JP2001064314A - Olefin polymerization catalyst and production of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerization catalyst that can efficiently give an olefin polymer having a high melt tension and excellent moldability by mixing at least two transition metal compounds with an aluminumoxy compound or an ionic compound that can react with the transition metal compounds to cationize them. SOLUTION: This catalyst comprises (A) at least two transition metal compounds selected from transition metal compounds in which the transition metals belong to group 4 in the periodic table and which are represented by formulae I and II and (B) at least one compound selected between an aluminumoxy compound and an ionic compound that can react with the transition metal compounds A to cationize them. The mixing ratio between components A and B in the catalyst is desirably 1:1 to 1:106 by mole in the case in which component B is an aluminumoxy compound and is desirably 10:1 to 1:100 by mole in the case in which component B is an ionic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst and a process for producing an olefin polymer. The present invention relates to an olefin polymerization catalyst for efficiently producing an olefin polymer suitably used for molding and a method for producing an olefin polymer.

[0002]

2. Description of the Related Art Conventionally, polypropylene has (1) high mechanical strength such as rigidity and excellent balance.
Various molded products, such as sheets, films, and injection molded products, because they are chemically stable, have excellent weather resistance, are resistant to chemicals, etc., and (3) have high melting points and excellent heat resistance. For example, it is widely used in various fields.

[0003] However, in order to further expand the field of use of this polypropylene, it is necessary to improve extrusion characteristics. That is, polypropylene has a low melt tension during melt extrusion, so drawdown is likely to occur, and there is a limit in producing a large blow molded article. In addition, demands for lightening, heat insulating properties, vibration damping properties, etc. of molded articles are increasing, and polypropylene foam molded articles having heat resistance are desired. However, conventional polypropylene has insufficient melt tension and is sufficiently satisfactory. In fact, it was not possible to obtain a foamed molded article.

[0004] Incidentally, as a method for improving the melt tension of polypropylene and improving the melt processability, there have been known (1) a method of mixing high-molecular-weight high-density polyethylene having a high melt tension (JP-A-6-55868). Gazette),
(2) A method of mixing high-density polyethylene having a high melt tension produced by a chromium-based catalyst (Japanese Patent Laid-Open No. 8-924)
No. 38), (3) a method of mixing low-density polyethylene produced by a general high-pressure radical polymerization method,
(4) A method of increasing the melt tension by irradiating light to general polypropylene, (5) A method of increasing the melt tension by irradiating light to general polypropylene in the presence of a crosslinking agent or a peroxide, (6) Attempts have been made on a method of grafting a radical polymerizable monomer such as styrene onto general polypropylene, and a method of (7) copolymerizing propylene with a polyene (JP-A-5-194778).

However, in the above-mentioned methods (1) to (3), the elasticity, strength and heat resistance of the component for increasing the melt tension are insufficient, so that the inherent characteristics of polypropylene are inevitably lost. Further, in the methods (4) and (5), it is difficult to control a cross-linking reaction occurring as a side reaction. There is a limit in arbitrarily controlling, and there is a problem that a control range is narrow.
Further, in the method (6), the chemical stability of the polypropylene is impaired, and in the case of the styrene-based graft, a problem occurs in the resin recyclability. In the method (7), the melt tension is reduced. The effect of improvement is small, sufficient effect is not exhibited, and generation of gel is also concerned.

[0006] On the other hand, there are known several techniques in which two types of transition metal compounds are mixed for the purpose of expanding the molecular weight distribution. For example, in JP-A-64-74202 and JP-A-3-203904, it is difficult to control the morphology, and it is difficult to substantially produce highly stereoregular polypropylene. JP-A-5-155933, JP-A-5-155933, JP-A-5-255436 and JP-A-5-255439 disclose that the disclosed catalyst achieves the above object in the production of a polypropylene-based polymer by using the disclosed catalyst. It is difficult. JP-A-6-17
No. 9776 discloses that polypropylene is produced in the presence of hydrogen at the time of polymerization, but the improvement of the processing characteristics aimed at by the present application cannot be expected. Moreover, it is difficult to control the morphology. JP-A-7-173209 discloses an inexpensive method for producing a mixture of a homopolymer or a copolymer by a single-stage reaction. However, since the reaction is a single-stage reaction, the degree of freedom in resin design is small. JP-A-7-
Japanese Patent Publication No. 304826 discloses a technique in which two types of transition metal compounds are mixed to improve the moldability, transparency, and mechanical strength of a substantially ethylene-based polymer. Have difficulty.

