JPH11228620A - Catalyst for polymerization of ethylene system and production of ethylenic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalyst giving an ethylenic polymer, comprising a solid catalyst carrying a reaction product from a chromium compound with an organic metal compound, and a transition metal compound with an organic aluminum compound on a carrier, and having high molecular weight and large melt tension and suitable for an inflation film generating slight fish eye. SOLUTION: This catalyst is obtained by adding (B) a reaction product of a chromium compound (e.g. chromium carboxylate) with an organic metal compound (e.g. methyl lithium), (C) a solid catalyst carrying a reaction product of a transition metal compound e.g. bis(cyclopentadienyl)zirconium dichloride} including a group having a conjugate π-electron as a ligand with an organic aluminum compound (e.g. aluminoxane), and preferably further (D) an organic metal compound, (E) a transition metal compound including a group having a conjugate π-electron as a ligand on (A) a carrier (e.g. magnesia or titania).

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 polymer having a high molecular weight, a high melt tension, and low generation of fish eyes, and a method for producing an ethylene polymer using the catalyst.

[0002]

2. Description of the Related Art Ethylene 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, as the ethylene polymer used for blown film molding or hollow molding, a polymer having a relatively high molecular weight, a wide molecular weight distribution, a large melt tension, and a low generation of fish eyes is suitable.

Hitherto, many methods have been proposed for producing an ethylene polymer having the above-mentioned properties by single-stage or multi-stage polymerization using a so-called Ziegler catalyst comprising a titanium compound, a magnesium compound and a halogen (Japanese Patent Application Laid-Open (JP-A) No. 2002-287686). JP-A-56-90809, JP-A-60-106806,
JP-A-2-123108, JP-A-4-18407, JP-A-5
-230136).

Chromium trioxide supported on an inorganic oxide,
A method for producing an ethylene-based polymer using a so-called Phillips catalyst is known, and uses a catalyst in which a chromium compound such as (pentamethylcyclopentadienyl) (2-methylpentadienyl) chromium is supported on an inorganic oxide. Also, a method of manufacturing by using the method has been proposed (JP-A-3-93804). Further, a method of producing the chromium catalyst using a catalyst obtained by treating the chromium catalyst with an organoaluminum compound such as aluminoxane has also been proposed (JP-A-2-105806, JP-A-2-185506).
No., JP-T-Hei 7-503739, U.S. Pat.No. 4,564,660
issue). 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 (JP-A-62-207307, JP-B-7-103177). ).

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 kinds of metallocene catalysts (JP-A-1-292009, JP-A-3-292009). -
JP 203903, JP-A-4-220405, JP-A-6-1222719
JP-A-7-173209, JP-A-8-41118, JP-A-8-100018, JP-B-8-13856, JP-A-8-259618).

However, the molecular weight and melt tension of ethylene polymers produced using these catalysts are not at a sufficient level for use in blown film molding. Therefore, the present inventors have solved the above-mentioned problems by developing an organochromium compound, a carrier, an aluminoxane and a transition metal compound having a group having a conjugated π electron as a ligand. A catalyst to be used without the use has been proposed (JP-A-9-369912).

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to further improve the above-mentioned invention, and to provide a high molecular weight, a high melt tension,
An object of the present invention is to provide a catalyst capable of producing a novel ethylene-based polymer suitable for an inflation film with less generation of fish eyes, and a method for producing an ethylene-based polymer using the catalyst.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned problems, and as a result, have found that a chromium compound (A1) was previously activated on a carrier (D) with an organometallic compound (A2). (A) and a solid catalyst supporting a reactant (B) in which a transition metal compound (B1) having a group having a conjugated π electron as a ligand is previously activated with an organoaluminum compound (B2). The present inventors have found that an ethylene-based polymer having the above-mentioned improvement can be obtained, and reached the present invention. Hereinafter, the ethylene-based polymerization catalyst according to the present invention will be specifically described.

The catalyst used in the production of the ethylene polymer according to the present invention has a reaction product (A) of a chromium compound (A1) and an organometallic compound (A2) and a conjugated π electron on a carrier (D). A solid catalyst supporting a reaction product (B) of a transition metal compound (B1) having a group as a ligand and an organoaluminum compound (B2), and optionally an organometallic compound (C) and / or a group having a conjugated π electron Is a catalyst comprising a transition metal compound (E) having a ligand as a ligand.

Carrier (D) usable in the present invention
Is an oxide of an element of Groups 2, 4, 13, or 14 of the periodic table (the group is based on the inorganic chemical nomenclature 1990 rules; the same applies hereinafter);
Or, it is a compound often used as a component of an ethylene-based polymerization catalyst, such as a phosphate of a Group 13 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 thereof include aluminum oxide and gallium phosphate, and these can be used alone or in combination of two or more. Carrier specific surface area 50~1000m ² / g, preferably 200~800m ² / g, a pore volume of 0.5~3.0cm ³ /
g, preferably 1.0 to 2.5 cm ³ / g, and the average particle size is 10 to 10.
Those having a thickness of 200 μm, preferably 30 to 150 μm are preferably used. As the carrier, those baked at 100 to 900 ° C. for 10 minutes to 24 hours in a stream of nitrogen gas dried under circulation of molecular sieves are preferably used. Preferably, the solid is calcined in a fluid state in a sufficient amount of nitrogen gas.

