JP2000080117A - Preparation of olefin polymerization catalyst component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a preparation process for a solid catalyst component which exhibits a high polymerization activity and also yields a polymer having a high bulk density and containing a reduced amount of fine powder when used in polymerization of an olefin. SOLUTION: The titled process comprises (A) a step wherein a metallocene transition metal compound is brought into contact with an activator, (B) a step wherein a product obtained in the above-mentioned process (A) is brought into contact with an α-olefin and (C) a step wherein a product obtained in the above-mentioned process (B) is added with a metallocene transition metal compound. As the activator, one or more compounds chosen from the group consisting of ionic compounds which is capable of reacting with aluminum oxy compounds, Lewis acids or metallocene transition metal compounds to convert them into cations, or an ion exchange lamellar silicate is preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a catalyst component for olefin polymerization. More specifically, the present invention relates to a method for producing a catalyst component capable of obtaining an olefin polymer in a high yield and excellent particle and powder properties when applied to slurry polymerization, gas phase polymerization, and the like.

[0002]

2. Description of the Related Art In producing an olefin polymer by polymerizing an olefin, there has been proposed a method in which a catalyst comprising (1) a metallocene transition metal compound and (2) an aluminoxane is used as a catalyst (Japanese Patent Publication No. 12283/1992).
JP-A-2-167307). The polymerization method using these catalysts has a higher polymerization activity per transition metal atom than the method using a so-called Ziegler-Natta catalyst comprising a titanium compound or a vanadium compound and an organoaluminum compound, and has a higher molecular weight distribution and It is said that a polymer having a sharp composition distribution can be obtained.

Also, a catalyst in which one or both of a metallocene transition metal compound and an aluminoxane are supported on an inorganic oxide or an organic substance such as silica or alumina has been proposed (JP-A-60-35007, JP-A-61-108).
Nos. 610, 61-276805 and 61-296008). The present inventors have previously proposed a catalyst having high activity and excellent particle properties and a method for polymerizing olefins using the same (Japanese Patent Laid-Open No. 7-22).
No. 8621, No. 9-278818, No. 9-3
No. 19119).

[0004]

Although each of these techniques is effective, it has been desired to develop a catalyst having more excellent particle properties and good polymerization activity.

[0005]

Means for Solving the Problems The present inventors have repeatedly studied a method for preparing a metallocene-based catalyst in order to achieve the above-mentioned object, and have found that this metallocene-based catalyst component is produced according to a specific process. The inventors have found that this object can be achieved, and have completed the present invention.

That is, the gist of the present invention is as follows:
(C) A method for producing a catalyst component for olefin polymerization containing (C). (A) Step of contacting a metallocene-based transition metal compound with an activator (B) Step of contacting an α-olefin with the contact product obtained in (A) above (C) Obtained in (B) above Step of adding a metallocene transition metal compound to the contact product

Another object of the present invention is to provide a group consisting of an activating compound in which an activator reacts with an aluminum oxy compound, a Lewis acid, and a metallocene transition metal compound to convert it into a cation. One or more compounds selected from the group consisting of: or the activator is an ion-exchange layered silicate, the method for producing the catalyst component for olefin polymerization, wherein the ion-exchanged layered silicate is treated with a salt or an acid. Of 4% by weight obtained by carrying out
The following ion-exchange layered silicates, the shape of the ion-exchanged layered silicates are spherical particles having an average particle size of 5 to 1000 μm, and the particles of the ion-exchanged layered silicate are finely compressed. The method for producing a catalyst component for olefin polymerization described above, wherein the crushing strength of the particles measured by a tester is 0.2 MPa or more.

Further, another gist of the present invention is that the step (A) is carried out in an inert hydrocarbon solvent, and the step (B)
In the presence of an organoaluminum compound, and, following the steps (A) to (C), performing a step of removing and drying the solvent to obtain a solid catalyst component as a step (D). A method for producing the olefin polymerization catalyst component,
Also exists.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION <Metallocene Transition Metal Compound>
The metallocene transition metal compound used in the method for preparing a catalyst component for olefin polymerization of the present invention contains one or two cyclopentadienyl rings (hereinafter, referred to as “Cp rings”) that may be substituted. Ligand and Long Period Table 3 ~
An organometallic compound comprising a transition metal atom of Group 6, or a cationic complex thereof. (The periodic table of atoms used herein is based on the group 18 system recommended by IUPAC in 1989.) Preferred examples of such a metallocene transition metal compound include the following general formula (1) or ( It is a compound represented by 2).

