JP2000086672A - Aluminoxane, catalyst for olefin polymerization and production of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aluminoxane that has high polymerization activity with excellent handleability and storage stability and can inexpensively and efficiently give a polymer with a largely saved amount of an organoaluminum compound by bringing aluminoxane into contact with an adsorption substance, then removing the adsorption substance. SOLUTION: Aluminoxane is brought into contact with an adsorption substance, for example, zeolite, activated carbon, alumina, phyllosilicates, montmorillonite or the like each having a specific surface area of >=30 m2/g according to the BET method or having a pore volume of >=0.001 cm3/g, Then, the adsorption substance is removed to give the objective aluminoxane. In a preferred embodiment, this aluminoxane, a compound of a transition metal selected from the groups 4-6 in the periodic table, an organo-aluminum compound, for example, a trialkylaluminum, or the like, are brought into contact with one another to prepare an olefin polymerization catalyst and the catalyst is used for polymerization of olefins.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminoxane, a catalyst for olefin polymerization and a method for producing an olefin polymer. The present invention relates to a method for producing an olefin polymer.

[0002]

2. Description of the Related Art In recent years, in producing an olefin polymer by polymerizing olefins in the presence of a catalyst, a method using a catalyst composed of a metallocene compound and an aluminoxane has been proposed (Japanese Patent Laid-Open No. 58-019309). Gazette, JP-A-2-167307, etc.). The polymerization method using these catalysts has a very high polymerization activity per transition metal compared with the method using the conventional Ziegler-Natta catalyst composed of a titanium compound or a vanadium compound and an organoaluminum compound, and also has a high molecular weight distribution. It is known that a polymer having a narrow range can be obtained.

Further, a method has been proposed in which a transition metal compound and an aluminoxane or an organoaluminum compound are used as catalyst components, and these are supported on an inorganic oxide such as silica or alumina to polymerize olefins (special feature). JP-A 61-108610, JP-A 1-10130
No. 3, etc.). However, in these methods described above, a large amount of aluminoxane is required to obtain sufficient polymerization activity, so that the activity per aluminum is low, which is uneconomical, and the produced polymer contains aluminum. Since a large amount remains, there was a problem that the catalyst residue had to be removed from the polymer.

A method using a clay mineral as a catalyst component has also been proposed (Japanese Patent Laid-Open No. 5-301917). Pretreatment with aluminum is indispensable, and the activity per aluminum is not sufficient, and the amount of catalyst residue in the product is large.

[0005]

SUMMARY OF THE INVENTION The present invention has been made from the above point of view, and it is inconvenient to handle and has poor storage stability.
Since a large amount of organoaluminum used in the entire polymerization system can be significantly reduced without using a large amount of highly dangerous methylaluminoxane, a large amount of metal content does not remain in the produced polymer, so It is an object of the present invention to provide an aluminoxane capable of inexpensively producing an olefin polymer, a catalyst for olefin polymerization, and a method for producing an olefin polymer.

[0006]

[In the formula, Q ¹ represents a bonding group bridging two conjugated five-membered ring ligands (C ₅ H _5-ab R ¹ _b ) and (C ₅ H _{5 -ac} R ² _c ), and Q ² Represents a bonding group that bridges the conjugated five-membered ring ligand (C ₅ H _{5-a- d} R ³ _d ) and the Z ¹ group. R ¹ , R ² and R ³ each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, and a is 0. , 1 or 2. b, c, and d each represent an integer of 0 to 5 when a=0, an integer of 0 to 4 when a=1, and an integer of 0 to 3 when a=2. The valence of p+q=M ¹ is −2, and the valence of r=M ¹ is shown. M ¹ represents a transition metal of Groups 4 to 6 of the Periodic Table. Further, X ¹ , Y ¹ and Z ¹ each represent a covalent bond or an ionic bond ligand, and X ² represents a covalent bond ligand. In addition, X ¹ and Y ¹ may be bonded to each other to form a ring structure. ]

10. An olefin polymer is produced by polymerizing an olefin using the olefin polymerization catalyst according to any one of 6 to 9 above. 11. 10. A method for producing an olefin polymer, which comprises polymerizing an olefin using the catalyst for an olefin polymer according to any one of 6 to 9 and an organoaluminum compound. 12. The method for producing an olefin polymer according to the above 10 or 11, wherein the organoaluminum compound is trialkylaluminum. 13. 10 to 1 in which the olefin is propylene
2. The method for producing an olefin polymer according to any one of 2 above.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. 1. Aluminoxane (A) obtained by contacting aluminoxane with an adsorptive substance and then removing the adsorptive substance, the aluminoxane (A) of the present invention comprises the aluminoxane described in (a) below and the adsorptive substance described in (b) below. It is obtained by removing the adsorptive substance after contacting with. The contact between the aluminoxane and the adsorptive substance is carried out in an inert gas such as nitrogen or a hydrocarbon such as pentane, hexane, heptane, toluene or xylene. The contact is performed in the temperature range of -30°C to the boiling point of each solvent, and preferably in the temperature range of room temperature to the boiling point of the solvent. The contact method is not particularly limited and may be batch-type stirring or flow-type contact. The contact ratio is usually 0.01 mg to 10000 mg of the adsorptive substance with respect to 1 mmol of Al atom in aluminoxane. Preferably, it is contacted with 0.1 mg to 1000 mg of the adsorptive substance.

The method of removing the adsorptive substance is not particularly limited, and the supernatant may be collected after standing, or if it is contacted by a flow system, it can be used without being removed. Usually, in the solution obtained by removing the adsorbent, the adsorbent is 1 mm of Al atom in the aluminoxane.
It is 0 to 100 mg with respect to ol. Preferably 0 to 1
It is 0 mg. (A) The aluminoxane used in the present invention is not particularly limited, and examples thereof include commercially available aluminoxanes. Further, a product obtained by bringing an organoaluminum compound into contact with water, or a product obtained by further modifying them with phenol or the like can be mentioned.

These are usually stored and handled in an inert hydrocarbon-free solvent such as an aliphatic hydrocarbon solvent such as heptane or hexane or an aromatic hydrocarbon solvent such as toluene. The method of contacting the organoaluminum compound with water is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization and then water is added, a crystal contained in a metal salt, etc. Examples thereof include a method of reacting water, water adsorbed on an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water.

Further, these are generally known as a linear aluminoxane represented by the following general formula (4) or a cyclic aluminoxane represented by the following general formula (5) or an aggregate of cyclic aluminoxanes.

[0011]

[Chemical 1] (In the formula, each R ⁹ represents an alkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, and they may be the same or different. Further, p is 3≦p≦40, r Is 1≦
It is an integer of r≦50. ) Specifically, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, methylisobutylalumoxane (methyl group:isobutyl group=0.01:0.99 to 0.
99:0.01) and modified products thereof with phenols. Of these, methylaluminoxane (also referred to as MAO) is particularly preferable. In the present invention, the aluminoxane may be used alone or in combination of two or more.

(B) Adsorbent substance used in the present invention The adsorbent substance (b) used in the present invention refers to a substance having an adsorptive ability. As for (b), in general, any type of substance may be used as long as it is a substance having adsorption ability. Examples thereof include porous materials, inorganic oxides, clays, clay minerals, ion-exchangeable layered compounds, and the like.

The adsorption capacity can be usually evaluated by the specific surface area or the pore volume. Used in the present invention (b)
Usually has a specific surface area of 30 m ² measured by the BET method.
/G or more or the pore volume is 0.001 cm ³ /g or more. Preferably, the specific surface area is 50 m ² /g or more or the pore volume is 0.01 cm ³ /g or more. The porous substance only needs to have pores, and is not limited by the material, the size, number, surface area, etc. of the pores. Examples of the porous substance include organic porous substances such as polymers and porous substances made of various inorganic oxides.
The inorganic oxide is not particularly limited,
-The oxide containing the group XIV element is mentioned. The elements of Group I to XIV of the periodic table may be one kind or two or more kinds. The inorganic oxide may be used alone or in combination of two or more. Further, it may be a synthetic product or a natural product. Specific examples include zeolite, alumina, silica alumina, silica gel and the like.

Further, (b) may be a substance having a layered structure having a space between layers, such as clay, clay mineral, or ion-exchangeable layered compound. Clay is an aggregate of fine hydrated silicate minerals, which is a substance that produces plasticity when kneaded with an appropriate amount of water, exhibits rigidity when dried, and sinters when baked at high temperatures. Further, the clay mineral refers to a hydrous silicate that is a main component of clay. These are not limited to naturally occurring ones but may be artificially synthesized ones.

The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other by weak binding forces, and the contained ions are exchangeable. Some clay minerals are ion-exchangeable layered compounds. For example, clay minerals include phyllosilicates. Examples of the phyllosilicic acid include phyllosilicic acid and phyllosilicate.
Examples of the phyllosilicate include natural products such as montmorillonite belonging to the smectite group, saponite, hectorite, illite belonging to the mica group, sericite, and mixed layer minerals of the smectite group and the mica group or the mica group and the vermiculite group. Be done.

As a synthetic product, tetrafluorosilicon mica,
Examples include laponite and smecton. Other, α-
Zr(HPO ₄ ) ₂ , γ-Zr(HPO ₄ ) ₂ , α-T
Ion-exchangeable compounds having a layered crystal structure that is not a clay mineral, such as i(HPO ₄ ) ₂ and γ-Ti(HPO ₄ ) _2, can be mentioned.

Clays and clay minerals which do not belong to the ion-exchange layered compound, and concrete examples of the component (b) include the knotoshi, which is called bentonite because of its low content of montmorillonite, and other components contained in montmorillonite. Clay, gyrome clay, fibrous morphology of sepiolite, palygorskite, and amorphous or low crystalline allophane and imogolite.

Among the above-mentioned clays, clay minerals or ion-exchange layered compounds, preferred as (b) are clays or clay minerals, most preferred are phyllosilicates, among which smectite is preferable and montmorillonite is preferable. More preferable. Zeolite can also be used as (b). Typical examples of the zeolite include natural products such as mordenite, synthetic products such as zeolite X, zeolite Y and zeolite A, and ZSM-5 (SiO.
₂ /Al ₂ O ₃ )≧20 high silica zeolite, AL
Zeolite-like compounds such as PO and SAPO, MCM-
41, MCM-50, and other amorphous zeolites.

Activated carbon can also be used as (b). The activated carbon is not particularly limited. Among the above-mentioned adsorptive substances, activated carbon, zeolite, silica gel, alumina, clay, clay minerals or ion-exchange layered compounds are preferable. Further, in the present invention, (b) may be used as it is, or may be used after being heated and dehydrated. Further, (b) is preferably subjected to chemical treatment from the viewpoint of removing impurities or changing the structure and function.