The chromium compound (A1) used in the present invention includes chromium carboxylate, chromium-1,3-diketo compound, chromate ester, chromamide compound, organic chromium compound and the like. Examples of the chromium carboxylate include compounds of chromium (II) or chromium (III) represented by the following general formula (1) or (2).

[0012]

Embedded image

(Wherein, R ¹ to R ⁵ are hydrogen or C 1
To 18 hydrocarbon groups, which may be the same or different. )

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

As the chromium-1,3-diketo compound,
A chromium (III) complex having 1 to 3 1,3-diketo compounds represented by the general formula (3) can be given.

## STR2 ## ^{_{Cr (Y) e (Z 1}} ) f (Z 2) g (3) ( wherein, Y is 1,3-diketo type chelate ligand,
Z ¹ and Z ² are selected from halogen, alkoxy, aryloxy, alkyl, aryl and amide, and may be the same or different. e + f + g = 3, e is 1-3. )

Specific examples include chromium-1,3-butanedionate, chromium acetylacetonate, and chromium-acetylacetonate.
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-1,2,3-triphenyl-1,
3-Propanedionate and the like are preferable, and chromium acetylacetonate is preferable.

The chromic ester is represented by the general formula (4)
The compound of chromium (VI) shown by these is mentioned.

[0018]

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

As a specific example, when M ¹ and M ² are carbon, bis (tert-butyl) chromate, bis (1,1-
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-trimethyl) Propyl) chromate, and bis (tert-butyl) chromate is preferred.

When M ¹ and M ² are silicon, bis (trimethylsilyl) chromate, bis (triethylsilyl) chromate, bis (tributylsilyl) chromate, bis (triisopentylsilyl) chromate, bis (tri-2-yl) chromate Ethylhexylsilyl) chromate, bis (tridecylsilyl) chromate, bis (tri (tetradecyl) silyl) chromate, bis (tribenzylsilyl) chromate, bis (triphenethylsilyl) chromate, bis (triphenylsilyl) chromate, bis (tri Tolylsilyl) chromate, bis (trixylylsilyl) 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, with bis (triphenylsilyl) chromate being preferred.

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

[0022]

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[0023]

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(Wherein R ¹² to R ⁴¹ are hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, which may be the same or different. M ³ to M ¹² are a carbon and / or silicon atom And L ¹ represents a ligand such as ether or nitrile, and h is 0 to 2.)

As specific examples, tris (dimethylamido) chromium (III), tris (diethylamido) chromium (III), tris (diisopropylamido) chromium (II)
I), tris (methylphenylamide) chromium (III),
Tris (diphenylamide) 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 (tert-butyltrimethylsilylamide)
Chromium (II) -THF 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 preferred.

As the organic chromium compound, chromium (II) represented by the general formula (7), (8) or (9),
Chromium (III) or chromium (IV) compounds are mentioned.

(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)

In the formula, Cp ¹ is cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, n-butylcyclopentadienyl, tert-butylcyclopentadienyl, trimethylsilylcyclopentadienyl, dimethylcyclopentadienyl Alkyl gels such as alkyl-substituted cyclopentadienyl groups such as pentadienyl and pentamethylcyclopentadienyl groups, alkylsilyl-substituted cyclopentadienyl groups such as trimethylsilylcyclopentadienyl group, and trimethylgermylcyclopentadienyl groups A ligand having a cyclopentadienyl skeleton such as a mill-substituted cyclopentadienyl group, or an indenyl group or a fluorenyl group having or not having the same substituent. R ⁴² and R ⁴³ are aryl having 1 to 20 carbons,
An alkyl, alkenyl, alkylaryl, arylalkyl, allyl, silylalkyl, or alkoxy group, which may be the same or different. R ⁴⁴ is an aryl, alkyl, alkenyl, alkylaryl, arylalkyl, allyl, silylalkyl group having 1 to 20 carbon atoms. L ² is a ligand such as ether, pyridine and THF. k is 1 or 2, m is 1 or 2,
n is 0 or 1, and p is 2-4. )

Specific examples include bis (cyclopentadienyl) chromium (II) and bis (indenyl) chromium (I
I), bis (fluorenyl) chromium (II), (pentamethylcyclopentadienyl) (cyclopentadienyl)
Chromium (II), (pentamethylcyclopentadienyl)
(Pentadienyl) chromium (II), (pentamethylcyclopentadienyl) (2-methylpentadienyl) chromium (II), (pentamethylcyclopentadienyl)
(2,4-dimethylpentadienyl) chromium (II),
(Pentamethylcyclopentadienyl) (dimethyl) chromium (III), (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, bis (allyl) chromium (I
I), 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.