[0007]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides an olefin polymer which has a high melt tension and excellent moldability, and is particularly suitable for forming large blow moldings, thick foams, sheets and the like. An object of the present invention is to provide an olefin polymerization catalyst and a method for producing an olefin polymer, which efficiently produce a coalesced product.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a catalyst component comprising at least two kinds of transition metal compounds, an aluminum oxy compound, and the above transition metal compound. Using a specific olefin polymerization catalyst containing at least one selected from ionic compounds capable of reacting and converting to cations, and performing multistage polymerization of olefins without using hydrogen in at least one polymerization step. To obtain an olefin polymer having a branch, and it has been further found that this object can be achieved by this polymer.
The present invention has been completed based on such findings.
That is, the present invention provides the following olefin polymerization catalyst and method for producing an olefin polymer. 1. (A) at least two transition metal compounds selected from the group of transition metal compounds belonging to Group 4 of the periodic table consisting of the following (A-1) and (A-2); (B) aluminum oxy compound (B-1) And an olefin polymerization catalyst comprising at least one selected from the group consisting of ionic compounds (B-2) that can be converted to cations by reacting with the transition metal compound. (A-1) A transition metal compound of Group 4 of the periodic table represented by the following general formula (1)

[0009]

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Wherein M ¹ represents titanium, zirconium or hafnium. R ^{1 to} R ¹¹ , X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group containing 1 to 20 carbon atoms, a silicon-containing group, and an oxygen-containing group. A group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group; R ³ and R ⁴ and R ⁸ and R ⁹ may be bonded to each other to form a ring; X ¹ and X
² is independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. Is shown. Y ¹ is a divalent cross-linking group bonding two ligands, and is a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, Tin-containing group, -O-, -C
O -, - S -, - SO 2 -, - NR 12 -, - PR 12 -,
—P (O) R ¹² —, —BR ¹² — or —AlR ¹² —, wherein R ¹² is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon having 1 to 20 carbon atoms. Represents a group. (A-2) a transition metal compound of Group 4 of the periodic table represented by the following general formula (2)

[0011]

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｛Where M¹Is titanium, zirconium or
Indicates hafnium, E¹And E^TwoIs each cyclopen
Tadienyl group, substituted cyclopentadienyl group, indenyl
Group, substituted indenyl group, heterocyclopentadienyl
Group, substituted heterocyclopentadienyl group, amide group,
Selected from sulfide groups, hydrocarbon groups and silicon-containing groups
A ligand¹And A^TwoForm a crosslinked structure through
And they are the same or different
May be X^ThreeRepresents a σ-binding ligand, and X^ThreeIs multiple
If there is more than one X^ThreeMay be the same or different,
Other X^Three, E¹, E^TwoOr Y^TwoAnd may be crosslinked.
Y^TwoRepresents a Lewis base;^TwoIf there are multiple
Y^TwoMay be the same or different, and the other Y^Two, E¹,
E^TwoOr X ^ThreeMay be cross-linked with A¹And A^TwoIs two
A divalent bridging group that binds two ligands and has 1 carbon atom
To 20 hydrocarbon groups, halogen-containing carbons having 1 to 20 carbon atoms
Hydride group, silicon-containing group, germanium-containing group, tin-containing
Group, -O-, -CO-, -S-, -SO_Two-, -NR¹²
-, -PR¹²-, -P (O) R¹²-, -BR¹²-Or-
AlR¹²-Indicates R¹²Is hydrogen atom, halogen atom, charcoal
A hydrocarbon group having 1 to 20 carbon atoms or a halogen group having 1 to 20 carbon atoms
Hydrocarbon-containing hydrocarbon groups, which are the same or different
It may be. q is an integer of 1 to 5 [(M¹Atom of
Valence-2), and r represents an integer of 0 to 3. ｝ 2. (A) At least two transition metals of Group 4 of the periodic table
Compound, (B) aluminum oxy compound (B-1) and
And can be converted to cations by reacting with the above transition metal compounds
Selected from the group of compounds consisting of the ionic compound (B-2)
Olefin polymerization containing at least one of
In the production method of multi-stage polymerization of olefin in the presence of a catalyst
And use hydrogen in at least one polymerization step
Of olefin polymers to polymerize olefins without
Construction method. 3. Component (A) of the olefin polymerization catalyst in the above item 2
Are (A-1) and (A-2) in the above 1 and the following (A
-3) Transition metallization of group 4 of the periodic table consisting of (A-7)
At least two transition metal compounds selected from the group of compounds
3. The method for producing an olefin polymer according to the above item 2, wherein (A-3) of the group 4 of the periodic table represented by the following general formula (3)
Transition metal compound

[0013]

