JPH09136912A - Polymerization catalyst for ethylene - Google Patents

Abstract

(57) Abstract: [PROBLEMS] To provide a catalyst for producing an ethylene polymer, which has no induction period and melt fracture, has a wide molecular weight distribution, has good dispersibility, and has a large melt tension. SOLUTION: Chromium carboxylate, chromium-1,3-
An organic chromium compound comprising at least one compound such as a diketo compound, a chromic acid ester and a chromium amide compound, (B) a carrier, (C) an aluminoxane and (D) a transition metal compound having a group having a conjugated π electron as a ligand, Further, if desired, an organometallic compound is added, (A)
An ethylene-based polymerization catalyst that is used without being calcined.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ethylene-based polymerization catalyst. More specifically, it relates to a novel catalyst for producing an ethylene polymer having a wide molecular weight distribution and a large melt tension.

[0002]

2. Description of the Related Art Ethylene polymers are generally and widely used as resin materials for various molded articles, and required characteristics differ depending on the molding method and application. In particular, a polymer having a relatively high molecular weight and a wide molecular weight distribution is suitable for an ethylene polymer used for blown film molding or blow molding. Conventionally, as a method for producing an ethylene-based polymer having the above-mentioned properties, a titanium compound, a magnesium compound, a single-stage or multi-stage polymerization using a so-called Ziegler catalyst composed of a halogen is used to produce an ethylene-based polymer having the above-mentioned properties. Many methods have been proposed. (JP-A-56-90809 and JP-A-6-90809)
0-106806, JP-A-2-123108, JP-A-4
-18407, JP-A-5-230136). A method for producing chromium trioxide on an inorganic oxide using a so-called Phillips catalyst is known, and chromium compounds such as (pentamethylcyclopentadienyl) chromium and (2-methylpentadienyl) chromium are prepared. A method of producing using a non-calcining type catalyst supported on an inorganic oxide has also been proposed (JP-A-3-93804). In order to broaden the molecular weight distribution, a method of producing a Phillips catalyst with an organoaluminum compound such as aluminoxane or a catalyst obtained by treating a non-calcined chromium catalyst with an organoaluminum compound such as aluminoxane has been proposed. (Japanese Patent Laid-Open No. 2-1
05806, Japanese Patent Laid-Open No. 2-185506, and Japanese Patent Laid-Open No. 7-50.
3739, U.S. Pat. No. 4,564,660). Furthermore,
A method of carrying out two-step polymerization using a catalyst obtained by combining a Phillips catalyst with an organoaluminum compound and a Ziegler catalyst has also been proposed. (JP-A-62-20
7307, Japanese Patent Publication No. 7-103177).

In recent years, there has been proposed a method for broadening the molecular weight distribution in a single stage by using a Phillips catalyst or Ziegler catalyst and a so-called metallocene catalyst or a catalyst in which two or more metallocene catalysts are combined (Patent Document 1). -503715, JP-A-1-2922009, JP-A-3-203903, JP-A-4-220405, JP-A-6
-122719, JP-A-7-173209, 8-411
18, JP-A-8-100018, JP-B-8-1385
6). However, it is difficult to say that the molecular weight distribution of the ethylene polymer produced using these catalysts is at a sufficient level. Further, the catalyst system composed of a chromium compound and aluminoxane disclosed in the above-mentioned Japanese Patent Publication No. 7-503739 is not practical because the production process is remarkably complicated when broadening the molecular weight distribution. Further, in the Filps catalyst disclosed in JP-A-1-292009, a catalyst composed of an aluminoxane and a metallocene complex, it takes several tens of minutes to start the polymerization of the Filps catalyst, and sometimes it takes 1 hour or more (so-called induction period exists), In the meantime, the metallocene-catalyzed polymerization proceeds to produce a polymer containing a small amount of the metallocene-catalyzed polymer or the Phillips-catalyzed polymer, and finally a blend of these polymers is formed. The resulting polymer has a wide molecular weight distribution, but has problems such as insufficient dispersibility, melt fracture, and low strength (for example, low breaking strength in a tensile test, that is, low tensile breaking elongation). is there.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a catalyst for improving the above-mentioned problems and for efficiently producing an ethylene polymer having a wide molecular weight distribution and a large melt tension. .

[0005]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have found that (A) a chromium compound, (B) a carrier, (C) an aluminoxane, and (D) a group having a conjugated π electron. An ethylene-based polymerization catalyst comprising a transition metal compound with a ligand of (A) without being calcined, a chromium compound being a chromium carboxylate salt, chromium-1,3
An ethylene-based polymerization catalyst as described above, which is at least one compound selected from a diketo compound, a chromic acid ester and a chromic amide compound; (B) a carrier, wherein the content of chromium atoms in the chromium compound is 0.01 to 5 weight. %, Or the ethylene-based polymerization catalyst described in (A), wherein (A) the aluminum atom of the aluminoxane is 5 to 500 relative to 1 mol of the chromium atom in the chromium compound.
The ethylene-based polymerization catalyst according to any one of 1 to 4, wherein the transition metal compound having a (D) conjugated π-electron group as a ligand is 0.01 mmol to 10 mol. The metal in the organometallic compound is based on 1 mol of the metal atom in the ethylene-based polymerization catalyst prepared by adding the organometallic compound to the polymerization catalyst and (D) the transition metal compound having a group having a conjugated π electron as a ligand. The above object was achieved by developing a catalyst for ethylene-based polymerization described in which the total amount of atoms is 1 to 2000 mol.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The catalyst for ethylene polymerization according to the present invention will be specifically described below. The ethylene-based polymerization catalyst of the present invention is a catalyst for ethylene-based polymerization consisting of a transition metal compound having an organochromium compound and an aluminoxane that are used without firing even after being supported on a carrier, and a group having a conjugated π electron as a ligand, And an ethylene-based polymerization catalyst in which an organometallic compound is further compounded, if desired.

Suitable chromium compounds for use in the present invention are carboxylate salts of chromium, chromium 1,3-diketo compounds, organic chromium compounds such as chromate esters and chromium amide compounds, and the like. Examples of the chromium carboxylate include compounds of chromium (II) or chromium (III) represented by the general formula (1) or the general formula (2).

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Embedded image (R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, and 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 hexanoate (I
I), chromium benzoate (II), chromium naphthenate (I
I), chromium oleate (II), chromium oxalate (I
I), chromium (III) formate, chromium (III) acetate, chromium (III) propionate, chromium (III) butyrate,
Chromium (III) pentanoate, Chromium hexanoate (II
I), chromium (III) 2-ethylhexanoate, chromium (III) benzoate, chromium (III) naphthenate, chromium (III) oleate, chromium (III) oxalate.
And the like, and chromium (II) acetate, chromium (II) 2-ethylhexanoate, chromium (III) acetate, and chromium (III) 2-ethylhexanoate are preferable.