Among these chromium compounds, chromate esters and chromamide compounds are preferred. These chromium compounds are preferably used without firing.

The organometallic compound (A2) used in the present invention
Is an organometallic compound of a Group 1, 2 or 3 element of the periodic table. Specific compounds when the metal is lithium, magnesium, or aluminum are exemplified. As the organometallic compound of lithium, methyl lithium, ethyl lithium,
Examples thereof include alkyl lithiums such as n-propyl lithium, n-butyl lithium, isobutyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, and isopentyl lithium.

As the organometallic compound of magnesium,
n-butylethylmagnesium, di-sec-butylmagnesium, n-butyl-sec-butylmagnesium, di-te
Examples thereof include dialkylmagnesium such as rt-butylmagnesium, dineopentylmagnesium, and di-n-hexylmagnesium.

As the organometallic compound of aluminum,
Trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, Trialkyl aluminum such as trioctyl aluminum and tricyclohexyl aluminum, dimethyl aluminum chloride,
Dialkylaluminum halides such as diethylaluminum chloride, diisobutylaluminum chloride,
Examples thereof include dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide, and dialkyl aluminum aryl oxides such as diethyl aluminum phenoxide.

As the organometallic compound comprising lithium and aluminum, lithium tetramethylaluminate,
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 triethyloctyl aluminate, lithium tributyl methyl aluminate, lithium tributyl ethyl aluminate, lithium tributyl propyl aluminate, lithium tetrabutyl aluminate, lithium tributylhexyl aluminate, lithium tributyl octyl aluminate , 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 propyl aluminate, lithium trioctyl butyl aluminate, lithium trioctyl Examples thereof include tylhexyl aluminate and lithium tetraoctyl aluminate.

Examples of the organometallic compound composed 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, butylmagnesium trimethylbutylaluminate, butylmagnesiumtrimethylhexylaluminate, butylmagnesiumtrimethyloctylaluminate, butylmagnesiumtriethylmethylaluminate, butylmagnesiumtetraethylaluminate, butylmagnesiumtriethylpropylaluminate, butylmagnesiumtriethyl Chill butyl aluminate, butyl magnesium tri-ethylhexyl aluminate, butyl magnesium triethylaluminum octyl aluminate, butylmagnesium triisobutyl methyl aluminate, butylmagnesium triisobutyl ethyl aluminate,
Butylmagnesium tetraisobutylaluminate, butylmagnesiumtriisobutylhexylaluminate, butylmagnesiumtriisobutyloctylaluminate, hexylmagnesiumtetramethylaluminate, hexylmagnesiumtrimethylethylaluminate, hexylmagnesiumtrimethylpropylaluminate, hexylmagnesiumtrimethylbutylaluminate , Hexyl magnesium trimethyl hexyl aluminate, hexyl magnesium trimethyl octyl aluminate, hexyl magnesium triethyl methyl aluminate, hexyl magnesium tetraethyl aluminate, hexyl magnesium triethyl propyl aluminate, hexyl magnesium triethyl butyl aluminate, hexylma Nesium triethylhexyl 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 the like, and Magnesium bis (tetramethyl aluminate), magnesium bis (tetraethyl aluminate), magnesium bis (tetrapropyl aluminate), magnesium bis (tetrabutyl aluminate), magnesium bis (tetraisobutyl aluminate), magnesium bis (tetrahexyl aluminum) Nate), magnesium bis (tetraoctyl) Aluminate) and the like.

The compound consisting of these two kinds of organometallic compounds can be obtained by contacting the corresponding two kinds of organometallic compounds. This contact can be performed in an inert hydrocarbon solvent such as pentane, hexane, heptane, octane, decane, cyclopentane, cyclohexane, benzene, toluene, xylene and the like. 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.

Further, as an organometallic compound of a Group 3 element,
Aluminoxanes represented by the general formula (10) or (11) are also included.

[0037]

Embedded image

Wherein R ⁴⁵ is a hydrocarbon group such as methyl, ethyl, propyl, n-butyl, isobutyl,
Preferred are a methyl and an isobutyl group. A plurality of R ⁴⁵ may be the same or different. It is 1 to 100, 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. Or a method in which solid, liquid or gaseous water is allowed to act on trialkylaluminum in a hydrocarbon solvent.

Further, an aluminoxane represented by the general formula (12) or (13) may be used.

[0041]

Embedded image

(Wherein R ⁴⁶ is a hydrocarbon group such as methyl, ethyl, propyl, n-butyl, isobutyl, etc.)
Preferred are a methyl group and an isobutyl group. Also, R ⁴⁷
Represents methyl, ethyl, propyl, n- butyl, hydrocarbon groups such as isobutyl or chlorine, halogen or hydrogen bromine, selected from hydroxyl, different groups and R ^46. A plurality of R ⁴⁶ and R ⁴⁷ may be the same or different. s is usually 1 to 100, preferably 3 or more, and s + t is 2 to 100,
Preferably it is 6 or more. ).