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[Wherein, M¹Is titanium, zirconium or
Indicates hafnium. R¹³~ R¹⁸Is independently hydrogen
Atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms or
A halogen-containing hydrocarbon group having 1 to 20 carbon atoms;^Fifteen
And R¹⁶, R¹⁶And R¹⁷And R¹⁷And R¹⁸At least of
A pair may be bonded to each other to form a ring;^Fouras well as
X^FiveAre each independently a hydrogen atom, halogen atom or carbon
Represents a hydrocarbon group of the formulas 1 to 20,^ThreeReplaces two ligands
A divalent cross-linking group to be bonded,
Hydrogen group, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, silicon
Element-containing group, germanium-containing group, tin-containing group, -O-,
-CO-, -S-, -SO_Two-, -NR¹²-, -PR¹²
-, -P (O) R¹²-, -BR¹²-Or-AlR¹²-
And R¹²Is a hydrogen atom, a halogen atom, a carbon number of 1 to 20
A hydrocarbon group or a halogen-containing hydrocarbon having 1 to 20 carbon atoms
Represents an elementary group. (A-4) group 4 of the periodic table represented by the following general formula (4)
Transition metal compound (R¹⁹ _FiveC_Five)_mM¹X¹ _4-m... (4) [where, M¹Represents titanium, zirconium or hafnium
And R¹⁹ _FiveC_FiveIs a hydrocarbon-substituted cyclopentadiene
Group, X¹Represents a hydrogen atom, a halogen atom or a carbon number of 1 to 2
And 0 represents a hydrocarbon group. m shows the integer of 2-4. 5 pieces
R¹⁹May be the same or different. m R¹⁹ _FiveC
_FiveMay be the same or different. (4-m) X¹
May be the same or different. (A-5) of group 4 of the periodic table represented by the following general formula (5)
Transition metal compound Cp_TwoM¹R²⁰ _aR^{twenty one} _b・ (5) [where M¹Represents a transition metal of Group 4 of the periodic table, and Cp
Is a cyclopentadienyl group, a substituted cyclopentadienyl
Group, indenyl group, substituted indenyl group, tetrahydro
Indenyl group, substituted tetrahydroindenyl group, fluoro
Cyclic unsaturated carbon such as enyl or substituted fluorenyl
It represents a hydrogen group or a chain unsaturated hydrocarbon group. R ²⁰, R
^{twenty one}Are independently σ-binding ligands, chelating properties
A ligand such as a ligand or a Lewis base;²⁰, R^{twenty one}Is
It may combine with each other to form a ring. a and b are respectively
An integer of 0 to 2 is independently shown. In addition, substituted cyclopentadiene
The number of substituents of the enyl group is 1 to 5, and
The number and types of the substituents on the tadienyl group are the same.
Or different. However, one cyclopentane
When the number of substituents of the dienyl group is 5, the other cyclo is
The number of substituents of the pentadienyl group is 1 to 4. (A-6) of the periodic table 4 group represented by the following general formula (6)
Transition metal compound CpM¹R²⁰ _aR^{twenty one} _bR^{twenty two} _c... (6) [where, M¹Represents a transition metal of Group 4 of the periodic table, and Cp represents
Cyclobentadenyl, substituted cyclobentadenyl
Group, indenyl group, substituted indenyl group, tetrahydroi
Ndenyl group, substituted tetrahydroindenyl group, fluor
Cyclic unsaturated hydrocarbon such as nyl group or substituted fluorenyl group
And represents an unsaturated group or a chain unsaturated hydrocarbon group. R²⁰, R^{twenty one}, R
^{twenty two}Are independently σ-binding ligands and chelating ligands.
A ligand such as a ligand or a Lewis base;²⁰, R^{twenty one},
R^{twenty two}And two or more of which may combine with each other to form a ring
No. a, b, and c each independently represent an integer of 0 to 2
You. (A-7) of the periodic table 4 group represented by the following general formula (7)
Transition metal compound

[0015]

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[Wherein M¹Is titanium, zirconium or
Represents a hafnium atom, and Cp is cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, tetrahydroindenyl group, substituted tetra
Hydroindenyl, fluorenyl or substituted fluor
Cyclic unsaturated hydrocarbon group such as an n-yl group or chain unsaturated carbon
Shows a hydrogen group. X⁶Is hydrogen atom, halogen atom, carbon number
An alkyl group having 1 to 20, an aryl group having 6 to 20 carbon atoms,
Alkylaryl group or arylalkyl group or charcoal
It represents an alkoxy group having a prime number of 1 to 20. Z is SiR^{twenty three} _Two,
CR^{twenty three} _Two, SiR^{twenty three} _TwoSiR^{twenty three} _Two, CR^{twenty three} _TwoCR^{twenty three} _Two,
CR^{twenty three} _TwoCR^{twenty three} _TwoCR^{twenty three} _Two, CR^{twenty three}= CR^{twenty three}, CR^{twenty three} _Two
SiR^{twenty three} _TwoOr GeR^{twenty three} _TwoAnd Y^ThreeIs -N (R^{twenty four})
-, -O-, -S- or -P (R^{twenty four})-. R above
^{twenty three}Is hydrogen or an alkyl having up to 20 non-hydrogen atoms
Le, aryl, silyl, halogenated alkyl, halogen
Selected from aryl halide groups and combinations thereof.
R^{twenty four}Is alkyl having 1 to 10 carbons or 6 carbons
10 to 10 aryl groups, or 1 or more aryl groups
R on^{twenty three}Form a linked ring system of up to 30 non-hydrogen atoms with
You may. w represents 1 or 2. ] 4. 2. The olefin polymerization catalyst according to 2 above, wherein
3. The olefin polymer according to the above 2, which is an olefin polymerization catalyst of
Manufacturing method of coalescence. 5. (A) Transition metal compound of group 4 of the periodic table as a component
At least one of them is a hafnium compound
5. A method for producing the olefin polymer according to any one of the above items 2 to 4.
Law. 6. The olefin polymerization catalyst comprises the component (A) and the component (B)
(C) containing an organoaluminum compound in addition to
6. The olefin polymer according to any one of the above 2 to 5,
Manufacturing method of coalescence. 7. Low content of component (A) in olefin polymerization catalyst
One and / or at least one of the components (B) is a carrier
7. The olef described in any one of the above 2 to 6 supported on
A method for producing a polymer. 8. Olefin polymerization catalyst
The method according to any one of the above 2 to 7, which is obtained by
A method for producing a refin polymer. 9. The terminal vinyl selectivity of the resulting olefin polymer is
The olef according to any one of the above items 2 to 8, which is 15% or more.
A method for producing a polymer.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is a method for producing an olefin polymerization catalyst and an olefin polymer as described above. Hereinafter, the present invention will be described in detail. 1. Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention comprises: (A) at least two transition metal compounds selected from the group of transition metal compounds belonging to Group 4 of the periodic table consisting of the following (A-1) and (A-2); (B) at least one selected from a compound group consisting of an aluminum oxy compound (B-1) and an ionic compound (B-2) which can be converted into a cation by reacting with the transition metal compound. It is a catalyst. (A-1) A transition metal compound of Group 4 of the periodic table represented by the following general formula (1).