As the chromium-1,3-diketo compound,
A chromium (III) complex having 1 to 3 of the 1,3-diketo compound represented by the general formula (3) can be mentioned. CrY _e · Z _f ¹ Z _g ² (3) (Y is a 1,3-diketo chelate ligand, and Z ¹ and Z ² are halogen, alkoxy, aryloxy, alkyl, aryl, or amide. It may be selected and may be the same or different.e + f + g = 3, e is a numerical value of 1 to 3) As a specific example, chromium-1,3-butanedionate,
Chromium acetylacetonate, chromium-2,4-hexanedionate, chromium-2,4-heptanedionate,
Chromium-2,4-octandionate, 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 mentioned, and chromium acetylacetonate is preferred.

The chromic acid ester has the general formula (4)
It is a compound of chromium (VI) represented by

Embedded image (R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ each have 1 carbon atom.
To 18 hydrocarbon groups, which may be the same or different. M ¹ and M ² each represent a carbon atom or a silicon atom. As specific examples, 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-trimethylpropyl) Chromate and the like are preferable, and bis (tert-butyl) chromate is preferable.

When M ¹ and M ² are silicon, bis (trimethylsilyl) chromate, bis (triethylsilyl) chromate, bis (tributylsilyl) chromate, bis (triisopentylsilyl) chromate, bis (tri-2-ethyl) Xylsilyl) chromate, bis (tridecylsilyl) chromate, bis (tri (tetradecyl) silyl) chromate, bis (tribenzylsilyl) chromate, bis (triphenethylsilyl) chromate, bis (triphenylsilyl) chromate, bis (tritolyl) Silyl) 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 chromium amide compound include compounds of chromium (II) or chromium (III) represented by the general formula (5) or (6).

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Embedded image (R ^{12 to} R ⁴¹ are each hydrogen or a hydrocarbon group having 1 to 18 carbon atoms and may be the same or different.
^{3 to} M ¹² are carbon and / or silicon atoms, L ¹ is a ligand such as ether or nitrile, and h is 0 to 2
Take the number of. )

Specific examples include tris (dimethylamido) chromium (III), tris (diethylamido) chromium (III), tris (diisopropylamido) chromium (III), tris (methylphenylamido) chromium (III), tris ( Diphenylamido) chromium (II
I), bis (bistrimethylsilylamido) chromium (I
I) -THF complex, bis (bistrimethylsilylamido) chromium (II) -diethyl ether complex, bis (methyltrimethylsilylamido) chromium (II) -THF
Complex, bis (methyltrimethylsilylamido) chromium (II) -diethyl ether complex, bis (tert-butyltrimethylsilylamido) chromium (II) -THF
Complex, bis (tert-butyltrimethylsilylamido) chromium (II) -diethyl ether complex, bis (phenyltrimethylsilylamido) chromium (II) -TH
F complex, bis (phenyltrimethylsilylamido) chromium (II) -jetyl ether complex, tris (bistrimethylsilylamido) chromium (III), tris (bistriethylsilylamido) chromium (III), tris (bistriphenylsilylamido) chromium (III) and the like, and tris (bistrimethylsilylamide)
Chromium (III) is preferred.

Other organic chromium compounds include:
Examples thereof include compounds of chromium (II), chromium (III) or chromium (IV) represented by the general formula (7), (8) or (9). _{^{(Cp 1) k (R 42}} ) 2-k Cr ··· (7) (Cp 1) (R 42) m (R 43) 2-m Cr (L 2) n ··· (8) (R 44 _{) p Cr ··· (9) (} Cp 1 is a cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n- butyl cyclopentadienyl group, tert- butyl cyclopentadienyl group A dimethylcyclopentadienyl group,
Alkyl-substituted cyclopentadienyl group such as pentamethylcyclopentadienyl group, Alkylsilyl-substituted cyclopentadienyl group such as trimethylsilylcyclopentadienyl group, Alkylgermyl-substituted cyclopenta group such as trimethylgermylcyclopentadienyl group A ligand having a cyclopentadienyl skeleton such as a dienyl group, an indenyl group with or without a similar substituent, and a fluorenyl group. R ⁴² and R ⁴³ are an aryl group having 1 to 20 carbon atoms, an alkyl group, an alkenyl group, an alkylaryl group, an arylalkyl group, a silylalkyl group, or an alkoxy group, and may be the same or different. R ⁴⁴ is an aryl group having 1 to 20 carbon atoms, an alkyl group, an alkenyl group, an alkylaryl group, an arylalkyl group, or a silylalkyl group. 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
Alternatively, 1 and p represent a numerical value of 2 to 4. )

Specifically, bis (cyclopentadienyl) chromium (II), bis (indenyl) chromium (I
I), bis (fluorenyl) chromium (II), (pentamethylcyclopentadienyl) (cyclopentadienyl) chromium (II), (pentamethylcyclopentadienyl) (pentadienyl) chromium (II), (pentamethyl Cyclopentadienyl) (2-methylcyclopentadienyl) chromium (II), (pentamethylcyclopentadienyl) (2,4-dimethylpentadienyl) chromium (II), (pentamethylcyclopentadienyl)
(Dimethyl) chromium (III), (pentamethylcyclopentadienyl) dimethylchromium (III) -THF complex, (pentamethylcyclopentadienyl) bis (trimethylsilylmethyl) chromium (III), (pentamethylcyclopentadienyl) ) (Dimethyl) chromium (II
I) -pyridine complex, (pentamethylcyclopentadienyl) bis (trimethylsilylmethyl) chromium (II
I) -pyridine complex, (pentamethylcyclopentadienyl) (dibenzyl) chromium (III) -pyridine complex, bis (allyl) chromium (II), tris (allyl)
Chromium (III), bis (benzene) chromium (II),
Bis (2,4-dimethylpentadienyl) chromium (I
I), octakis (trimethylsilylmethyl) tetrachrome (II), tetrakis (trimethylsilylmethyl)
Examples thereof include chromium (IV), and pentamethylcyclopentadienyl (dimethyl) chromium (III) · THF complex is preferable. Among the chromium compounds listed above,
Chromic acid ester compounds and chromium amide compounds are particularly preferable.