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

Embedded image May be connected in blocks or may be connected regularly or irregularly at random. The method for producing such an aluminoxane is the same as that for the above-described aluminoxane of the general formula. Instead of one kind of trialkylaluminum, two or more kinds of trialkylaluminum are used, or one or more kinds of trialkylaluminum and one kind The above dialkylaluminum monohalide or dialkylaluminum monohydride may be used.

In the present invention, the organometallic compound (A2) can be used alone or in combination of two or more of the above-mentioned organometallic compounds.

Among the organometallic compounds (A2), when a reaction product with the chromium compound (A1) is obtained, an organomagnesium compound and an aluminoxane are preferable, and n-butylethylmagnesium, methylaluminoxane and iso-butylaluminoxane are more preferable. preferable.

In the transition metal compound (B1) having a group having a conjugated π electron as a ligand used in the present invention, the ligand of the group having a conjugated π electron is a cyclopentadienyl skeleton,
A ligand having an amidinato skeleton or an allyl skeleton. As the ligand having a cyclopentadienyl skeleton, for example, cyclopentadienyl, or methylcyclopentadienyl, ethylcyclopentadienyl, n-butylcyclopentadienyl, tert-butylcyclopentadienyl, trimethylsilylcyclo Alkyl-substituted cyclopentadienyl groups such as pentadienyl, dimethylcyclopentadienyl and pentamethylcyclopentadienyl groups, alkylsilyl-substituted cyclopentadienyl groups such as trimethylsilylcyclopentadienyl group, and trimethylgermylcyclopentadiene Examples thereof include an alkylgermyl-substituted cyclopentadienyl group such as an enyl group, or an indenyl group or a fluorenyl group having or not having the same substituent.

The ligand having an amidinato skeleton includes, for example, an amidinate 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-dimethylphenyl) benzamidinato group. In addition, examples of the ligand having an allyl skeleton include an allyl group having or not having the same substituent as described above.

In the transition metal compound (B1) having a conjugated π electron group as a ligand used in the present invention, the transition metal is a transition metal element belonging to Group 3, 4, 5, or 6 of the periodic table. Is preferably a transition metal element of Group 4 of the periodic table, and is preferably selected from titanium, zirconium and hafnium, and particularly preferably zirconium and hafnium.

Specific transition metal compounds (B1) include:
General formulas (14), (15), (16), (17), (1
8), (19) or the transition metal compound represented by (20).

[0050]

(Cp ² ) (Cp ³ ) _u Me (Q ¹ ) _3-u (14)

[0051]

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

[0052]

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

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[Wherein Cp ² and Cp ³ are the above-mentioned ligands having a cyclopentadienyl skeleton, which may be the same or different, and R ⁴⁸ to R ⁵⁰ are hydrogen, and have 1 to 20 carbon atoms. A hydrocarbon group such as alkyl, alkenyl, aryl, araryl, aralkyl, and alicyclic, an alkylsilyl group or an alkylgermyl group, which may be the same or different, and R ⁵¹ has 1 to 20 carbon atoms. X ¹ and X ² are carbon or nitrogen, which may be the same or different, and Q ¹ and Q ² are hydrogen, a hydrocarbon having 1 to 20 carbon atoms, an alkoxyl group or an alkylsilylene group. , An alloxy group, a siloxy group or a halogen, which may be the same or different, and Y is -O-,-
^{S -, - NR 52 -,} - PR 52 - (R 52 represents hydrogen, carbon 1
To 20 hydrocarbon groups, alkyl halides or aryl halides. ), Me is a transition metal, and u is 0 or 1. ]

In the above formula, the hydrocarbon group having 1 to 20 carbon atoms of R ⁴⁸ to R ⁵⁰ includes, for example, methyl, ethyl, propyl, butyl, isobutyl, tert-butyl,
Amyl, isoamyl, hexyl, heptyl, octyl,
Nonyl, decyl, alkyl groups such as cetyl can be exemplified,
Examples of the aryl group include phenyl, examples of the alkylsilyl group include trimethylsilyl, and examples of the alkylgermyl group include trimethylgermyl.

In the above formula, specific examples of the alkylene group represented by R ⁵¹ include methylene, ethylene, propylene, isopropylidene, cyclopentylidene, cyclohexylidene, tetrahydropyran-4-ylidene, diphenylmethylene and the like. Examples of the alkylsilylene group include dimethylsilylene and diphenylsilylene groups, and examples of the alkylgermylene group include dimethylgermylene and diphenylgermylene groups.

[0060] Among Y ^{are, -NR 52 -, - PR 52} - type ligand is preferred. Specific examples of R ^{52 in} the ligands —NR ⁵² — and —PR ⁵² — represented by Y include methyl, ethyl, propyl, butyl, isobutyl, tert-butyl,
Amyl, isoamyl, hexyl, heptyl, octyl,
Examples include an alkyl group such as nonyl, decyl, and cetyl, and a phenyl group and a benzyl group.