Here, the chemical treatment is not limited to a surface treatment for removing impurities adhering to the surface, and affects the crystal structure of (b) or the layered structure of (b). Either of them may be used. Specific examples thereof include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment can increase the surface area by removing impurities on the surface and eluting cations such as aluminum, iron and magnesium in the crystal structure.
Alkali treatment destroys the crystal structure of (b),
It may bring about a structural change.

Further, in the salt treatment and the organic substance treatment, it is possible to change the surface area, the layered structure, etc. by forming an ionic complex, a molecular complex, an organic complex and the like. It is also possible to obtain an interlayer material in which the interlayer is expanded by utilizing the ion exchange property and substituting the exchangeable ion between layers with another bulky ion. In the present invention, it is preferable to use (b) which has been subjected to heat dehydration treatment or chemical treatment.

Further, (b) may be used after being treated with a silane compound or an aluminum compound. Examples of the silane compound include trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride, tert.
-Butyldimethylsilyl chloride, tert-butyldiphenylsilyl chloride, trialkylsilyl chlorides such as phenethyldimethylsilyl chloride, dimethylsilyl dichloride, diethylsilyl dichloride, diisopropylsilyl dichloride, bis(phenethyl)silyl dichloride, diphenylsilyl dichloride, dimesi Dialkylsilyl dichlorides such as tylsilyl dichloride and ditolylsilyl dichloride, methylsilyl trichloride,
Replacing alkylsilyl trichlorides such as ethyl silyl trichloride, isopropyl silyl trichloride, phenyl silyl trichloride, mesityl silyl trichloride, tolyl silyl trichloride, phenethyl silyl trichloride, etc., and other halogen elements above Halides, bis(trimethylsilyl)amide, bis(triethylsilyl)amide, bis(triisopropylsilyl)amide, bis(dimethylethylsilyl)amide, bis(diethylmethylsilyl)amide, bis(dimethylphenylsilyl)amide, bis Disilazanes such as (dimethyltolyl)amide and bis(dimethylmesityl)amide; polysilanols commonly referred to by the common name of peralkylpolysiloxypolyols; tetraalkylsilanes such as dimethyldiphenylsilane, diethyldiphenylsilane and diisopropyldiphenylsilane. , Trialkylsilanes such as trimethylsilane, triethylsilane, triisopropylsilane, tritert-butylsilane, triphenylsilane, tritolylsilane, trimesitylsilane, methyldiphenylsilane, dinaphthylmethylsilane, and bis(diphenyl)methylsilane. Inorganic silicon compounds such as silicon tetrachloride and silicon tetrabromide. Of these, disilazanes are preferable, and trialkylsilane chlorides are more preferable.

The aluminum compound is represented by the linear aluminoxane represented by the general formula (4), the cyclic aluminoxane represented by the general formula (5), or an aggregate of the cyclic aluminoxane and the following general formula (6). Al group-containing aluminum compound, R ¹⁰ _m Al(OR ¹¹ ) _n X _3-mn (6) (wherein R ¹⁰ and R ¹¹ are each an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms). Represents a group, X represents a hydrogen atom or a halogen atom, m is 0<m≦3, preferably 2 or 3, and most preferably 3 and n is 0≦.
n<3, preferably 0 or 1. ) And the like. Among these, the alkyl group-containing aluminum compound represented by the general formula (6) is preferable. Specifically, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, tri-t-butyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, dimethyl aluminum methoxide, diethyl aluminum methoxide, dimethyl. Examples thereof include halogens such as aluminum hydroxide and diethylaluminum hydroxide, alkylaluminums containing alkoxy groups or hydroxyl groups, hydrogen atom-containing alkylaluminums such as dimethylaluminum hydride and diisobutylaluminum hydride, and modified products thereof.

Of these, trialkylaluminum is preferable, and triisobutylaluminum is preferable as the trialkylaluminum. In the present invention, treatment with a silane compound or an aluminum compound is carried out (b)
Is preferably used. The method of contacting the aluminoxane with the adsorptive substance, the conditions, etc., the method for removing the adsorptive substance, the conditions, etc. are as described above. 2. Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention is produced by contacting the (A) aluminoxane, (B) a transition metal compound of Groups 4 to 6 of the periodic table, and (C) an organoaluminum compound as necessary. Obtained.