The carrier used in the present invention is an oxide of an element of Group 2, 4, 13 or 14 of the Periodic Table (according to the 1990 rules of Inorganic Chemistry) or a phosphate of an element of Group 13 or an inorganic halide. What is often used as a component or carrier of such an ethylene polymerization catalyst is usually used. Examples of oxides of Group 2, 4, 13 or 14 elements of the periodic table and phosphates of Group 13 elements include magnesia, titania, zirconia, alumina, silica, silica-titania, silica-zirconia, silica-alumina and phosphorus. Aluminum oxide, gallium phosphate, or a mixture thereof may be used. The carrier has a specific surface area of 50 to 1000
m ² / g, preferably 200~800m ² / g, a pore volume of 0.5~3.0cm ³ / g, preferably 1.0 to
One having a density of 2.5 cm ³ / g is preferably used. Oxides of Group 2, 4, 13 or 14 elements and phosphates of Group 13 elements in the Periodic Table are in the range of 100 to 900 ° C. under a dry nitrogen gas flow through the molecular sieves layer.
Those dried by heating for from minutes to 24 hours are preferably used.
It is particularly preferable to dry under a solid fluid state with a sufficient amount of nitrogen gas. The inorganic halide is a halide of an element belonging to Group 2 or 13 of the periodic table, and examples thereof include magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, aluminum chloride, gallium chloride, or a mixture thereof.

Examples of the aluminoxane used in the present invention include compounds represented by the general formula (10) or (11).

[0018]

[Chemical 6]

[0019]

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(R ⁴⁵ is methyl, ethyl, propyl, n
A hydrocarbon group such as -butyl and isobutyl, preferably a methyl group and an isobutyl group. r is 1 to 1
00, preferably 4 or more, particularly preferably 8
That is all. ) The production method of this kind of compound is known, for example, salts having water of crystallization (copper sulfate hydrate, aluminum sulfate hydrate, etc.)
Of pentane, hexane, heptane, cyclohexane, decane, benzene, to a suspension of an inert hydrocarbon solvent such as toluene, a method obtained by adding tolualkylaluminum, trialkylaluminum in the hydrocarbon solvent described above, A method of acting solid, liquid or gaseous water can be exemplified. Further, an aluminoxane represented by the general formula (12) or (13) may be used.

[0021]

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[0022]

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(R ⁴⁶ is methyl, ethyl, propyl, n
A hydrocarbon group such as -butyl and isobutyl, preferably a methyl group and an isobutyl group. R ⁴⁷ is selected from hydrocarbon groups such as methyl, ethyl, propyl, n-butyl and isobutyl, halogen such as chlorine and bromine, hydrogen and hydroxyl group, and is different from R ⁴⁶ . R ⁴⁷ may be the same or different. s is usually an integer of 1 to 100, preferably 3 or more, and s + t is 2 to 100, preferably 6 or more. ) In the general formula (12) or (13), [OA
The 1 (R ⁴⁶ )] _s unit and the [O-A1 (R ⁴⁷ )] _t unit may be block-bonded or may be bonded regularly or irregularly at random. The method for producing such an aluminoxane is the same as that for the aluminoxane represented by the general formula described above. Instead of one kind of trialkylaluminum, two or more kinds of trialkylaluminum are used or one or more kinds of trialkylaluminum and one kind are used. The above dialkylaluminum monohalide or dialkylaluminum monohydride may be used.

The ligand of the group having a conjugated π electron used in the present invention is a ligand having a cyclopentadienyl skeleton, an amidinato skeleton or an allyl skeleton. Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n-butylcyclopentadienyl group, and a tert-butylcyclopentadienyl group. Alkyl-substituted cyclopentadienyl groups such as enyl group, dimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, alkylsilyl-substituted cyclopentadienyl groups such as trimethylsilylcyclopentadienyl group,
Examples thereof include an alkylgermyl-substituted cyclopentadienyl group such as a trimethylgermylcyclopentadienyl group, an indenyl group with or without a similar substituent, a fluorenyl group, and the like.

The ligand having an amidinato skeleton includes, for example, an amidinato group, an alkyl-substituted amidinato group such as N, N ^, -bis (n-butyl) amidinato group, N, N ^, -bis (trimethylsilyl) amidinato group, and the like. Alkylsilyl-substituted amidinato group of N, N ^, -
Aryl-substituted amidinato group such as bis (phenyl) amidinato group, N, N ^, -bis (n-butyl) benzamidinato group, N, N ^, -bis (2,6-dimethylphenyl) benzamidinato group, etc. And an amidinato group having a plurality of kinds of substituents. In addition, examples of the ligand having an allyl skeleton include an allyl group 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 (according to the rules of Inorganic Chemistry Nomenclature 1990), preferably Group 4 of the Periodic Table. Transition metal elements, namely titanium, zirconium,
It is preferably selected from hafnium, and particularly preferably zirconium and hafnium. The transition metal compound used in the present invention includes general formulas (14), (15),
(16), (17), (18), (19) or (2
0) Formula (Cp ² ) (Cp ³ ) _u Me (Q ¹ ) _3-u・ ・ ・ (14) R ⁵¹ (Cp ² ) (Cp ³ ) Me (Q ¹ ) (Q ² ) ・ ・ ・ (15) ) R ⁵¹ (Cp ² ) (Y) Me (Q ¹ ) (Q ² ) ... (16)

[0027]

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[0028]

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[In the formula, Cp ² and Cp ³ are ligands having the above-mentioned cyclopentadienyl skeleton, and may be the same or different, and R ⁴⁸ to R ⁵⁰ are hydrogen and 1 to 20 carbon atoms. Is 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. An alkylene group, an alkylgermylene group or an alkylsilylene group, X ¹ and X ² are carbon or nitrogen, and they may be the same or different,
Q ¹ and Q ² are hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an allyloxy group, a siloxy group or halogen, which may be the same or different, and Y is —O.
-, - S -, - NR 52 -, - PR 52 - (. R 52 represents hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated alkyl or halogenated aryl) an electron donor ligand represented by And Me is a transition metal and u is 0 or 1. ] The transition metal compound represented by these is mentioned.

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴⁸ to R ⁵⁰ in the above general formula include methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, hexyl, heptyl, octyl, Examples thereof include alkyl groups such as nonyl, decyl and cetyl, examples of aryl groups include phenyl, examples of alkylsilyl groups include trimethylsilyl, and examples of alkylgermyl groups include trimethylgermyl. In the above general formula, R ⁵¹ is an alkylene group having 1 to 20 carbon atoms, an alkylgermylene group or an alkylsilylene group. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylidene group, a cyclopentylidene group, a cyclohexylidene group, a tetrahydropyran-4-ylidene group, a diphenylmethylene group, and the like. , A dimethylsilylene group, a diphenylsilylene group, and the like, and an alkylgermylene group includes a dimethylgermylene group, a diphenylgermylene group, and the like. X ¹ and X ² are carbon or nitrogen, which may be the same or different, and
^1, Q ^{2 is} a hydrocarbon group having 1 to 20 carbon atoms such as alkyl, alkenyl, aryl, araryl and aralkyl, an alkoxy group, an allyloxy group, a siloxy group or a halogen, which may be the same or different. Furthermore, Y is -O
-, - S -, - NR 52 -, - PR 52 - is an electron donor ligand represented by. Where R ⁵² is hydrogen or 1 carbon atom
To 20 hydrocarbon groups such as alkyl, alkenyl, aryl, araryl and aralkyl, or alkyl halides or aryl halides. In particular,
Methyl, ethyl, propyl, butyl, isobutyl, te
Examples thereof include alkyl groups such as rt-butyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl and cetyl, as well as phenyl group and benzyl group. In ^{this, -NR 52 -, - PR 52} - type ligand is preferred.