[0018]

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[In the formula, M ¹ represents titanium, zirconium or hafnium. R ^{1 to} R ¹¹ , X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group containing 1 to 20 carbon atoms, a silicon-containing group, and an oxygen-containing group. A group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group; R ³ and R ⁴ and R ⁸ and R ⁹ may be bonded to each other to form a ring; X ¹ and X
² is independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. Is shown. Y ¹ is a divalent cross-linking group bonding two ligands, and is a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, Tin-containing group, -O-, -C
O -, - S -, - SO 2 -, - NR 12 -, - PR 12 -,
—P (O) R ¹² —, —BR ¹² — or —AlR ¹² —, wherein R ¹² is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon having 1 to 20 carbon atoms. Represents a group. (A-2) A transition metal compound of Group 4 of the periodic table represented by the following general formula (2).

[0020]

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Ｍ where M¹Is titanium, zirconium or
Indicates hafnium, E¹And E^TwoIs each cyclopen
Tadienyl group, substituted cyclopentadienyl group, indenyl
Group, substituted indenyl group, heterocyclopentadienyl
Group, substituted heterocyclopentadienyl group, amide group,
Selected from sulfide groups, hydrocarbon groups and silicon-containing groups
A ligand¹And A^TwoForm a crosslinked structure through
And they are the same or different
May be X^ThreeRepresents a σ-binding ligand, and X^ThreeIs multiple
If there is more than one X^ThreeMay be the same or different,
Other X^Three, E¹, E^TwoOr Y^TwoAnd may be crosslinked.
Y^TwoRepresents a Lewis base;^TwoIf there are multiple
Y^TwoMay be the same or different, and the other Y^Two, E¹,
E^TwoOr X ^ThreeMay be cross-linked with A¹And A^TwoIs two
A divalent bridging group that binds two ligands and has 1 carbon atom
To 20 hydrocarbon groups, halogen-containing carbons having 1 to 20 carbon atoms
Hydride group, silicon-containing group, germanium-containing group, tin-containing
Group, -O-, -CO-, -S-, -SO_Two-, -NR¹²
-, -PR¹²-, -P (O) R¹²-, -BR¹²-Or-
AlR¹²-Indicates R¹²Is hydrogen atom, halogen atom, charcoal
A hydrocarbon group having 1 to 20 carbon atoms or a halogen group having 1 to 20 carbon atoms
Hydrocarbon-containing hydrocarbon groups, which are the same or different
It may be. q is an integer of 1 to 5 [(M¹Atom of
Valence-2), and r represents an integer of 0 to 3.オ レ フ ィ ン The olefin polymerization catalyst of the present invention has a low content as the component (A).
It contains at least two transition metal compounds,
As the combination, the transition metal compound of (A-1)
Containing two or more transition metal compounds of (A-2)
Including the above, transition metal compounds of (A-1) and (A-2)
May be included.

Next, in the olefin polymerization catalyst of the present invention,
The component (A) will be described in detail. (A-1) The transition metal compound is a single-bridge type complex.
You. In the general formula (1), R¹~ R¹¹, X¹as well as
X^TwoAmong them, chlorine atom, bromine atom
And a fluorine atom and an iodine atom. Carbon number 1
Examples of the 20 hydrocarbon groups include a methyl group and an ethyl group.
Group, n-propyl group, isopropyl group, n-butyl group,
Isobutyl group, tert-butyl group, n-hexyl group,
alkyl group such as n-decyl group, phenyl group, 1-naph
Aryl group such as tyl group and 2-naphthyl group, benzyl group
And aralkyl groups such as
0 halogen-containing hydrocarbon groups include trifluoromethyl
One or more hydrogen atoms of the above hydrocarbon groups such as tyl are suitable
And a group substituted with a halogen atom. Silicon content
Examples of the group include a trimethylsilyl group and dimethyl (t-butyl).
G) a silyl group. As the oxygen-containing group,
Methoxy group, ethoxy group, etc .;
Examples include a thiol group and a sulfonic acid group.
You. Examples of the nitrogen-containing group include a dimethylamino group.
And a phosphorus-containing group such as a phenylphosphine group.
Is mentioned. Also, R^ThreeAnd R^FourAnd R⁸And R ⁹Hate
They may be bonded together to form a ring such as fluorene. R
^ThreeAnd R^FourAnd R ⁸And R⁹As a specific example of the above, R¹~
R¹¹Groups excluding hydrogen atoms from those listed in
Can be R^Four, R⁸Is a hydrogen atom and carbon number 6 or less
The lower alkyl group is preferable, and a hydrogen atom, a methyl group,
And isopropyl and cyclohexyl groups are more preferred.
And a hydrogen atom is particularly preferred. Also, R^Three, R⁶, R
⁸And R¹¹Is preferably an alkyl group having 6 or less carbon atoms.
Methyl, ethyl, isopropyl, cyclohexyl
Xyl groups are more preferred, and isopropyl groups are particularly preferred.
New R^Four, R^Five, R⁷, R⁹And R^TenAs a hydrogen source
Children are preferred. X ¹, X^TwoAs a halogen atom,
Til, ethyl and propyl groups are preferred.