Each component will be described below. (A) Aluminoxane The aluminoxane described in 1 above is brought into contact with an adsorptive substance.
Aluminoxane obtained by removing adsorbents after
(A). (B) Transition metal compound As the (B) transition metal compound used in the present invention
Is a transition metal compound of Groups 4 to 6 of the Periodic Table. period
As a transition metal compound of Groups 4 to 6 of the Table, from the viewpoint of activity,
Those represented by the general formulas (1) to (3) are preferable.
Can be mentioned as. Q¹ _a(C_FiveH_5-abR¹ _b)(C_FiveH_5-acR² _c) M¹X¹ _pY¹ _q・・・ (1) Q²a(C_FiveH_5-adR³ _d) Z¹M¹X¹ _pY¹ _q...(2) M¹X² _r (3) [wherein Q¹Is two conjugated five-membered ring ligands (C_FiveH_5-ab
R¹ _b) And (C_FiveH_{Five -ac}R² _c) Crosslinkability
Shows the group, Q²Is a conjugated five-membered ring ligand (C_FiveH_{5-a- d}R³
_d) And Z¹The bonding group which bridge|crosslinks a group is shown. R¹, R²Over
And R³Are a hydrocarbon group, a halogen atom, and an alcohol, respectively.
Xy group, silicon-containing hydrocarbon group, phosphorus-containing hydrocarbon group, nitrogen
Represents a hydrogen atom-containing hydrocarbon group or a boron atom-containing hydrocarbon group, and a is
It is 0, 1 or 2. b, c and d are such that when a=0,
Each is an integer of 0-5, and when a=1, 0-4 respectively
And an integer of 0 to 3 when a=2.
p+q=M¹Valence-2, r=M¹Indicates the valence of. M¹
Indicates a transition metal of Groups 4 to 6 of the Periodic Table. Also, X¹, Y
¹, Z¹Is a covalent or ionic bond, respectively
Represents a child, X²Represents a covalent ligand. Na
Oh, X¹And Y¹Are linked to each other and have a ring structure
May be formed. ] This Q¹And Q²Specific examples of (1) methylene
Group, ethylene group, isopropylene group, methylphenyl
Tylene group, diphenylmethylene group, cyclohexylene group
C1-C4 alkylene groups such as, cycloalkylene
A group or its side chain lower alkyl or phenyl substituent,
(2) silylene group, dimethylsilylene group, methylpheny
Lucyrylene group, diphenylsilylene group, disilylene group,
Silylene groups such as tetramethyldisilylene groups, oligos
Rylene group or its side chain lower alkyl or phenyl group
Substitution, (3) (CH₃)₂Ge group, (C₆H_Five)₂Ge
Group, (CH₃)₂P group, (C₆H_Five)₂P group, (C_FourH
₉) N group, (C₆H_Five) N group, (CH₃) B group, (C_Four
H₉) B group, (C₆H_Five) B group, (C₆H_Five) Al group,
(CH₃O) germanium such as Al group, phosphorus, nitrogen,
Hydrocarbon groups containing boron or aluminum [lower alkyl
Group, phenyl group, hydrocarbyloxy group (preferably
Lower alkoxy group) and the like] and the like. these
Among them, alkylene group and silylene group are preferred from the viewpoint of activity.
Good Also, (C_FiveH_5-abR¹ _b), (C_FiveH_5-ac
R² _c) And (C_FiveH_5-adR ³ _d) Is a conjugated five-membered ring coordination
A child, R¹, R²And R³Are each a hydrocarbon
Groups, halogen atoms, alkoxy groups, silicon-containing hydrocarbons
Group, phosphorus-containing hydrocarbon group, nitrogen-containing hydrocarbon group or boron
It represents a contained hydrocarbon group, and a is 0, 1 or 2. b,
c and d are integers of 0 to 5 when a=0, and a
=1 is an integer of 0 to 4, respectively, and a=2 is an integer.
Each represents an integer of 0 to 3. Here, as a hydrocarbon group
Is preferably one having 1 to 20 carbon atoms, and particularly one having 1 to 20 carbon atoms.
12 is preferable. This hydrocarbon group is a monovalent group
Bond with the cyclopentadienyl group, which is a conjugated five-membered ring group
And if there are more than one,
The two are bonded to each other to form a cyclopentadienyl group.
A ring structure may be formed together with the part. That is, both
A typical example of a 5-membered ring ligand is a substituted or unsubstituted cyclopentane.
Interdienyl group, indenyl group and fluorenyl group
It Halogen atoms include chlorine, bromine, iodine and fluorine.
A fluorine atom is mentioned, and the alkoxy group has 1 carbon atom.
Preferably, those of 12 to 12 are mentioned. Silicon-containing hydrocarbon
Examples of the group include -Si(R^Four) (R^Five) (R⁶)
(R^Four, R^FiveAnd R⁶Is a hydrocarbon group having 1 to 24 carbon atoms)
Etc., such as phosphorus-containing hydrocarbon groups, nitrogen-containing hydrocarbon water
Examples of the elementary group and the boron-containing hydrocarbon group are P-
(R⁷) (R⁸), -N(R⁷) (R⁸) And -B(R
⁷) (R⁸) (R⁷And R⁸Is carbonized water having 1 to 18 carbon atoms
Base) and the like. R¹, R²And R³Is that
If there are multiple Rs, multiple Rs¹, Multiple R²And multiple
R³Are the same or different in each
May be. In addition, in the general formula (1), a conjugated five-membered ring
Order (C_FiveH_5-abR¹ _b) And (C_FiveH
_5-acR² _c) May be the same or different.
On the other hand, M¹Represents a transition metal element of Groups 4 to 6 of the Periodic Table,
Specific examples are titanium, zirconium, hafuniu.
Mu, vanadium, niobium, molybdenum, tungsten
Among these, from the aspect of activity among these
Titanium, zirconium and hafnium are preferred.
Z¹Is a covalent ligand, specifically halogen
Atom, oxygen (-O-), sulfur (-S-), carbon number 1-2
0, preferably 1 to 10 alkoxy group, 1 to 2 carbon atoms
0, preferably 1 to 12 thioalkoxy group, carbon number 1
~40, preferably 1-18 nitrogen-containing hydrocarbon radicals, charcoal
Phosphorus-containing hydrocarbon having a prime number of 1 to 40, preferably 1 to 18
Indicates a group. X¹And Y¹Are connected to each other
You may form a ring structure. That is, X¹Each other
To form a ring structure, or Y¹What
May combine with each other to form a ring structure, or
X¹And Y¹May combine with each other to form a ring structure.
Yes. X¹And Y¹Are covalent ligands or
A binding ligand, specifically a hydrogen atom or halogen
Atom, hydrocarbon having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms
Group, alkoxy having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms
Group, amino group, 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms
Phosphorus-containing hydrocarbon group (eg, diphenylphosphine group
Etc.) or silicon having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms
Containing hydrocarbon groups (eg, trimethylsilyl groups, etc.),
A hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms
Or a halogen-containing boron compound (for example, B(C₆H_Five)
_Four, BF_Four) Is shown. Among these, halogen atoms and charcoal
Hydrogenated groups are preferred. This X¹And Y¹Identical to each other
Or may be different. Also, X²Is a covalent bond
Ligand, specifically, a halogen atom,
Is a rubiruamino group or a hydrocarbyloxy group
And preferably an alkoxy group. (I) Transition metals represented by the general formulas (1) and (2)
The following compounds may be mentioned as specific examples of the compound.
Wear. Bis(cyclopentadienyl)titanium dichloride
De,bis(methylcyclopentadienyl)titanium di
Chloride, bis(dimethylcyclopentadienyl)tita
Bis(trimethylcyclopentadiene)
Nyl)titanium dichloride, bis(tetramethylcyclo)
Lopentadienyl) titanium dichloride, bis(pen
Tamethylcyclopentadienyl)titanium dichloride
De,bis(n-butylcyclopentadienyltitanium
Dichloride, bis(indenyl) titanium dichloride
De,bis(fluorenyl)titanium dichloride,bis
(Cyclopentadienyl)titanium chlorohydride,
Bis(cyclopentadienyl)methyl titanium chloride
De,bis(cyclopentadienyl)ethyl titanium
Lolid, bis(cyclopentadienyl)phenyl titani
Umchloride, bis(cyclopentadienyl)dimethyl
Titanium, bis(cyclopentadienyl)diphenyl
Titanium, bis(cyclopentadienyl)dineopen
Tiltitanium, bis(cyclopentadienyl) dihydride
Rotitanium, (cyclopentadienyl) (indeni
Ru) titanium dichloride, (cyclopentadienyl)
(Fluorenyl)titanium dichloride, bis(cyclo
Pentadienyl)zirconium dichloride, bis(meth)
Rucyclopentadienyl) zirconium dichloride, bi
Su (dimethylcyclopentadienyl) zirconium di
Lolid, bis(trimethylcyclopentadienyl)zyl
Conium dichloride, bis(tetramethylcyclopenta
Dienyl)zirconium dichloride, bis(pentamethyi)
Rucyclopentadienyl) zirconium dichloride, bi
Sus (n-butylcyclopentadienyl zirconium dioxide
Lolid, bis(indenyl)zirconium dichloride,
Bis(fluorenyl)zirconium dichloride, bis
(Cyclopentadienyl)zirconium chlorohydrido
De,bis(cyclopentadienyl)methyl zirconium
Chloride, bis(cyclopentadienyl)ethyl zirco
Nium chloride, bis(cyclopentadienyl) phenyl
Ruzirconium chloride, bis(cyclopentadiene
)Dimethylzirconium, bis(cyclopentadiene)
Le) diphenyl zirconium, bis (cyclopentadiene)
Nyl)dineopentyl zirconium, bis(cyclopen
Tadienyl)dihydrozirconium, (cyclopentadi
(Enyl) (indenyl) zirconium dichloride, (si
Clopentadienyl)(fluorenyl)zirconium di
Conjugated five-membered ring coordination without having a bridging linking group such as chloride
A transition metal compound having two children, methylenebis(indenyl)titanium dichloride,
Ethylene bis(indenyl)titanium dichloride,
Tylene bis(indenyl)titanium chlorohydride,
Ethylene bis(indenyl)methyl titanium chloride
De, ethylene bis(indenyl)methoxychlorotitani
Um, ethylenebis(indenyl)titanium dietoki
Cid, ethylene bis(indenyl) dimethyl titanium
, Ethylene bis(4,5,6,7-tetrahydroin
Denyl) titanium dichloride, ethylene bis(2-me
Tylindenyl) titanium dichloride, ethylene bis
(2,4-Dimethylindenyl)titanium dichloride
De, ethylenebis(2-methyl-4-trimethylsilyl)
Indenyl) titanium dichloride, ethylene bis
(2,4-dimethyl-5,6,7-trihydroindeni
Ru) titanium dichloride, ethylene (2,4-dimethyl)
(Lucyclopentadienyl) (3',5'-dimethylcyclo)
Lopentadienyl) titanium dichloride, ethylene
(2-Methyl-4-t-butylcyclopentadienyl)
(3'-t-butyl-5'-methylcyclopentadiene
Ru) Titanium dichloride, ethylene (2,3,5-to
Limethylcyclopentadienyl)(2',4',5'-to
Limethylcyclopentadienyl) titanium dichloride
De, isopropylidene bis(2-methylindenyl) thi
Tanium dichloride, isopropylidene bis(indeni
Ru) Titanium dichloride, isopropylidene bis
(2,4-Dimethylindenyl)titanium dichloride
, Isopropylidene (2,4-dimethylcyclopenta
Dienyl) (3'5'-dimethylcyclopentadienyl
Ru) Titanium dichloride, isopropylidene (2-me
Tyl-4-t-butylcyclopentadienyl)(3'-
t-butyl-5'-methylcyclopentadienyl)tita
Aluminum dichloride, methylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl)titanium
Dichloride, methylene (cyclopentadienyl) (3,
4-dimethylcyclopentadienyl)titanium chloro
Hydride, methylene (cyclopentadienyl) (3,4
-Dimethylcyclopentadienyl) dimethyl titanium
Methylene, methylene (cyclopentadienyl) (3,4-dimme
Cyclopentadienyl)diphenyltitanium,
Tylene (Cyclopentadienyl) (Trimethylcyclope
Tandienyl)titanium dichloride, methylene
Ropentadienyl) (tetramethylcyclopentadienyl)
Ru) Titanium dichloride, isopropylidene (cyclo
Pentadienyl) (3,4-dimethylcyclopentadiene
Nyl) titanium dichloride, isopropylidene (shik
Ropentadienyl) (2,3,4,5-tetramethylsilane
Clopentadienyl) titanium dichloride, isopro
Pyridene (cyclopentadienyl) (3-methylindene
Nyl) titanium dichloride, isopropylidene (shik
Lopentadienyl) (fluorenyl) titanium dichloride
Lido, isopropylidene (2-methylcyclopentadiene
Nyl)(fluorenyl)titanium dichloride, isop
Ropylidene (2,5-dimethylcyclopentadienyl)
(3,4-dimethylcyclopentadienyl)titanium
Dichloride, isopropylidene (2,5-dimethyl
Lopentadienyl) (fluorenyl) titanium dichloride
Lido, ethylene (cyclopentadienyl) (3,5-di
Methylcyclopentadienyl)titanium dichloride,
Ethylene(cyclopentadienyl)(fluorenyl)ti
Tanium dichloride, ethylene (2,5-dimethyl
Lopentadienyl) (fluorenyl) titanium dichloride
Lido, ethylene (2,5-diethylcyclopentadiene
Le) (fluorenyl) titanium dichloride, dipheni
Lumethylene (cyclopentadienyl) (3,4-diethyl
Cyclopentadienyl)titanium dichloride, dif
Phenylmethylene (cyclopentadienyl) (3,4-di
Ethylcyclopentadienyl)titanium dichloride,
Cyclohexylidene (cyclopentadienyl) (fluor
(Renyl) titanium dichloride, cyclohexylidene
(2,5-dimethylcyclopentadienyl) (3',
4'-dimethylcyclopentadienyl)titanium di
Lolid, methylenebis(indenyl)zirconium dioxide
Lolid, ethylene bis(indenyl)zirconium dioxide
Chloride, methylenebis(indenyl)zirconium chloride
Rohydride, ethylenebis(indenyl)methylzirco
Nium chloride, ethylenebis(indenyl)methoxy
Chlorozirconium, ethylene bis(indenyl)zil
Conium diethoxide, ethylenebis(indenyl)di
Methyl zirconium, ethylene bis (4,5,6,7-
Tetrahydroindenyl)zirconium dichloride, d
Tylene bis(2-methylindenyl)zirconium dioxide
Lolid, ethylene bis(2,4-dimethylindenyl)
Zirconium dichloride, ethylene bis(2-methyl-
4-Trimethylsilylindenyl)zirconium dichloride
Lido, ethylene bis(2,4-dimethyl-5,6,7-
Trihydroindenyl)zirconium dichloride, ethyl
Len (2,4-dimethylcyclopentadienyl)
(3',5'-dimethylcyclopentadienyl)zirco
Aluminum dichloride, ethylene (2-methyl-4-t-bu)
Tylcyclopentadienyl)(3'-t-butyl-5'
-Methylcyclopentadienyl) zirconium dichloride
De, ethylene (2,3,5-trimethylcyclopentadiene
Nyl)(2',4',5'-trimethylcyclopentadi
(Enyl) zirconium dichloride, isopropylidene bi
Bis(2-methylindenyl)zirconium dichloride,
Isopropylidene bis(indenyl)zirconium dioxide
Lolid, isopropylidene bis(2,4-dimethylin
Denyl) zirconium dichloride, isopropylidene
(2,4-dimethylcyclopentadienyl) (3'5'
-Dimethylcyclopentadienyl) zirconium dichloride
Lido, isopropylidene (2-methyl-4-t-butyl)
Cyclopentadienyl)(3'-t-butyl-5'-me
Tylcyclopentadienyl)zirconium dichloride,
Methylene (cyclopentadienyl) (3,4-dimethyl
Cyclopentadienyl) zirconium dichloride, methyl
Ren (cyclopentadienyl) (3,4-dimethyl
Lopentadienyl) zirconium chlorohydride, methyl
Ren (cyclopentadienyl) (3,4-dimethyl
Lopentadienyl) dimethyl zirconium, methylene
(Cyclopentadienyl)(3,4-dimethylcyclope
N-dienyl)diphenylzirconium, methylene
Clopentadienyl) (trimethylcyclopentadienyl)
Ru) zirconium dichloride, methylene (cyclopenta
Dienyl) (tetramethylcyclopentadienyl) dil
Conium dichloride, isopropylidene (cyclopenta
Dienyl) (3,4-dimethylcyclopentadienyl)
Zirconium dichloride, isopropylidene (cyclope
Ntadienyl) (2,3,4,5-tetramethylcyclo
Pentadienyl) zirconium dichloride, isopropyl
Ridene (cyclopentadienyl) (3-methylindeni
Z) Zirconium dichloride, isopropylidene
Lopentadienyl) (fluorenyl) zirconium di
Lolid, isopropylidene (2-methylcyclopentadiene
(Enyl) (fluorenyl) zirconium dichloride, a
Sopropylidene (2,5-dimethylcyclopentadiene
)(3,4-Dimethylcyclopentadienyl)zirco
Indium dichloride, isopropylidene (2,5-dimethyl
Rucyclopentadienyl) (fluorenyl) zirconium
Mudic chloride, ethylene (cyclopentadienyl)
(3,5-Dimethylcyclopentadienyl) zirconium
Mudic chloride, ethylene (cyclopentadienyl)
Ruorenyl) zirconium dichloride, ethylene (2,
5-dimethylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, ethylene (2,5-diethyl
Cyclopentadienyl)(fluorenyl)zirconium
Dichloride, diphenylmethylene (cyclopentadiene
)(3,4-Diethylcyclopentadienyl)zirco
Nium dichloride, diphenylmethylene (cyclopenta
Dienyl) (3,4-diethylcyclopentadienyl)
Zirconium dichloride, cyclohexylidene (cyclo
Pentadienyl)(fluorenyl)zirconium dichloride
Lido, cyclohexylidene (2,5-dimethylcyclope
(3',4'-dimethylcyclopentadiene)
(Enyl) zirconium dichloride, methylene bis (yne
Denyl) hafnium dichloride, ethylene bis (indene
Nyl)hafnium dichloride, methylenebis(indeni)
Hafnium chlorohydride, ethylene bis(indene)
Nyl)methyl hafnium chloride, ethylene bis(yne
Denyl)methoxychlorohafnium, ethylene bis(a)
Ndenyl)hafnium diethoxide, ethylene bis(a)
Ndenyl)dimethyl hafnium, ethylene bis(4,
5,6,7-Tetrahydroindenyl)hafnium dich
Lolid, ethylenebis(2-methylindenyl) hafni
Umdichloride, ethylenebis(2,4-dimethylin)
Denyl) hafnium dichloride, ethylene bis(2-me
Cyl-4-trimethylsilylindenyl)hafnium di
Chloride, ethylene bis(2,4-dimethyl-5,6,6
7-trihydroindenyl)hafnium dichloride, d
Tylene bis(2,4,7-trimethylindenyl) huff
Aluminum dichloride, ethylene bis(2,4,7-trimethyl
Tylindenyl) titanium dichloride, ethylene bis
(2,4,7-Trimethylindenyl)zirconium di
Chloride, ethylene (2,4-dimethylcyclopentadiene
(Enyl) (3',5'-dimethylcyclopentadienyl
Hafnium dichloride, ethylene (2-methyl-4)
-T-butylcyclopentadienyl) (3'-t-butyl
Ru-5'-methylcyclopentadienyl)hafnium di
Chloride, ethylene (2,3,5-trimethylcyclopentene
Tadienyl) (2',4',5'-trimethylcyclope
Hafnium dichloride, isopropylide
Bis(2-methylindenyl)hafnium dichloride
De, isopropylidene bis(indenyl) hafnium di
Chloride, isopropylidene bis(2,4-dimethyl
Ndenyl) hafnium dichloride, isopropylidene
(2,4-dimethylcyclopentadienyl) (3'5'
-Dimethylcyclopentadienyl) hafnium dichloride
, Isopropylidene (2-methyl-4-t-butyloxy)
Clopentadienyl)(3'-t-butyl-5'-methyl
(Lucyclopentadienyl) hafnium dichloride, methyl
Ren (cyclopentadienyl) (3,4-dimethyl
Lopentadienyl) hafnium dichloride, methylene
(Cyclopentadienyl)(3,4-dimethylcyclope
Hafnium chlorohydrido, methylene
(Cyclopentadienyl)(3,4-dimethylcyclope
Ntadienyl) dimethyl hafnium, methylene (cyclo
Pentadienyl) (3,4-dimethylcyclopentadiene
Nyl)diphenylhafnium, methylene (cyclopenta
Dienyl) (trimethylcyclopentadienyl) hafni
Umdichloride, methylene (cyclopentadienyl)
(Tetramethylcyclopentadienyl)hafnium dich
Lolid, isopropylidene (cyclopentadienyl)
(3,4-Dimethylcyclopentadienyl)hafnium
Dichloride, isopropylidene (cyclopentadiene
(2,3,4,5-tetramethylcyclopentadiene)
Nil) hafnium dichloride, isopropylidene (shik
Lopentadienyl)(3-methylindenyl)hafuniu
Mudichloride, isopropylidene (cyclopentadiene
(Fluorenyl) hafnium dichloride, isopro
Pyridene (2-methylcyclopentadienyl) (fluor
Renyl) hafnium dichloride, isopropylidene
(2,5-Dimethylcyclopentadienyl) (3,4-
Dimethylcyclopentadienyl) hafnium dichloride
Isopropylidene (2,5-dimethylcyclopenta
Dienyl)(fluorenyl)hafnium dichloride, d
Tylene (cyclopentadienyl) (3,5-dimethyl
Clopentadienyl) hafnium dichloride, ethylene
(Cyclopentadienyl)(fluorenyl)hafnium
Dichloride, ethylene (2,5-dimethylcyclopenta
