JPH09278818A - Catalyst for olefin polymerization and production of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerization catalyst which has a high activity per unit amount of a transition metal and per unit amount of an aluminum component and with which a polymer having excellent powder properties is obtained. SOLUTION: Ethylene is contacted with catalyst ingredients comprising (A) a metallocene transition metal compound and (B) spherical clay mineral particles, a clay, or a lamellar ion-exchange compound, and optionally further containing (C) an organoaluminum compound to conduct prepolymerization. Thus, a polyethylene having a weight-average mol.wt. measured by GPC of 30,000 or higher is formed in an amount of 0.01-1,000g per g of the component (B) to produce the objective catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and a method for obtaining an olefin polymer with a high yield and an excellent particle shape and powder property by the catalyst. More specifically, when the present invention is applied to a slurry polymerization method or a gas phase polymerization method, it is possible to produce an olefin polymer having a high bulk density, crushing particles, and producing an excellent powder property without generation of fine powder. TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and a method for obtaining an olefin polymer in high yield using this catalyst.

[0002]

2. Description of the Related Art When an olefin is polymerized in the presence of a catalyst to produce an olefin polymer, (1)
A method using a metallocene compound and a compound comprising (2) aluminoxane is already known (Japanese Patent Publication No. 4-12).
283, JP-A-60-35007, etc.). The polymerization method using these catalysts has a higher polymerization activity per transition metal than the conventional method using a so-called Ziegler-Natta catalyst, and a polymer having a narrow molecular weight distribution or composition distribution can be obtained.

However, these catalyst systems are often soluble in the reaction system, and the olefin polymer obtained by slurry polymerization or gas phase polymerization has extremely poor particle properties, which is a major problem in the production process. Has become. In order to solve these problems, a catalyst in which one or both of a transition metal compound and an aluminoxane are supported on an inorganic oxide or an organic substance such as silica or alumina has been proposed (Japanese Patent Laid-Open No. 60-35007). 61-3
1404, 61-108610, 61.
-276805 and 61-296008). However, the polymers obtained by these methods are
There are many fine powders and coarse particles, and many of them have poor particle properties such as low bulk density, and further have low polymerization activity per solid catalyst component. The present inventors have previously proposed a catalyst having high activity and excellent particle properties and an olefin polymerization method using the same (Japanese Patent Laid-Open No. 7-228621).
However, crushing of particles and generation of fine powder were observed in the actual polymerization reaction, which was not always sufficient.

[0004]

The present invention has a high polymerization activity per transition metal and per aluminum component.
Another object of the present invention is to provide a catalyst having excellent particle properties of the obtained polymer.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve such an object, and as a result, found that the molecular weight of polyethylene produced by prepolymerization plays a very important role in the polymerization activity and particle properties. The present invention has been reached.
That is, the present invention relates to [A] a metallocene-based transition metal compound, [B] a clay mineral having a spherical particle shape, a clay or ion-exchange layered compound, and optionally [C].
Ethylene is brought into contact with a catalyst component composed of an organoaluminum compound to give polyethylene having a weight average molecular weight of 30,000 or more by GPC of 0.01 to 1 g per 1 g of the component [B]
Olefin polymerization catalyst formed by prepolymerizing 1000 g, and a method for producing an olefin polymer characterized by polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst and optionally an organoaluminum compound. Is provided.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The atom designations used in this invention are those recommended by IUPAC in 1989.
It is based on the periodic rate of the tribe system. The metallocene-based transition metal compound which is the component [A] used in the catalyst of the present invention has one or two optionally substituted cyclopentadienyl-based ligands, that is, substituents bonded to form a condensed ring. An organometallic compound comprising 1 to 2 cyclopentadienyl ring-containing ligands which may be formed and a transition metal of Groups 3, 4, 5 and 6 of the long periodic table, or a cation-type complex thereof is there. Preferred as such metallocene-based transition metal compound is the following general formula [1] or [2]
It is a compound represented by these.

[0007]

(CpR ¹ _a H _5-a ) _p (CpR ² _b H _5-b ) _q MR ³ _r ... [1] [(CpR ¹ _a H _5-a ) _p (CpR ² _b H _5-b ) _Q MR ³ _r L _m ] ^{n +} [R ⁴ ] ⁿ -... [2]

Here, a and b are in the range of 0 to 5, and Cp
R ¹ _a H _5-a and CpR ² _b H _{5- b} represent a cyclopentadienyl (Cp) group or a derivative thereof. [1],
[2] In the formula, R ¹ and R ² are an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing substituent, a phosphorus-containing substituent, a nitrogen-containing substituent, and an oxygen-containing substituent But it can be different.

Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-
Butyl group, pentyl group, isopentyl group, hexyl group,
Alkyl group such as heptyl group, octyl group, nonyl group, decyl group, phenyl group, p-tolyl group, o-tolyl group, m
-Aryl group such as tolyl group, fluoromethyl group, fluoroethyl group, fluorophenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, bromomethyl group, bromoethyl group, bromophenyl group, iodomethyl group, iodoethyl group, iodophenyl group, etc. A halo-substituted hydrocarbon group, a trimethylsilyl group, a triethylsilyl group, a silicon-containing substituent such as a triphenylsilyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and a t-butoxy group. Examples thereof include an alkoxy group, a phenoxy group, a methylphenoxy group, a pentamethylphenoxy group, a p-tolyloxy group, an m-tolyloxy group, and an aryloxy group such as an o-tolyloxy group. Of these, a methyl group, an ethyl group,
Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a propyl group, an isopropyl group, a butyl group, an isobutyl group and a t-butyl group, an alkoxy group such as a trimethylsilyl group and a methoxy group, and an aryloxy group such as a phenoxy group.

R ¹ and R ² may be bonded to each other to form a cross-linking group. Specifically, methylene group, alkylene group such as ethylene group, ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group, alkylidene group such as diphenylmethylidene group, dimethylsilylene group, diethylsilylene group, dialkyl group Silicon-containing cross-linking groups such as propyl silylene group, diisopropyl silylene group, diphenyl silylene group, methyl ethyl silylene group, methylphenyl silylene group, methyl isopropyl silylene group, methyl-t-butyl silylene group, dimethylgermylene group, diethylgermylene group Gels such as group, dipropylgermylene group, diisopropylgermylene group, diphenylgermylene group, methylethylgermylene group, methylphenylgermylene group, methylisopropylgermylene group, methyl-t-butylgermylene group Sulfonium-containing crosslinking group such as an amino group etc., phosphinyl group, and the like.