[0010]

## STR1 ## _{^{R 1 m (C 5 R 2}} a) (C 5 R 3 b) MX 1 X 2 (1) (C 5 R 2 5) MX 3 X 4 X 5 (2)

The meanings of the symbols in the formulas (1) and (2) are as follows. R ¹ : ^First of the long period table of carbon, silicon, germanium, etc.
Is a covalent bond crosslinking group containing Group 4 elements, two cyclopentadienyl rings what binds _{^{C 5 R 2 a, C 5}} R 3 b: each good cyclopentadiene ring which may have a substituent ( Cp ring). R ² or R ³
Need not all be the same

R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a silicon-containing group, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group, an alkoxy group, an aryloxy group, and an amino group. An atom or an atomic group bonded to the Cp ring, wherein two R ² and R ³ are bonded to two adjacent carbon atoms on the Cp ring; May combine with each other at the ends to form a ring

M: 0 or 1 a, b: Integer of 4 or 5 representing the number of R ² and R ³ , wherein m is 0 when m = 0 and m is 1 when M = 1. A transition metal atom selected from the group consisting of titanium, zirconium, and hafnium X ^{1 to} X ⁵ : each independently a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group,
An atom or a substituent selected from the group consisting of an aryloxy group, an amide group, and a trifluoromethanesulfonic acid group

In the formula (1), R ¹ is carbon, silicon,
It is a covalent bond bridging group containing an element of Group 14 of the long period table such as germanium, and specifically, a methylene group, an alkylene group such as an ethylene group, an ethylidene group, a propylidene group, an isopropylidene group, a phenylmethylidene group Alkylidene group such as diphenylmethylidene group, dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diisopropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methylisopropylsilylene group, methyl-t A silicon-containing cross-linking group such as -butylsilylene group, dimethylgermylene group, diethylgermylene group, dipropylgermylene group, diisopropylgermylene group, diphenylgermylene group, methylethylgermylene group, methylphenylgermylene group, Methyly Propyl gel Mi alkylene group, such as a germanium-containing crosslinking group such as methyl -t- Buchirugerumiren group, alkyl phosphinyl group, an imino group, and the like. Of these, alkylene groups, alkylidene groups,
And a silicon-containing crosslinking group are particularly preferably used.

[0015] a ^{_{C 5 R 2 a, C 5}} R 3 b may cyclopentadiene ring optionally has have a substituent (Cp ring), R ^2, R ³ are each independently a hydrogen atom, a halogen A bond to a Cp ring selected from the group consisting of an atom, a silicon-containing group, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, and an amino group. Atom or atomic group. It is not necessary that all of R ² or R ³ be the same.

Specific examples include halogen atoms such as fluorine, chlorine, bromine and iodine, trimethylsilyl groups,
Silicon-containing groups such as triethylsilyl group and triphenylsilyl group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group,
n-pentyl group, n-hexyl group, cyclopentyl group,
Cyclohexyl group, n-heptyl group, n-nonyl group, n
A hydrocarbon group having 1 to 20 carbon atoms such as decyl group, phenyl group, 4-methylphenyl group, naphthyl group, or monofluoromethyl group, difluoromethyl group, trifluoromethyl group, 1,1,1-tri Fluoroethyl group, pentafluorophenyl group, 4-fluorophenyl group, 2-
A halogen-containing hydrocarbon group having 1 to 20 carbon atoms such as fluorophenyl group, monochloromethyl group, monobromomethyl group, alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, 4-methyl Examples include an aryloxy group such as a phenoxy group and a pentamethylphenoxy group, and an amino group such as a dimethylamino group, a diethylamino group, a diisopropylamino group, a diphenylamino group, a dicyclohexylamino group, a pyridyl group, and an indolyl group. Among them, particularly preferred are a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an alkyl group having 1 to 6 carbon atoms such as a cyclohexyl group or a cycloalkyl group, Or a phenyl group.

Here, two R ² and R ³ are Cp
When attached to two adjacent carbon atoms on the ring,
At the ω-terminal, they may be bonded to each other to form a ring. Specific examples thereof include a cyclic group having 4 to 7 carbon atoms, that is, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, an octahydrofluorenyl group. , Azulenyl group, tetrahydroazulenyl group and the like.

M is 0 when two cyclopentadienyl rings are not linked via the bridging group R ¹ , and is 1 when they are linked. a and b represent 4 or 5 representing the number of R ² and R ³
Where m is 0 when m = 0 and 4 when m = 1.

X ^{1 to} X ⁵ each independently represent a hydrogen atom,
Halogen atom such as chlorine and bromine, methyl group, ethyl group, n
-Propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-nonyl group, n-decyl Group, phenyl group, hydrocarbon group having 1 to 20 carbon atoms such as 4-methylphenyl group, alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, 4-methylphenoxy group, pentamethyl It represents an atom or a substituent selected from the group consisting of an aryloxy group such as a phenoxy group, a dimethylamide group, a diethylamide group, a diisopropylamide group, a diphenylamide group, an amide group such as a dicyclohexylamide group, and a trifluoromethanesulfonic acid group.