The general formulas (14), (15), (16),
Specific examples of the transition metal compound represented by (17), (18), (19) or (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, pentamethylcyclopentadienyl zirconium trichloride, penta Methylcyclopentadienyl zirconium trimethyl and the like can be exemplified.

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. Ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride,
Examples include 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, Dimethylsilylene (tert-butylamide) (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (tert-butylamide) (tetramethylcyclopentadienyl) zirconium dibenzyl, dimethylsilylene (benzylamide) (tetramethylcyclopentadienyl) ) Zirconium dibenzyl, dimethylsilylene (phenylamide) (tetramethylcyclopentadienyl) zirconium dichloride and the like.

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'-
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, (pentamethylcyclopentadienyl) (N, N'-bis (phenyl) methylamidinato) zirconium dichloride, (indenyl) (N,
N'-bis (trimethylsilyl) benzamidinato)
Zirconium dichloride, (indenyl) (N, N'-
Bis (n-butyl) benzamidinato) zirconium dichloride and (indenyl) (N, N'-bis (phenyl) benzamidinato) zirconium dichloride can be exemplified.

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.

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

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, dimethylsilylene bis (N, N'-bis (n-butyl) amidinato) zirconium dichloride, isopropylidenebis (N, N'-bis (trimethylsilyl) amidinato)
Zirconium dichloride, isopropylidene bis (N,
N'-bis (phenyl) amidinato) zirconium dichloride, isopropylidenebis (N, N'-bis (n
-Butyl) amidinato) zirconium dichloride.

Specific examples of the compounds of formulas (14) to (20) wherein Me is hafnium or titanium include transition metal compounds in which zirconium is replaced by hafnium or titanium in the above-mentioned zirconium compounds. In the present invention, one or a combination of two or more of the above-mentioned transition metal compounds can be used.

Examples of the organoaluminum compound (B2) used in the present invention include, in addition to the organoaluminum compounds described for the organometallic compound (A2), general formulas (10) to (1)
The compound shown by 3) is mentioned. Of these, aluminoxanes are preferred.

The solid catalyst of the present invention comprises a support (D), a reaction product (A) of a chromium compound (A1) and an organometallic compound (A2), and a transition using a group having a conjugated π electron as a ligand. It is obtained by supporting a reaction product (B) of a metal compound (B1) and an organoaluminum compound (B2).

The chromium compound (A1) and the organometallic compound (A
The reaction product (A) of 2) and the reaction product (B) of a transition metal compound (B1) having a group having a conjugated π electron as a ligand and an organoaluminum compound (B2) are isobutane, pentane,
It is obtained by contacting each with each other in an inert hydrocarbon solvent such as hexane, heptane, cyclohexane, decane, benzene, and toluene. Contact temperature is -80 to 120
° C, preferably 0 to 70 ° C, and the contact time is 1 minute to 10 hours, preferably 10 minutes to 5 hours.

A reaction product (A) of a chromium compound (A1) and an organometallic compound (A2) on a carrier (D), a transition metal compound (B1) having a group having a conjugated π electron as a ligand, and an organoaluminum The order in which the reactant (B) of the compound (B2) is supported is arbitrary, and the reactant (A) and the reactant (B) can be separately supported, simultaneously supported, or in advance. A) and the reactant (B) may be mixed and then supported.
When the same compound as the organoaluminum compound (B2) for obtaining the reactant (B) is used as the organometallic compound (A2), the chromium compound (A1), the organoaluminum compound ((A2) and (B2) )) And a transition metal compound (B1) having a group having a conjugated π-electron as a ligand may be supported in a single reactor after the reaction.

A reaction product (A) of a chromium compound (A1) and an organometallic compound (A2) on a carrier (D), and a transition metal compound (B1) having a group having a conjugated π electron as a ligand and an organoaluminum The method of supporting the reactant (B) of the compound (B2) is performed in advance by isobutane, pentane, hexane, heptane,
After suspending the carrier (D) in an inert hydrocarbon solvent such as cyclohexane, decane, benzene, and toluene, the reactant (A) and the inert hydrocarbon solution of the reactant (B) are brought into contact with each other. The contact temperature is 0 to 120 ° C., preferably 10 to 100 ° C., the contact time is 1 minute to 10 hours, preferably 30 minutes to 5 hours.
800 ml. After the contact, the solvent is removed under reduced pressure or separated by filtration to obtain a solid catalyst.

The use ratio of these four components is as follows:
g, the content of chromium atoms in the chromium compound (A1) is 0.01 to 5% by weight, preferably 0.05 to 3% by weight. The metal atoms in A2) are from 1 to 600 mol, preferably from 5 to 400 mol, and the content of aluminum atoms in the organoaluminum compound (B2) is 0.
1 to 25% by weight, preferably 1 to 20% by weight, based on 1 mole of aluminum atom in the organoaluminum compound (B2), 0.1 to 1 mole, preferably 1 mole of metal atom in the transition metal compound (B1) The metal atom in the transition metal compound (B1) is from 1 to 10 mol, preferably from 10 to 1 mol, per 1 mol of the chromium atom in the chromium compound (A1).