Further, R ^{1 s} or R ^{2 s} may be bonded to each other to form a ring. Specific examples thereof include an indenyl group, a tetrahydroindenyl group, a fluorenyl group and an octahydrofluorenyl group, which may be substituted. R ³ is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted, hydrogen, halogen, a silicon-containing substituent, an alkoxy group, an aryloxy group, an amido group, or a thioalkoxy group, and specifically, methyl Group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and other alkyl groups, phenyl group, Aryl group such as p-tolyl group, o-tolyl group, m-tolyl group, fluoromethyl group, fluoroethyl group, fluorophenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, bromomethyl group, bromoethyl group, bromophenyl group , Halo-substituted hydrocarbon groups such as iodomethyl group, iodoethyl group and iodophenyl group, fluorine, chlorine, odor , Halogen such as iodine, trimethylsilyl group,
Triethylsilyl group, silicon-containing substituents such as triphenylsilyl group, methoxy group, ethoxy group, propoxy group,
Isopropoxy group, butoxy group, isobutoxy group, t-
Alkoxy groups such as butoxy group, phenoxy, methylphenoxy, pentamethylphenoxy group, p-tolyloxy group, m-tolyloxy group, aryloxy groups such as o-tolyloxy group, dimethylamide group, diethylamide group,
Dipropylamide group, diisopropylamide group, ethyl-t-butylamide group, amide group such as bis (trimethylsilyl) amide group, methylthioalkoxy group, ethylthioalkoxy group, propylthioalkoxy group, butylthioalkoxy group, t-butylthio group Examples thereof include thioalkoxy groups such as alkoxy groups and phenylthioalkoxy groups. Of these, preferred are hydrogen, methyl group, ethyl group, propyl group, isopropyl group, butyl group, phenyl group, halogen such as chlorine, methoxy group, ethoxy group, propoxy group, isopropoxy group, dimethylamide group, methylthioalkoxy group. And hydrogen, a methyl group, and chlorine are particularly preferable.

R^ThreeIs R¹Or R^TwoOr C
and a specific example of such a ligand.
And CpH_Four(CH_Two)_nO- (1 ≦ n ≦ 5), Cp
Me _Four(CH_Two)_nO- (1 ≦ n ≦ 5), CpH_Four(M
e_TwoSi) (t-Bu) N-, Cp (Me_Four(Me_TwoS
i) (t-Bu) N- etc. (Cp is cyclopentadienyl)
Group, Me represents methyl, and Bu represents a butyl group).
You.

Further, R^ThreeBound to each other and bidentate ligand
May be formed. Such R^ThreeAs a specific example of
-OCH_TwoO-, -OCH_TwoCH_TwoO-, -O (o-C
₆H _Four) O- and the like. M is the periodic table 3rd, 4th,
Atoms of groups 5 and 6, specifically, scandium and iodine
Thorium, lanthanum, cerium, praseodymium, neo
Jim, samarium, europium, gadolinium, tell
Bium, Dysprosium, Holmium, Erbium, Tu
Lithium, ytterbium, lutium, actinium,
Thorium, protactinium, uranium, titanium,
Zirconium, hafnium, vanadium, niobium, tan
Tal, chrome, molybdenum, tungsten
You. Of these, Group 4 titanium, zirconium,
Haunium is preferably used. Also these are mixed
You may use it.

L is an electrically neutral ligand, and m is an integer of 0 or more, specifically diethyl ether,
Ethers such as tetrahydrofuran, dioxane,
Examples thereof include nitriles such as acetonitrile, amides such as dimethylformamide, phosphines such as trimethylphosphine, and amines such as trimethylamine. Preferred are tetrahydrofuran, trimethylphosphine and trimethylamine.

[R ⁴ ] ^n- is one or more anions that neutralize cations, and specific examples include tetraphenylborate, tetra (p-tolyl) borate, carbadodecaborate and dicarbaundeca. Examples thereof include borate, tetrakis (pentafluorophenyl) borate, tetrafluoroborate, hexafluorophosphate and the like. Preferably, tetraphenyl borate,
Tetra (p-tolyl) borate, tetrafluoroborate and hexafluorophosphate. a and b are 0
Is an integer of up to 5. Also, p, q, and r are the valences of M
When the metallocene-based transition metal compound is of the formula [1], it is 0 or a positive integer satisfying p + q + r = V. When the metallocene-based transition metal compound is of the formula [2], p + q + r = V. It is 0 or a positive integer that satisfies −n. Usually, p and q are integers of 0 to 3, preferably 0 or 1.
It is. r is an integer of 0 to 3, preferably 1 or 2. n is an integer satisfying 0 ≦ n ≦ V.

