JPH07216014A - Catalyst for polymerizing olefin and production of olefinic polymer - Google Patents

Abstract

PURPOSE:To obtain the subject catalyst, containing a component prepared by reacting an inorganic oxide with an alkylmagnesium compound, an organoaluminum halide compound, a transition metallic compound, etc., containing cyclopentadienyl group and capable of efficiently providing a polymer good in particle properties. CONSTITUTION:This polymerization catalyst is obtained by combining (A) a solid catalyst component prepared by bringing (i) an inorganic oxide (e.g. silica) into contact with (ii) an alkylmagnesium compound (e.g. dibutylmagnesium), (iii) an organoaluminum halide (e.g. dimethylaluminum monochloride) and (iv) a transition metallic compound containing at least one of a (substituted) cyclopentadienyl group [e.g. bis(cyclopentadienyl)dichlorotitanium], a (substituted) indenyl group, a 7-24C aralkyl group, etc., and reacting the components with (B) an organoaluminum compound (e.g. trimethylaluminum). The resultant catalyst is capable of providing an olefinic polymer good in particle properties thereof (e.g. polypropylene) without using an expensive raw material.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an olefin polymer and a catalyst for olefin polymerization used in the method. More specifically, without using an expensive methylaluminoxane or a boron compound, a metallocene-supported catalyst having a high activity and capable of being used in combination or mixed with an existing catalyst is used to obtain a polymer having good particle properties. The present invention relates to a method for efficiently producing an olefin homopolymer or copolymer, and an olefin polymerization catalyst used in the method.

[0002]

2. Description of the Related Art Olefinic polymers such as polyethylenes and polypropylenes are widely used in many fields as general-purpose resins. It is known that this olefin polymer is produced by a catalyst system based on a Ziegler-Natta type catalyst, but in recent years, the Kaminsky type catalyst, which is a highly active homogeneous catalyst, has attracted attention. It's coming. However, this Kaminsky type catalyst
(1) Since a large amount of expensive methylaluminoxane or boron compound is used as an essential component, it is inevitable that the catalyst cost will be high. (2) Since it is a homogeneous catalyst,
Main process for polyolefin production (slurry polymerization method,
It is impossible to apply it to the gas phase polymerization method) due to poor particle properties of the resulting polymer, and (3) it is difficult to use it in combination with an existing catalyst or to use it in a mixture for the above reasons. is doing. Therefore, in order to eliminate such drawbacks, it has been desired to develop a supported catalyst having high activity without using methylaluminoxane or a boron compound. For such a supported catalyst, a pioneering example of achieving this object is described in "Macromolecular Chemistry", Vol. 194, page 1745 (1993). Therefore, the activity of the catalyst is improved to a certain extent. However, this catalyst has a problem that the catalyst activity is further improved and the particle properties of the resulting polymer are improved when it is used on an industrial level.

[0003]

Under the circumstances described above, the present invention is a metallocene which has high activity without using expensive methylaluminoxane or a boron compound and is applicable to a slurry / gas phase process. Develop a supported catalyst,
The object of the present invention is to provide a method for efficiently producing an olefin homopolymer or copolymer having good polymer particle properties.

[0004]

Means for Solving the Problems That is, the present invention provides (1) (A) (a) an inorganic oxide, (b) an alkyl magnesium compound, (c) an organic aluminum halide compound, and (d) cyclopenta. Solid catalyst component obtained by contacting and reacting with a transition metal compound containing at least one group selected from a dienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group and an aralkyl group having 7 to 24 carbon atoms An olefin polymerization catalyst containing (2) a solid component obtained by contacting (A) (a) an inorganic oxide with (b) an alkylmagnesium compound,
(C) an organic aluminum halide compound and (d) a cyclopentadienyl group, a substituted cyclopentadienyl group,
An olefin polymerization catalyst containing a solid catalyst component obtained by contacting and reacting with a transition metal compound containing at least one group selected from an indenyl group, a substituted indenyl group and an aralkyl group having 7 to 24 carbon atoms, (3) ( A) (a) inorganic oxide, (b) alkyl magnesium compound, (c) organic aluminum halide compound, and (d) cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group and carbon An olefin polymerization catalyst comprising a solid catalyst component obtained by contacting and reacting a transition metal compound containing at least one group selected from the aralkyl groups of the formulas 7 to 24, and (B) an organoaluminum compound, (4) (A) a solid component obtained by bringing (a) an inorganic oxide into contact with (b) an alkylmagnesium compound;
(C) an organic aluminum halide compound and (d) a cyclopentadienyl group, a substituted cyclopentadienyl group,
A solid catalyst component obtained by contacting and reacting with a transition metal compound containing at least one group selected from an indenyl group, a substituted indenyl group and an aralkyl group having 7 to 24 carbon atoms, and (B) an organoaluminum compound. Olefin polymerization catalyst, (5) (A) (a) inorganic oxide, (b) alkyl magnesium compound, (c) organic aluminum halide compound, and (d) cyclopentadienyl group, substituted cyclopentadienyl group , An indenyl group, a substituted indenyl group, and a transition metal compound containing at least one group selected from an aralkyl group having 7 to 24 carbon atoms are contacted and reacted to polymerize an olefin in the presence of a catalyst containing a solid catalyst component. Or a method for producing an olefin-based polymer, which comprises copolymerizing (6) (A) (a) an inorganic oxide and ( ) And a solid component obtained by contacting the alkyl magnesium compound,
(C) an organic aluminum halide compound and (d) a cyclopentadienyl group, a substituted cyclopentadienyl group,
Polymerization of an olefin in the presence of a catalyst containing a solid catalyst component obtained by contacting and reacting with a transition metal compound containing at least one group selected from an indenyl group, a substituted indenyl group and an aralkyl group having 7 to 24 carbon atoms, or (7) (A) (a) Inorganic oxide, (b) Alkyl magnesium compound, (c) Organic aluminum halide compound, and (d) Cyclo Solid catalyst obtained by contacting and reacting with a transition metal compound containing at least one group selected from pentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group and aralkyl group having 7 to 24 carbon atoms To polymerize or copolymerize an olefin in the presence of a catalyst composed of the component and (B) an organoaluminum compound. A method for producing an olefin-based polymer, and (8) a solid component obtained by bringing (A) (a) an inorganic oxide into contact with (b) an alkylmagnesium compound,
(C) an organic aluminum halide compound and (d) a cyclopentadienyl group, a substituted cyclopentadienyl group,
A solid catalyst component obtained by contacting and reacting with a transition metal compound containing at least one group selected from an indenyl group, a substituted indenyl group and an aralkyl group having 7 to 24 carbon atoms, and (B) an organoaluminum compound. The present invention provides a method for producing an olefin polymer, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst.