Specific examples of Y ¹ include methylene, ethylene, ethylidene, isopropylidene, cyclohexylidene, 1,2-cyclohexylene, dimethylsilylene, tetramethyldisilylene, dimethylgermylene, methylborylidene (CH _3- B =), methylaluminidene (CH
_3- Al =), phenylphosphylidene (Ph-P
=), Phenylphosphoridene (PhPO =), 1,2-
Phenylene, vinylene (-CH = CH-), vinylidene (CH ₂ = C =), methylimide, oxygen (-O-), include sulfur (-S-), among others, methylene, ethylene, ethylidene, isopropylidene It is preferable in terms of achieving the object of the present invention.

M ¹ represents titanium, zirconium or hafnium, with hafnium being particularly preferred. Specific examples of the transition metal compound represented by the general formula (1) include:
1,2-ethanediyl (1- (4,7-diisopropylindenyl)) (2- (4,7-diisopropylindenyl) hafnium dichloride, 1,2-ethanediyl (9-fluorenyl) (2- (4,7 -Diisopropylindenyl) hafnium dichloride, isopropylidene (1- (4,7-diisopropylindenyl)) (2-
(4,7-diisopropylindenyl) hafnium dichloride, 1,2-ethanediyl (1- (4,7-dimethylindenyl)) (2- (4,7-diisopropylindenyl) hafnium dichloride, 1,2-ethanediyl (9-fluorenyl) (2- (4,7-dimethylindenyl)) hafnium dichloride, isopropylidene (1
-(4,7-dimethylindenyl)) (2- (4,7-
Examples thereof include, but are not limited to, diisopropylindenyl) hafnium dichloride, and those in which hafnium in these compounds is replaced with zirconium or titanium.

The transition metal compound represented by the general formula (1) is described in, for example, Japanese Patent Application Laid-Open No.
It can be produced by the method described in JP-A-130807. As the component (A-1), two or more types may be used in combination. (A-2) In the transition metal compound represented by the general formula (2) (hereinafter sometimes referred to as a double-bridge type complex), M ¹ represents titanium, zirconium or hafnium, but zirconium and hafnium Is preferred. As described above, E ¹ and E ² represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, and an amide group, respectively. -N <), phosphide group (-P <), hydrocarbon group [>CR-,> C
<] And a silicon-containing group [>SiR-,> Si <] (however,
R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms or a hetero atom-containing group), and forms a crosslinked structure via A ¹ and A ² . E ¹ and E ² may be the same or different. As E ¹ and E ² , a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferred.

Specific examples of the σ-binding ligand represented by X ³ include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a 6 to 20 carbon atoms.
Aryloxy group, C1-20 amide group, C1-20 silicon-containing group, C1-20 phosphide group, C1-20 sulfide group or C1-20
Acyl group and the like. If this X ³ there is a plurality, the plurality of X ³ may be the same or different, the other X
^It may be crosslinked with ³ , E ¹ , E ² or Y ² .

On the other hand, Y^TwoSpecific examples of Lewis bases represented by
Include amines, ethers, phosphines, thios
Ethers and the like can be mentioned. This Y^TwoIs multiple
If there is more than one Y^TwoMay be the same or different,
Other Y^TwoAnd E¹, E^TwoOr X ^ThreeAnd may be crosslinked.
Next, A¹And A^TwoAt least one of the crosslinking groups represented by
One is a cross-linking group comprising a hydrocarbon group having 1 or more carbon atoms.
Preferably. These crosslinking groups include, for example,
General formula

[0028]

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(R ²⁵ and R ²⁶ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and are bonded to each other to form a ring structure. And e represents an integer of 1 to 4. Specific examples thereof include methylene, ethylene, ethylidene, propylidene, isopropylidene, cyclohexylidene, and the like. Examples thereof include a 1,2-cyclohexylene group and a vinylidene group (CH ₂ ＣC ＝). Among them, a methylene group, an ethylene group and an isopropylidene group are preferred. This A ¹
And A ² may be the same or different.