The catalyst of the present invention can produce any of an isotactic polymer, a syndiotactic polymer and an atactic polymer. The metallocene-based transition metal compounds described above specifically include bis (methylcyclopentadienyl) zirconium dichloride and bis (ethylcyclopentadienyl) as compounds corresponding to the formula [1] when zirconium is taken as an example. ) Zirconium dichloride, bis (methylcyclopentadienyl) zirconium dimethyl, bis (ethylcyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dihydride, bis (ethylcyclopentadienyl) zirconium dihydrogen Compound, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (ethyltetrame Le cyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride,
Bis (dimethylcyclopentadienyl) zirconium dimethyl, bis (trimethylcyclopentadienyl) zirconium dimethyl, bis (tetramethylcyclopentadienyl) zirconium dimethyl, bis (ethyltetramethylcyclopentadienyl) zirconium dimethyl, bis (indenyl) ) Zirconium dimethyl, bis (dimethylcyclopentadienyl) zirconium dihydride, bis (trimethylcyclopentadienyl) zirconium dihydride, bis (ethyltetramethylcyclopentadienyl) zirconium dihydride, bis (trimethylsilylcyclopenta) Dienyl) zirconium dimethyl, bis (trimethylsilylcyclopentadienyl) zirconium dihydride, bis (trifluoromethylcyclopentadienyl) zirco Umujikuroraido, bis (trifluoromethyl cyclopentadienyl) zirconium dimethyl, bis (trifluoromethyl cyclopentadienyl)
Zirconium dihydride, isopropylidene-bis (indenyl) zirconium dichloride, isopropylidene-bis (indenyl) zirconium dimethyl, isopropylidene-bis (indenyl) zirconium dihydride, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium Dichloride, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, ethyl tetramethylcyclopentadienyl (cyclopentadienyl) zirconium dihydrogen Compound, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl Zirconium dimethyl, dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dihydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) Zirconium dimethyl, bis (cyclopentadienyl) zirconium diethyl, bis (cyclopentadienyl) zirconium dipropyl, bis (cyclopentadienyl) zirconium diphenyl, methylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, ethylcyclo Pentadienyl (cyclopentadienyl) zirconium dichloride, Methylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, Ethyl Cyclopentadienyl (cyclopentadienyl) zirconium dimethyl, methylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, ethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, dimethylcyclopentadienyl (Cyclopentadienyl) zirconium dichloride, trimethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, tetramethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, Tetramethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, indenyl (cyclopentadienyl) zirconium dichloride, dime Tylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, trimethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, tetramethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadiene) (Enyl) zirconium dimethyl, ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, indenyl (cyclopentadienyl) zirconium dimethyl, dimethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, trimethylcyclopenta Dienyl (cyclopentadienyl) zirconium dihydride, bis (pentamethylcyclopentadienyl) zirconium dihydride, indenyl (cyclopen Dienyl) zirconium dihydride, trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, trifluoromethylcyclopentadienyl (cyclopentadienyl) Zirconium dichloride, trifluoromethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, trifluoromethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, bis (cyclopentadienyl) (trimethylsilyl) (methyl) Zirconium, bis (cyclopentadienyl) (triphenylsilyl) (methyl) zirconium, bis (cyclopentadienyl) [tris (trimethylsilyl) silyl ]
(Methyl) zirconium, bis (cyclopentadienyl) [bis (methylsilyl) silyl] (methyl) zirconium, bis (cyclopentadienyl) (trimethylsilyl) (trimethylsilylmethyl) zirconium, bis (cyclopentadienyl) (trimethylsilyl) (Benzyl) zirconium, methylene-bis (cyclopentadienyl) zirconium dichloride, ethylene-bis (cyclopentadienyl) zirconium dichloride,
Isopropylidene-bis (cyclopentadienyl) zirconium dichloride, dimethylsilyl-bis (cyclopentadienyl) zirconium dichloride, methylene-bis (cyclopentadienyl) zirconium dimethyl, ethylene-bis (cyclopentadienyl) zirconium dimethyl, Isopropylidene-bis (cyclopentadienyl) zirconium dimethyl, dimethylsilyl-bis (cyclopentadienyl) zirconium dimethyl, methylene-bis (cyclopentadienyl) zirconium dihydride, ethylene-bis (cyclopentadienyl) zirconium Dihydride, isopropylidene-bis (cyclopentadienyl) zirconium dihydride, dimethylsilyl-bis (cyclopentadienyl) zirconium dihydride, bis (cyd Lopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (cyclopentadienyl) Zirconium trifluoromethanesulfonato chloride, bis (cyclopentadienyl) zirconium bis (benzene sulfonate), bis (cyclopentadienyl) zirconium bis (pentafluorobenzene sulfonate), bis (cyclopentadienyl) zirconium benzene sulfonate Chloride, bis (cyclopentadienyl) zirconium (ethoxy) trifluoromethanesulfonate, bis (tetramethylcyclopentadienyl)
Zirconium bis (trifluoromethanesulfonate),
Bis (indenyl) zirconium bis (trifluoromethane sulfonate), ethylene bis (indenyl) zirconium bis (trifluoromethane sulfonate), isopropylidene-bis (indenyl) zirconium bis (trifluoromethane sulfonate), (tertiary butylamide) dimethyl (Tetramethylcyclopentadienyl) silanedibenzylzirconium (tertiary butylamido) dimethyl (2,3,4,5-tetramethylcyclopentadienyl) silanedibenzylzirconium, indenylzirconium tris (dimethylamide), inde Nylzirconium tris (diethylamide), indenylzirconium tris (di-n-propylamide), cyclopentadienylzirconium tris (dimethylamide), methylcyclopentadi Nyl zirconium tris (dimethylamide), (tertiary butylamide) (tetramethylcyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (methylamide)-(tetramethylcyclopentadienyl) -1,2-ethane Diyl zirconium dichloride, (ethylamido) (tetramethylcyclopentadienyl) methylene zirconium dichloride, (tertiary butylamido) dimethyl- (tetramethylcyclopentadienyl) silane zirconium dichloride, (benzylamido) dimethyl (tetramethylcyclopentadienyl) (Enyl) silane zirconium dichloride,
(Phenylphosphido) dimethyl (tetramethylcyclopentadienyl) silane zirconium dibenzyl, (phenylamido) dimethyl (tetramethylcyclopentadienyl) silane zirconium dichloride, (2-methoxyphenylamido) dimethyl (tetramethylcyclopentadiene) (Enyl) silane zirconium dichloride, (4
-Fluorophenylamido) dimethyl (tetramethylcyclopentadienyl) silanezirconium dichloride, ((2,6-di (1-methylethyl) phenyl) amido) dimethyl (tetramethylcyclopentadienyl)
And amido zirconium dichloride.