The present invention will be described in more detail below. The olefin polymerization catalyst of the present invention comprises (A) an inorganic oxide, (b) an alkyl magnesium compound, (c) an organic aluminum halide compound, and (d) a cyclopentadienyl group, a substituted cyclopentadienyl group. Group, an indenyl group, a substituted indenyl group and a transition metal compound containing at least one group selected from an aralkyl group having 7 to 24 carbon atoms, including a solid catalyst component obtained by contacting and reacting,
It is preferably composed of this and (B) an organoaluminum compound. Particularly, the component (A) is a solid component obtained by contacting (a) an inorganic oxide with (b) an alkylmagnesium compound, (c) an organic aluminum halide compound and (d) a cyclopentadienyl group. , A solid catalyst component obtained by contacting and reacting with a transition metal compound containing at least one group selected from a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group and an aralkyl group having 7 to 24 carbon atoms. Is preferred.

In the olefin polymerization catalyst of the present invention,
As the inorganic oxide as the component (a), for example, SiO
₂ , Al ₂ O ₃ , MgO, ZrO, TiO, etc., or their composite oxides, and also their mixtures are used. Among these inorganic oxides, SiO ₂ or Al ₂ O ₃
Are preferably used, and SiO ₂ is particularly preferable. The above inorganic oxides include sodium, potassium, magnesium,
Carbonate, nitrate, sulfate, and oxide components of metals such as calcium and aluminum may be contained. The inorganic oxide preferably has an average particle size in the range of 1 to 1000 μm, more preferably 5 to 200 μm, and particularly preferably 10 to 100 μm. Also, 10 to 1000 m ² / g, preferably 50 to
500m ² / g, more preferably 100 to 500 m ² /
It is desirable to have a specific surface area of g, and the pore volume thereof is 0.2 to 3.5 ml / g, preferably 0.5 to 3.0 ml / g, more preferably 0.8 to
It is preferably 2.5 ml / g. The inorganic oxide used in the present invention is preferably dehydrated in advance by a method such as heating or refluxing in an organic solvent. In this case, the heating temperature varies depending on the type of the inorganic oxide, but is preferably 50 to 1200 ° C, more preferably 100 to 900 ° C.

In the olefin polymerization catalyst of the present invention,
As the alkylmagnesium compound as the component (b), compounds represented by the general formula (1), MgR ¹ _m X ¹² _-m (1) are preferably used. In the above general formula (1), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and preferable examples thereof include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms and 6 to 6 carbon atoms. Examples thereof include a cycloalkyl group having 20 carbon atoms, a cycloalkenyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms. X ¹ represents a halogen atom such as a chlorine atom or a bromine atom, and m is a number satisfying 0 <m ≦ 2. When R ¹ are a plurality, each R ¹ may be the same or different, when plural X ^1, each X ¹ may be the same or different. Specific examples of such compounds include dibutylmagnesium, dipropylmagnesium, butylethylmagnesium, dihexylmagnesium, diphenylmagnesium, dioctylmagnesium, di-2-ethylhexylmagnesium, butylmagnesium chloride, ethylmagnesium chloride, phenylmagnesium chloride. , Or a complex of these with another organic compound, for example, an organoaluminum compound. In the present invention, a dialkylmagnesium compound is preferably used, and more preferably a dialkylmagnesium compound having an alkyl group having 1 to 6 carbon atoms is used. When the alkylmagnesium compound is used by dissolving it in a hydrocarbon compound, an ether compound such as diethyl ether or an aluminum alkoxide compound such as aluminum isopropoxide may coexist.
These alkylmagnesium compounds may be used alone or in combination of two or more.

In the olefin polymerization catalyst of the present invention,
As the organic aluminum halide compound which is the component (c), a compound represented by the general formula (2) AlR ² _n X ² _3-n (2) is used. In the above general formula (2), R ² represents a hydrocarbon group, which may be a saturated group or an unsaturated group, a linear group, a branched group, or a cyclic group. Further, it may have a hetero atom such as sulfur, nitrogen, oxygen, silicon and phosphorus, but preferably has 1 to 2 carbon atoms.
0 alkyl group, C2-20 alkenyl group, C6-20 cycloalkyl group, C6-20 cycloalkenyl group, C6-20 aryl group, C7-20 aryl An alkyl group can be mentioned.
X ² represents a halogen atom such as a chlorine atom or a bromine atom,
n is a number of 0 <n ≦ 2. When R ² are a plurality, each R ² may be the same or different, if X ² is more, each X ² may be the same or different.