In the present invention, the organometallic compound (C)
Can be used together with the above-mentioned catalyst. As the organometallic compound (C), those similar to the above-mentioned organometallic compound (A2) can be used, preferably an organometallic compound of Groups 1 and 2, more preferably an organolithium compound, an organomagnesium compound, especially Preferred are n-butyllithium and n-butylethylmagnesium. The addition of the organometallic compound (C) is effective for improving the polymerization activity and preventing the polymer from adhering to the reactor wall.

The amount of the organometallic compound (C) used is such that the total amount of the metal atoms in the organometallic compound (C) is usually 1 to 2,000 mol per mol of the metal atom in the transition metal compound (B1).
Preferably, the amount is from 1 to 1500 mol.

In the present invention, a transition metal compound (E) having the above-mentioned solid catalyst and a group having a conjugated π electron as a ligand may be used. Here, the transition metal compound (E) having a group having a conjugated π electron as a ligand may be the same as or different from the transition metal compound (B1) used in preparing the solid catalyst, One type or a combination of two or more types can be used.

The polymerization of ethylene using the above catalyst can be carried out by a liquid phase polymerization method such as slurry polymerization or solution polymerization or a gas phase polymerization method. Liquid phase polymerization is usually carried out in a hydrocarbon solvent, and the hydrocarbon solvent may be an inert hydrocarbon solvent such as propane, butane, isobutane, hexane, cyclohexane, heptane, benzene, toluene, xylene, or a mixture thereof. Is used. Further, the polymerization can be carried out in two or more stages by changing the reaction 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 . By controlling the polymerization temperature, controlling the amount of the catalyst component, or allowing hydrogen to coexist in the polymerization reactor, the molecular weight and molecular weight distribution of the obtained polymer can be adjusted. Further, if necessary, propylene, 1-
Butene, 1-hexene, 4-methyl-1-pentene, 1
Α-Olefins such as octene may be copolymerized alone or in a mixture of two or more α-olefins. The content of α-olefin in the obtained ethylene polymer is 20.
Mol% or less is preferable, and particularly preferable is 15 mol% or less.

[0080]

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. The catalyst components used in the examples and comparative examples, the polymer pretreatment for measuring the physical properties, and the methods for measuring the physical properties of the ethylene-based polymer are as follows.

[Catalyst component] (A1) Chromium compound (A1-1) bis (tert-butyl) chromate: Synth.
mun., 10 , 905 (1980). (A1-2) Tris (bistrimethylsilylamide) chromium: synthesized by the method described in J. Chem. Soc., (A), 1433 (1971).

(A2) and (C) Organometallic compounds (1) n-butylethylmagnesium (BEM): manufactured by Tosoh Akzo Co., Ltd., (2) n-butyllithium (BL): Aldrich (Aldri)
ch)

(B1) and (E) a group having a conjugated π electron
The transition metal compound as a ligand (B1-1) bis (n- butylcyclopentadienyl) zirconium dichloride: Kanto Chemical Co. (B1-2) (pentamethylcyclopentadienyl) (N,
N'-bis (phenyl) methylamidinato) zirconium dichloride: synthesized according to the method described in Japanese Patent Application No. 8-220207.

(B2) Organoaluminum compound (1) Triethylaluminum (TEA): manufactured by Tosoh Akzo (2) Triisobutylaluminum (TIBA): manufactured by Tosoh Akzo (3) Methylaluminoxane (MAO): Tosoh Akzo Company

(D) Carrier silica: Grade CARiACT manufactured by Fuji Silysia Chemical Ltd.
P-3

[Polymer Pretreatment for Measurement of Physical Properties] Using a plastograph manufactured by Toyo Seiki Co., Ltd., 0.2% by weight of B225 manufactured by Ciba Geigy was added as an additive.
The mixture was kneaded at 90 ° C. for 7 minutes.

[Method for Measuring Physical Properties] (1) Molecular weight distribution (Mw / Mn): Number average molecular weight (Mw) was determined by gel permeation chromatography (GPC) under the following conditions.
n) and the weight average molecular weight (Mw)
The ratio (Mw / Mn) to n was determined. The larger the value of Mw / Mn, the wider the molecular weight distribution. -Apparatus: WATERS 150C model-Column: Shodex-HT806M-Solvent: 1,2,4-trichlorobenzene-Temperature: 135 ° C-Sample concentration: 2mg / 5ml-Universal rating using monodisperse polystyrene fraction

(2) Melt flow rate: JIS-K-6
According to 760, the measured value at a temperature of 190 ° C. and a load of 21.6 kg was indicated as HLMFR. (3) Density: measured according to JIS-K-6760.

(4) Fish eye; 2 manufactured by Toyo Seiki Co., Ltd.
0.5 m thickness obtained by pressing using an axial stretching device
m, a 90 mm × 90 mm press plate was stretched by heating under the following conditions to form a film:-Preheating time: 3 minutes 30 seconds-Stretching speed: 3 m / min-Stretching magnification: 5 times maximum (length) x ( Horizontal) 5 times. Observation of the presence or absence of fish eyes in the obtained film was evaluated as ○ for those without fish eyes, and as X for those with fish eyes.