Of these, a hydrogen atom, a chlorine atom, a methyl group, an ethyl group, a dimethylamide group, a diethylamide group, and a trifluoromethanesulfonic acid group are preferred. Specific examples of such a metallocene transition metal compound used in the present invention include the following compounds.

(1) Having a pentadienyl group monosubstituted with an alkyl group, a cycloalkyl group or a phenyl group bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethyl Cyclopentadienyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (i-
Propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (i-butylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride, bis ( Cyclopentylcyclopentadienyl) zirconium dichloride, bis (cyclohexylcyclopentadienyl) zirconium dichloride, bis (phenylcyclopentadienyl) zirconium dichloride, bis (benzylcyclopentadienyl) zirconium dichloride

(2) having a pentadienyl group which is di-substituted or more (tri-, tetra- or penta-substituted) with an alkyl group, a cycloalkyl group or a phenyl group; bis (1,2-dimethylcyclopentadienyl) zirconium dichloride; Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1,
2,3-trimethylcyclopentadienyl) zirconium dichloride, bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride, bis (1,2,3,4-tetramethylcyclopentadienyl) zirconium dichloride, Bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (1-ethyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1-n-propyl-3-
Methylcyclopentadienyl) zirconium dichloride, bis (1-i-propyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1-n-
Butyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1-i-butyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1-t-butyl-3-methylcyclopentadienyl)
Zirconium dichloride, bis (1-cyclohexyl-3-methylcyclopentadienyl) zirconium dichloride

(3) those in which substituents bonded to two adjacent carbon atoms on a Cp ring form a ring bis (indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) ) Zirconium dichloride, bis (2-methylindenyl) zirconium dichloride, bis (2,4-dimethylindenyl) zirconium dichloride, bis (2-methyl-
4,5,6,7-tetrahydroindenyl) zirconium dichloride, cyclopentadienylfluorenylzirconium dichloride, cyclopentadienyloctahydroindenylzirconium dichloride, bis (azulenyl) zirconium dichloride, bis (4H-
5,6,7,8-tetrahydroazulenyl) zirconium dichloride, bis (2-methyl-4H-5,6,6)
7,8-tetrahydroazulenyl) zirconium dichloride

(4) m = 1, that is, having a crosslinking group dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2-methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis ( 3-methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (3-ethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (3-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis ( 3-trimethylsilylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediyl Bis (indenyl) zirconium dichloride, dimethylsilanediylbis (2-methylindenyl) zirconium dichloride, dimethylsilanediylbis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl- 4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl-4-phenylindenyl)
Zirconium dichloride, dimethylsilanediylbis (2-methyl-4-naphthylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Dimethylsilanediylbis (4,5-benzoindenyl) zirconium dichloride, 1,2-ethanediylbis (cyclopentadienyl) zirconium dichloride, 1,2-ethanediylbis (indenyl) zirconium dichloride, 1,2-ethanediylbis (2-methyl Indenyl) zirconium dichloride, 1,2-
Ethanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride, 1,2-ethanediylbis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, 1,2-ethanediylbis (2
-Methyl-4,5,6,7-tetrahydroindenyl)
Zirconium dichloride, 1,2-ethanediyl bis (4,5-benzoindenyl) zirconium dichloride, isopropylidene bis (cyclopentadienyl) zirconium dichloride, isopropylidene bis (indenyl) zirconium dichloride, isopropylidene bis (2-methylindenyl) ) Zirconium dichloride, isopropylidenebis (2-methyl-4-phenylindenyl) zirconium dichloride, isopropylidenebis (4,5,6,7-tetrahydroindenyl)
Zirconium dichloride, isopropylidene bis (2
-Methyl-4,5,6,7-tetrahydroindenyl)
Zirconium dichloride, isopropylidenebis (4,5-benzoindenyl) zirconium dichloride

A metallocene transition metal compound in which the transition metal atom of these compounds is substituted by titanium or hafnium may be used, and one or both of the chlorine atoms in the “dichloride” portion may be a hydrogen atom or a methyl group. Compounds substituted with a amide group, a diethylamide group, a methoxide group or the like are also used.