Dienyl)(fluorenyl)hafnium dichloride, d
Tylene (2,5-diethylcyclopentadienyl)
Fluorenyl) hafnium dichloride, diphenyl methyl
(Cyclopentadienyl) (3,4-diethylcyclo
Pentadienyl) hafnium dichloride, diphenylmeth
Tylene (cyclopentadienyl) (3,4-diethyl
Clopentadienyl) hafnium dichloride, cyclohe
Xylidene (cyclopentadienyl) (fluorenyl)
Hafnium dichloride, cyclohexylidene (2,5-
Dimethylcyclopentadienyl) (3',4'-dimethyl)
Such as rucyclopentadienyl) hafnium dichloride
Has two conjugated five-membered ring ligands bridged by an alkylene group
Transition metal compounds, dimethylsilylene bis(indenyl)titanium dichloride
Lolid, dimethyl silylene bis (4,5,6,7-teto
Lahydroindenyl) titanium dichloride, dimethyl
Silylene bis(2-methylindenyl)titanium dioxide
Lolid, dimethylsilylene bis(2,4-dimethylin
Denyl) titanium dichloride, dimethyl silylene bis
(2,4-dimethylcyclopentadienyl) (3',
5'-dimethylcyclopentadienyl)titanium di
Lolid, dimethylsilylene bis(2-methyl-4,5-
Benzoindenyl)titanium dichloride, dimethyl
Rylene bis(2,2,7-trimethylindenyl) tita
Nium dichloride, dimethyl silylene bis (2,2,7
-Trimethylindenyl) hafnium dichloride, dime
Tillsilylene bis(2,2,7-trimethylindeni
Z) Zirconium dichloride, dimethyl silylene bis
(2-Methyl-4-naphthylindenyl)titanium di
Chloride, dimethylsilylene bis(2-methyl-4-phenyl)
(Phenylindenyl) titanium dichloride, phenyl
Tillsilylene bis(indenyl)titanium dichloride
Phenylmethylsilylene bis(4,5,6,7-the
Trahydroindenyl)titanium dichloride, phenyl
Rumethylsilylene bis(2,4-dimethylindenyl)
Titanium dichloride, phenylmethylsilylene (2,
4-dimethylcyclopentadienyl)(3',5'-di
Methylcyclopentadienyl)titanium dichloride,
Phenylmethylsilylene (2,3,5-trimethyl
Lopentadienyl)(2',4',5'-trimethylsi
Clopentadienyl) titanium dichloride, phenyl
Methylsilylene bis(tetramethylcyclopentadiene
Ru) Titanium dichloride, diphenylsilylene bis
(2,4-Dimethylindenyl)titanium dichloride
De,diphenylsilylene bis(indenyl)titanium
Dichloride, diphenylsilylene bis(2-methylin
Denyl) titanium dichloride, tetramethyldisilire
Bis(indenyl)titanium dichloride, tetrame
Tilldisilirene bis(cyclopentadienyl) titaniu
Mudichloride, tetramethyldisilylene (3-methylsilane
Clopentadienyl)(indenyl)titanium dichloride
Lido, dimethylsilylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl)titanium
Dichloride, dimethylsilylene (cyclopentadiene
)(Trimethylcyclopentadienyl)titanium di
Chloride, dimethylsilylene (cyclopentadienyl)
(Tetramethylcyclopentadienyl) titanium dioxide
Lolid, dimethylsilylene (cyclopentadienyl)
(3,4-diethylcyclopentadienyl)titanium
Dichloride, dimethylsilylene (cyclopentadiene
Ru) (triethylcyclopentadienyl) titanium di
Chloride, dimethylsilylene (cyclopentadienyl)
(Tetraethylcyclopentadienyl) titanium dioxide
Lolid, dimethylsilylene (cyclopentadienyl)
(Fluorenyl)titanium dichloride, dimethylsilyl
Ren (cyclopentadienyl) (2,7-di-t-butyl
Rufluorenyl) titanium dichloride, dimethylsilyl
Ren (cyclopentadienyl) (octahydrofluore
Nyl) titanium dichloride, dimethyl silylene (2-
Methylcyclopentadienyl)(fluorenyl)titani
Umdichloride, dimethylsilylene (2,5-dimethyl
Cyclopentadienyl)(fluorenyl)titanium di
Chloride, dimethylsilylene (2-ethylcyclopenta
Dienyl)(fluorenyl)titanium dichloride, di
Methylsilylene (2,5-diethylcyclopentadiene
)(Fluorenyl)titanium dichloride, diethyl
Silylene (2-methylcyclopentadienyl) (2',
7'-di-t-butylfluorenyl)titanium dichloride
Lido, dimethylsilylene (2,5-dimethylcyclopen
Tadienyl) (2',7'-di-t-butyl fluoreni
) Titanium dichloride, dimethylsilylene (2-E
Cylcyclopentadienyl)(2',7'-di-t-bu
Tylfluorenyl)titanium dichloride, dimethyl
Rylene (diethylcyclopentadienyl) (2,7-di
-T-butylfluorenyl)titanium dichloride, di
Methylsilylene (methylcyclopentadienyl) (oct
Tahido fluorenyl) titanium dichloride, dimethyl
Silylene (dimethylcyclopentadienyl) (octahi
Drofluorenyl) titanium dichloride, dimethyl
Rylene (ethylcyclopentadienyl) (octahydro
Fluorenyl) titanium dichloride, dimethylsilyl
(Diethylcyclopentadienyl) (octahydrofuran
Fluorenyl) titanium dichloride, dimethylsilylene
Bis(indenyl)zirconium dichloride, dimethyl
Silylene bis(4,5,6,7-tetrahydroindeni
Z) Zirconium dichloride, dimethyl silylene bis
(2-Methylindenyl)zirconium dichloride, di
Methylsilylene bis(2,4-dimethylindenyl)di
Ruconium dichloride, dimethyl silylene bis (2,4
-Dimethylcyclopentadienyl) (3',5'-dime
Tylcyclopentadienyl)zirconium dichloride,
Dimethyl silylene bis(2-methyl-4,5-benzoy
Ndenyl)zirconium dichloride, dimethylsilylene
Bis(2-methyl-4-naphthylindenyl)zirconi
Umdichloride, dimethylsilylene bis(2-methyl-
4-phenylindenyl)zirconium dichloride, fluorine
Phenylmethylsilylenebis(indenyl)zirconium
Dichloride, phenylmethylsilylene bis (4,5,
6,7-Tetrahydroindenyl)zirconium dichloride
Lido, phenylmethylsilylene bis(2,4-dimethyl
Indenyl) zirconium dichloride, phenylmethyl
Silylene (2,4-dimethylcyclopentadienyl)
(3',5'-dimethylcyclopentadienyl)zirco
Nium dichloride, phenylmethylsilylene (2, 3,
5-trimethylcyclopentadienyl) (2', 4',
5'-trimethylcyclopentadienyl)zirconium
Dichloride, phenylmethylsilylene bis (tetramethyi
Lucyclopentadienyl) zirconium dichloride, di
Phenylsilylene bis(2,4-dimethylindenyl)
Zirconium dichloride, diphenylsilylene bis(a
Ndenyl)zirconium dichloride, diphenylsilyl
Bis(2-methylindenyl)zirconium dichloride
De, tetramethyldisililen bis(indenyl) zirco
Nium dichloride, tetramethyldisilylene bis
Lopentadienyl) zirconium dichloride, tetrame
Tyldisililen (3-methylcyclopentadienyl)
(Indenyl)zirconium dichloride, dimethylsilyl
Ren (cyclopentadienyl) (3,4-dimethyl
Lopentadienyl) zirconium dichloride, dimethyl
Silylene (cyclopentadienyl) (trimethylcyclo
Pentadienyl) zirconium dichloride, dimethyl
Rylene (cyclopentadienyl) (tetramethylcyclo
Pentadienyl) zirconium dichloride, dimethyl
Rylene (cyclopentadienyl) (3,4-diethyl
Clopentadienyl) zirconium dichloride, dimethy
Lucilene (cyclopentadienyl) (triethylsic)
Lopentadienyl) zirconium dichloride, dimethyl
Silylene (cyclopentadienyl) (tetraethyl
Lopentadienyl) zirconium dichloride, dimethyl
Silylene(cyclopentadienyl)(fluorenyl)di
Ruconium dichloride, dimethyl silylene (cyclopen
Tadienyl) (2,7-di-t-butylfluorenyl)
Zirconium dichloride, dimethyl silylene (cyclope
Ntadienyl) (octahydrofluorenyl) zirconi
Umdichloride, dimethylsilylene (2-methylcyclo
Pentadienyl)(fluorenyl)zirconium dichloride
Lido, dimethylsilylene (2,5-dimethylcyclopen
Tadienyl) (fluorenyl) zirconium dichloride
Demethyldimethylene (2-ethylcyclopentadiene
Le) (fluorenyl) zirconium dichloride, dimethy
Lucillene (2,5-diethylcyclopentadienyl)
(Fluorenyl)zirconium dichloride, diethyl
Rylene (2-methylcyclopentadienyl) (2',
7'-di-t-butylfluorenyl)zirconium di
Lolid, dimethylsilylene (2,5-dimethylcyclope
Ntadienyl)(2',7'-di-t-butylfluore
Nyl)zirconium dichloride, dimethylsilylene (2
-Ethylcyclopentadienyl)(2',7'-di-t
-Butylfluorenyl) zirconium dichloride, dime
Tylsilylene (diethylcyclopentadienyl) (2,
7-di-t-butylfluorenyl)zirconium dichloride
Lido, dimethylsilylene (methylcyclopentadiene
)(Octahydrfluorenyl)zirconium dichloride
De, dimethyl silylene (dimethyl cyclopentadiene
(Octahydrofluorenyl) zirconium dichloride
Lido, dimethyl silylene (ethylcyclopentadiene
(Octahydrofluorenyl) zirconium dichloride
Lido, dimethylsilylene (diethylcyclopentadiene
(Octahydrofluorenyl) zirconium dichloride
Lido, dimethyl silylene bis(indenyl)hafnium
Dichloride, dimethylsilylene bis (4,5,6,7-
Tetrahydroindenyl) hafnium dichloride, dime
Tillsilylenebis(2-methylindenyl)hafnium
Dichloride, dimethylsilylene bis(2,4-dimethyl
Indenyl) hafnium dichloride, dimethylsilylene
Bis(2,4-dimethylcyclopentadienyl)
(3',5'-Dimethylcyclopentadienyl)hafni
Umdichloride, dimethylsilylene bis(2-methyl-
4,5-Benzoindenyl)hafnium dichloride, di
Methylsilylene bis(2-methyl-4-naphthylindene
Nyl) hafnium dichloride, dimethyl silylene bis
(2-Methyl-4-phenylindenyl)hafnium di
Chloride, phenylmethylsilylene bis (indenyl)
Hafnium dichloride, phenylmethyl silylene bis
(4,5,6,7-Tetrahydroindenyl)hafuniu
Mudic chloride, phenylmethylsilylene bis(2,4-
Dimethylindenyl) hafnium dichloride, phenyl
Methylsilylene (2,4-dimethylcyclopentadiene
)(3',5'-dimethylcyclopentadienyl)ha
Funnium dichloride, Phenylmethylsilylene (2,
3,5-trimethylcyclopentadienyl) (2',
4',5'-trimethylcyclopentadienyl)hafni
Umdichloride, phenylmethylsilylene bis (tetra
Methylcyclopentadienyl) hafnium dichloride,
Diphenylsilylene bis(2,4-dimethylindeni
Le) Hafnium dichloride, diphenylsilylene bis
(Indenyl)hafnium dichloride, diphenylsilyl
Renbis(2-methylindenyl)hafnium dichloride
De, tetramethyldisilylenebis(indenyl)hafni
Ummdichloride, tetramethyldisilylenebis(cyclo
Pentadienyl) hafnium dichloride, tetramethyl
Disilylene (3-methylcyclopentadienyl) (yne
Denyl) hafnium dichloride, dimethylsilylene
Clopentadienyl) (3,4-dimethylcyclopenta
Dienyl) hafnium dichloride, dimethylsilylene
(Cyclopentadienyl) (trimethylcyclopentadiene
(Enyl) hafnium dichloride, dimethylsilylene
Clopentadienyl) (tetramethylcyclopentadiene)
Nyl) hafnium dichloride, dimethyl silylene (siku
Ropentadienyl) (3,4-diethylcyclopentadiene
(Enyl) hafnium dichloride, dimethylsilylene
Clopentadienyl) (triethylcyclopentadienyl)
Hafnium dichloride, dimethylsilylene (cyclo)
Pentadienyl) (tetraethylcyclopentadienyl)
Hafnium dichloride, dimethylsilylene (cyclo)
Pentadienyl)(fluorenyl)hafnium dichloride
De, dimethylsilylene (cyclopentadienyl) (2,
7-di-t-butylfluorenyl) hafnium dichlorine
De, dimethylsilylene (cyclopentadienyl) (oct
Tahydrofluorenyl) hafnium dichloride, dimethy
Lucillene (2-methylcyclopentadienyl) (full
(Olenyl) hafnium dichloride, dimethylsilylene
(2,5-dimethylcyclopentadienyl) (fluorescein
Nyl)hafnium dichloride, dimethylsilylene (2-
Ethylcyclopentadienyl)(fluorenyl)hafni
Umdichloride, dimethylsilylene (2,5-diethyl
Cyclopentadienyl)(fluorenyl)hafnium di
Chloride, diethyl silylene (2-methylcyclopenta
Dienyl) (2',7'-di-t-butyl fluorenyl
Hafnium dichloride, dimethylsilylene (2,5)
-Dimethylcyclopentadienyl) (2',7'-di-
t-Butylfluorenyl) hafnium dichloride, dime
Tylsilylene (2-ethylcyclopentadienyl)
(2',7'-di-t-butylfluorenyl) hafuniu
Mudichloride, dimethylsilylene (diethylcyclopen
Tadienyl) (2,7-di-t-butylfluorenyl)
Hafnium dichloride, dimethylsilylene (methyl
Lopentadienyl) (octahydrfluorenyl) hafni
Umdichloride, dimethylsilylene (dimethylcyclope
Ntadienyl) (octahydrofluorenyl) hafuniu
Mudichloride, dimethylsilylene (ethylcyclopenta
Dienyl) (octahydrofluorenyl) hafnium di
Chloride, dimethylsilylene (diethylcyclopentadiene
(Enyl) (octahydrofluorenyl) hafnium dich
Two silylene group-bridged conjugated five-membered ring ligands such as lolide
Transition metal compounds, dimethylgermylene bis(indenyl)titanium di
Chloride, dimethylgermylene (cyclopentadiene
)(Fluorenyl)titanium dichloride, methyla
Lumilenbis(indenyl)titanium dichloride, f
Phenylamylene bis(indenyl)titanium dichloride
De,phenylphosphylene bis(indenyl)titaniu
Mudichloride, ethylborenbis(indenyl)titani
Umdichloride, Phenylamylenebis(indenyl)
Titanium dichloride, phenylamylene (cyclopen
Tadienyl) (fluorenyl) titanium dichloride,
Dimethylgermylene bis(indenyl)zirconium di
Chloride, dimethylgermylene (cyclopentadiene
Lu) (fluorenyl) zirconium dichloride, methyl
Alylene bis(indenyl) zirconium dichloride
De, phenylamylene bis(indenyl) zirconium
Dichloride, phenylphosphylene bis(indenyl)
Zirconium dichloride, ethyl boren bis (indeni
Le) zirconium dichloride, phenylamylene bis
(Indenyl)zirconium dichloride, phenylami
Len(cyclopentadienyl)(fluorenyl)zirco
Indium dichloride, dimethylgermylene bis(indeni
Hafnium dichloride, dimethylgermylene
Lopentadienyl) (fluorenyl) hafnium dichlor
Lido, methylaluminene bis(indenyl)hafnium
Dichloride, phenylamylene bis(indenyl) huff
Indium dichloride, phenylphosphylene bis (indene
Nyl) hafnium dichloride, ethyl boren bis(yne
Denyl) hafnium dichloride, phenylamylene bis
(Indenyl)hafnium dichloride, phenylamile
(Cyclopentadienyl) (fluorenyl) hafuniu
Germanium such as mucichloride, aluminum, boron
Conjugates crosslinked with hydrocarbon radicals containing elemental, phosphorus or nitrogen
A transition metal compound having two membered ring ligands, pentamethylcyclopentadienyl-bis(phenylene)
A) aminotitanium dichloride, indenyl-bis
(Phenyl)aminotitanium dichloride, pentamethyi
Rucyclopentadienyl-bis(trimethylsilyl)a
Minotitanium dichloride, pentamethylcyclopenta
Dienylphenoxytitanium dichloride, dimethyl
Rylene (tetramethylcyclopentadienyl) t-butyl
Luminotitanium dichloride, dimethylsilylene (Te
Tramethylcyclopentadienyl)phenylaminotita
Nium dichloride, dimethyl silylene (tetrahydro
Ndenyl)decylaminotitanium dichloride, dimethy
Lucillene (tetrahydroindenyl) [bis (trime
Cylsilyl)amino]titanium dichloride, dimethyl
Germylene (tetramethylcyclopentadienyl) fe
Nylaminotitanium dichloride, pentamethylcyclo
Pentadienyltitanium trimethoxide, pentamethyi
Rucyclopentadienyl titanium trichloride, pen
Tamethylcyclopentadienyl-bis(phenyl)ami
Nozirconium dichloride, indenyl-bis(phenylene
Le) aminozirconium dichloride, pentamethylsiku
Lopentadienyl-bis(trimethylsilyl)aminodi
Ruconium dichloride, pentamethylcyclopentadiene
Nylphenoxyzirconium dichloride, dimethylsilyl
Ren (tetramethylcyclopentadienyl) t-butyl
Amino zirconium dichloride, dimethyl silylene (the
Tramethylcyclopentadienyl)phenylaminodil
Conium dichloride, dimethyl silylene (tetrahydro
Indenyl)decylaminozirconium dichloride, di
Methylsilylene (tetrahydroindenyl) [bis(to
Limethylsilyl)amino]zirconium dichloride, di
Methylgermylene (tetramethylcyclopentadiene
) Phenylaminozirconium dichloride, pentame
Cylcyclopentadienyl zirconium trimethoxy
De, pentamethylcyclopentadienyl zirconium
Lichloride, pentamethylcyclopentadienyl-bis
(Phenyl)aminohafnium dichloride, indenyl
-Bis(phenyl)aminohafnium dichloride, pen
Tamethylcyclopentadienyl-bis(trimethylsilyl
A) aminohafnium dichloride, pentamethylcyclo
Pentadienylphenoxyhafnium dichloride, dime
Tylsilylene (tetramethylcyclopentadienyl) t
-Butylaminohafnium dichloride, dimethylsilyl
(Tetramethylcyclopentadienyl)phenylami
Nohafnium dichloride, dimethyl silylene (tetrahy
Droindenyl)decylaminohafnium dichloride,
Dimethylsilylene (tetrahydroindenyl) [bis
(Trimethylsilyl)amino]hafnium dichloride,
Dimethylgermylene (tetramethylcyclopentadiene
)Phenylamino hafnium dichloride, pentamethy
Rucyclopentadienyl hafnium trimethoxide, pe
N-methylcyclopentadienyl hafnium trichlor
Transition metal compounds having one conjugated five-membered ring ligand such as
(1,1'-dimethylsilylene) (2,2'-isopene
Ropylidene)-bis(cyclopentadienyl)titaniu
Mudichloride, (1,1'-dimethylsilylene) (2,
2'-Dimethylsilylene)-bis(cyclopentadienyl)
Le) titanium dichloride, (1,1'-dimethylsilyl)
Len)(2,2'-isopropylidene)-bis(cyclo
Pentadienyl)dimethyltitanium, (1,1'-di
Methylsilylene)(2,2'-isopropylidene)-bi
Sus(cyclopentadienyl)dibenzyltitanium,
(1,1'-Dimethylsilylene) (2,2'-isopro
Pyridene)-bis(cyclopentadienyl)bis(tri
Methylsilyl) titanium, (1,1'-dimethylsilyl)
Len)(2,2'-isopropylidene)-bis(cyclo
Pentadienyl)bis(trimethylsilylmethyl)tita
Nium, (1,2'-dimethylsilylene) (2,1'-
Ethylene)-bis(indenyl)titanium dichloride
De, (1,1'-dimethylsilylene) (2,2'-ethyl
Len)-bis(indenyl)titanium dichloride,
(1,1'-ethylene) (2,2'-dimethylsilyle
N)-bis(indenyl)titanium dichloride,
(1,1'-dimethylsilylene) (2,2'-cyclohexyl
Xylidene)-bis(indenyl)titanium dichloride
De, (1,1'-dimethylsilylene) (2,2'-iso
Propylidene)-bis(cyclopentadienyl)zirco
Aluminum dichloride, (1,1'-dimethylsilylene)
(2,2'-Dimethylsilylene)-bis(cyclopenta
Dienyl)zirconium dichloride, (1,1'-dime
Tylsilylene)(2,2'-isopropylidene)-bis
(Cyclopentadienyl)dimethyl zirconium,
(1,1'-Dimethylsilylene) (2,2'-isopro
Pyridene)-bis(cyclopentadienyl)dibenzyl
Zirconium, (1,1'-dimethylsilylene) (2,
2'-isopropylidene)-bis(cyclopentadiene)
Ru)bis(trimethylsilyl)zirconium, (1,
1'-dimethylsilylene) (2,2'-isopropylidene
)-Bis(cyclopentadienyl)bis(trimethyl
Silylmethyl)zirconium, (1,2'-dimethylsi
Rylene)(2,1'-ethylene)-bis(indenyl)
Zirconium dichloride, (1,1'-dimethylsilylate
)(2,2'-Ethylene)-bis(indenyl)zyl
Conium dichloride, (1,1'-ethylene) (2,
2'-Dimethylsilylene)-bis(indenyl)zirco
Aluminum dichloride, (1,1'-dimethylsilylene)
(2,2'-Cyclohexylidene)-bis(indeni
Z) Zirconium dichloride, (1,1'-dimethyl
Rylene)(2,2'-isopropylidene)-bis(shik
Lopentadienyl)hafnium dichloride, (1,1'
-Dimethylsilylene) (2,2'-dimethylsilylene)
-Bis(cyclopentadienyl)hafnium dichloride
De, (1,1'-dimethylsilylene) (2,2'-iso
Propylidene)-bis(cyclopentadienyl) dimethyl
Ruhafnium, (1,1'-dimethylsilylene) (2,
2'-isopropylidene)-bis(cyclopentadiene)
Le) dibenzylhafnium, (1,1'-dimethylsilyl)
Len)(2,2'-isopropylidene)-bis(cyclo
Pentadienyl)bis(trimethylsilyl)hafuniu
, (1,1'-dimethylsilylene) (2,2'-iso
Propylidene)-bis(cyclopentadienyl)bis
(Trimethylsilylmethyl)hafnium, (1,2'-
Dimethylsilylene)(2,1'-ethylene)-bis(ii)
Ndenyl)hafnium dichloride, (1,1'-dimethyl)
Lucillene)(2,2'-ethylene)-bis(indeni
Le) hafnium dichloride, (1,1'-ethylene)
(2,2'-Dimethylsilylene)-bis(indenyl)
Hafnium dichloride, (1,1'-dimethylsilyle
)(2,2'-Cyclohexylidene)-bis(indene)
Nyl) Hafnium dichloride and other ligands
Transition metal compounds with two bridged conjugated five-membered ring ligands
And further in the compounds described in 1 to
Chlorine atom of these compounds is replaced with bromine atom, iodine atom, hydrogen source
Child, methyl group, phenyl group, benzyl group, methoxy group,
Some examples include those that have been replaced with dimethylamino groups, etc.
it can. (II) Specific examples of the transition metal compound represented by the general formula (3)
The following compounds can be mentioned as