General formulas (14), (15), (16),
As the transition metal compound represented by the formula (17), (18), (19) or (20), specific compounds in which Me is zirconium are exemplified. Examples of the transition metal compound represented by the general formula (14) include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, and bis (n
-Propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride , Bis (pentamethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (n-butylcyclopentadienyl) zirconium dichloride, (cyclopenta Dienyl) (indenyl) zirconium dichloride, (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclopentadienyl zirconium trichloride, cyclopentadienyl dil Bromide trimethyl, pentamethylcyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trimethyl like.

Examples of the transition metal compound represented by the general formula (15) include dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, isopropylidenebis (methylcyclopentadienyl) zirconium dichloride, 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-butylcyclopentadiene) Le) (tert-butyl) zirconium dimethyl and the like. The general formula (1
Examples of the transition metal compound represented by the formula 6) include ethylene (tert-butylamide) (tetramethylcyclopentadienyl) zirconium dichloride, ethylene (methylamide) (tetramethylcyclopentadienyl) zirconium dichloride, and dimethylsilylene (tert-). Butyramide) (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (tert-
Butyramide) (tetramethylcyclopentadienyl)
Examples thereof include zirconium dibenzyl, dimethylsilylene (benzylamide) (tetramethylcyclopentadienyl) zirconium dibenzyl, dimethylsilylene (phenylamide) (tetramethylcyclopentadienyl) zirconium dichloride and the like.

The transition metal compound represented by the general formula (17) includes (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, (penta Methylcyclopentadienyl (N, N ^, -bis (trimethylsilyl) benzamidinato) 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 −
Examples thereof include 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) diclonium 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) amidinato)
Zirconium dichloride, dimethyl silylene (indenyl) (N, N ^, -bis (phenyl) amidinato) zirconium chloride, dimethyl silylene (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) benzamidinato) zirconium dichloride,
Examples include bis (N, N ^, -bis (phenyl) benzamidinato) zirconium dichloride and bis (N, N ^, -bis (n-butyl) benzamidinato) zirconium dichloride. Examples of the transition metal compound represented by the general formula (20) include dimethylsilylenebis (N, N
^, -Bis (trimethylsilyl) amidinato) zirconium dichloride, dimethylsilylenebis (N, N ^, -bis (phenyl) amidinato) zirconium dichloride, dimethylsilylenebis (N, N ^, -bis (n-butyl) amidinato) zirconium dichloride, isopropyi Redene bis (N, N ^, -bis- (trimethylsilyl)
Amidinato) zirconium dichloride, isopropylidene bis (N, N ^, -bis (phenyl) amidinato)
Zirconium dichloride, isopropylidene bis (N,
Examples include N ^, -bis (n-butyl) amidinato) zirconium dichloride and the like.

In the zirconium compound as described above,
It is also possible to exemplify a transition metal compound in which zirconium is changed to hafnium or titanium. As the transition metal compound according to the present invention, the above-mentioned transition metal compounds may be used alone or in combination of two or more.

The catalyst of the present invention is formed by contacting the catalyst component (A) chromium compound, the catalyst component (B) carrier, the catalyst component (C) aluminoxane, and the catalyst component (D) transition metal compound. The order of contacting each of these components is not particularly limited. For example, 1. 1. A method for forming a catalyst by simultaneously contacting these four components in advance in a reactor for catalyst preparation or in an ethylene polymerization reactor in the presence or absence of ethylene. The catalyst component (A), the catalyst component (B) and the catalyst component (C) are brought into contact with each other in a catalyst preparation reactor in advance, and the catalyst component (D) is further added to the reactor for catalyst preparation or in the presence or absence of ethylene. 2. a method of contacting in the lower ethylene polymerization reactor to form a catalyst; The catalyst component (A), the catalyst component (B) and the catalyst component (D) are brought into contact with each other in a catalyst preparation reactor in advance, and the catalyst component (C) is further added to the reactor for catalyst preparation or in the presence or absence of ethylene. 3. a method of contacting in the lower ethylene polymerization reactor to form a catalyst; The catalyst component (B), the catalyst component (C) and the catalyst component (D) are brought into contact with each other in a catalyst preparation reactor in advance, and the catalyst component (A) is further added to the catalyst preparation reactor or in the presence or absence of ethylene. 4. Method of contacting in lower ethylene polymerization reactor to form catalyst; The catalyst component (A) and the catalyst component (B) are contacted in advance in a catalyst preparation reactor, and the catalyst component (C) and the catalyst component (D) are further added in the catalyst preparation reactor or in the presence or absence of ethylene. 5. a method of contacting in the lower ethylene polymerization reactor to form a catalyst; The catalyst component (A) and the catalyst component (C) are contacted with each other in a catalyst preparation reactor in advance, and the catalyst component (B) and the catalyst component (D) are further added in the reactor for catalyst preparation or in the presence or absence of ethylene. 6. a method of contacting in the lower ethylene polymerization reactor to form a catalyst; The catalyst component (A) and the catalyst component (D) are contacted with each other in a catalyst preparation reactor in advance, and the catalyst component (B) and the catalyst component (C) are further added in the catalyst preparation reactor or in the presence or absence of ethylene. 7. Method of contacting in lower ethylene polymerization reactor to form catalyst; The catalyst component (B) and the catalyst component (C) are contacted in advance in a catalyst preparation reactor, and the catalyst component (A) and the catalyst component (D) are further added in the catalyst preparation reactor or in the presence or absence of ethylene. 8. a method of contacting in the lower ethylene polymerization reactor to form a catalyst; The catalyst component (B) and the catalyst component (D) are contacted in advance in a catalyst preparation reactor, and the catalyst component (A) and the catalyst component (C) are further added in the reactor for catalyst preparation or in the presence or absence of ethylene. 10. a method of contacting in the lower ethylene polymerization reactor to form a catalyst; The catalyst component (C) and the catalyst component (D) are contacted with each other in a catalyst preparation reactor in advance, and the catalyst component (A) and the catalyst component (B) are further contacted with the catalyst preparation reactor or in the presence or absence of ethylene. Examples include a method of contacting in the lower ethylene polymerization reactor to form a catalyst. In particular, the catalyst component (A), the catalyst component (B) and the catalyst component (C) are brought into contact with each other in advance in a catalyst preparation reactor, and the catalyst component (D) is further added in the catalyst preparation reactor or in the presence of ethylene. Alternatively, a method of contacting in an ethylene polymerization reactor in the absence of the catalyst to form a catalyst is more preferable, and the catalyst component (A), the catalyst component (B) and the catalyst component (C) are contacted in advance in a reactor for catalyst preparation. After obtaining the solid catalyst component, the catalyst component (D) is further contacted in an ethylene polymerization reactor in the presence or absence of ethylene to form a catalyst.