Among the above compounds, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (i-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclohexane) (Pentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1-ethyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1-n-butyl-3-methyl) Cyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (2-methylindenyl) zirconium dichloride, bis (2,4-dimethylindenyl) zirconium dichloride, Scan (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (2-
Methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride, 1,2-ethanediylbis (cyclopentadienyl) zirconium dichloride,
1,2-ethanediylbis (indenyl) zirconium dichloride, 1,2-ethanediylbis (2-methylindenyl) zirconium dichloride, 1,2-ethanediylbis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, 1,2 -Ethanediylbis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidenebis (cyclopentadienyl) zirconium dichloride, isopropylidenebis (indenyl) zirconium dichloride, isopropylidenebis (2-methyl Indenyl) zirconium dichloride, isopropylidenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidenebis (2-methyl-4,5,6 7-tetrahydroindenyl) zirconium dichloride, and those in which the transition metal atom of these compounds is replaced by hafnium, or a dihydrido compound in which both chlorine atoms in the “dichloride” portion are replaced by hydrogen atoms, methyl groups, diethylamide groups, dimethyl body,
The bis (diethylamide) form is preferred.

When an asymmetric carbon is generated in these metallocene transition metal compounds, unless otherwise specified,
1 shows one or a mixture of two or more stereoisomers (including a racemate). Examples of the metallocene transition metal compound represented by the formula (2) include the following compounds.

Cyclopentadienyltrimethyltitanium,
Cyclopentadienyltripropyltitanium, methylcyclopentadienyltrimethyltitanium, isopropylcyclopentadienyltrimethyltitanium, 1,2-dimethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadi Enyltripropyltitanium, indenyltriethyltitanium, 2-methylindenyltriethyltitanium, 2,4-dimethylindenyltriethyltitanium,
Tetrahydroindenyltriethyltitanium, 2-methyltetrahydroindenyltriethyltitanium, and compounds in which the titanium atom is replaced by zirconium or hafnium. At least one of the alkyl groups bonded to titanium in these compounds is a halogen atom, an alkoxy group,
A compound substituted with an aryloxy group can also be used.

<Activator> The compound used as an activator in the present invention reacts with (a) an aluminum oxy compound (ii) a Lewis acid and (iii) a metallocene transition metal compound to convert it into a cation. Or at least one compound selected from the group consisting of ionic compounds, and ion-exchange layered silicates.

Examples of the aluminum oxy compound include a cyclic compound represented by the general formula (R-Al-O) _n ,
A chain compound represented by the general formula R (R-Al-O) _n AlR ₂ is used. Here, R is generally an alkyl group having 1 to 8 carbon atoms, and n is an integer of about 1 to 20. Such a compound can be obtained by contacting a solution of a trialkylaluminum in an organic solvent (eg, benzene) with water, or contacting a trialkylaluminum with a hydrate such as copper sulfate hydrate. .

Examples of the Lewis acid include a magnesium-containing Lewis acid, an aluminum-containing Lewis acid, and a boron-containing Lewis acid, and a boron-containing Lewis acid is particularly preferable. Specific examples of the boron-containing Lewis acid include trifluoroborane, triphenylborane, tris (pentafluorophenyl) borane and the like, and tris (pentafluorophenyl) borane is particularly preferred.

The ionic compound capable of reacting with the metallocene-based transition metal compound to convert it into a cation is a salt composed of a cationic compound and an anionic compound, and reacting with the metallocene-based transition metal compound. Thus, the cation is converted to a cation, and the cation and the anion portion form an ion pair, thereby stabilizing the cation. Of these compounds, ionic compounds containing a boron atom are preferably used, such as triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferrocarbon. Cenium tetra (pentafluorophenyl) borate and the like can be mentioned, and N, N-dimethylanilinium tetrakispentafluorophenyl borate is particularly preferable.

The ion-exchangeable layered silicate is a silicate compound having a crystal structure in which surfaces constituted by ionic bonds and the like are stacked in parallel with each other due to weak ionic bonds and the like.
It means that the contained ions are exchangeable. Ion-exchange layered silicates are naturally produced mainly as a main component of clay minerals, but these ion-exchanged layered silicates are not limited to natural ones and may be artificially synthesized.

Specific examples of such ion-exchangeable layered silicates include kaolins such as dickite, nacrite, kaolinite, anoxite, metahalloysite, halloysite, and serpentine members such as chrysotile, lizardite, and antigolite. , Montmorillonite, zaukonite, beidellite, nontronite, saponite, bentonite, hectorite, smectites such as stevensite, vermiculites such as vermiculite,
Illite, sericite, mica such as chlorite, attapulgite, sepiolite, palygorskite, pyrophyllite, talc, chlorite, allophane, imogolite, and the like. These may form a mixed layer.

Among these, montmorillonite, saukonite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite,
Smectites, such as teniolite, vermiculites, and micas are preferred. These ion-exchange layered silicates may be used as they are without any particular treatment, or may be subjected to granulation and classification such as ball mill, sieve powder, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, formic acid, acetic acid, It may be used after treatment such as acid treatment by contact with an organic acid such as benzoic acid or a polyacid such as heteropoly acid. Further, they may be used alone or as a mixture of two or more.