Preparation of Solid Catalyst (1) In a flask purged with nitrogen, 0.5 mmol / l of a toluene solution of a transition metal compound (B1) shown in Table 1 was added to 0.5 mol / l of a toluene solution.
/ L of a toluene solution of the organoaluminum compound (B2) shown in Table 1 in a molar ratio (Zr / Al molar ratio) of the metal (Zr) of the transition metal compound (B1) and the aluminum (Al) of the organoaluminum compound (B2). ) Were mixed as shown in Table 1 and reacted at room temperature for 1 hour. The slurry was prepared by adding 3 g of silica (D) calcined in nitrogen at 400 ° C. for 8 hours and 30 ml of toluene to another nitrogen-purged flask so that the supported amount of transition metal atoms was as shown in Table 1. The reaction product (B) was added and stirred at 40 ° C. for 1 hour.
Further, this slurry solution was added to another 0.1 mol / l toluene solution of a chromium compound (A1) shown in Table 1 and 0.5 mol / l toluene solution of an organometallic compound (A2) shown in Table 1 in another nitrogen-purged flask. The reaction product (A) obtained by reacting the solution at room temperature for 1 hour was added so that the amount of supported chromium atoms was as shown in Table 1, and stirred at 40 ° C. for 1 hour. Removal of the solvent under vacuum gave a solid catalyst.

Preparation of solid catalyst (2) In a flask purged with nitrogen, 0.1 mol / l of a toluene solution of chromium compound (A1) shown in Table 1 was added to 0.5 mol / l
The toluene solution of the organometallic compound (A2) shown in Table 1 of
Mixing was performed so that the metal / chromium molar ratio shown in Table 1 was obtained, and the mixture was reacted at room temperature for 1 hour. In another nitrogen-purged flask,
3 g of silica (D) calcined in nitrogen at 400 ° C. for 8 hours
The reaction product (A) was added to a slurry containing 30 ml of toluene and 30 ml of toluene so that the amount of chromium atoms carried was as shown in Table 1, and the mixture was stirred at 40 ° C. for 1 hour. Further, this slurry solution was added to another flask with a nitrogen purge at 0.5 mmol /
1) A toluene solution of the transition metal compound (B1) shown in Table 1
0.5 mol / l of the organoaluminum compound (B
The reaction product (B) obtained by reacting the toluene solution of 2) at room temperature for 1 hour was added so that the amount of the supported transition metal atoms becomes the amount shown in Table 1, and the mixture was stirred at 40 ° C. for 1 hour. Removal of the solvent under vacuum gave a solid catalyst.

Preparation of solid catalyst (3) 0.1 mol / l of a toluene solution of chromium compound (A1) shown in Table 1 in a nitrogen-purged flask, and 0.5 mol / l of an organometallic compound shown in Table 1 ((A2) + (B2)) and 0.5 mmol / l of a toluene solution of the transition metal compound (B1) shown in Table 1 were reacted at room temperature for 1 hour.
The above reaction was carried out such that a slurry obtained by adding 3 g of silica (D) calcined in nitrogen at 400 ° C. for 8 hours and 30 ml of toluene in another nitrogen-purged flask so that the supported amount of chromium atoms was as shown in Table 1. (A) + (B)) and add 4
Stirred at 0 ° C. for 1 hour. Removal of the solvent under vacuum gave a solid catalyst.

Example 1 Polymerization of Ethylene 1.5 liters of isobutane was charged into a 3 liter autoclave in which nitrogen was replaced, and the temperature was raised to the polymerization temperature.
Then, a hydrogen / ethylene mixed gas having a mixing ratio shown in Table 2 was injected until the partial pressure became 10 kg / cm ² , and a solid catalyst shown in Table 1 was further added to initiate polymerization. Polymerization was performed for 60 minutes while maintaining the mixed gas partial pressure at 10 kg / cm ² . Subsequently, the content gas was released out of the system to terminate the polymerization, and polyethylene was obtained. About the obtained polyethylene, the yield, HLMFR, M
Table 2 shows w / Mn, density, melt tension, and the presence or absence of fish eyes.

Examples 2 to 5: Polymerization of ethylene Into a 3 liter autoclave with nitrogen substitution,
3 ml (1.5 mmol) of a 0.5 mol / l organometallic compound (C) hexane solution and 1.5 liters of isobutane shown in (1) were charged and heated to the polymerization temperature. Then, a hydrogen / ethylene mixed gas having a mixing ratio shown in Table 2 was mixed with a partial pressure of 10%.
kg / cm ² , and a solid catalyst shown in Table 1 was further added to initiate polymerization. 10kg /
cm ² and polymerization was carried out for 60 minutes. Subsequently, the content gas was released out of the system to terminate the polymerization, and polyethylene was obtained. Table 2 shows the yield, HLMFR, Mw / Mn, density, melt tension, and presence or absence of fish eyes of the obtained polyethylene.