In the transition metal compound represented by the general formula (2), E ¹ and E ² are a cyclopentadienyl group,
In the case of a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group, the bond of the A ¹ and A ² cross-linking groups may be a (1,1 ′) (2,2 ′) double cross-linking type. , (1,2 ') (2,1') double cross-linking type. Among the transition metal compounds represented by the general formula (2), the general formula (2-a)

[0031]

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A transition metal compound having a double-bridged biscyclopentadienyl derivative represented by the following formula as a ligand is preferable. In the general formula (2-a), M ¹ , A ¹ ,
A ² , q and r are the same as above. X ³ represents a σ-bonding ligand, and when X ³ there are a plurality, the plurality of X ³ may be the same or different, may be crosslinked with other X ³ or Y ^2. As a specific example of X ³ , general formula (2)
It includes the same as those exemplified in the explanation of X ^3. Y ² represents a Lewis base, if Y ² there is a plurality, the plurality of Y ² may be the same or different, the other Y
² or X ³ may be crosslinked. Specific examples of Y ² include the same as those exemplified in the description of Y ^{2 in} the general formula (2). R ^{27 to} R ³² each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group, a silicon-containing group or a hetero atom-containing group having 1 to 20 carbon atoms is shown, and at least one of them is not a hydrogen atom. Further, R ^{27 to} R ³² may be the same or different, and adjacent groups may be bonded to each other to form a ring.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand has a ligand of (1,1 ′) (2,2 ′) double-bridged type and (1,2 ′). ')
Any of the (2,1 ′) double cross-linking type may be used. Specific examples of the transition metal compound represented by the general formula (2) include (1,1′-ethylene) (2,2′-ethylene)-
Bis (indenyl) zirconium dichloride, (1,
2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) (2,2′-methylene) -bis (indenyl) zirconium dichloride, (1,2 ′ -Methylene) (2,
1′-methylene) -bis (indenyl) zirconium dichloride, (1,1′-isopropylidene) (2,2 ′
-Isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-isopropylidene) (2,
1'-isopropylidene) -bis (indenyl) zirconium dichloride, (1,1'-ethylene) (2,2 '
-Ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-
(Ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1,2′- Ethylene) (2,1'-
Ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1,1′-ethylene) (2,2 ′
-Ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2
1'-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,1'-ethylene)
(2,2′-ethylene) -bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (5,6-dimethylindenyl) zirconium Dichloride, (1,1′-ethylene) (2,2′-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) -bis (4 -Phenylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (4-phenylindenyl) zirconium dichloride, (1,1'-ethylene) (2,2'- Ethylene) -bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene)
(2,1′-ethylene) -bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,
1′-ethylene) (2,2′-ethylene) -bis (5
6-benzoindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-isopropylidene) -bis ( Indenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride,
(1,1′-isopropylidene) (2,2′-ethylene) -bis (indenyl) zirconium dichloride,
(1,2′-methylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,1′-
Methylene) (2,2′-ethylene) -bis (indenyl) zirconium dichloride, (1,1′-ethylene)
(2,2′-methylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) (2,2′-
(Isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,1′-isopropylidene) (2,2 ′) −
Methylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) (2,2′-methylene)
(3-methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′-isopropylidene) (3-methylcyclopentadienyl) (cyclopentadienyl )
Zirconium dichloride, (1,1'-propylidene)
(2,2′-propylidene) (3-methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1,1′-ethylene) (2,2′-methylene) -bis (3-methylcyclopenta Dienyl) zirconium dichloride, (1,1′-methylene) (2,2 ′
-Ethylene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′-ethylene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1 ,
1′-ethylene) (2,2′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,1′-methylene) (2,2′-methylene) -bis (3-methyl Cyclopentadienyl) zirconium dichloride, (1,1′-methylene) (2,2 ′
-Isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,1'-isopropylidene) (2,2'-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,1′-ethylene) (2,2′-methylene) -bis (3,4-dimethylcyclopentadienyl)
Zirconium dichloride, (1,1'-ethylene)
(2,2′-isopropylidene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride,
(1,1′-methylene) (2,2′-methylene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,1′-methylene) (2,2′-isopropylidene)- Bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′-isopropylidene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, 1,2′-ethylene) (2,1′-
Methylene) -bis (3-methylcyclopentadienyl)
Zirconium dichloride, (1,2'-ethylene)
(2,1′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,
2'-methylene) (2,1'-methylene) -bis (3-
Methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,2′-isopropylidene)
(2,1′-isopropylidene) -bis (3-methylcyclopentadienyl) zirconium dichloride, (1,
2′-ethylene) (2,1′-methylene) -bis (3
4-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride, (1,2′- Methylene) (2,1′-methylene) -bis (3,4-dimethylcyclopentadienyl) zirconium dichloride,
(1,2′-methylene) (2,1′-isopropylidene) -bis (3,4-dimethylcyclopentadienyl)
Zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (3,4-
Examples thereof include (dimethylcyclopentadienyl) zirconium dichloride and those obtained by substituting zirconium in these compounds with titanium or hafnium. As the component (A-2), two or more types may be used in combination.

Next, the component (B) in the olefin polymerization catalyst of the present invention will be described. The component (B) in the present invention is at least one selected from the group consisting of an aluminum oxy compound (B-1) and an ionic compound (B-2) that can be converted to a cation by reacting with the transition metal compound. Is used. As the aluminum oxy compound of the component (B-1), a general formula (8)

[0035]

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(Wherein, R ³³ represents an alkyl group, alkenyl group, aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, w represents an average degree of polymerization, and is usually an integer of 2 to 50, preferably 2 to 40. In addition, each ^R33 may be the same or different. Aluminoxane represented by the general formula (9):

[0037]

Embedded image

(Wherein, R ³³ and w are the same as those in the above formula (8)). Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The method 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 during polymerization and then water is added, and a crystal water contained in a metal salt or the like is used. A method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water.