Specific examples of the organic aluminum halide compound represented by the above general formula (2) include dimethyl aluminum monochloride, diethyl aluminum monochloride, dibutyl aluminum monochloride, diisopropyl aluminum monochloride, diisobutyl aluminum monochloride, diethyl. Aluminum monobromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, isobutyl aluminum dichloride, butyl aluminum dibromide and the like can be mentioned. Among these, organoaluminum compounds having chlorine such as ethylaluminum dichloride, ethylaluminum sesquichloride and diethylaluminum monochloride are suitable. These organic aluminum halide compounds may be used alone or in combination of two or more.

The component (d) used in the olefin polymerization catalyst of the present invention is selected from cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group and aralkyl group having 7 to 24 carbon atoms. The transition metal compound containing at least one group is preferably a compound represented by the general formula (3) R ³ _p MX ³ _r ... (3). In the above general formula (3), M is a transition element of Group IV of the periodic table, preferably titanium, zirconium, hafnium or the like. R ³ is a cyclopentadienyl group, a substituted cyclopentadienyl group,
Indenyl group, substituted indenyl group or C7-2
4, preferably 7 to 13 aralkyl groups, and preferably a titanium compound having at least one cyclopentadienyl group and substituted cyclopentadienyl group. R
^Three groups may be bonded to each other via an alkylene group having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, a substituted alkylene group or a silylene group, or a substituted silylene group. X ³ is a halogen atom such as chlorine, bromine or fluorine, a hydrogen atom or a carbon number of 1 to 24,
Preferably 1 to 12 hydrocarbon residues, p and r
Are numbers satisfying 2 ≦ p ≦ 4, 0 ≦ r ≦ 2 and p + r = 4, respectively.

When R ³ in the formula is a substituted cyclopentadienyl group or a substituted indenyl group, the substituent is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group or a propyl group, or It is a hydrogen atom. Examples of the aralkyl group represented by R ³ include a benzyl group, a phenethyl group, a benzhydryl group, a trityl group, a phenylbutyl group and a phenylpropyl group. When an alkylene group, a substituted alkylene group or a silylene group, or a substituted silylene group which bonds R ^3's together, is present, the alkylene group,
When R ³ is a substituted alkylene group, a silylene group or a substituted silylene group, R ³ is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group, the ring is usually bonded. Particularly, as the substituted silylene group, a dimethylsilylene group, a diethylsilylene group, a methylethylsilylene group, a diethoxysilylene group,
A diphenylsilylene group and the like can be exemplified. Further, as the hydrocarbon residue represented by X ³ , a methyl group,
Alkyl group such as ethyl group, propyl group, aryl group such as phenyl group, tolyl group, benzyl group, phenethyl group, benzhydryl group, trityl group, aralkyl group such as phenylbutyl group, phenylpropyl group, ethoxy group, propoxy group, Preferable examples are alkoxy groups such as phenoxy group, aryloxy groups and the like. Also, r is 2
In the case of, each X ³ may be the same or different.