Examples of the compound corresponding to the general formula [2] include bis (methylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex and bis (ethylcyclopentadienyl) zirconium (chloride) ( Tetraphenyl borate)
Tetrahydrofuran complex, bis (methylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (ethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (methylcyclopentadienyl) ) Zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (ethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (dimethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) Tetrahydrofuran complex, bis (trimethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydro Orchid complex, bis (tetramethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (ethyltetramethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (indenyl) Zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (dimethylcyclopentadienyl)
Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (trimethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (tetramethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) Tetrahydrofuran complex, bis (ethyltetramethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (indenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (dimethylcyclopentadienyl) zirconium (Hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (trimethylcyclopentadienyl) zirconium Chloride) (tetraphenylborate) tetrahydrofuran complex, bis (ethyl tetramethylcyclopentadienyl) zirconium (hydride)
(Tetraphenyl borate) tetrahydrofuran complex,
Bis (trimethylsilylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (trimethylsilylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (trifluoromethylcyclopentadienyl) Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (trifluoromethylcyclopentadienyl)
Zirconium (hydride) (tetraphenylborate)
Tetrahydrofuran complex, isopropylidene-bis (indenyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (indenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (indenyl) zirconium ( (Hydrido) (tetraphenylborate) tetrahydrofuran complex, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) ) (Tetraphenyl borate)
Tetrahydrofuran complex, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran Complex, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex , Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium (chloride) (tetraphenylborate) tetra Drofuran complex, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (Cyclopentadienyl) zirconium (chloride)
(Tetraphenyl borate) tetrahydrofuran complex,
Bis (cyclopentadienyl) (methyl) zirconium (tetraphenylborate) tetrahydrofuran complex,
Bis (cyclopentadienyl) (ethyl) zirconium (tetraphenylborate) tetrahydrofuran complex,
Bis (cyclopentadienyl) (propyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (phenyl) zirconium (tetraphenylborate) tetrahydrofuran complex, methylcyclopentadienyl (cyclopentadienyl) zirconium (Chloride) (tetraphenylborate) tetrahydrofuran complex, ethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (ethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate ) Tetrahydrofuran complex, methylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) Lahydrofuran complex, ethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, methylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, ethyl Cyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, dimethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, trimethylcyclopentadienyl (Cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, tetramethylcyclyl Pentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (pentamethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, indenyl (cyclopentadienyl) zirconium (chloride) ) (Tetraphenylborate) tetrahydrofuran complex, dimethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, trimethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenyl Borate) tetrahydrofuran complex, tetramethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl ) (Tetraphenylborate) tetrahydrofuran complex, bis (pentamethylcyclopentadienyl)
Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, cyclopentadienyl (indenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, dimethylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate ) Tetrahydrofuran complex, trimethylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (pentamethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, indenyl ( Cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, trimethylsilane Lecyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, trifluoromethylcyclo Pentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (trimethylsilyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (triphenyl (Silyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) [tris (trimethylsilyl) Silyl] zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (trimethylsilylmethyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl)
(Benzyl) zirconium (tetraphenylborate)
Tetrahydrofuran complex, methylene-bis (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, ethylene-bis (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis ( Cyclopentadienyl)
Zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, dimethylsilyl-bis (cyclopentadienyl) zirconium (chloride)
(Tetraphenyl borate) tetrahydrofuran complex,
Methylene-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, ethylene-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, isopropylidene-bis (cyclopentadiene) (Enyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, dimethylsilyl-bis (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, methylene-bis (cyclopentadienyl) zirconium (hydride) ( Tetraphenylborate) tetrahydrofuran complex, ethylene-bis (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydro Run complex, isopropylidene - bis (cyclopentadienyl) zirconium (hydride)
(Tetraphenyl borate) tetrahydrofuran complex,
Dimethylsilyl-bis (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) zirconium (methanesulfonato) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) Zirconium (p-toluenesulfonato) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) zirconium (trifluoromethanesulfonato) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) zirconium (benzenesulfonato) ) (Tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) zirconium (pentafluorobenzenesulfonato) (tetraphe Ruborate) tetrahydrofuran complex, bis (tetramethylcyclopentadienyl) zirconium (trifluoromethanesulfonate) (tetraphenylborate) tetrahydrofuran complex, bis (indenyl) zirconium (trifluoromethanesulfonate) (tetraphenylborate) tetrahydrofuran complex, ethylenebis (Indenyl) zirconium (trifluoromethanesulfonato) (tetraphenylborate)
Tetrahydrofuran complex, isopropylidene-bis (indenyl) zirconium (trifluoromethanesulfonato) (tetraphenylborate) tetrahydrofuran complex and the like.

Further, regarding other Group 3, 4, 5, and 6 metal compounds such as titanium compounds and hafnium compounds,
The same compounds as described above can be mentioned. Further, a mixture of these compounds may be used. In the present invention, as the component (B), clay, clay minerals or ion-exchangeable layered compounds are used. Clay minerals are minerals whose main component is silicate, and clay is usually composed mainly of clay minerals. Further, the ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak binding force to each other, and means a compound whose contained ions are exchangeable. Most clay minerals are ion-exchangeable layered compounds. Further, these clays, clay minerals, and ion-exchange layered compounds are not limited to naturally-occurring ones, but may be artificially synthesized ones.

As the component [B], clay, clay minerals, hexagonal closest packing type, antimony type, CdCl ₂
Examples thereof include ionic crystalline compounds having a layered crystal structure such as C type and CdI ₂ type. Specific examples of the component [B] include kaolin, bentonite, kibushi clay, gairome clay, allophane, hissingelite, pyrophyllite, talc, ummo group, montmorillonite group, vermiculite, ryokdee group, palygorskite, kaolinite, nacrite. , Dickite, halloysite and the like.

When a compound having a pore volume of 20 Å or more and a pore volume of 0.1 cc / g or less is used as the component (B), it tends to be difficult to obtain high polymerization activity. Also, S
A colloidal inorganic compound such as iO ₂ may be allowed to coexist. Examples of pillars include oxides formed by intercalating the above hydroxide ions between layers and then heating and dehydrating.

The component [B] may be used as it is, or may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Further, they may be used alone or as a mixture of two or more of the above solids. In the present invention, preferred as the component [B] is water content of 3% by weight or less, which is obtained by performing salt treatment and / or acid treatment.
It is at least one compound selected from the group consisting of (1) ion-exchange layered compounds excluding silicates and (2) inorganic silicates.

An excellent component [B] can be obtained by salt treatment and / or acid treatment of at least one compound selected from the group consisting of ion-exchange layered compounds other than silicates and inorganic silicates. The acid strength of the solid can be changed by salt treatment and / or acid treatment. In addition, the salt treatment forms an ion complex, a molecular complex, an organic derivative, and the like, and can change the surface area and the interlayer distance. That is, by utilizing the ion exchange property and substituting the exchangeable ion between layers with another large bulky ion, it is possible to obtain a layered material in a state where the layers are expanded. In the present invention, the exchangeable Group 1 metal cations of at least one compound selected from the group consisting of ion-exchangeable layered compounds excluding silicates and inorganic silicates before being treated with salts are used. 40% or more, preferably 6
0% or more of cations dissociated from salts shown below,
Ion exchange is required.

The present invention for the purpose of such ion exchange
The salt used in the salt treatment of is composed of a group 2-14 atom.
A cation containing at least one atom selected from the group
A compound containing, preferably a group 2-14 atom
A positive atom containing at least one atom selected from the group consisting of
Consists of ions, halogen atoms, inorganic acids and organic acids
Composed of at least one anion selected from the group
Compound, and more preferably from 2 to 14 group atoms
Cation containing at least one atom selected from the group
And Cl, Br, I, F, PO_Four, SO_Two, NO_Three, C
O_Three, C_TwoO_Four, ClO_Four, OOCCH_Three, CH_ThreeCO
CHCOCH_Three, OCl_Two, O (NO_Three) _Two, O (Cl
O_Four)_Two, O (SO_Four), OH, O_TwoCl_Two, OC
l_Three, OOCH, OOCCH_TwoCH_Three, C_TwoH_FourO_FourOh
And C_FiveH_FiveO₇At least one selected from the group consisting of
It is a compound consisting of anions of species.