An example of the method of contacting the catalyst components (A) to (D) will be given below. The catalyst component (B) was previously mixed with isobutane, pentane, hexane, heptane, cyclohexane,
After suspending in an inert hydrocarbon solvent such as decane, benzene or toluene, the above-mentioned inert hydrocarbon solution of the catalyst components (A), (C) and (D) is contacted. Preferably, the catalyst components (A) to (C) are contacted to obtain a solid catalyst component, the solid catalyst component is suspended in the above-mentioned inert hydrocarbon solvent, and then contacted with the catalyst component (D). Let 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 solvent amount is 5 to 800 ml per 1 g of the catalyst component (B).
The content ratio of these four catalyst components is usually 0.01 to 5% by weight, preferably 0.05 to 3% by weight of chromium atom in the catalyst component (A) per 1 g of the catalyst component (B).
% By weight, 1 to 600 mol, preferably 5 to 400 mol, of aluminum atom of the catalyst component (C), and 1 mol of chromium atom in the catalyst component (A), relative to 1 mol of chromium atom in the catalyst component (A). In contrast, the amount of the catalyst component (D) is 0.01 mmol to 10 mol, preferably 0.1 mmol to 5 mol. In these contacting processes, it may be dried under reduced pressure at 100 ° C. or lower and used as a solid catalyst component, but it is important that the organic chromium compound after being loaded on the carrier is not calcined. The calcination means treatment in a gas containing oxygen in a temperature range of 300 to 1000 ° C. Since the organic chromium compound is changed to hexavalent chromium oxide by firing, the effect of the present invention cannot be obtained even if the components (C) and (D) are brought into contact with each other.

Further, an organometallic compound can be used together with the above-mentioned catalyst. In this case, it is effective in improving the polymerization activity and preventing the polymer from adhering to the reactor wall. The organometallic compound used in the present invention is an organometallic compound of an element of Group 1, 2 or 3 of the Periodic Table (according to the rules of Inorganic Chemistry Nomenclature 1990), and the metal is lithium, magnesium or aluminum. Specific compounds are exemplified.
Examples of organometallic compounds of lithium include methyllithium,
Examples thereof include alkyl lithium such as ethyl lithium, 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,
Examples thereof include dialkyl magnesium such as n-butylethyl magnesium, di-sec-butyl magnesium, n-butyl-sec-butyl magnesium, di-tert-butyl magnesium, dineopentyl magnesium and di-n-hexyl magnesium. As an organometallic compound of aluminum, trimethylaluminum,
Triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-
sec-Butylaluminium, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, trialkylaluminum such as tricyclohexylaluminum, dimethylaluminum chloride, diethylaluminium chloride, dialkylalkylaluminum halide such as diisobutylaluminum chloride. Examples thereof include dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide, and dialkyl aluminum ary-loxides such as diethyl aluminum phenoxide.

As the organometallic compound composed of lithium and aluminum, lithium tetramethylaluminate,
Lithium trimethylethylaluminate, lithium trimethylpropylaluminate, lithium trimethylbutylaluminate, lithium trimethylhexylaluminate, lithium trimethyloctylaluminate, lithium triethylmethylaluminate, lithium tetraethylaluminate, lithium triethylpropylaluminate, lithium triethylbutyl Aluminate, lithium triethylhexylaluminate, lithium triethyloctylaluminate, lithium tributylmethylaluminate, lithium tributylethylaluminate, lithium tributylpropylaluminate, lithium tetrabutylaluminate, lithium tributylhexylaluminate, lithium tributyloctylaluminate , Lithium Isobutyl methyl aluminate,
Lithium triisobutylethylaluminate, lithium triisobutylpropyloaluminate, lithium triisobutylbutylaluminate, lithium triisobutylhexylaluminate, lithium triisobutyloctylaluminate, lithium trihexylmethylaluminate, lithium trihexylethylaluminate, 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 trio Examples include octylhexyl 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 trimethylhexyl aluminate, ethyl. Magnesium trimethyloctylaluminate, ethylmagnesium triethylmethylaluminate, ethylmagnesium tetraethylaluminate, ethylmagnesium triethylpropylaluminate, ethylmagnesium triethylbutylaluminate, ethylmagnesium triethylhexylaluminate
, Ethylmagnesium triethyloctylaluminate, ethylmagnesium tributylmethylaluminate, ethylmagnesium tributylethylaluminate, ethylmagnesium tetrabutylaluminate, ethylmagnesium tributylhexylaluminate, ethylmagnesium tributyloctylaluminate, 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 aluminate, butyl magnesium tetraethyl aluminate, butyl magnesium triethyl propyl aluminate, butyl magnesium tri Chill butyl aluminate, butyl magnesium tri-ethylhexyl aluminate, butyl magnesium triethylaluminum octyl aluminate, butylmagnesium triisobutyl methyl aluminate, butylmagnesium triisobutyl ethyl aluminate,
Butyl magnesium tetraisobutyl aluminate, butyl magnesium triisobutyl hexyl aluminate, butyl magnesium triisobutyl octyl aluminate, hexyl magnesium tetramethyl aluminate, hexyl magnesium trimethylethyl aluminate, hexyl magnesium trimethylpropyl aluminate, hexyl magnesium trimethylbutyl aluminate Hexylmagnesium trimethylhexylaluminate, hexylmagnesium trimethyloctylaluminate, hexylmagnesium triethylmethylaluminate, hexylmagnesium tetraethylaluminate, hexylmagnesium triethylpropylaluminate, hexylmagnesium triethylbutylaluminate, hexylma Nesium triethylhexylaluminate, hexylmagnesium triethyloctylaluminate, hexylmagnesium tributylmethylaluminate, hexylmagnesium tributylethylaluminate, hexylmagnesium tetrabutylaluminate, hexylmagnesium tributylhexylaluminate, hexylmagnesium tributyloctylaluminate, and the like, and Magnesium bis (tetramethylaluminate,) magnesium bis (tetraethylaluminate), magnesium bis (tetrapropylaluminate), magnesium bis (tetrabutylaluminate), magnesium bis (tetraisobutylaluminate), magnesium bis (tetrahexylaluminum) 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, and this contact is achieved by pentane, hexane, heptane, octane, decane, cyclopentane, cyclohexane. It can be carried out in an inert hydrocarbon solvent such as benzene, toluene or xylene. The contact temperature is -50 to 2
00 ° C., preferably −20 to 100 ° C., more preferably 0 to 50 ° C., contact time is 0.05 to 200 hours,
It is preferably about 0.2 to 20 hours. Regarding the use of the organometallic compound according to the present invention, the above-mentioned organometallic compounds can be used alone or in combination of two or more kinds. The amount of the organic metal compound used is 1 mol of the metal atom in the transition metal compound,
The total amount of metal atoms in the organometallic compound is usually 1 to 200.
It is used in an amount of 0 mol, preferably 1 to 1500 mol.