Specific examples of the transition metal compound as the component (d) include bis (cyclopentadienyl) dichlorotitanium, bis (cyclopentadienyl) methylchlorotitanium, bis (cyclopentadienyl) dimethyltitanium and bis ( Cyclopentadienyl) ethoxychlorotitanium, bis (cyclopentadienyl) propoxychlorotitanium, bis (cyclopentadienyl) phenoxychlorotitanium, bis (cyclopentadienyl) propylchlorotitanium, bis (cyclopentadienyl) diphenyl Titanium, bis (cyclopentadienyl) ditolyl titanium, bis (cyclopentadienyl) titanium benzyl, bis (cyclopentadienyl) titanium monochloromonohalide, bis (methylcyclopentadienyl) Methyl titanium, tetracyclopentadienyl titanium, bis (indenyl) dichlorotitanium, bis (indenyl) dimethyltitanium, ethylenebis (indenyl) titanium dichloride, ethylenebis (tetrahydroindenyl) titanium dichloride, tetraneopentyltitanium, tetraneophile Titanium, tetrabenzyltatinium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) methylchlorozirconium, bis (cyclopentadienyl) dimethylzirconium, bis (indenyl) dimethylzirconium, bis (indenyl) dichloro Zirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium Bis (methylcyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) zirconium monochloro monohydride, bis (cyclopentadienyl)
Zirconium dibenzyl, tetracyclopentadienyl zirconium, tetrabenzyl zirconium, bis (cyclopentadienyl) ethoxychlorozirconium, bis (cyclopentadienyl) propoxychlorozirconium, bis (cyclopentadienyl) phenoxychlorozirconium, bis (Cyclopentadienyl) propylchlorozirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl)
Ditolyl zirconium, bis (cyclopentadienyl)
Monomethyl monohalide zirconium, bis (cyclopentadienyl) monoethyl monochloride zirconium,
Bis (cyclopentadienyl) monophenylmonochlorid zirconium, tetraneopentylzirconium, tetraneophyllzirconium, bis (cyclopentadienyl) dimethylhafnium, bis (cyclopentadienyl) dichlorohafnium, bis (cyclopentadienyl) Methylchlorohafnium, bis (cyclopentadienyl) ethylchlorohafnium, bis (cyclopentadienyl) propylchlorohafnium, bis (cyclopentadienyl) phenylchlorohafnium, bis (cyclopentadienyl) diphenylhafnium, bis (cyclo Pentadienyl) ditolylhafnium, bis (cyclopentadienyl) monochloromonohalide hafnium, bis (cyclopentadienyl) monomethylmonohalide hafnium, bis (cyclo Lopentadienyl) dibenzylhafnium, ethylenebis (indenyl) dichlorohafnium, ethylenebis (tetrahydroindenyl) dichlorohafnium, tetraneopentylhafnium, tetraneophyllhafnium, cyclopentadienyltitanium trichloride, cyclopentadienyltitaniummethyldichloride, Cyclopentadienyl titanium ethyl dichloride, cyclopentadienyl indenyl titanium dichloride, cyclopentadienyl titanium trimethyl, cyclopentadienyl titanium triphenyl,
Cyclopentadienyl titanium dimethyl hydride, cyclopentadienyl zirconium trichloride,
Cyclopentadienyl zirconium methyl dichloride,
Cyclopentadienyl zirconium ethyl dichloride,
Cyclopentadienyl indenyl zirconium dichloride, cyclopentadienyl zirconium trimethyl, cyclopentadienyl zirconium triphenyl, cyclopentadienyl zirconium dimethyl hydride, cyclopentadienyl hafnium trichloride, cyclopentadienyl hafnium methyl dichloride, cyclopenta Dienyl hafnium ethyl dichloride, cyclopentadienyl indenyl hafnium dichloride, cyclopentadienyl hafnium trimethyl, cyclopentadienyl hafnium triphenyl, cyclopentadienyl hafnium dimethyl hydride and the like are exemplified, and preferably bis (cyclopentadiene (Enyl) dichlorotitanium, bis (cyclopentadienyl) dimethyltitanium, bis (cyclopenta) (Enyl) dichlorozirconium, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) dichlorohafnium, bis (cyclopentadienyl) dimethylhafnium, cyclopentadienyltitanium trichloride, cyclopentadienylzirconium trichloride , Cyclopentadienyl hafnium trichloride.

Specific examples of the transition metal compound of the component (d) include ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) diethyl zirconium, ethylene bis (indenyl) diphenyl zirconium monochloride, ethylene bis (indenyl). Methylzirconium, ethylenebis (indenyl) ethylzirconium monochloride, ethylenebis (indenyl)
Methylzirconium monobromide, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (4
5,6,7-Tetrahydro-1-indenyl) dimethylzirconium, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) methylzirconium monochloride, ethylenebis (4,5,6,7-tetrahydro-
1-indenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl)
Zirconium dibromide, ethylene bis (4-methyl-
1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) zirconium dichloride, ethylenebis (6-methyl-1-indenyl) zirconium dichloride, ethylenebis (7-methyl-1)
-Indenyl) zirconium dichloride, ethylenebis (5-methoxy-1-indenyl) zirconium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-
Dimethyl-1-indenyl) zirconium dichloride,
Ethylene bis (4,7-dimethoxy-1-indenyl)
Zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) Zirconium dichloride, isopropylidene (cyclopentadienyl-2,7)
-Di-t-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) Phenyl) zirconium dichloride, dimethylsilylene bis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (indenyl) zirconium dichloride,
Dimethylsilylenebis (cyclopentadienyl) zirconium monochloride monohydride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) methylzirconium monochloride, dimethylsilylenebis (cyclopentadienyl) Dimethyl zirconium, dimethyl silylene bis (cyclopentadienyl) diphenyl zirconium, silylene bis (cyclopentadienyl)
Zirconium dichloride, silylene bis (cyclopentadienyl) dimethyl zirconium, diethyl silylene bis (cyclopentadienyl) zirconium dichloride,
Diethyl silylene bis (cyclopentadienyl) dimethyl zirconium, dimethyl silylene bis (methyl cyclopentadienyl) zirconium dihydride, dimethyl silylene bis (indenyl) zirconium dichloride, dimethyl silylene bis (indenyl) zirconium monochloride, dimethyl silylene bis (Indenyl) ethoxyzirconium chloride, dimethylsilylene bis (indenyl) dimethylzirconium,
Dimethyl silylene bis (indenyl) diethyl zirconium, dimethyl silylene bis (indenyl) diphenyl zirconium, dimethyl silylene bis (indenyl) dibenzyl zirconium, dimethyl silylene bis (indenyl) methyl zirconium monobromide, dimethyl silylene bis (indenyl) ethyl zirconium monochloride, Dimethyl silylene bis (indenyl) benzyl zirconium monochloride, dimethyl silylene bis (indenyl) zirconium bromide, dimethyl silylene bis (indenyl) methyl zirconium monochloride, dimethyl silylene bis (4,5,6,7-tetrahydro-1)
-Indenyl) dimethylzirconium, dimethylsilylenebis (4,5,6,7-tetrahydro-1-indenyl) ethylzirconium ethoxide, dimethylsilylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, Dimethylsilylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dibromide, dimethylsilylenebis (4-methyl-1-indenyl) zirconium dichloride, dimethylsilylenebis (5-methyl-1-indenyl) zirconium Dichloride, dimethylsilylenebis (6-methyl-1-indenyl) zirconium dichloride, dimethylsilylenebis (7-methyl-1-indenyl) zirconium dichloride, dimethylsilylenebis (5-methoxy-1-indenyl) Benzalkonium dichloride, dimethylsilylene bis (2,3-dimethyl-1-indenyl)
Zirconium dichloride, dimethyl silylene bis (4,
7-Dimethyl-1-indenyl) zirconium dichloride, dimethylsilylene bis (4,7-dimethoxy-1-)
Indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dimethoxide, dimethylsilylenebis (indenyl) zirconium diethoxide, dimethylsilylenebis (indenyl) methoxyzirconium chloride, dimethylsilylenebis (indenyl) ethoxyzirconium chloride, dimethylsilylenebis ( Indenyl) methylzirconium ethoxide, dimethylsilylene bis (4,5,6,7-tetrahydro-
1-indenyl) zirconium dimethoxide, dimethylsilylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium diethoxide, dimethylsilylenebis (4,5,6,7-tetrahydro-1-indenyl) methoxy Zirconium chloride, dimethyl silylene bis (4,5,6,7-tetrahydro-1-indenyl) ethoxy zirconium chloride, dimethyl silylene bis (4,5,6,7-tetrahydro-1-indenyl) methyl zirconium ethoxide, diethyl silylene Bis (indenyl) zirconium dichloride, diethylsilylene bis (indenyl) dimethyl zirconium, diethylsilylene bis (4,5,6,7-tetrahydro-
1-indenyl) zirconium dichloride, dimethylsilylenebis (fluorenyl) zirconium dichloride,
Dimethylsilylenebis (fluorenyl) dimethylzirconium, dimethylsilylenebis (fluorenyl) diphenylzirconium, dimethylsilylenebis (fluorenyl) zirconium dichloride, dimethylsilylenebis (fluorenyl) dimethylzirconium, dimethylsilylenebis (fluorenyl) zirconium dichloride and zirconium in the above zirconium compound Metal
Transition metal compounds in which titanium metal or hafnium metal is replaced are also included. Of course, two or more kinds of these compounds may be mixed and used.