Specifically, CaCl_Two, CaSO_Four, C
aC_TwoO_Four, Ca (NO_Three)_Two, Ca_Three(C₆H
_FiveO₇)_Two, MgCl_Two, MgBr_Two, MgSO_Four, M
g (PO_Four)_Two, Mg (ClO_Four)_Two, MgC_TwoO_Four,
Mg (NO_Three)_Two, Mg (OOCCH_Three)_Two, MgC_Four
H_FourO_Four, Sc (OOCCH_Three)_Two, Sc_Two(CO_Three)
_Three, Sc_Two(C_TwoO_Four)_Three, Sc (NO_Three)_Three, Sc_Two
(SO_Four)_Three, ScF_Three, ScCl_Three, ScBr_Three, S
cI_Three, Y (OOCCH_Three)_Three, Y (CH_ThreeCOCHC
OCH_Three)_Three, Y_Two(CO_Three)_Three, Y_Two(C
_TwoO_Four)_Three, Y (NO_Three)_Three, Y (ClO_Four)_Three, YP
O_Four, Y_Two(SO_Four)_Three, YF_Three, YCl_Three, La (O
OCCH_Three)_Three, La (CH_ThreeCOCHCOC
H_Three)_Three, La_Two(CO_Three)_Three, La (NO_Three)_Three, L
a (ClO_Four)_Three, La_Two(C_TwoO_Four)_Three, LaP
O_Four, La_Three(SO_Four)_Three, LaF_Three, LaCl_Three, L
aBr_Three, LaI_Three, Sm (OOCCH_Three)_Three, Sm
(CH_ThreeCOCHCOCH_Three)_Three, Sm_Two(C
O_Three)_Three, Sm (NO_Three)_Three, Sm (ClO_Four)_Three, S
m_Two(C_TwoO_Four)_Three, Sm_Two(SO_Four)_Three, SmF_Three,
SmCl_Three, SmI_Three, YP (OOCCH_Three)_Three, Yb
(NO _Three)_Three, Yb (ClO_Four)_Three, Yb (C_TwoO_Four)
_Three, Yb_Two(SO_Four)_Three, YbF_Three, YbCl_Three, Ti
(OOCCH_Three)_Four, Ti (CO_Three)_Two, Ti (N
O_Three)_Four, Ti (SO_Four)_Two, TiF_Four, TiCl_Four,
TiBr_Four, TiI_Four, Zr (OOCCH_Three)_Four, Zr
(CH_ThreeCOCHCOCH_Three)_Four, Zr (CO_Three)_Two,
Zr (NO_Three)_Four, Zr (SO_Four)_Two, ZrF_Four, Zr
Cl_Four, ZrBr_Four, ZrI_Four, ZrOCl_Two, ZrO
(NO_Three)_Two, ZrO (ClO_Four)_Two, ZrO (S
O_Four), Hf (OOCCH_Three)_Four, Hf (CO_Three)_Two,
Hf (NO_Three)_Four, Hf (SO_Four)_Two, HfOCl_Two,
HfF_Four, HfCl_Four, HfBr_Four, HfI _Four, V (C
H_ThreeCOCHCOCH_Three)_Three, VOSO_Four, VOC
l_Three, VCl_Three, VCl_Four, VBr_Three, Nb (CH_ThreeC
OCHCOCH_Three)_Five, Nb_Two(CO_Three) _Five, Nb (N
O_Three)_Five, Nb_Two(SO_Four)_Five, NbF_Five, NbC
l_Five, NbBr _Five, NbI_Five, Ta (OOCC
H_Three)_Five, Ta_Two(CO_Three)_Five, Ta (NO_Three) _Five, T
a_Two(SO_Four)_Five, TaF_Five, TaCl_Five, TaB
r_Five, TaI_Five, Cr (CH_ThreeCOCHCOC
H_Three)_Three, Cr (OOCH)_TwoOH, Cr (N
O_Three)_Three, Cr (ClO_Four)_Three, CrPO_Four, Cr
_Two(SO_Four)_Three, CrO_TwoCl_Two, CrF_Three, CrCl
_Three, CrBr_Three, CrI_Three, MoOCl_Four, MoC
l_Three, MoCl_Four, MoCl_Five, MoF₆, MoI_Two,
WCl_Four, WCl_Five, WF_Five, WBr_Five, Mn (OOC
CH_Three)_Two, Mn (CH_ThreeCOCHCOCH_Three)_Two, M
nCO_Three, Mn (NO_Three)_Two, MnO, Mn (Cl
O_Four)_Two, MnF_Two, MnCl_Two, MnBr_Two, MnI
_Two, Fe (OOCCH_Three)_Two, Fe (CH_ThreeCOCHC
OCH_Three)_Three, FeCO_Three, Fe (NO_Three)_Three, Fe
(ClO_Four)_Three, FePO_Four, FeSO_Four, Fe_Two(S
O_Four)_Three, FeF_Three, FeCl_Three, FeBr_Three, FeI
_Two, FeC₆H_FiveC₇, Co (OOCCH_Three)_Two, Co
(CH_ThreeCOCHCOCH_Three)_Three, CoCH_Three, Co
(NO_Three)_Two, CoC_TwoO_Four, Co (ClO_Four) _Two, C
o_Three(PO_Four)_Two, CoSO_Four, CoF_Two, CoC
l_Two, CoBr_Two, CoI_Two, NiCO_Three, Ni (NO
_Three)_Two, NiC_TwoO_Four, Ni (ClO_Four)_Two, NiSO
_Four, NiCl_Two, NiBr_Two, Pb (OOCC
H_Three)_Two, Pb (NO_Three)_Two, PbSO_Four, PbC
l_Two, PbBr_Two, CuCl_Two, CuBr_Two, Cu (N
O_Three)_Two, CuC_TwoO_Four, Cu (ClO_Four)_Two, CuS
O_Four, Cu (OOCCH_Three)_Two, Zn (OOCCH_Three)
_Two, Zn (CH_ThreeCOCHCOCH_Three)_Two, Zn (OO
CH)_Two, ZnCO_Three, Zn (NO_Three)_Two, Zn (Cl
O_Four)_Two, Zn _Three(PO_Four)_Two, Zn (SO_Four), Zn
F_Two, ZnCl_Two, ZnBr_Two, ZnI _Two, Cd (OO
CCH_Three)_Two, Cd (CH_ThreeCOCHCOCH_Three)_Two,
Cd (OOCCH_TwoCH_Three)_Two, Cd (NO_Three)_Two, C
d (ClO_Four)_Two, Cd (SO_Four), CdF_Two, CdC
l_Two, CdBr_Two, CdI_Two, AlCl_Three, AlI_Three,
AlBr_Three, AlF_Three, Al_Two(SO_Four)_Three, AlPO
_Four, Al_Two(C_TwoO_Four)_Three, Al (NO_Three)_Three, Al
(CH_ThreeCOCHCOCH_Three)_Three, GeCl_Four, GeB
r_Four, GeI_Four, Sn (OOCCH_Three)_Four, Sn (SO
_Four)_Two, SnF_Four, SnCl_Four, SnBr_Four, Sn
I_Four, Pb (OOCCH_Three)_Four, PbCO_Three, PbHP
O_Four, Pb (NO_Three)_Two, Pb (ClO_Four)_Two, PbS
O_Four, PbF_Two, PbCl_Two, PbBr_Two, PbI_Twoetc
Is mentioned.