The aluminoxane may be insoluble in a hydrocarbon solvent or may be soluble in a hydrocarbon solvent. Preferably, it is soluble in a hydrocarbon solvent and the residual organoaluminum compound measured by ¹ H-NMR is 10% by weight or less. More preferably, the residual organoaluminum compound is 3 to 5% by weight or less, particularly preferably 2 to 4% by weight or less. The use of such an aluminoxane is preferable because the ratio of the aluminoxane supported on the carrier (also referred to as a supporting ratio) increases. Furthermore, since it is soluble in a hydrocarbon solvent, there is an advantage that unsupported aluminoxane can be recycled and reused. Furthermore, since the properties of the aluminoxane are stable, there is an advantage that no special treatment is required for use. The use of such an aluminoxane is preferable because the average particle size and the particle size distribution (generally referred to as morphology) of the polyolefin obtained by polymerization are improved. If the residual organoaluminum compound exceeds 10% by weight, the supporting rate may decrease, and the polymerization activity may decrease.

As a method of obtaining such an aluminoxane, for example, a method of evaporating a solvent of an aluminoxane solution by heating and reducing the pressure under reduced pressure to dryness (also referred to as a dry-up method) may be mentioned. In the dry-up method, the evaporation of the solvent by heating and decompression is preferably 80 ° C. or lower, more preferably 60 ° C. or lower. In addition, as a method for removing components insoluble in a hydrocarbon solvent from aluminoxane, for example, a method in which a component insoluble in a hydrocarbon solvent is spontaneously settled and then separated by decantation is used. Alternatively, a method of separation by an operation such as centrifugation may be used.
Thereafter, it is preferable to filter the recovered soluble components using a G5 glass filter or the like under a nitrogen stream, since insoluble components are sufficiently removed. The gel component of the aluminoxane thus obtained may increase with time, but is preferably used within 48 hours after preparation, particularly preferably immediately after preparation. The ratio of the aluminoxane to the hydrocarbon solvent is not particularly limited, but is preferably used at a concentration such that the aluminum atom in the aluminoxane is 0.5 to 10 mol per liter of the hydrocarbon solvent.

The hydrocarbon solvent includes:
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane and cycloaliphatic rings such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane And petroleum fractions such as formula hydrocarbons, naphtha, kerosene, and light gas oil.

These aluminoxanes may be used alone.
Alternatively, two or more kinds may be used in combination. On the other hand, (B
-2) As a component, reacts with the transition metal compound to
Any ionic compound that can be converted to thione
Can be used, but particularly efficiently forms active polymerization sites
From the point of view, for example, the following general formulas (10) and (11) ([L¹-R³⁴]^{h +})_a([Z]^-)_b ... (10) ([L^Two]^{h +})_a([Z]^-)_b ... (11) (where L^TwoIs M^Two, R³⁵R³⁶M^Three, R³⁷ _Three C or R³⁸
M^ThreeIt is. ) [In the formulas (10) and (11), L¹Is a Lewis base, [Z]
^-Is a non-coordinating anion [Z¹]^-Or [Z^Two]^-This
Here [Z¹]^-Is an anion in which a plurality of groups are bonded to an element,
That is, [M^FourG¹G^Two... G^f(Where M^FourIs
Group 5 to 15 element of the periodic table, preferably 13 of the periodic table
Group 15 elements are shown. G¹~ G^fAre hydrogen atoms,
Halogen atom, alkyl group having 1 to 20 carbon atoms, 2 carbon atoms
Dialkylamino group having 1 to 40 carbon atoms and alcohol having 1 to 20 carbon atoms
Xy group, aryl group having 6 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, alkyl aryl having 7 to 40 carbon atoms
Group, an arylalkyl group having 7 to 40 carbon atoms, 1 carbon atom
To 20 halogen-substituted hydrocarbon groups and 1 to 20 carbon atoms
Siloxy group, organic metalloid group, or 2 to 20 carbon atoms
Represents a hetero atom-containing hydrocarbon group. G¹~ G^fOut of
Two or more may form a ring. f is [(central metal
M^Four+1)]. ), [Z ^Two]
^-Is the logarithm of the reciprocal of the acid dissociation constant (pK_a) Is -10 or less
Of Bronsted acid alone or Brønsted acid and Louis
Conjugated bases in combination with succinic acids, or generally with super strong acids
Shows the conjugate base defined. Also, the Lewis base is coordinated
May be. Also, R³⁴Is a hydrogen atom, carbon number 1-20
Alkyl group, aryl group having 6 to 20 carbon atoms, alkyl
An aryl group or an arylalkyl group;³⁵And R
³⁶Is cyclopentadienyl group, substituted cyclopen
Tadienyl group, indenyl group or fluorenyl group, R³⁷
Is an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkyl
It represents an aryl group or an arylalkyl group. R³⁸Is Tet
Macrocycles such as laphenylporphyrin and phthalocyanine
Shows a ligand. h is [L¹-R³⁴], [L^Two] Ion
Valence is an integer of 1 to 3, a is an integer of 1 or more, and b = (h ×
a). M^TwoAre periodic table Nos. 1-3, 11-13,
Containing a Group 17 element,^ThreeIs the periodic table 7th
Shows Group 12 elements. ] Is preferably used.
be able to.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ³⁴ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ³⁵ and R ³⁶ include cyclopentadienyl group, methylcyclopentane Examples thereof include a dienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Specific examples of R ³⁷ include a phenyl group, a p-tolyl group and a p-methoxyphenyl group, and specific examples of R ³⁸ include tetraphenylporphine, phthalocyanine, allyl, methallyl, and the like. . Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I _3. Specific examples of M ³ include Mn, F
e, Co, Ni, Zn and the like.