The above-mentioned ion-exchange layered silicate can exchange cations between layers with other cations by utilizing its ion-exchange property. Specifically, Na existing between the layers
⁺ , Li ^{+ and the} like are replaced by treatment with salts, acids, alkalis, organic compounds and the like having other cations.

The ion exchange method is not particularly limited.
For example, ion exchange can be performed by dispersing the ion-exchangeable layered silicate in an aqueous solution of a salt, acid, alkali or organic compound and stirring the resultant. At this time, the ion exchange amount can be adjusted to a desired value by selecting the concentration of salt, acid, alkali or organic compound, temperature, treatment time and the like.

As the acids used for the ion exchange treatment, the above-mentioned acids for the acid treatment can be used. The cations between layers can also be exchanged by treating with ammonium salts such as ammonium chloride and ammonium sulfate and then heating. In addition, salts composed of a cation containing at least one kind of atom selected from Group 2 to 14 atoms and at least one kind of anion can be used for the ion exchange treatment. Examples of such salts include magnesium and aluminum. , Titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, tin, and other chlorides, bromides, iodides, sulfates, nitrates, chlorates, and perchlorates.

Examples of the ion-exchangeable organic compound include monobutylammonium ion, dibutylammonium ion, tributylammonium ion, tetrabutylammonium ion, anilinium ion, dimethylanilinium ion, tetraphenylphosphonium ion, and tetrabutylphosphonium ion. And an organic compound having an ammonium ion or a phosphonium ion having at least one hydrocarbon substituent. Further, organometallic compounds such as porphyrin and crown ether complex salts can be introduced.

By selecting the processing conditions,
It is also possible to exchange atoms in the layer structure. When using these ion-exchangeable layered silicates for the polymerization of the catalyst component obtained in the method of the present invention, the catalyst components may be used in any shape depending on the polymerization equipment used. In particular, when applied to a gas phase polymerization method, a slurry polymerization method, etc., the bulk density of the catalyst and the obtained polymer is increased by granulating and using spherical particles having an average particle size of 5 μm to 1000 μm. This is advantageous in terms of operation because it is possible. More preferably, the particle size is from 20 to 100 μm.

The particles of the ion-exchangeable layered silicate have a crushing strength of 0.2 MPa as measured by a micro-compression tester.
More preferably, it is the above. In addition, when these ion-exchangeable layered silicates are dried under reduced pressure, for example, at 200 ° C. to reduce the water content to 4% by weight or less before reacting with the metallocene-based transition metal compound, the catalytic activity is increased by the contained water. It is preferable without being inhibited.

<Solid Carrier> In the present invention, when the metallocene-based transition metal compound is brought into contact with the activator in the step (A), a solid carrier may be present.
The solid carrier used here is not particularly limited, and for example, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO _2
2 , inorganic compounds such as metal oxides such as B ₂ O ₃ , CaO, ZnO, and BaO, and mixtures thereof; and organic substances such as polymer particles such as polyethylene, polypropylene, and polystyrene. Among them, especially SiO ₂ , Al ₂ O
₃ or mixtures thereof are preferred.

<Step (A): Contact between Metallocene Transition Metal Compound and Activator> The method of contact treatment between the metallocene transition metal compound and the activator is not particularly limited. For example, an inert gas such as nitrogen is used. It is preferable to carry out the reaction under an atmosphere in an inert hydrocarbon solvent such as a paraffinic hydrocarbon such as pentane, hexane and heptane, and an aromatic hydrocarbon solvent such as benzene, toluene and xylene. The contact condition is not particularly limited. For example, the contact temperature is from -20 ° C to 150 ° C.
It is generally carried out at a temperature of between 0 ° C. and particularly between room temperature and the boiling point of the solvent, and the contact time is generally in the range of several minutes to several hours. When an ion exchange layered silicate is used as the activator, the quantitative ratio of the activator and the metallocene transition metal compound is 1 μmol to 1000 μl of the metallocene transition metal compound per 1 g of the activator.
Preferably it is in the amount of μmol.

<Step (B): Contact with α-olefin>
The α-olefin is then contacted with the contact product obtained in the above step (A). This step is usually performed in a slurry state in a hydrocarbon solvent. The type of the hydrocarbon solvent is not particularly limited, and for example, the hydrocarbon solvent used in the above-described contact treatment step can be used as it is.

As the α-olefin, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 3
-Methyl-1-butene, 3-methyl-1-pentene, 4
Olefins such as -methyl-1-pentene, vinylcycloalkane, styrene, derivatives thereof and mixtures thereof are used.