The polymerization catalyst of the present invention includes the above (a),
In addition to the component (A) consisting of the components (b), (c) and (d), it preferably contains an organoaluminum compound as the component (B). As such an organic aluminum compound, various compounds such as an aluminum compound having a halogen atom, a hydrogen atom, an alkoxy group, aluminoxane, or a mixture thereof can be used. Specifically, trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, diethyl aluminum monochloride, diisopropyl aluminum monochloride, diisobutyl aluminum monochloride, dioctyl aluminum monochloride, diethyl aluminum monoethoxide, dimethyl aluminum monoethoxide. , Diethyl aluminum monobutoxide, diethyl aluminum monophenoxide, ethyl aluminum dichloride, isopropyl aluminum dichloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and the like. Among these, triethyl aluminum and triisobutyl aluminum are preferable. These organoaluminum compounds may be used alone or in combination of two or more.

The solid catalyst component (A) in the olefin polymerization catalyst of the present invention composed of the above components can be prepared as follows. First, above (a)
The inorganic oxide as the component and the alkylmagnesium compound as the component (b) are desirably contacted and reacted with each other in advance. As a contacting method, a method of directly contacting each other is possible, but in an inert solvent such as a hydrocarbon. It is preferable to contact with. Contact treatment is a specific surface area of inorganic oxide 1m ² / g
Per 0.0001 mmol or more, preferably 0.000
It is carried out with an alkylmagnesium compound of 01 mmol or more, more preferably 0.001 mmol or more. The contact temperature is −20 to 200 ° C., preferably 0 to 150 ° C., and the contact time is 1 minute or longer, preferably 10 minutes to 24 hours. In the present invention, the solid component may be washed with an inert solvent such as hydrocarbon after the contact.

The solid component obtained from the components (a) and (b) is then contacted with and reacted with the components (c) and (d). The order of bringing the component (c) and the component (d) into contact with the solid component is not particularly limited. That is, the solid component may be brought into contact with the component (c) and the component (d) at the same time, or any two components among the above three components may be brought into contact with each other and the remaining one component may be brought into contact therewith. Further, either the component (c) or the component (d) may be brought into contact with the solid component, washed with an inert solvent such as hydrocarbon, and then the remaining components may be brought into contact. In each of the above contact,
It is preferable to dilute each component with an inert solvent such as hydrocarbon. Hydrocarbon solvents that can be used as such an inert solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, tetradecane, and kerosene; cyclopentane, methylcyclopentane, cyclohexane, methyl. Cyclohexane,
Alicyclic hydrocarbons such as cyclooctane and cyclohexene; benzene, toluene, xylene, ethylbenzene,
Examples thereof include aromatic hydrocarbons such as cumene and cymene; halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene, carbon tetrachloride, and chlorobenzene.

When the component (c) and the component (d) are brought into contact with the solid component consisting of the components (a) and (b),
The proportion of the component (c) and the solid component used is 0.001 to 1000 g / g of aluminum atom / solid component in the component (c),
Preferably 0.01 to 100 g / g, more preferably 0.1
Within a range of up to 50 g / g, and the ratio of the component (d) and the solid component used is 0.0001 to 10 in terms of titanium atom / solid component.
It is used within the range of 0 g / g, preferably 0.001 to 10 g / g, and more preferably 0.01 to 1 g / g. The contact temperature at this time is −20 to 200 ° C., preferably 0 to 1
The contact time at 50 ° C. is 1 minute or longer, preferably 10 minutes or longer. In the present invention, it is preferred to wash the solid component with the component (c) or the component (d) and then wash with an inert solvent such as a hydrocarbon. The obtained solid catalyst component can be stored in a dry state or in an inert solvent such as the above hydrocarbon.