Example 6: Copolymerization of ethylene and 1-hexene
In a 3-liter autoclave replaced with nitrogen, add Table 1 in advance.
3 ml (1.5 mmol) of a 0.5 mol / l organometallic compound (C) in hexane, 1.5 liters of isobutane, and 1-hexene were charged and the temperature was raised to the polymerization temperature. Then, a hydrogen / ethylene mixed gas having a mixing ratio shown in Table 2 was injected until the partial pressure became 10 kg / cm ² , and the solid catalyst shown in Table 1 was further contacted for 20 seconds with 0.5 mmol.
/ L of a hexane solution of the transition metal compound (E) 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 content gas was released out of the system to terminate the polymerization, and poly (ethylene / 1-hexene) was obtained. Table 2 shows the yield, HLMFR, Mw / Mn, density, melt tension, and presence or absence of fish eyes of the obtained copolymer.

Example 7: Polymerization of ethylene Polyethylene seed polymer (metallocene polymer having an MFR of about 2 g / 10 min and a density of about 0.945 g / cm ³ ) 140
The gas-phase reactor having an internal volume of 3.9 m ³ containing kg was sufficiently purged with nitrogen, and the temperature was raised to 75 ° C. Then, ethylene was added to 28
kg / hr and hydrogen were supplied at 2.8 g / hr, and the total pressure in the reactor was maintained at 20 kg / cm ² . Further, the solid catalyst shown in Table 1 was continuously supplied at a rate of 10 g / hr, and the organometallic compound shown in Table 1 was continuously supplied at a rate of 250 ml / hr, and gas phase polymerization was performed to obtain polyethylene at a production rate of 20 kg / hr. . The residence time of the polymer at this time was 4.5 hours. About the obtained polyethylene, its HLMF
Table 2 shows R, Mw / Mn, density, melt tension, and the presence or absence of fish eyes.

Comparative Example 1 Preparation of Solid Catalyst (4 ) 3 g of silica (D) 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. 0.1 mol / l of Table 1 was added to this slurry.
A hexane solution of the chromium compound (A1) shown in
Stirred at 0 ° C. for 2 hours. The solvent was removed under vacuum. Next, 30 ml of toluene was added to obtain a slurry. 2.8 mol / l of methylaluminoxane ((A2))
+ (B2)) was added in the amount shown in Table 1 and the mixture was stirred at 40 ° C. for 2 hours, and then the solvent was removed under vacuum. Next, 30 ml of hexane was added to obtain a slurry. To this slurry, 0.5 mmol / l of the transition metal compound (B1) shown in Table 1 was added, and the mixture was stirred at room temperature for 5 minutes. Removal of the solvent under vacuum gave a solid catalyst.

In a 3-liter autoclave in which the polymerization of ethylene was replaced with nitrogen, Table 1 was prepared in advance.
3 ml (1.5 mmol) of a 0.5 mol / l organometallic compound (C) hexane solution and 1.5 liters of isobutane shown in (1) were charged and heated to the polymerization temperature. Then, a hydrogen / ethylene mixed gas having a mixing ratio shown in Table 1 was mixed with a partial pressure of 10%.
kg / cm ² , and a solid catalyst shown in Table 1 was further added to initiate polymerization. 10kg /
cm ² and polymerization was carried out for 60 minutes. Subsequently, the content gas was released out of the system to terminate the polymerization, and polyethylene was obtained. Table 2 shows the yield, HLMFR, Mw / Mn, density, melt tension, and presence or absence of fish eyes of the obtained polyethylene.

[0099]

[Table 1]

[0100]

[Table 2]

[0101]

According to the present invention, it is possible to produce an ethylene polymer having a high molecular weight, a high melt tension and a low generation of fish eyes, which is extremely valuable industrially.

[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.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshifumi Morimoto, Oita City, Oita Prefecture, 2nd Nakanosu, Japan Polyolefin Co., Ltd. Oita Research Laboratories (72) Inventor Shintaro Shinozawa 2nd, Oita City, Oita City, 2nd Nakanosu, Japan Polyolefin Co., Ltd. Oita Research Institute

Claims (4)

[Claims] 1. A reaction product (A) of a chromium compound (A1) and an organometallic compound (A2) on a carrier (D), and a transition metal compound (B1) having a group having a conjugated π electron as a ligand An ethylene-based polymerization catalyst comprising a solid catalyst supporting a reaction product (B) of a compound and an organoaluminum compound (B2). 2. An ethylene-based polymerization catalyst obtained by adding the organometallic compound (C) to the ethylene-based polymerization catalyst according to claim 1. 3. An ethylene-based polymerization catalyst obtained by adding a transition metal compound (E) having a group having a conjugated π electron as a ligand to the ethylene-based polymerization catalyst according to claim 1 or 2. 4. A method for producing an ethylene polymer, comprising using the catalyst according to claim 1.