The polymerization of α-olefin proceeds by this contact treatment, and the temperature at this time is -50 to 10
The temperature is preferably 0 ° C., preferably 0 to 100 ° C., and the time is 0.1 to 100 hours, preferably 0.1 to 20 hours. The polymerization amount is 1 g of the solid carrier component.
Is preferably 0.01 to 1000 g, particularly 0.1 to 100 g, particularly preferably 1 to 50 g.

When ethylene is used as the α-olefin, the weight average molecular weight of the obtained polyethylene is preferably 30,000 or more, particularly preferably 50,000 or more. In this step, for example, an organoaluminum compound represented by the following formula (3) may be added as necessary.

[0048]

## STR2 ## ^{_{R 4 c AlX 6 3-c}} (3)

(Wherein, in the formula (3), R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, X ⁶ is an atom or a substituent selected from the group consisting of a halogen atom, a hydrogen atom, an alkoxy group and an amide group) And c is a number satisfying 0 <c ≦ 3.)

Examples of such organoaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethylaluminum hydride, diisobutylaluminum hydride and the like. Halogen-containing alkyl aluminum such as alkyl aluminum hydride, diethyl aluminum chloride and diisobutyl aluminum chloride, alkyl aluminum alkoxide such as diethyl aluminum methoxide and diisobutyl aluminum methoxide, and alkyl aluminum amide such as diethyl aluminum (diethyl amide) and diisobutyl aluminum (diethyl amide) No.

These organoaluminum compounds may be used alone or in combination of two or more such as, for example, a combination of triethylaluminum and triisobutylaluminum, or a combination of a trialkylaluminum and a halogen-containing alkylaluminum. May be used in combination. In addition, aluminoxanes such as methylaluminoxane can also be used.

<Step (C): Addition of Metallocene Transition Metal Compound> In the present invention, a metallocene transition metal compound is further added to the contact product obtained in the above step (B). The metallocene transition metal compound used here may be appropriately selected from those already exemplified, and the step (A)
It may be the same as or different from that used in.

The amount added is 0.1 to 1000 times, preferably 0.2 to 100 times the amount used in step (A). The method of adding the metallocene-based transition metal compound is not particularly limited, but a method of adding the metallocene-based transition metal compound to the contact product obtained in the step (B) as a powder, a method of dissolving it in a solvent such as a hydrocarbon, and a method of adding Further, there is a method in which the product of the step (B) is dried and powdered and then added by any of the above methods. Among these, a method of adding in the presence of a solvent is preferable because uniform mixing can be performed.

<Step (D): Removal and Drying of Solvent> The catalyst component obtained by adding and mixing the metallocene transition metal compound may be used as it is, but if a solvent is used, it is removed. More preferably, it is used as a dry powder.
Drying is generally performed at 0 ° C. under reduced pressure or under a dry inert gas flow.
It is performed at a temperature of 100 ° C.

<Use as Catalyst Component> The catalyst component obtained by the method of the present invention is used for the polymerization of α-olefin. Examples of the α-olefin include so-called olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene and 4-methyl-1-pentene, and vinylcycloalkanes such as vinylcyclohexane. And aromatic vinyl compounds such as ethylidene norbornene derivatives, styrene and styrene derivatives. These monomers can be used for both homopolymerization and copolymerization.

In the polymerization, for example, a liquid medium such as a paraffinic hydrocarbon such as butane, pentane, hexane, heptane, toluene and cyclohexane, an α-olefin or the like, or a liquid phase of a solvent or a monomer substantially does not exist. It is preferable to carry out by gas phase polymerization in the state. The gas phase polymerization can be carried out using a reaction apparatus such as a fluidized bed, a stirred bed, and a stirred fluidized bed equipped with a stirrer / mixer. Although conditions such as polymerization temperature and polymerization pressure are not particularly limited, the polymerization temperature is generally -5.
The temperature is 0 to 200 ° C, preferably 0 to 100 ° C, and the polymerization pressure is usually in the range of 1 to 200 kg / cm ² G, preferably 1 to 50 kg / cm ² G.

[0057]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples unless departing from the gist thereof. The preparation and polymerization of the following catalyst components were all performed in a purified nitrogen atmosphere. The solvent was used after being purified by dehydration with a molecular sieve 13X.

<Measurement Method> (1) Average Particle Size The average particle size is measured by a particle size distribution measuring apparatus (“LMS-24”, manufactured by Seishin Enterprise Co., Ltd.) using a laser diffraction method. Light source: semiconductor laser (wavelength 670 nm). ). In the measurement, ethanol was used as a dispersion medium, and the refractive index was 1.
33, the particle size distribution and the average particle size were calculated as the shape factor of 1.0.