Solid of component (A) prepared as described above
Contacting the catalyst component with the organoaluminum compound of component (B)
To achieve this, the solid catalyst component and the organoaluminum compound should be combined.
It is possible to carry out the polymerization after contacting the product in advance,
Both may be introduced separately in the system. Also solid
Pre-contact the body catalyst component with the organoaluminum compound
It is introduced into the polymerization system from
You may introduce a thing. Organoaluminum compound in this case
The use ratio of the solid catalyst component and Al / Ti is 1 to 100
00, preferably 10-5000, more preferably 20
It is a value in the range of up to 1000. Olefin Polymerization of the Invention
In the catalyst for use, it is used as a co-catalyst.
Machine aluminum compound is sufficient, but if necessary
In addition, aluminoxanes such as methylaluminoxane and B
(C₆H_Five)₃, (C₆H_Five)₃C ・ B (C
₆F _Five)₂, BF₃Can be used in combination with boron compounds such as
Yes. Also, the Ziegler touch that is commonly used in the industry.
It can be used together or mixed with a medium.

In the method for producing an olefin-based polymer of the present invention, olefins are homopolymerized or olefins and other olefins and / or other polymerizable unsaturated compounds are co-polymerized in the presence of the above-mentioned polymerization catalyst. Polymerization produces an olefin-based polymer. The above polymerization can be carried out in the same manner as the olefin polymerization using a Ziegler catalyst which is commonly used in the art. The olefins are not particularly limited, but include, for example, ethylene; propylene; 1-butene; 1-pentene; 1-hexene; 1-octene; 4
Examples include α-olefins such as -methylpentene-1 and 1,4-hexadiene; dienes such as 1,9-decadiene. These olefins may be used alone or in combination of two or more. When copolymerizing two or more olefins, the above olefins can be combined arbitrarily.

In the production method of the present invention, the above-mentioned olefins may be copolymerized with other polymerizable unsaturated compounds. Examples of the other polymerizable unsaturated compound used at this time include styrene, Aromatic vinyl compounds such as p-methylstyrene, isopropylstyrene and t-butylstyrene, conjugated diolefins such as butadiene, isoprene and chloroprene, 1,5-hexadiene; 1,6
-Heptadiene; 1,7-octadiene; 1,8-nonadiene; 1,9-decadiene; 2,5-dimethyl-1,
5-hexadiene; non-conjugated diolefins such as 1,4-dimethyl-4-t-butyl-2,6-heptadiene,
Cyclobutene; Cyclopentene; Cyclohexene; Cycloheptene; Cyclooctene; Norbornene;
5,8-Dimethano-1,2,3,4,4a, 5,8,8
a-Octahydronaphthalene; cyclic olefins such as 2-norbornene, cyclic diolefins such as norbornadiene, 5-ethylidene norbornene, 5-vinyl norbornene, dicyclopentadiene, polyenes such as 1,5,9-decatriene, acrylic Unsaturated esters such as ethyl acid and methyl methacrylate, lactones such as β-propiolactone, β-butyrolactone and γ-butyrolactone, lactams such as ε-caprolactam and δ-valerolactam, epoxypropane; 1,2 -Epoxides such as epoxybutane and the like can be mentioned.

The production method of the present invention is particularly preferably applied to the production of ethylene-based or propylene-based polymers. In this case, ethylene or propylene may be polymerized alone, or ethylene or propylene and the above The olefins and / or other polymerizable unsaturated compound described above may be copolymerized. If necessary, electron donors such as ethers, esters, alcohols, ketones, amines, silane compounds and carboxylic acids may be added during the polymerization. In the present invention, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method or a suspension polymerization method may be used. The phase polymerization method is particularly preferred. The polymerization temperature and the polymerization pressure are not particularly limited, but the polymerization temperature is usually 20 to 220 ° C., preferably 40.
To 190 ° C., and the polymerization pressure is usually atmospheric pressure to 100 Kg / cm ² , preferably ^{2 to} 80 Kg / cm ² .
Selected in the range of ² . Further, the polymerization may be carried out in the presence of an inert gas such as nitrogen gas. When a polymerization solvent is used, the same one as in the case of olefin polymerization using a general Ziegler catalyst can be used, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, cyclopentane, methylcyclopentane,
Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, octane, decane, and kerosene, and halogenated hydrocarbons such as chloroform and dichloromethane can be used. it can. These solvents may be used alone or in combination of two or more. Further, a monomer such as α-olefin may be used as a solvent. The molecular weight of the obtained olefin polymer can be adjusted by adjusting the temperature, the catalyst components, the addition of hydrogen and the like as in the conventional catalyst.

In the production method of the present invention, prepolymerization can be carried out using the above-mentioned polymerization catalyst. The prepolymerization can be performed by bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited, and a known method can be used. The olefin used in the prepolymerization is not particularly limited and may be the same as those exemplified above, for example, ethylene, α-olefin having 3 to 20 carbon atoms, or a mixture thereof. It is advantageous to use the same olefin as that used. In the present invention, the olefin polymer can be polymerized by any method such as a batch system or a continuous system. It is also possible to carry out the polymerization in two or more steps under different polymerization conditions. 1 is a flowchart showing an example of the embodiment of the present invention.