In carrying out the present invention, the polymerization method of ethylene may be 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 carried out in a hydrocarbon solvent, and as the hydrocarbon solvent, propane, butane, isobutane, hexane, cyclohexane, heptane, benzene, toluene,
A single or a mixture of inert hydrocarbon solvents such as xylene 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 3
The temperature is 00 ° C, and practically 20 to 200 ° C. The molecular weight of the obtained polymer can be adjusted by controlling the polymerization temperature or by allowing hydrogen and the like to coexist in the polymerization reactor.
Moreover, the molecular weight distribution of the polymer obtained by controlling the amount of the catalyst component can be controlled. Further, if necessary, propylene, 1-butene, 1-hexene, 4-methyl-1-
It is also possible to introduce α-olefins such as pentene and 1-octene alone or in combination into two or more kinds for copolymerization. The α-olefin content in the obtained ethylene-based polymer is preferably 20 mol% or less, and particularly preferably 15 mol% or less.

[0045]

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 ethylene (co) polymerization conditions (catalyst species, catalyst amount, polymerization temperature, hydrogen / ethylene weight ratio) used in the examples are shown in Table 1. The measurement methods used in Examples and Comparative Examples are shown below. 1 Polymer pretreatment for measuring physical properties; using Plastograph manufactured by Toyo Seiki Co., Ltd., with 0.3 wt% of B225 manufactured by Ciba-Geigy Co., Ltd. added, under nitrogen, at 190 ° C., 7
Kneaded for minutes. 2 molecular weight, molecular weight distribution; gel permeation chromatograph (GP
It measured by C) and the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated | required. The molecular weight distribution is represented by the ratio of Mw to Mn (Mw / Mn), and the larger Mw / Mn, the wider the molecular weight distribution. The measurement conditions are as follows. -Device: WATERS 150C model-Column: Shodex-HT806M-Solvent: 1,2,4-trichlorobenzene-Temperature: 135 ° C-Sample concentration: 2 mg / 5 ml-Universal rating using monodisperse polystyrene fraction 3 Melt flow rate; JIS K-7210, Table 1,
According to the condition 14, the measured value at a temperature of 190 ° C. and a load of 21.6 Kg is shown as HLMFR. 4 density; measured according to JIS K-6760. 5 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 / mi
n. , Winding speed 6.5 m / min. It measured on condition of. 6 Presence or absence of melt fracture; confirmed from the strand at the time of measuring melt flow rate. 7 Tensile elongation at break; Tensilon manufactured by Toyo Sokki Co., Ltd. was used and measured according to JIS K-6760.

The compounds used in the examples were obtained as follows. 8 Chromium Compound Bis (tert-butyl) chromate is commercially available from Synth.
Commun. , 10 , 905 (1980) by the method described in J. Chem. soc. (A), 1433
(Pentamethylcyclopentadienyl) (dimethyl) chromium-THF by the method described in (1971).
The complex is described by J. Am. Chem. Soc. , 111 , 91
27 (1989).
Chromium acetate and chromium acetylacetonate are manufactured by Wako Pure Chemical Industries, and bis (cyclopentadienyl) chromium is STREM.
The one manufactured by the company was used.

A transition metal compound dimethylsilylene (tert-butylamido) (tetramethylcyclopentadienyl) titanium dichloride used as a ligand having 9 conjugated π-electrons is prepared by the method described in JP-A-3-163088. Dienyl) (N, N ^, -bis (trimethylsilyl) benzamidinato) zirconium dichloride is
J. Org Chem. , 491 , 153 (1995)
Was synthesized by the method described in 1. Bis (methylcyclopentadienyl) zirconium dichloride, bis (n
As for -propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, and ethylenebis (indenyl) zirconium zirrolide, those manufactured by Witco were used. 10 Organometallic compound n-Butyllithium is manufactured by Aldrich, and other n-
Butylethyl magnesium, triisobutylaluminum, etc. used were those manufactured by Tosoh Akzo. The ethylene (co) polymerization conditions (catalyst species, catalyst amount, polymerization temperature, hydrogen / ethylene weight ratio) in the examples are shown in Table 1.

Preparation of the solid catalyst component (1) Silica manufactured by Fuji Silysia Co., Ltd. (grade CARiA manufactured by Fuji Silysia Co., Ltd.) was fired in a nitrogen-substituted flask at 400 ° C. for 8 hours in nitrogen.
3 g of CTP-3) and 30 ml of hexane were added to form a slurry. To this slurry, 0.1 mol / liter of a hexane solution of the chromium compound shown in Table 1 was added so that the amount of chromium atoms supported would be the amount shown in Table 1, and the mixture was added at 40 ° C. for 2 hours.
Stirred for hours. The solvent was removed under vacuum. Then, 30 ml of toluene was added to form a slurry. Toluene slurry of 1.1 mol / liter methylaluminoxane manufactured by Tosoh Akzo Co. was added to this slurry so that the molar ratio of aluminum atom to chromium atom in methylaluminoxane would be the value shown in Table 1, and 2 at 40 ° C. Stir for hours and then remove the solvent under vacuum. Next, 30 ml of hexane was added to form a slurry. 0.05 mmol / in this slurry
1 liter of a hexane solution of the transition metal compound shown in Table 1 was added, and the mixture was stirred at room temperature for 5 minutes. The solvent was removed under vacuum to obtain a solid catalyst component (1).