Tetra-n-butoxytitanium, tetra-i-propoxytitanium, tetraphenoxytitanium, tetracrezoxytitanium, tetrachlorotitanium, tetrakis(diethylamino)titanium, tetrabromotitanium, and titanium were replaced by zirconium and hafnium. A compound etc. can be mentioned. Among these transition metal compounds, alkoxytitanium compounds, alkoxyzirconium compounds and alkoxyhafnium compounds are preferable.

In the catalyst of the present invention, the above component (B)
These transition metal compounds may be used alone or in combination of two or more. (C) Organoaluminum Compound As the organoaluminum compound, the linear aluminoxane represented by the general formula (4) or the general formula (5) is used.
Examples of the cyclic aluminoxane represented by or a cyclic aluminoxane aggregate and an alkyl group-containing aluminum compound represented by the general formula (6). Among these,
The alkyl group-containing aluminum compound represented by the general formula (6) is preferable. Specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trialkylaluminum such as tri-t-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride,
Alkyl aluminum containing hydrogen atom such as dimethyl aluminum methoxide, diethyl aluminum methoxide, dimethyl aluminum hydroxide, diethyl aluminum hydroxide, etc. halogen, alkoxy group-containing or alkyl aluminum, dimethyl aluminum hydride, diisobutyl aluminum hydride, etc. Examples include modified products.