The acid treatment not only removes impurities on the surface but also elutes a part or all of cations such as Al, Fe and Mg having a crystal structure. The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid. The salt and the acid used for the treatment may be two or more. When the salt treatment and the acid treatment are combined, there are a method of performing an acid treatment after performing the salt treatment, a method of performing the salt treatment after performing the acid treatment, and a method of simultaneously performing the salt treatment and the acid treatment. .

The treatment conditions with salts and acids are not particularly limited, but usually, the salt and acid concentrations are 0.1 to 3
0% by weight, treatment temperature from room temperature to boiling point, treatment time from 5 minutes to
The condition of 24 hours is selected, and the condition is such that at least a part of the substances constituting at least one compound selected from the group consisting of ion-exchange layered compounds excluding silicates and inorganic silicates is eluted. It is preferable. Further, salts and acids are generally used in an aqueous solution.

In the present invention, the above-mentioned salt treatment and / or acid treatment is carried out, but the shape may be controlled by pulverization or granulation before treatment, during treatment or after treatment. Further, another chemical treatment such as an alkali treatment or an organic substance treatment may be used in combination. The component [B] thus obtained is preferably one having a pore volume of 0.1 cc / g or more, particularly 0.3 to 5 cc / g, having a radius of 20 Å or more as measured by the mercury penetration method.

At least one compound selected from the group consisting of ion-exchangeable layered compounds excluding these silicates and inorganic silicates usually contains adsorbed water and interlayer water.
In the present invention, these adsorbed water and interlayer water are removed to obtain the component [B]. Here, the adsorbed water is water adsorbed on the surface of a clay, a clay mineral, or an ion-exchange layered compound particle or a crystal fracture surface, and the interlayer water is water existing between crystal layers. In the present invention, it is desirable to use a material obtained by removing these adsorbed water and / or interlayer water by heat treatment. There is no particular limitation on the method of heating the clay, the clay mineral and the intercalated water and the intercalated water, and methods such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. Used. The temperature at the time of heating is 100 ° C. or higher, preferably 150 ° C. or higher so that interlayer water does not remain. However, high temperature conditions that cause structural destruction are not preferable. Further, a heat dehydration method for forming a crosslinked structure such as heating under air flow is not preferable because the polymerization activity of the catalyst is reduced. Heating time is 0.5
It is more than one hour, preferably more than one hour. At that time, the water content of the component (B) after removal is 3% by weight or less, preferably 0% by weight when the water content is 0% by weight when dehydrated for 2 hours under the condition of a temperature of 200 ° C. and a pressure of 1 mmHg. Is 1
It is necessary that the content is not more than wt% and the lower limit is not less than 0 wt%. In the present application, the water content is 3% by weight after being dehydrated.
The component [B] prepared below needs to be handled so as to maintain the same water content when contacting the component [A] and, if necessary, the component [C].

As the component (B), spherical particles having an average particle size of 5 μm or more are used. Preferably, the average particle size is 10 μm
The above spherical particles are used. More preferably, spherical particles having an average particle diameter of 10 μm or more and 100 μm or less are used. The average particle size referred to here is an optical micrograph of the particle (magnification: 100
2) is represented by the number average particle size calculated by image processing. As the component (B), a natural product or a commercially available product may be used as it is, as long as the particles have a spherical shape, or the one in which the particle shape and particle size are controlled by granulation, sizing, fractionation or the like is used. May be. The granulation method used here is, for example, a stirring granulation method, a spray granulation method, a tumbling granulation method, pre-quetting, compacting, extrusion granulation method, fluidized bed granulation method, emulsion granulation method,
Examples of the method include in-liquid granulation method and compression molding granulation method, but the method is not particularly limited as long as the method can granulate the component (B). The granulation method is preferably a stirring granulation method, a spray granulation method, a tumbling granulation method, or a fluidized bed granulation method, and particularly preferably a stirring granulation method or a spray granulation method. In this case, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene or xylene is used as a dispersion medium for the raw material slurry. Water is preferably used as the dispersion medium.

The concentration of the component [B] in the raw material slurry liquid for spray granulation from which spherical particles are obtained is 0.1 to 70%, preferably 1 to 50%, particularly preferably 5 to 30%. The inlet temperature of hot air for spray granulation to obtain spherical particles varies depending on the dispersion medium, but when water is taken as an example, the temperature is 80 to 260 ° C, preferably 100 to 220 ° C. Moreover, you may use an organic substance, an inorganic solvent, an inorganic salt, and various binders at the time of granulation. Examples of the binder used include sugar, dextrose, corn syrup, gelatin, glue, carboxymethyl celluloses, polyvinyl alcohol, water glass,
Magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycol, starch, casein, latex, polyethylene glycol,
Examples thereof include polyethylene oxide, tar, pitch, alumina sol, silica gel, gum arabic and sodium alginate.

The spherical particles obtained as described above are used in the polymerization step after prepolymerization, but 0.2 MPa or more for suppressing crushing and generation of fine powder in the polymerization step.
It is particularly desirable to have a compressive fracture strength of 0.5 MPa or more. In the case of such a particle strength, the effect of improving the particle properties by prepolymerization is particularly effectively exhibited.
Further, examples of the organoaluminum compound used as the component [C] in the present invention are as follows:

[0032]

Embedded image AlR ⁶ _j X _3-j

(Wherein R ⁶ is a C _1-20 hydrocarbon group, X is hydrogen, halogen, an alkoxy group, j is a number of 0 <j ≦ 3)
And trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum, or halogen- or alkoxy-containing alkylaluminums such as diethylaluminum monochloride and diethylaluminum methoxide. In addition, aluminoxane such as methylaluminoxane can be used. Of these, trialkyl aluminum is particularly preferred.