[0023]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 Preparation of solid catalyst component Silica gel (Davison 952 grade, specific surface area 2
80 m ² / g) was heat-treated under a nitrogen stream at 450 ° C. for 240 minutes, and this was placed in a three-necked flask with a stirrer and an internal volume of 500 ml
6 g was added. In addition, 200 ml of hexane,
Add 13.5 mmol of butylethylmagnesium and add 25
Contacted at 30 ° C. for 30 minutes. After washing the solid phase portion with hexane, the solid phase portion was suspended in 200 ml of hexane, and 67.5 mmol of ethylaluminum dichloride was added.
Contacted at 30 ° C. for 30 minutes. After washing the solid phase with hexane, the liquid phase was replaced with 300 ml of toluene. Dicyclopentadienyl titanium dichloride 3
46 mmol was added and the mixture was contacted at 25 ° C. for 24 hours. The solid phase portion was washed with toluene to obtain a solid catalyst component. Production of polyethylene (slurry polymerization) 3 liters of hexane was introduced into a stainless steel autoclave with an internal volume of 7 liters equipped with a stirrer, the temperature was raised to 80 ° C., and 6 kg / cm ² of ethylene was introduced. Hexane 30 ml, triisobutylaluminum 4.0 mmol, solid catalyst component 0.045 mmol-T in the catalyst charging pipe.
The i atom was added and immediately charged into the autoclave to start the polymerization reaction. Ethylene was continuously fed through the pressure regulator so that the pressure became constant. Depressurize after 120 minutes,
The solid part was filtered off and dried.

Example 2 Production of Polyethylene (Slurry Polymerization) 3 liters of hexane and 300 ml of 1-octene were introduced into a stainless steel autoclave with an internal volume of 7 liters equipped with a stirrer, the temperature was raised to 80 ° C., and further 6 kg of ethylene was added.
/ Cm ² was introduced. Hexane (30 ml), triisobutylaluminum (4.0 mmol), and solid catalyst component (0.045 mmol-Ti atom) prepared in the same manner as in Example 1 were added to the catalyst charging tube and immediately charged into the autoclave to start the polymerization reaction. . Ethylene was continuously fed through the pressure regulator so that the pressure became constant. After 120 minutes, the pressure was released, the solid portion was filtered off and dried.

Example 3 Production of Polyethylene (Slurry Polymerization) 3 liters of hexane and 300 ml of 1-octene were introduced into a stainless steel autoclave with an internal volume of 7 liters equipped with a stirrer, the temperature was raised to 80 ° C., and further hydrogen was 1 kg / cm 3.
² , ethylene 6 kg / cm ² was introduced. Hexane (30 ml), triisobutylaluminum (4.0 mmol), and solid catalyst component (0.045 mmol-Ti atom) prepared in the same manner as in Example 1 were added to the catalyst charging tube and immediately charged into the autoclave to start the polymerization reaction. . Ethylene was continuously fed through the pressure regulator so that the pressure became constant. After 120 minutes, the pressure was released, the solid portion was filtered off and dried. Example 4 Preparation of solid catalyst component Example 1 except that cyclopentadienyl titanium trichloride was used instead of dicyclopentadienyl titanium dichloride.
A solid catalyst component was prepared in the same manner as in. Production of Polyethylene (Slurry Polymerization) The procedure of Example 2 was repeated except that the solid catalyst component prepared above was used.

Example 5 Preparation of solid catalyst component A solid catalyst component was prepared in the same manner as in Example 1 except that diethyl aluminum dichloride was used instead of ethyl aluminum dichloride. Production of Polyethylene (Slurry Polymerization) The procedure of Example 2 was repeated except that the solid catalyst component prepared above was used. Example 6 Production of Polyethylene (Gas Phase Polymerization) 100 g of sodium chloride particles as a catalyst dispersant was placed in a stainless steel autoclave equipped with a stirrer and having an inner volume of 4.5 liters, and the autoclave was vacuum dried at 85 ° C. for 2 hours. , Re-pressurized with nitrogen. The temperature was maintained at 80 ° C. and 8 kg / cm ^{2 of} ethylene and 30 g of 1-butene were introduced. To the catalyst charging tube, 30 ml of heptane, 4.0 mmol of triisobutylaluminum, and 0.045 mmol-Ti atom of a solid catalyst component prepared in the same manner as in Example 1 were added,
It was immediately introduced into the autoclave to start the polymerization reaction. Ethylene was continuously fed through the pressure regulator so that the pressure became constant. After 120 minutes, the pressure was released and the contents were taken out. This was poured into 3 liters of water to dissolve sodium chloride, and suction filtration was performed.
After washing with methanol, it was dried at 80 ° C. for 6 hours to obtain polyethylene.

Table 1 shows the results of measuring the catalytic activity, intrinsic viscosity, average particle size and bulk density of the polymers obtained in Examples 1 to 6 by the following methods. (1) Catalytic activity: Calculated from the amount of polymer obtained with respect to the amount of catalyst used. (2) Intrinsic viscosity [η]: Decalin was measured at 135 ° C. (3) Average particle size: After the particle size distribution was determined using a sieve, the size of the sieve was multiplied by the ratio of the particle size distribution to obtain the sum. (4) Bulk density: measured according to JIS-K6721.

