparation of solid catalyst (A5) 15 g of silica (a-1-1) 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 replaced with chromium. The amount of supported atoms was added so as to be as 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 60 ° C./hr at a flow rate of m / sec.
When the temperature reached 350 ° C., nitrogen was switched to air, and calcination was performed at this temperature for 18 hours while flowing at the same linear velocity. Thereafter, the atmosphere was switched to nitrogen, and the temperature was lowered to room temperature to obtain a solid catalyst (A5).

In a 3-liter autoclave in which the polymerization of ethylene was replaced with nitrogen, Table 1 was prepared in advance.
2.8 mol, manufactured by Tosoh Akzo Co., Ltd., in which the molar ratio of the aluminum atom in methylalumoxane to the chromium atom in the solid catalyst (A5) is as shown in Table 1.
/ L of a toluene solution of methylaluminoxane (a-3-1),
0.5 mmol / l of a hexane solution of a transition metal compound shown in Table 1 and 1.5 liter of isobutane were 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.
Keep the mixed gas partial pressure at 14.0 kg / cm ² ,
Polymerization was carried out for 0 minutes. Then, the polymerization was terminated by discharging the content gas out of the system. Table 1 shows the results.

[0104]

[Table 1]

[0105]

[Table 2]

[0106]

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 generation of gels and fish eyes, and particularly suitable for blown film molding and hollow molding. It can be manufactured efficiently and efficiently.

[Brief description of the drawings]

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

Continuation of the front page (72) Inventor Shintaro Inazawa Oita City, Oita City, Oita Prefecture

Claims (4)

[Claims] A chromium compound (a-2), an aluminoxane (a-3) and a transition metal compound (a-4) having a group having a conjugated π electron as a ligand are supported on a carrier (a-1). And a transition metal compound (B) having a group having a conjugated π electron as a ligand. 2. An ethylene-based polymerization catalyst obtained by adding the organometallic compound (C) to the ethylene-based polymerization catalyst according to claim 1. 3. A chromium compound (a-2) is supported on a carrier (a-1), and after being converted to chromium oxide by calcination in the presence of oxygen, it has an aluminoxane (a-3) and a conjugated π electron. The catalyst for ethylene-based polymerization according to claim 1, wherein a solid catalyst (A) supporting a transition metal compound (a-4) having a group as a ligand is used. 4. 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.