(2) Crushing strength The crushing strength was measured using a micro-crushing tester “MC manufactured by Shimadzu Corporation”
Using "TM-500", the crushing strength of arbitrary 10 or more particles was measured, and the average value was calculated as the crushing strength. (3) Moisture content The moisture content was measured by Karl Fischer titration using a moisture meter vaporizer. The sample used was handled under a nitrogen atmosphere, and the time when the temperature was 200 ° C. and the titration speed was 0.2 μg / sec was defined as the end point of the titration.

<Example 1> (1) Preparation of catalyst component 1.5 L of a catalyst dried at 80 ° C for 2 hours under a stream of dry nitrogen.
Add 600 ml of heptane into the autoclave and stir
The temperature was controlled at 30 ° C. As an activator
Chromium nitrate removes sodium ions in mica
Trivalent chromium ion treated with salts to exchange for cation
Granules of exchangeable synthetic mica (average particle size 35 μm, crush strength
2.5 MPa) was previously dried under reduced pressure at 200 ° C. for 2 hours.
Using 10.0 g of a water content of 0.5 wt%,
Bis (n-butyl) as a metallocene transition metal compound
Cyclopentadienyl) hafnium dichloride 39m
g of 200 ml of heptane solution and add about 0.5 k with nitrogen.
g / cm^TwoAfter pressurizing to G (gauge pressure),
Stirred for minutes. Then hept of triethyl aluminum
Tan solution (1.1 g phase as triethylaluminum)
After the addition of (ii), the temperature was raised to 60 ° C, and the temperature was maintained.
And stirred for 10 minutes. Internal pressure is 0.2kg / cm ^TwoG
The process (A) was completed by purging with nitrogen until the temperature was lowered.

Subsequent to the step (A), ethylene is added to 0.1.
It was supplied into the system at a rate of 45 L / min. The supply of ethylene was continued until the integrated supply reached about 7 times the amount of the synthetic mica charged. After the completion of the supply, ethylene was purged while cooling the autoclave to complete the step (B). After purging with ethylene, the content was withdrawn from the autoclave withdrawal line into a flask having a 2 L internal volume sufficiently purged with nitrogen, the autoclave was washed with 500 ml of heptane, and the washing liquid was added to the flask. After the flask was allowed to stand and solids settled, 950 ml of the supernatant in the flask was removed by decantation. 361 mg of bis (n-butylcyclopentadienyl) hafnium dichloride which is a metallocene transition metal compound is added to the remaining slurry.
Was added in the solid state, and the mixture was stirred at room temperature for 15 minutes, and the obtained solid was dried under reduced pressure at 70 ° C. for 2 hours to complete the steps (C) and (D) to obtain a catalyst component.

(2) Olefin Polymerization In a stainless steel autoclave having a capacity of 3.0 L, which had been dried at 100 ° C. for 30 minutes under a stream of nitrogen, 1500 ml of heptane at room temperature was added to the catalyst component prepared in the above (1). 0.8 g (corresponding to 0.1 g as synthetic mica), a heptane solution of triethylaluminum (corresponding to 280 mg of triethylaluminum), and 80 ml of 1-butene were introduced. At the same time as raising the temperature to 80 ° C, the total pressure is 22k
g / cm ² G until ethylene was charged to initiate polymerization. After the polymerization was carried out for 1 hour while maintaining the total pressure at 22 kg / cm ² G, the system was cooled, ethylene was purged to extract a polymer slurry, and the mixture was filtered. The obtained polymer was 10
After drying at 0 ° C. for 12 hours, 180.3 g of ethylene / 1
-A butene copolymer was obtained. Table 1 shows the results.

Example 2 30 ° C. at 100 ° C. under nitrogen flow
100 g of dried sodium chloride was introduced into a 1.5 L stainless steel autoclave that had been dried for 5 minutes, and the temperature was raised to 50 ° C. When the temperature was stabilized, a solution of triethylaluminum in heptane (equivalent to 50 mg of triethylaluminum) and Example 1 (1)
0.64 g of the catalyst component prepared in
8 g), and the inside of the system was replaced with ethylene. Then, the temperature was raised to 85 ° C., and at the same time, the total pressure was 0.69 MPa.
The polymerization was started by charging ethylene until a-G was reached.
Maintaining the total pressure at 0.69 MPa-G,
Polymerization was performed for minutes. Thereafter, sodium chloride was removed by washing with water to obtain a polymer. The polymer is treated at 50 ° C. for 6 hours.
After drying under reduced pressure at 80 ° C for 3 hours,
5.9 g of polyethylene were obtained. Table 1 shows the results.