In the present invention, the component [A], the component [B] and, if necessary, the component [C] are brought into contact with ethylene to preliminarily polymerize them to obtain a catalyst. [A] component, [B]
The method of contacting the components and, if necessary, the component [C] is not particularly limited, but they can be contacted in the following contacting order. The component (A) is brought into contact with the component (B). After the component [A] and the component [B] are brought into contact, the component [C] is added. After the component [A] is brought into contact with the component [C], the component [B] is added. After the component [B] is brought into contact with the component [C], the component [A] is added.

In addition, the three components may be contacted at the same time. Upon or after the contact of each component of the catalyst, a solid such as a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or alumina may be used. The contact may be carried out in an inert gas such as nitrogen or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene or xylene. The contact temperature is between -20 ° C and the boiling point of the solvent, and preferably between room temperature and the boiling point of the solvent.

The amount of each component of the catalyst used is 0.0001 to 10 mmol, preferably 0.001 to 5 mmol, of the component [A], and 0.001 to 5 mmol of the component [C] per 1 g of the component [B].
01 to 10000 mmol, preferably 0.1 to 100
mmol. Further, the atomic ratio of the transition metal in the component [A] to the aluminum in the component [C] is 1: 0.01 to.
It is 1,000,000, preferably 0.1 to 100,000.

Preliminary polymerization with ethylene is preferably carried out in an inert solvent under mild conditions, and 1 g of component [B] is used.
Per 0.01 to 1000 g, preferably 0.1 to 1
It is desirable to carry out so that 00 g of polymer is produced.
The prepolymerization is carried out by supplying ethylene while contacting the above components. The prepolymerization temperature is −50 to 100 ° C., preferably 0 to 100 ° C., and the prepolymerization time is 0.1 to 100 hours, preferably 0.1 to 20 hours.

The weight average molecular weight of the prepolymerized polyethylene is preferably 30,000 or more, particularly preferably 50,
It is more than 000. If the molecular weight is too small, the powder properties such as the decrease in bulk density and the generation of fine powder due to the crushing of particles in the polymerization system will be impaired, and not only the production efficiency of the reactor will decrease, but also the powder transfer in the process.・ May cause problems such as adhesion and blockage during the handling process. In particular, in gas phase polymerization, there may be cases where it is impossible to continue stable operation due to poor flow and adhesion phenomena in the reactor.

The solid catalyst thus obtained may be used as it is for the polymerization reaction without washing, or may be used after washing. Further, when it is carried out in a solvent such as an inert hydrocarbon, it may be used as a slurry as it is, or the solvent may be distilled off and dried to be used as a powder. The olefin polymerization reaction is carried out using the solid catalyst component prepolymerized with ethylene obtained above, but an organoaluminum compound is used if necessary.

Examples of the organoaluminum compound used in this case include the same compounds as the above-mentioned component [C]. The amount of the organoaluminum compound used at this time is selected so that the molar ratio of the transition metal in the catalyst component [A] to the aluminum in the organoaluminum compound is 1: 0 to 10,000. As the olefin that can be polymerized by the solid catalyst for olefin polymerization as described above, ethylene, propylene, butene-1, 3-methylbutene-1,
Examples thereof include 3-methylpentene-1,4-methylpentene-1, vinylcycloalkane, styrene and derivatives thereof. The polymerization can be suitably applied to not only homopolymerization but also generally known random copolymerization and block copolymerization.

The polymerization reaction is carried out in the presence or absence of a solvent such as an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene and cyclohexane, or a liquefied α-olefin. The temperature is −50 ° C. to 250 ° C., and the pressure is not particularly limited, but it is preferably atmospheric pressure to about 2000 kg / cm ² . Further, hydrogen may be present as a molecular weight regulator in the polymerization system.

[0042]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited by these examples without departing from the gist thereof. In addition, FIG.
FIG. 3 is a flow chart for facilitating the understanding of the technical contents included in the present invention, and the present invention is not limited by the flow chart unless it deviates from the gist thereof. The following catalyst synthesis step and polymerization step were all performed in a purified nitrogen atmosphere. The solvent used was dehydrated with Molecular Sieve-4A.

The molecular weight of the prepolymerized PE was measured by gel permeation chromatography (GPC) according to "Gel Permeation Chromatography" published by Maruzen by Takeuchi. That is, a standard polystyrene of known molecular weight (monodisperse polystyrene manufactured by Tosoh Corporation) is used and converted into a number average molecular weight (Mn) and a weight average molecular weight (Mw) by the universal method, and Mw /
The value of Mn was determined. Measured by Waters 150C-
Using ALC / GPC, column was AD80 manufactured by Showa Denko
Three M / S were used. The sample was diluted with O-dichlorobenzene to 0.2 wt% and used in 200 μl.
It was carried out at a temperature of 1 ° C and a flow rate of 1 ml / min.

Example 1 (1) Chemical Treatment of Clay Mineral 1 kg of synthetic mica (ME-100 manufactured by Corp Chemical) in 3.8 liters of demineralized water in which 0.2 kg of zinc sulfate was dissolved.
Was dispersed, stirred at room temperature for 1 hour, and filtered. After sufficiently washing with demineralized water, the solid content concentration was adjusted to 25%, and the slurry was introduced into a spray dryer to obtain spherical granulated particles.
The particles were further dried under reduced pressure at 200 ° C. for 2 hours. The crush strength of the particles was 0.7 MPa.

(2) Preparation of catalyst 4.4 L of n-heptane and 150 g of the particles of the synthetic mica obtained in the above (1) were introduced into a reactor with a capacity of 10 L equipped with an induction stirrer. A solution of bis (n-butylcyclopentadienyl) zirconium dichloride 12.0 mmol dissolved in 600 ml of toluene was added thereto, and the mixture was stirred at room temperature for 10 minutes.

(3) Prepolymerization Following the above stirring mixture, triethylaluminum 7 was added.
2 mmol was added and the system temperature was 40 ° C. Here, ethylene gas was introduced, and 600 g of ethylene was polymerized over 2 hours while maintaining the temperature at 40 ° C. A part of this prepolymerization catalyst was sampled and the molecular weight of the polyethylene part was measured by GPC.
It was 4,000.