Preparation of solid catalyst component (2) Silica manufactured by Fuji Silysia Co., Ltd. (grade CARiA manufactured by firing in a nitrogen-substituted flask at 400 ° C. for 8 hours in nitrogen)
3 g of CTP-3) and 30 ml of hexane were added to form a slurry. To this slurry, 1.1 m manufactured by Tosoh Akzo
ol / liter of a toluene slurry of methylaluminoxane was added so that the molar ratio of aluminum atoms to chromium atoms in methylaluminoxane was the value shown in Table 1 when the loading amount of chromium atoms was set to the amount shown in Table 1. , 40 ° C
The mixture was stirred at rt for 2 h then the solvent was removed under vacuum. Next, 30 ml of hexane was added to form a slurry. To this slurry, 0.1 mol / liter of a hexane solution of the chromium compound shown in Table 1 was added so that the amount of chromium atoms supported became the amount shown in Table 1, and the mixture was stirred at 40 ° C. for 2 hours. The solvent was removed under vacuum. Then, 30 ml of toluene was added to form a slurry. 0.05 mmol / liter of a hexane solution of the transition metal compound shown in Table 1 was added to this slurry, and the mixture was stirred at room temperature for 5 minutes. The solvent was removed under vacuum to obtain a solid catalyst component (2).

Preparation of solid catalyst component (3) Silica manufactured by Fuji Silysia Co., Ltd. (grade CARiA manufactured by Fuji Silica Co., Ltd.), which was calcined in a nitrogen-substituted flask at 400 ° C. for 8 hours in nitrogen.
3 g of CTP-3) and 30 ml of hexane were added to form a slurry. To this slurry, 0.1 mol / liter of a hexane solution of the chromium compound shown in Table 1 was added so that the amount of chromium atoms supported would be the amount shown in Table 1, and the mixture was added at 40 ° C. for 2 hours.
Stirred for hours. The solvent was removed under vacuum. Then, 30 ml of toluene was added to form a slurry. Toluene slurry of 1.1 mol / liter methylaluminoxane manufactured by Tosoh Akzo Co. was added to this slurry so that the amount of chromium atoms supported was such that the molar ratio of aluminum atoms to chromium atoms in methylaluminoxane was the value shown in Table 1. Add 4
The mixture was stirred at 0 ° C for 2 hours, and then the solvent was removed under vacuum to obtain a solid catalyst component (3).

Preparation of solid catalyst component (4) Silica manufactured by Fuji Silysia Co., Ltd. (grade CARiA manufactured by Fuji Silica Co., Ltd.), which was calcined in a nitrogen-purged flask at 400 ° C. for 8 hours in nitrogen.
3 g of CTP-3) and 30 ml of toluene were added to form a slurry. To this slurry, 1.1 m manufactured by Tosoh Akzo
ol / liter of a toluene slurry of methylaluminoxane was added so that the molar ratio of aluminum atoms to chromium atoms in methylaluminoxane was the value shown in Table 1 when the loading amount of chromium atoms was set to the amount shown in Table 1. , 40 ° C
The mixture was stirred at rt for 2 h then the solvent was removed under vacuum. Next, 30 ml of hexane was added to form a slurry. To this slurry, 0.1 mol / liter of a hexane solution of the chromium compound shown in Table 1 was added so that the amount of chromium atoms supported became the amount shown in Table 1, and the mixture was stirred at 40 ° C. for 2 hours. The solvent was removed under vacuum to obtain a solid catalyst component (4).

(Examples 1 to 6) Polymerization of ethylene A solid catalyst component (1) shown in Table 1 and 600 ml of isobutane were placed in a 1.5-liter autoclave in which nitrogen was substituted.
Was 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 added at a partial pressure of 1
Polymerization was initiated by press-fitting until the pressure reached 4.0 kg / cm ² .
After that, the mixed gas partial pressure was maintained at 14.0 kg / cm ² and polymerization was carried out for 30 minutes. Then, the content gas was discharged to the outside of the system to terminate the polymerization. Table 2 shows the results.
Shown in

(Examples 7 to 12) Polymerization of ethylene A solid catalyst component (1) shown in Table 1 and 0.5 mol / l of the organometallic compound shown in Table 1 were placed in a nitrogen-substituted 1.5 liter autoclave. Hexane solution 1.2m
1 (0.6 mmol) and 600 ml of isobutane 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 added at a partial pressure of 14.0 kg.
Polymerization was initiated by press-fitting until the pressure reached / cm ² . Polymerization was carried out for 30 minutes while maintaining the mixed gas partial pressure at 14.0 kg / cm ² . Then, the polymerization was terminated by discharging the content gas out of the system. Table 2 shows the results.

(Examples 13 to 18) Copolymerization of ethylene A solid catalyst component (3) shown in Table 1 and 600 ml of isobutane were placed in a 1.5-liter autoclave substituted with nitrogen.
Was 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 of the mixed gas reached 14.0 kg / cm ² ,
Polymerization was initiated by adding 0.5 mmol / liter of a hexane solution of the transition metal compound shown in Table 1. Polymerization was carried out for 30 minutes while maintaining the mixed gas partial pressure at 14.0 kg / cm ² . Then, the content gas was discharged to the outside of the system to terminate the polymerization. Table 2 shows the results.

(Examples 19 to 24) Polymerization of ethylene In a 1.5-liter autoclave whose atmosphere was replaced by nitrogen, 600 ml of isobutane and solid catalyst component (3) shown in Table 1 in advance.
Was 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 added at a partial pressure of 1
After press-fitting to 4.0 kg / cm ² , 0.5 mm
Polymerization was initiated by adding 1.2 ml (0.6 mmol) of a hexane solution of the transition metal compound shown in Table 1 at 0.5 mol / liter and a hexane solution of the organic metal compound shown in Table 1 at 0.5 mol / liter. The mixed gas partial pressure was 14.0 and polymerization was started. Polymerization was carried out for 30 minutes while maintaining the mixed gas partial pressure at 14.0 kg / cm ² . Then, the polymerization was terminated by discharging the content gas out of the system. Table 2 shows the results.

(Examples 25 to 30) Polymerization of ethylene A solid catalyst component (2) shown in Table 1 and 0.5 mol / liter of the organometallic compound shown in Table 1 were charged in a nitrogen-substituted 1.5 liter autoclave. Hexane solution 1.2m
1 (0.6 mmol) and 600 ml of isobutane 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 added at a partial pressure of 14.0.
Polymerization was initiated by press-fitting until the pressure reached kg / cm ² . The mixed gas partial pressure was 14.0 and polymerization was started. Set the mixed gas partial pressure to 1
Polymerization was carried out for 30 minutes while maintaining the pressure at 4.0 kg / cm ² . Then, by releasing the content gas out of the system,
The polymerization was terminated. Table 2 shows the results.