Comparative Example 1 Preparation of solid catalyst component A solid catalyst component was prepared in the same manner as in Example 1 except that ethyl aluminum dichloride was replaced with triethyl aluminum. Production of Polyethylene (Slurry Polymerization) The procedure of Example 1 was repeated except that the solid catalyst component prepared above was used. As a result, only a trace amount of the polymer was obtained. Comparative Example 2 Preparation of solid catalyst component A solid catalyst component was prepared in the same manner as in Example 1 except that butylethylmagnesium was not added. Production of Polyethylene (Slurry Polymerization) The procedure of Example 1 was repeated except that the solid catalyst component prepared above was used. As a result, only a trace amount of the polymer was obtained.

Comparative Example 3 Preparation of solid catalyst component A solid catalyst component was prepared in the same manner as in Example 1 except that titanium tetrachloride was used instead of dicyclopentadienyl titanium dichloride. Production of Polyethylene (Slurry Polymerization) The procedure of Example 1 was repeated except that the solid catalyst component prepared above was used. As a result, the catalytic activity is 75 kg /
g-Ti, intrinsic viscosity [η] is 12.7 deciliter / g,
Polyethylene having an average particle size of 280 μm and a bulk density of 0.29 g / cm ³ was obtained.

[0030]

[Table 1]

[0031]

EFFECT OF THE INVENTION The polymerization catalyst used in the production of the olefin polymer of the present invention is a metallocene-supported catalyst having high activity without using expensive methylaluminoxane or boron compound. Due to
It is possible to efficiently produce an olefin-based homopolymer or copolymer having a good polymer particle property. Further, the catalyst has an advantage that it can be used in combination with or mixed with an existing catalyst and can be used in an existing plant. The method for producing an olefin-based polymer of the present invention is
Especially ethylene polymers such as high density polyethylene (H
It is suitable for manufacturing DPE) and linear low density polyethylene (L-LDPE).

[Brief description of drawings]

FIG. 1 is a flowchart showing an example of an embodiment of the present invention.

Claims (8)

[Claims] 1. (A) (a) inorganic oxide, (b) alkyl magnesium compound, (c) organic aluminum halide compound, and (d) cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group. A catalyst for olefin polymerization comprising a solid catalyst component obtained by contacting and reacting a transition metal compound containing at least one group selected from a substituted indenyl group and an aralkyl group having 7 to 24 carbon atoms. 2. A solid component obtained by bringing (A) (a) an inorganic oxide into contact with (b) an alkylmagnesium compound, (c) an organic aluminum halide compound and (d) a cyclopentadienyl group. , Substituted cyclopentadienyl group, indenyl group, substituted indenyl group and carbon number 7
To 24 aralkyl groups, a catalyst for olefin polymerization containing a solid catalyst component obtained by contacting and reacting with a transition metal compound containing at least one group selected from aralkyl groups. 3. (A) (a) inorganic oxide, (b) alkyl magnesium compound, (c) organic aluminum halide compound, and (d) cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group , An olefin polymerization comprising a solid catalyst component obtained by contacting and reacting a transition metal compound containing at least one group selected from a substituted indenyl group and an aralkyl group having 7 to 24 carbon atoms, and (B) an organoaluminum compound. Catalyst. 4. A solid component obtained by bringing (A) (a) an inorganic oxide into contact with (b) an alkylmagnesium compound, (c) an organic aluminum halide compound and (d) a cyclopentadienyl group. , Substituted cyclopentadienyl group, indenyl group, substituted indenyl group and carbon number 7
A catalyst for olefin polymerization comprising a solid catalyst component obtained by contacting and reacting with a transition metal compound containing at least one group selected from -24 aralkyl groups, and (B) an organoaluminum compound. 5. (A) (a) inorganic oxide, (b) alkylmagnesium compound, (c) organic aluminum halide compound, and (d) cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group , A transition metal compound containing at least one group selected from a substituted indenyl group and an aralkyl group having 7 to 24 carbon atoms, and polymerizing or copolymerizing an olefin in the presence of a catalyst containing a solid catalyst component obtained by contacting and reacting the same. A method for producing an olefin-based polymer, comprising: 6. A solid component obtained by bringing (A) (a) an inorganic oxide into contact with (b) an alkylmagnesium compound, (c) an organic aluminum halide compound and (d) a cyclopentadienyl group. , Substituted cyclopentadienyl group, indenyl group, substituted indenyl group and carbon number 7
To 24 aralkyl groups are polymerized or copolymerized in the presence of a catalyst containing a solid catalyst component obtained by contacting and reacting with a transition metal compound containing at least one group selected from aralkyl groups. Method for producing polymer. 7. (A) (a) inorganic oxide, (b) alkyl magnesium compound, (c) organic aluminum halide compound, and (d) cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group , A solid catalyst component obtained by contacting and reacting a transition metal compound containing at least one group selected from a substituted indenyl group and an aralkyl group having 7 to 24 carbon atoms, and (B) a catalyst comprising an organoaluminum compound. A method for producing an olefin-based polymer, which comprises polymerizing or copolymerizing an olefin in the presence thereof. 8. A solid component obtained by bringing (A) (a) an inorganic oxide into contact with (b) an alkylmagnesium compound, (c) an organic aluminum halide compound and (d) a cyclopentadienyl group. , Substituted cyclopentadienyl group, indenyl group, substituted indenyl group and carbon number 7
To 24 aralkyl groups are contacted with and reacted with a transition metal compound containing at least one group selected from aralkyl groups, and (B) an olefin is polymerized or co-polymerized in the presence of a catalyst consisting of the organoaluminum compound (B). A method for producing an olefin-based polymer, which comprises polymerizing.