(4) Ethylene-butene copolymerization Gas phase polymerization was continuously carried out using the prepolymerization catalyst obtained above. That is, 90 mg / hr of the above solid catalyst component (as a portion not containing prepolymerized polyethylene) and 200 mg of triethylaluminum in a gas phase polymerization reactor in which a mixed gas of ethylene and butene (butene / ethylene = 7.1 mol%) circulates. / Hr was supplied intermittently. The conditions of the polymerization reaction were a temperature of 88 ° C., a pressure of 20 kg / cm ² G and an average residence time of 3.5 hours, and the average polymerization rate of the produced polyethylene was 1.8 kg / hr. Further, the obtained polymer powder maintained a clean spherical shape and had a bulk density of 0.49.
Fine particles of g / cm ³ or less than 106 μm were not observed at all.

Example 2 A catalyst was prepared in the same manner as in Example 1 except that dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride was used as the zirconocene compound in (2) of Example 1. Prepolymerization was performed. The weight average molecular weight of the prepolymerized polyethylene part was 75,000. Further, in the ethylene-butene copolymerization, the composition of the ethylene-butene mixed gas is butene / ethylene = 3.6 mol%.
The same procedure as in Example 1 was carried out except that The obtained polymer powder maintained a spherical shape as in Example 1, and had a bulk density of 0.51.
It was g / cm ³ , and no fine powder was observed.

Example 3 (1) Chemical treatment of clay mineral Demineralized water in which 1.25 kg of magnesium chloride was dissolved 6.
1 kg of commercially available montmorillonite (Kunipia F, manufactured by Kunimine Industries Co., Ltd.) was dispersed in 3 liters and stirred at 80 ° C. for 1 hour. This solid component was washed with water, dispersed in 7 liters of an 8% aqueous hydrochloric acid solution, stirred at 90 ° C. for 2 hours, and washed with demineralized water. This montmorillonite water slurry solution was adjusted to a solid content concentration of 15%, and spray granulated by a spray dryer.

(2) Preparation of catalyst In a reactor equipped with an induction stirrer having a capacity of 10 liters, the above (1) was added.
3. 0.8 kg of montmorillonite obtained in 4. and toluene 4.
0 liter was introduced and the temperature was raised to 70 ° C. 4.6 for this
20 mol of toluene solution of triethylaluminum
After dropwise adding for 1 minute and stirring at 70 ° C. for 1 hour, the supernatant liquid was extracted and washed with toluene. Bis (cyclopentadienyl) zirconium dichloride 0.0
A 64 mol toluene solution was added, and the mixture was stirred at room temperature for 1 hour.

(3) Prepolymerization of ethylene To the solid catalyst slurry obtained in (2) above, 0.13 mmol of triethylaluminum was added. Ethylene was introduced into this and polymerization was carried out at 60 ° C. for 1 hour to produce 4.5 g of polyethylene per solid catalyst component. The weight average molecular weight of this polyethylene part by GPC was 52,000.

(4) Ethylene-butene copolymerization Using the prepolymerized catalyst obtained in (3) above, continuous ethylene-butene copolymerization was carried out by the n-hexane slurry method. That is, the reaction temperature is 60 ° C., the pressure is 22 kg / cm ² G,
3. Average residence time 3.0 hours, hydrogen / ethylene composition of gas phase part 0.02 mol%, butene / ethylene composition of gas phase part 4.
Solid catalyst 1.9 g / h in the reaction system controlled to 8 mol%
r and triethylaluminum 0.44 g / hr were continuously supplied to carry out continuous polymerization, and the produced polyethylene was continuously extracted at about 13 kg / hr. The obtained polymer particles maintain a clean spherical shape and have a bulk density of 0.42 g / cm.
^{Was 3} .

Example 4 Ethylene-hexene copolymerization was carried out using the prepolymerized catalyst obtained in Example 1 (3) above. That is, 500 ml of purified heptane and 70 ml of 1-hexene were charged into a 1 liter autoclave, and the temperature was raised to 65 ° C. Here, 30 mg of the prepolymerized catalyst obtained in the above Example 1 (3) was introduced as a solid catalyst component containing no prepolymerized polyethylene, and then ethylene was supplied to carry out polymerization for 60 minutes while maintaining 22 kg / cm ² G. Continued. Then, the gas in the gas phase was purged to terminate the polymerization. The copolymer obtained is 35
The bulk density was 0.38 g / cm ³ .

Comparative Example 1 In (3) of Example 1, the prepolymerization temperature was 80 ° C. The weight average molecular weight of the prepolymerized polyethylene obtained here was 27,000. When ethylene-butene copolymerization was carried out in the same manner as in Example 1, the polymer particles were crushed, the bulk density was 0.31 g / cc, and the total amount of powder of 100 μm or less was 1.2% by weight.

Comparative Example 2 Catalyst preparation and ethylene copolymerization were carried out in the same manner as in Example 3 except that ethylene bis (indenyl) zirconium dichloride was used as the zirconocene compound. The weight average molecular weight of polyethylene obtained by the prepolymerization was 23.
000, and some of the polymer particles obtained by continuous polymerization had a spherical shape, but the bulk density was 0.2 due to crushing.
It was as low as 7 g / cm ³ .

[Brief description of drawings]

FIG. 1 is a flowchart for facilitating the understanding of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naoko Kusaka 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Co., Ltd. Yokkaichi Research Institute

Claims (4)

[Claims] 1. An [A] metallocene-based transition metal compound,
[B] A catalyst component comprising a clay mineral having a spherical particle shape, a clay or an ion-exchange layered compound, and optionally [C] an organoaluminum compound is contacted with ethylene, and the weight average molecular weight by GPC is 30,000 or more. The polyethylene of 0.01 to 10 per 1 g of the component [B]
A catalyst for olefin polymerization, which is formed by prepolymerizing 00 g. 2. The component [B] has a water content of 3% by weight or less obtained by subjecting it to salt treatment and / or acid treatment,
The catalyst for olefin polymerization according to claim 1, which is at least one compound selected from the group consisting of (1) ion-exchangeable layered compounds excluding silicates and (2) inorganic silicates. 3. The crushing strength of the spherical particles of the component (B) is 0.
It is 2 MPa or more, The catalyst for olefin polymerization of Claim 1 characterized by the above-mentioned. 4. A method for producing an olefin polymer, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1 and optionally an organoaluminum compound.