Comparative Example 1 (1) Preparation of Catalyst Component Before contacting ethylene with bis (n-butylcyclopentadienyl) hafnium dichloride, a metallocene-based transition metal compound, 390 mg of the entire amount was added. A catalyst component was prepared in the same manner as in Example 1, (1) except that it was not added after the treatment (the step (C) was not performed). (2) Olefin polymerization Example 1 (2) using the catalyst component produced in (1) above.
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

<Comparative Example 2> (1) Preparation of Catalyst After performing step (A) in the same manner as in Example 1, the content was sufficiently purged with nitrogen from the extraction line below the autoclave without performing step (B). The displaced flask was withdrawn into a 2 L internal volume flask, the autoclave was washed with 500 ml of heptane, and the washing solution was added to the flask. After the flask was allowed to stand and a solid content settled, 950 ml of the supernatant in the flask was removed by decantation. 7
The catalyst was dried under reduced pressure at 0 ° C. for 2 hours to prepare a catalyst component. (2) Polymerization of olefin Example 1 (2) using the catalyst component produced in (1) above.
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

Example 3 (1) Preparation of Catalyst Component Instead of bis (n-butylcyclopentadienyl) hafnium dichloride, bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride was used. A catalyst component was prepared in the same manner as in Example 1 (1) except that 35 mg was used in step (A) and 311 mg was used in step (C). (2) Polymerization of olefin Example 1 (2) using the catalyst component produced in (1) above.
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

Comparative Example 3 (1) Preparation of Catalyst Component Bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride was added in a total amount of 346 mg before contact with ethylene, and after decantation. A catalyst component was prepared in the same manner as in Example 3 (1), except that was not added (step (C) was not performed). (2) Polymerization Example 1 (2) using the catalyst component produced in (1) above.
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

Example 4 (1) Preparation of Catalyst Instead of bis (n-butylcyclopentadienyl) hafnium dichloride, bis (2-methyl-4,5,6,6) was used.
A catalyst component was prepared in the same manner as in Example 1 (1), except that 34 mg of 7-tetrahydroindenyl) zirconium dichloride was used in step (A) and 308 mg in step (C). (2) Polymerization Example 1 (2) using the catalyst component produced in (1) above.
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

Comparative Example 4 (1) Preparation of Catalyst Bis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride was added to a total amount of 342 mg before contacting with ethylene, followed by decantation. A catalyst component was prepared in the same manner as in Example 4 (1), except that it was not added later (the step (C) was not performed). (2) Polymerization Example 1 (2) using the catalyst component produced in (1) above.
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

[0070]

[Table 1]

<Evaluation of Results> From the results shown in Table 1, the polymer produced using the catalyst component prepared by the method of the present invention has a higher yield than the polymer obtained by the method of Comparative Example. It can be seen that the bulk density is also high.

[0072]

According to the method of the present invention, a solid catalyst component having high polymerization activity is obtained, and by using this to carry out olefin polymerization, a polymer having a high bulk density and a small amount of fine powder can be produced. it can.

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Claims (9)

[Claims] 1. A method for producing a catalyst component for olefin polymerization, comprising the following steps (A) to (C). (A) Step of contacting a metallocene-based transition metal compound with an activator (B) Step of contacting an α-olefin with the contact product obtained in (A) above (C) Obtained in (B) above Step of adding a metallocene transition metal compound to the contact product 2. The method according to claim 1, wherein the activator is an aluminum oxy compound,
The olefin polymerization according to claim 1, wherein the olefin polymerization is at least one compound selected from the group consisting of a Lewis acid and an ionic compound capable of reacting with a metallocene-based transition metal compound to convert it into a cation. For producing a catalyst component for use. 3. The method for producing a catalyst component for olefin polymerization according to claim 1, wherein the activator is an ion-exchange layered silicate. 4. The olefin polymerization according to claim 3, wherein the ion-exchanged layered silicate is an ion-exchanged layered silicate having a water content of 4% by weight or less, obtained by performing a salt treatment or an acid treatment. For producing catalyst components for 5. The ion-exchange layered silicate is a spherical particle having an average particle diameter of 5 to 1000 μm.
3. The method for producing a catalyst component for olefin polymerization according to item 1. 6. The process for producing a catalyst component for olefin polymerization according to claim 5, wherein the particles of the ion-exchange layered silicate have a crushing strength of 0.2 MPa or more as measured by a micro compression tester. 7. The process for producing a catalyst component for olefin polymerization according to claim 1, wherein the step (A) is carried out in an inert hydrocarbon solvent. 8. The process for producing a catalyst component for olefin polymerization according to claim 1, wherein the step (B) is carried out in the presence of an organoaluminum compound. 9. The method for producing a catalyst component for olefin polymerization according to claim 7, wherein the following step (D) is performed following steps (A) to (C). (D) Step of removing and drying the solvent to obtain a solid catalyst component