Among them, trialkylaluminum is preferable, and triisobutylaluminum is preferable as trialkylaluminum. In the method for producing the olefin polymerization catalyst of the present invention, the order of contacting each component is not particularly limited, and the components can be contacted in the following order. When the component (A) and the component (B) are used, for example, a method of contacting the component (A) with the component (B),
Examples include a method of contacting the component (A) with the component (B), and a method of simultaneously contacting the two components. Of these, the contact method is preferred.

Further, the component (A), the component (B) and the component (C)
When using a component, for example, a method of contacting the component (A) and the component (B) and then the component (C),
A method of contacting the component (A) and the component (C) and then the component (B), a method of contacting the component (B) and the component (C) and then the component (A), and further, Three
A method of bringing the components into contact with each other at the same time may be mentioned. Of these, the contact method is preferred.

Further, during or after the contact of the respective components, a polymer such as polyethylene, polypropylene, polystyrene or the like, or a solid of an inorganic oxide such as silica or alumina may be coexistent or contacted. This improves the morphology of the resulting polymer. The contact of the above catalyst components can be carried out in an inert gas such as nitrogen at a temperature not higher than the polymerization temperature, but may be carried out in the range of -30 to 200°C.

Regarding the contact ratio of each component, when the components (A) and (B) are used, the amount of the component (A) is the mole of aluminum and the amount of the component (B) is the mole of the transition metal. In the case of being expressed, 2 moles of the component (A) per 1 mole of the component (B).
Contact is made so as to be ˜200,000 mol. Preferably, the amount of the component (A) is 200 to 2 with respect to 1 mol of the component (B).
Contact is made so that the amount becomes 0000 mol.

Further, the component (A), the component (B) and the component (C)
When the component is used, the amount of the component (A) is represented by moles of aluminum, the amount of the component (B) is represented by moles of the transition metal, and the amount of the component (C) is represented by moles of aluminum, the component (B) 1 2 to 200,000 mol of the component (A) per mol,
The component (C) is brought into contact in an amount of 0.0001 to 200,000 mol. Preferably, the component (A) is contacted with 200 to 20000 mol and the component (C) is contacted with 30 to 5000 mol with respect to 1 mol of the component (B).