(Examples 31 to 36) Polymerization of ethylene A 600 liter solid catalyst composition (4) shown in Table 1 and 600 ml of isobutane were charged in advance in a nitrogen-substituted 1.5 liter autoclave, and the temperature was raised to the polymerization temperature. Then, a hydrogen / ethylene mixed gas having a mixing ratio shown in Table 2 was added at a partial pressure of 1
After press-fitting to 4.0 kg / cm ² , 0.5 mm
Polymerization was initiated by adding 1.2 ml (0.6 mmol) of a hexane solution of the transition metal compound shown in Table 1 at 0.5 mol / liter and a hexane solution of the organic metal compound shown in Table 1 at 0.5 mol / liter. Mixed gas partial pressure 14.0 kg / cm
Polymerization was carried out for 30 minutes while maintaining the value at ² . Then, the polymerization was terminated by discharging the content gas out of the system.
Table 2 shows the results.

(Examples 37 to 42) Copolymerization of ethylene and 1-hexene 600 ml of isobutane, a solid catalyst composition (3) shown in Table 1, was charged into a 1.5-liter autoclave purged with nitrogen and heated to the polymerization temperature. Warmed. Then, 1 / hexene and a hydrogen / ethylene mixed gas having a mixing ratio shown in Table 2 were injected until the mixed gas partial pressure reached 14.0 kg / cm ² , and then 0.5 mmol / liter shown in Table 1. Hexane solution of transition metal compound and 0.5 ml / liter of hexane solution of organometallic compound shown in Table 1 (1.2 ml)
(0.6 mmol) was added to initiate polymerization. Polymerization was carried out for 30 minutes while maintaining the mixed gas partial pressure at 14.0 kg / cm ² . Then, the polymerization was terminated by discharging the content gas out of the system. Table 2 shows the results.

Comparative Example 1 Ethylene was polymerized in the same manner as in Example 1 except that the solid catalyst component (1) containing no chromium compound was used. The results are shown in Tables 1 and 2. (Comparative Examples 2 to 4) Polymerization of ethylene was carried out in the same manner as in Example 1 except that the transition metal compound was not used. The results are shown in Tables 1 and 2.

Comparative Example 5 Preparation of Solid Catalyst Component (5 ) 30 g of DAVISON silica (grade 952) dried at 150 ° C. was placed in a flask, and Wako Pure Chemical Industries, Ltd. chromium acetate dissolved in 100 ml of distilled water was added. The amount of chromium atoms supported was added 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 40 ° C. under reduced pressure. The obtained powder is put in a cylindrical firing electric furnace (diameter 38 mm, with perforated plate), and first heated with nitrogen gas at a temperature rising rate of 90 ° C./hr while flowing at a linear velocity of 4 cm / sec. did. When the temperature reached 600 ° C., nitrogen was changed to air and the mixture was baked at this temperature for 8 hours while flowing at the same linear velocity, then the atmosphere was changed to nitrogen and the temperature was lowered to room temperature to obtain solid catalyst component (5).

Polymerization of ethylene In a 1.5 liter autoclave purged with nitrogen, the solid catalyst component (5) shown in Table 1 and the molar ratio of aluminum atoms in methylalumoxane to chromium atoms in the solid catalyst component are shown in Table 1. 1. Toluene slurry having a concentration of 1.1 mol / liter of methylaluminoxane manufactured by Tosoh Akzo Co., Ltd. having a value shown in 1 and 0.2 g / liter of a hexane solution of the transition metal compound shown in Table 1 and 600 ml of isobutane were charged, and the polymerization temperature was changed. The temperature was raised to. Then, a mixed gas of hydrogen / ethylene was injected until the partial pressure became 14.0 kg / cm ² , and the polymerization was started. Mixed gas partial pressure 14.0 kg / c
Polymerization was carried out for 30 minutes while maintaining the pressure at m ² . Polymerization was then terminated by releasing the content gas. Table 2 shows the results.

[0062]

EFFECTS OF THE INVENTION Ethylene polymers as raw materials for blown films or blow moldings are required to have a relatively high molecular weight and a wide molecular weight distribution. Many such ethylene polymers have been proposed in the past. With the ethylene-based polymerization catalysts that have been used, the molecular weight distribution is insufficient, the manufacturing process is complicated and unsuitable for industrial production, or the ethylene-based polymerization in which a Phillips catalyst, an aluminoxane and a metallocene complex are combined. Even when an ethylene-based polymer having a wide molecular weight distribution is obtained, such as a catalyst for use, the obtained polymer has poor dispersibility and low melt tension,
There were many things that needed improvement, such as melt fracture and low tensile rupture strength. The ethylene-based polymerization catalyst proposed by the present invention solves all of these problems, and the obtained ethylene-based polymer has a relatively high molecular weight, a wide molecular weight distribution, a high melt tension, and a melt fracture. It is an ethylene-based polymerization catalyst having sufficient tensile rupture strength and capable of efficiently and easily producing an inflation-film or an ethylene-based polymer for blow molding.

[Brief description of the drawings]

FIG. 1 is a flow chart for preparing an ethylene-based polymerization catalyst according to the present invention.

[Table 1]

[Table 1]

[Table 1]

[Table 2]

[Table 2]

[Table 2]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shintaro Inazawa Oita City, Oita Prefecture Nakanosu 2, Nihon Polyolefin Co., Ltd. Oita Research Center

Claims (6)

[Claims] 1. (A) a chromium compound, (B) a carrier,
An ethylene-based polymerization catalyst comprising (C) an aluminoxane and (D) a transition metal compound having a group having a conjugated π electron as a ligand, which is used without firing (A). 2. The catalyst for ethylene polymerization according to claim 1, wherein the chromium compound is at least one compound of a chromium carboxylate, a chromium-1,3-diketo compound, a chromate ester and a chromium amide compound. 3. The ethylene-based polymerization catalyst according to claim 1, wherein the content of chromium atoms in the chromium compound (A) is 0.01 to 5% by weight based on the carrier (B). 4. A transition in which the aluminum atom of the aluminoxane (C) is 5 to 500 moles per 1 mole of the chromium atom in the chromium compound (A), and the group having a conjugated π electron (D) is a ligand. 0.01 mmol to 10 of metal compound
The ethylene-based polymerization catalyst according to claim 1, which is in a molar amount. 5. An ethylene-based polymerization catalyst obtained by adding an organometallic compound to the ethylene-based polymerization catalyst according to claim 1. 6. The total amount of metal atoms in the organometallic compound is 1 to 2000 mol per 1 mol of the metal atom in the transition metal compound having (D) a group having a conjugated π electron as a ligand. 5. The ethylene-based polymerization catalyst according to item 5.