In the present invention, at least one of the catalyst components may be supported on a suitable carrier for use. (D) Carrier The type of carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers and organic carriers can be used. In particular, from the viewpoint of morphology control, the inorganic oxide carrier or other carriers can be used. Inorganic carriers are preferred. Further, the above-mentioned (b) adsorptive substance can also be used as the carrier.

Specific examples of the inorganic oxide carrier include S
iO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , F
e ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO
₂ , silica-alumina, zeolite, ferrite, glass fiber, etc. Among these, especially S
iO ₂ or Al ₂ O ₃ is preferred. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate or the like.

On the other hand, as a carrier other than the above, MgC
l₂, Mg(OC₂H_Five)₂Magnesium compounds such as
General formula represented by MgR¹³ _XX¹ _yMagne represented by
Examples thereof include sium compounds and their complex salts. This
Here, R¹³Is an alkyl group having 1 to 20 carbon atoms, and 1 to carbon atoms
An alkoxy group having 20 or an aryl group having 6 to 20 carbon atoms,
X ¹Is a halogen atom or an alkyl group having 1 to 20 carbon atoms
, X is 0-2, y is 0-2, and x+y=2
Is. Each R¹³And each X¹Can be the same,
May be different.

As the organic carrier, polystyrene,
Styrene-divinylbenzene copolymer, polyethylene,
Examples thereof include polymers such as polypropylene, substituted polystyrene, polyarylate, starch, carbon and the like. As the carrier used in the present invention, MgC
l ₂ , MgCl(OC ₂ H ₅ ), Mg(OC ₂ H ₅ ) ₂ ,
SiO ₂ , Al ₂ O _{3 and the} like are preferable. The properties of the carrier vary depending on the type and production method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm, and more preferably 20 to 100 μm.

When the particle size is small, the amount of fine powder in the polymer increases,
If the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper. The specific surface area of the carrier is usually 1 to 1000 m ² /g, preferably 50 to
500 m ² /g, pore volume is usually 0.1-5 cm ³ /g,
It is preferably 0.3 to ³ cm ³ /g.

If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be obtained, for example, from the volume of nitrogen gas adsorbed according to the BET method (see J. Am. Chem. Soc, Volume 60, page 309 (1983)). Further, it is desirable that the carrier is usually used after calcined at 150 to 1000°C, preferably 200 to 800°C.

Regarding the order of loading the component (D) and the other components, usually, after the component (A) is loaded on the component (D),
The component (B) is contacted. In this case, the component (C) is
The component (B) may or may not be contacted before and after the contact. Moreover, after bringing the component (B) into contact with the component (A),
It may be supported on the component (D). In this case, the (C) component and the (D) component may or may not be contacted before and after the (B) component is contacted.

Preferably, the component (A) is supported on the component (D) and then the component (B) is contacted. In addition, the component (D) is usually added to 1 mol of the component (B),
Use 0.001 g to 10 g. Preferably 0.01 g
Use ~1 g. 3. Method for Producing Olefin Polymer The method for producing an olefin polymer of the present invention is a method for homopolymerizing olefins, or olefins and other olefins, using the above-mentioned catalyst for olefin polymerization or, if necessary, organoaluminum. And/or other monomers (ie, different olefins with each other, olefins with other monomers, or different olefins with other monomers). (Copolymerization of) can be suitably carried out.

Regarding the polymerization conditions, the polymerization temperature is usually −
It is in the range of 50 to 200°C, preferably -20 to 150°C, more preferably 0 to 120°C. Polymerization pressure is usually 0 to 200 kg/cm ² G, preferably 0.1 to 150 k
g/cm ² G, more preferably 0.2 to 100 kg/cm
It is in the range of ² G. The polymerization time is usually 10 seconds to
It is in the range of 40 hours, preferably 30 seconds to 30 hours, more preferably 1 minute to 10 hours. Further, the amount of the catalyst used is advantageously selected so that the molar ratio of the raw material monomer/the component (B) is preferably 1 to 10 ⁸ , more preferably 100 to 10 ⁷ .

As the organoaluminum, those represented by the above general formulas (4) to (6) can be used.
The amount of the organoaluminum is 0.01 to 100 mmol, preferably 0.1 per 1 mol of the transition metal compound.
~30 mmol. The olefins are not particularly limited, but α-olefins having 2 to 20 carbon atoms are preferable. Particularly preferred are ethylene and propylene.
Examples of this α-olefin include ethylene, propylene, 1-butene, and 3-methyl-1.
-Butene, 4-methyl-1-butene, 4-phenyl-1
-Butene, 1-pentene, 3-methyl-1-pentene,
4-methyl-1-pentene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1
-Hexene, 5-methyl-1-hexene, 6-phenyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane, etc. Α-olefins, hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene, 3,4-dichloro-1-
Examples thereof include halogen-substituted α-olefins such as butene, cyclopentene, cyclohexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene and 5-benzylnorbornene. it can.

Further, styrene compounds may be used as the olefins in the present invention. Examples of the styrene compound include styrene, p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene, o-
Ethyl styrene, o-propyl styrene, o-isopropyl styrene, m-methyl styrene, m-ethyl styrene, m-isopropyl styrene, m-butyl styrene,
Mesityl styrene, 2,4-dimethyl styrene, 2,5
-Alkyl styrenes such as dimethyl styrene and 3,5-dimethyl styrene, alkoxy styrenes such as p-methoxy styrene, o-methoxy styrene and m-methoxy styrene, p-chloro styrene, m-chloro styrene, o
-Chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene,
halogenated styrenes such as m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene,
Further, trimethylsilylstyrene, vinyl benzoate, divinylbenzene and the like can be mentioned.

The other olefins described above may be appropriately selected from the above olefins. In the present invention, the olefins may be used alone or in combination of two or more. When copolymerizing two or more kinds of olefins, the above olefins can be arbitrarily combined.

In the present invention, among the above-mentioned olefins, the above-mentioned α-olefin is preferable. Further, in the present invention, the above-mentioned olefins and other monomers may be copolymerized, and examples of the other monomer used at this time include butadiene, isoprene, 1,4-pentadiene, 1, Chain diolefins such as 5-hexadiene, norbornene, 1,4,5,8-dimethano-
1,2,3,4,4a,5,8,8a-octahydronaphthalene, polycyclic olefins such as 2-norbornene, norbornadiene, 5-ethylidene norbornene,
Examples thereof include cyclic diolefins such as 5-vinylnorbornene and dicyclopentadiene, and unsaturated esters such as ethyl acrylate and methyl methacrylate.

The method for polymerizing the olefins is not particularly limited, and slurry polymerization method, solution polymerization method,
Any polymerization method such as a gas phase polymerization method, a bulk polymerization method and a suspension polymerization method can be adopted. When a polymerization solvent is used, the solvent is benzene, toluene, xylene, n-hexane, n-heptane, cyclohexane, methylene chloride, chloroform, 1,2-dichloroethane,
Examples include hydrocarbons such as chlorobenzene and halogenated hydrocarbons. These may be used alone or in combination of two or more. Moreover, the monomer used for polymerization can also be used depending on the kind.

The amount of catalyst used in the polymerization reaction is
The component (B) is usually 0.1 to 1 per liter of the solvent.
From the viewpoint of polymerization activity and reactor efficiency, it is advantageous to select it in the range of 00 μmol, preferably 0.5 to 25 μmol. Examples of the method for adjusting the molecular weight of the polymer include the type and amount of each catalyst component, the selection of the polymerization temperature and the introduction of hydrogen. Further, in the present invention, the olefin polymerization catalyst can be used after being prepolymerized. The prepolymerization conditions may be those described above.

[0048]

EXAMPLES The present invention will be described in more detail with reference to the following examples.
However, the present invention is not limited to this without departing from the gist thereof.
It is not restricted by the examples. [Example 1] Chemical treatment of montmorillonite Commercial montmorillonite (Kunipia Co., Ltd., Kunipia)
F) 40 g was crushed with a crusher for 4 hours. 500 mL volume
Crushed montmorillonite 2 in a 3-neck separable flask
Add 0g and dissolve 20g magnesium chloride hexahydrate
Disperse in 100 mL of deionized water and stir at 90°C.
For 0.5 hours. After the treatment, the solid component was washed with water.
This processing operation is repeated once more to treat magnesium chloride.
Got ri montmorillonite. Next, add this to 6% aqueous hydrochloric acid.
Disperse in 160 mL of liquid and stir at reflux for 2 hours
Was processed for a while. After treatment, repeat washing with water until the filtrate becomes neutral.
Return and dry to obtain chemically treated montmorillonite
It was Chemical treatment of montmorillonite with silane compound Chemical treatment obtained above in a Schlenk tube of 300 mL volume
Montmorillonite (water content 15% by weight: 1 at 150°C
It was calculated from the weight loss during the heat dehydration treatment for a certain period of time. ) 1.0
g and disperse in 25 mL of toluene to make a slurry.
It was In this, methylphenethylsilyl dichloride 1.
13 g (5.2 mmol) was added. The obtained slurry
The mixture was stirred at room temperature for 60 hours and then heated to 100°C.
And reacted for 1 hour. After the reaction, remove the supernatant and
The body component was washed with 200 mL of toluene. This filtrate operation
Was repeated. Then, a new torque is added to this cleaning slurry.
Add ene to bring the total volume to 50 mL and use silane-treated montmorillon
Lonite slurry-(toluene slurry concentration 0.02 g/
mL) was obtained. Silane treated monoxide measured by BET method
The specific surface area of morillonite was 220 m/g. Preparation of montmorillonite treated MAO 200mL Schlenk under dehydrated toluene under nitrogen stream
(23.4 mL), then TI to remove impurities in the solvent
BA (triisobutylaluminum: 2.0 mol/
L, 1.5 mL, 3 mmol), and after stirring,
MAO (methylaluminoxane: 1.47 mol/L,
(5.1 mL, 7.5 mmol) was added and the mixture was stirred. So
Take 10mL of this in a 20mL Schlenk and put it in
The silane-treated montmorillonite slurry-0.
Add 5 ml (0.01 g montmorillonite amount)
It was After stirring for 10 minutes, leave it for 1 hour,
Night-treated MAO was obtained. Polymerization of Propylene 1L stainless steel pressure resistant autoclave with stirrer
After heating to 80°C and drying under sufficient reduced pressure, dry nitrogen is used in the atmosphere.
It returned to pressure and cooled to room temperature. Dry deoxidation under a stream of dry nitrogen
400 mL of elemental heptane and triisobutylaluminum
0.25 mL (0.5 mol) of a heptane solution (2 mol/L)
mmol) and stirred at 350 r.p.m for a while.
On the other hand, the montmorillonite-treated MAO supernatant obtained above
Rac-Me to only (10 mL)₂Si(2-Me-4,5
-BenzInd)₂ZrCl₂Heptane slurry
(1 μmol/L) 0.25 mL (0.25 μmol)
Was added and stirred at room temperature for 10 minutes. Then the mixed solution
Was quickly put into the autoclave. At 400r.p.m
Start stirring and add propylene to a gauge pressure of 8.0 kg/cm. ²
Slowly pressurize and at the same time slowly raise the temperature to 80°C.
The temperature was raised. Polymerization was carried out for 1 hour. Not reacted after the reaction
The corresponding propylene was removed by depressurization. 2 reaction mixtures
L was added to methanol to precipitate polypropylene,
54.8 g of polypropylene was obtained by filtering and drying.
Obtained. The activity is 2400 kg PP/g·Zr·hr.
It was [Comparative Example 1] Use MAO without montmorillonite treatment
Polymerization of propylene was carried out in the same manner as in Example 1 except that
35.6 g of polypropylene was obtained. Activity is 1560k
It was gPP/g.Zr.hr. [Example 2] Firing of silica Silica (P-10) manufactured by Fuji Davisson was used in an electric furnace.
Under nitrogen stream, 120°C for 30 minutes, 200°C for 24 minutes
Baking was performed for 0 minutes. Preparation of montmorillonite treated MAO MAO (1.51
M, 50 mL, 75 mmol), and obtained in Example 1
Silane-treated montmorillonite slurry-1.5mL
(0.03g) was charged. After stirring for 30 minutes, leave still
Then, montmorillonite-treated MAO was obtained. Preparation of MAO/silica carrier Made of 500 mL glass with a dropping funnel that has been fully nitrogen-substituted
Charge toluene (500 mL) into the container and obtain the
Add rica (4.04g) and stir at 400r.p.m.
Montmorillonite treated MAO toluene obtained above at ℃
Add solution (29.8 mL) slowly over 45 minutes
It was 1 hour at 0℃, 1 hour at room temperature 4 hours at 80℃
The reaction was carried out. After the reaction was completed, the mixture was allowed to cool and cooled to 60°C.
At this time, the supernatant was washed with toluene (200 mL) three times, and hepta
Wash with decantation (3 times) with water (200 mL).
I got the target. Finally, as heptane slurry,
Saved in The amount of Al supported is determined by the UV quantitative method.
It was As a result, the amount of Al supported was 12.0% by weight.
It was Polymerization of Propylene 1L stainless steel pressure resistant autoclave with stirrer
After heating to 80°C and drying under sufficient reduced pressure, dry nitrogen is used in the atmosphere.
It returned to pressure and cooled to room temperature. Dry deoxidation under a stream of dry nitrogen
400 mL of elemental heptane and triisobutylaluminum
0.25 mL of heptane solution (2.0 mol/L)
Add (0.5 mmol) and stir at 350r.p.m for a while.
I stirred. On the other hand, 50 mL Schlen that has been sufficiently replaced with nitrogen
Toluene (10 mL) and triiso
Butyl aluminum heptane solution (2 mol/L)
Add 25 mL (0.5 mmol) and then above
The obtained MAO/silica carrier heptane slurry (20 m
L, 2.5 mmol) and rac-Me₂Si(2-M
e-4,5-BenzInd)₂ZrCl₂Heptane
Add the slurry (1.0 μmol/L, 1 mL, 1 μmol), and add 5
Stir for minutes. After that, the supported catalyst slurry was autoclaved.
I put it into the oven quickly. Then, stir at 400 r.p.m.
Start the propylene with a gauge pressure of 8.0 kg/cm. ²Niyu
The pressure is raised slowly, and at the same time the temperature is slowly raised to 70°C.
Warmed. Polymerization was carried out for 1 hour. After the reaction is complete, unreacted
Propylene was removed by depressurization. 2 L of reaction mixture
Add to methanol to precipitate polypropylene and filter
By drying, 57 g of polypropylene was obtained. Live
The sex was 616 kg PP/g·Zr·hr. [Comparative Example 2] In the preparation of MAO/silica support, MA
Treated with silane-treated montmorillonite slurry as O
MAO/Siri obtained using MAO (1.43M, 75mmol)
A carrier (the amount of Al supported was 14.4% by weight).
The same procedure as in Example 2 was carried out except that it was used. As a result,
16 g of propylene was obtained. Activity is 173kgPP/
It was g·Zr·hr. [Example 3] Preparation of zeolite-treated MAO Silane-treated montmorillonite slurry-0.5 mL (0.
01g montmorillonite amount) reduced to 150°C for 24 hours
Tosoh Y-type zeolite obtained by pressure treatment (0.01 g,
Pore volume = 0.297 cm³/G) except for
A zeolite-treated MAO was obtained in the same manner as in Example 1. Polymerization of Propylene The supernatant of MAO treated with montmorillonite was used as the zeolite.
The same procedure as in Example 1 was repeated except that the treated MAO supernatant was replaced.
Polymerization of pyrene was performed to obtain 49.0 g of polypropylene.
It was The activity is 2150 kg PP/g·Zr·hr.
It was [Example 4] Preparation of activated carbon-treated MAO Silane-treated montmorillonite slurry-0.5 mL (0.
01g montmorillonite amount) reduced to 150°C for 24 hours
Activated carbon manufactured by Hiroshima Wako Co., Ltd. (0.01 g,
Pore volume=1.17 cm³/G) except that the example
The same procedure as in 1 was performed to obtain activated carbon-treated MAO. Polymerization of propylene The supernatant of MAO treated with montmorillonite is treated with the above-mentioned activated carbon.
The propylene was prepared in the same manner as in Example 1 except that the MAO supernatant was replaced.
Polymerization was carried out to obtain 40.0 g of polypropylene.
The activity was 1750 kg PP/g·Zr·hr. [Example 5] rac-Me₂Si(2-Me-4,5-B
ezInd)₂ZrCl₂Heptane slurry (1μ
mol/L) 0.25 mL (0.25 μmol)
Cyclopentadienylzirconium heptane slurry
(1 μmol/L) 0.1 mL (0.1 μmol),
Propylene in ethylene, gauge pressure 8.0 kg/cm²
Gauge pressure 5.0 kg/cm²And the temperature of 80 ℃
Polymerization was carried out in the same manner as in Example 1 except that the temperature was changed to 60°C.
142 g of polyethylene was obtained. Activity is 15600 kg
It was PE/g*Zr*hr. [Comparative Example 3] Using MAO not treated with montmorillonite
Polymerization was conducted in the same manner as in Example 5 except that
100 g was obtained. Activity is 11000kg PE/g·Zr
・It was hr.

[0049]

EFFECT OF THE INVENTION Since the catalyst for producing an olefin polymer of the present invention has a high polymerization activity, the amount of organoaluminum used can be greatly reduced, and the amount of metal remaining in the polymer is small. It becomes unnecessary, and the olefin polymer can be produced efficiently and inexpensively.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuhiro Goto 1 1 Anezaki Coast, Ichihara City, Chiba Prefecture (72) Inventor Haruhito Sato 1 1 Anezaki Coast, Ichihara City, Chiba Prefecture FH Term (Reference) 4H048 AA02 AA03 AB40 AD17 VA00 VA20 VA30 VA45 VA75 VA80 VB10 4J028 AA01A AB00A AB01A AC01A AC10A AC20A AC28A AC29A AC31A AC39A AC41A AC42A AC44A BA01B BB01B BC15B BC25B CA03B CA27B CA28B CA30B CA54B EB01 EB02 EB03 EB04 EB05 EB07 EB08 EB09 EB10 EB12 EB13 EB14 EB15 EB16 EB17 EB18 EB21 EB22 EB25 EB26 GB01 4J030 CC10 CD11 CE02 CF02 CG08

Claims (13)

[Claims] 1. An aluminoxane obtained by contacting an aluminoxane with an adsorptive substance and then removing the adsorptive substance. 2. The adsorptive substance has a specific surface area of 30 m ² /g or more measured by BET method or a pore volume of 0.00.
The aluminoxane according to claim 1, which is 1 cm ³ /g or more. 3. The aluminoxane according to claim 1 or 2, wherein the adsorptive substance is any one of zeolite, activated carbon, alumina, silica gel, clay, clay mineral, and ion-exchange layered compound. 4. The aluminoxane according to claim 1, wherein the adsorptive substance is a phyllosilicate. 5. The aluminoxane according to claim 1, wherein the adsorptive substance is montmorillonite. 6. A catalyst for olefin polymerization obtained by contacting (A) the aluminoxane according to any one of claims 1 to 5 with (B) a transition metal compound selected from Groups 4 to 6 of the periodic table. 7. Obtained by contacting (A) the aluminoxane according to any one of claims 1 to 5, (B) a transition metal compound selected from Groups 4 to 6 of the Periodic Table, and (C) an organoaluminum compound. Olefin polymerization catalyst used. 8. At least one of (A) the aluminoxane according to any one of claims 1 to 5, (B) a transition metal compound selected from Groups 4 to 6 of the periodic table, and (C) an organoaluminum compound ( The catalyst for polymerizing olefins according to claim 6 or 7, which is supported on a carrier D). 9. The method according to claim 6, wherein (B) the transition metal compound selected from Groups 4 to 6 of the periodic table is one of the following general formulas (1) to (3). Catalyst for olefin polymers. _{^{Q 1 a (C 5 H 5}} -ab R 1 b) (C 5 H 5-ac R 2 c) M 1 X 1 p Y 1 q ··· (1) Q 2 a (C 5 H 5-ad R ³ _d )Z ¹ M ¹ X ¹ _p Y ¹ _q ...(2) M ¹ X ² _r ...(3) [In the formula, Q ¹ is two conjugated five-membered ring ligands (C ₅ H _5-ab
R ¹ _b ) and (C ₅ H _{5 -ac} R ² _c ) are bonded to each other, and Q ² is a conjugated five-membered ring ligand (C ₅ H _{5-a- d} R ³
_d ) represents a binding group that bridges the Z ¹ group. R ¹ , R ² and R ³ each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, and a is 0. , 1 or 2. b, c, and d are integers of 0 to 5 when a=0, and 0 to 4 when a=1.
And an integer of 0 to 3 when a=2.
The valence of p+q=M ¹ is −2, and the valence of r=M ¹ is shown. M ¹
Indicates a transition metal of Groups 4 to 6 of the Periodic Table. Also, X ¹ , Y
¹ and Z ¹ each represent a covalent or ionic bond ligand, and X ² represents a covalent ligand. In addition, X ¹ and Y ¹ may be bonded to each other to form a ring structure. ] 10. A method for producing an olefin-based polymer, which comprises polymerizing an olefin using the catalyst for olefin polymerization according to claim 6. 11. A method for producing an olefin polymer, which comprises polymerizing olefins using the catalyst for olefin polymerization according to any one of claims 6 to 9 and an organoaluminum compound. 12. The method for producing an olefin polymer according to claim 10, wherein the organoaluminum compound is trialkylaluminum. 13. The method for producing an olefin polymer according to claim 10, wherein the olefin is propylene.