[Z ¹ ] ⁻ , that is, [M ⁵ G ¹ G
² ... G ^f ], B and A are specific examples of M ^5.
l, Si, P, As, Sb, etc., preferably B and Al
Is mentioned. Specific examples of G ¹ , G ^{2 to} G ^f include dimethylamino and diethylamino as dialkylamino groups, and methoxy, ethoxy, n-butoxy groups as alkoxy or aryloxy groups.
Methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.
Fluorine, chlorine, bromine, halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group and 3,5-dimethylphenyl group; Iodine, a p-fluorophenyl group as a hetero atom-containing hydrocarbon group, 3,5
-Difluorophenyl group, pentachlorophenyl group,
Organic metalloid groups such as 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) methyl group, etc. as pentamethylantimony group, trimethylsilyl group, trimethyl Examples include a germyl group, a diphenylarsine group, a dicyclohexylantimony group, and diphenylboron.

Further, a non-coordinating anion, ie, pKa
Specific examples of the conjugated base [Z ² ] ⁻ of a Brönsted acid alone or a combination of a Brönsted acid and a Lewis acid having a -10 or less are trifluoromethanesulfonic acid anion (CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetate anion (CF ₃ CO ₂ ) ^-
Hexafluoroantimony anion (SbF ₆ ) ⁻ , fluorosulfonic acid anion (FSO ₃ ) ⁻ , chlorosulfonic acid anion (ClSO ₃ ) ⁻ , fluorosulfonic acid anion / 5-antimony fluoride (FSO ₃ / Sb)
F ₅₎ ^-, fluorosulfonic acid anion / 5- fluoride arsenic ^{_{(FSO 3 / AsF 5) -}} , trifluoromethanesulfonic acid / antimony pentafluoride (CF ₃ SO ₃ / Sb
F ₅ ) ^{— and the} like.

Specific examples of the component (B-2) include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, and tetraphenylborate. Methyl (tri-n-butyl) ammonium, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, tetraphenylborate Methylpyridinium, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium), tetrakis (pentafluorophenyl) Triethylammonium, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Tetraethylammonium, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate,
Methylanilinium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Benzylpyridinium, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), tetrakis ( Triphenylphosphonium pentafluorophenyl) borate, dimethyl tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate Nilinium, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocete) ), Decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Sodium, manganese tetraphenylporphyrin, tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, silver hexafluorophosphate, Kisafuruoro arsenic, silver perchlorate, silver trifluoroacetate, and the like of silver trifluoromethanesulfonate. As the component (B-2), the above-mentioned boron compounds are preferable.

As the component (B-2), an ionic compound which can be converted to a cation by reacting with the transition metal compound of the component (A) may be used alone or in combination of two or more. Is also good. In the olefin polymerization catalyst of the present invention, as the component (B), only the component (B-1) may be used, only the component (B-2) may be used, or the component (B-1) may be used. And the component (B-2) may be used in combination.

Further, in the present invention, the above-mentioned components (A) and (B) may be contained as main components, or the components (A), (B) and (C) It may contain an aluminum compound as a main component. Here, as the organoaluminum compound of the component (C), the general formula (12) R ³⁹ _v AlQ _3-v (12) (where R ³⁹ is an alkyl group having 1 to 10 carbon atoms, and Q is Hydrogen atom, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
In which v is an integer of 1 to 3).

Specific examples of the compound represented by the general formula (12) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride,
Examples include diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.

These organoaluminum compounds may be used alone or in combination of two or more. When the (B-1) compound is used as the (B) catalyst component, the molar ratio of the (A) catalyst component to the (B) catalyst component in this polymerization catalyst is preferably 1: 1 to 1 : 1
0 ^6, more preferably 1:10 to 1:10 ⁴ ranges desirable, when departing from the above range, the catalyst cost per unit weight polymer increases, not practical. When the compound (B-2) is used, the molar ratio is preferably 10: 1 to 1: 100, more preferably 2: 1 to 1: 100.
A range of 10 is desirable. If the ratio is outside this range, the cost of the catalyst per unit weight of polymer increases, which is not practical.

The molar ratio of the catalyst component (A) to the optional catalyst component (C) is preferably from 1: 1 to 1: 20,000, more preferably from 1: 5 to 1: 5.
1: 2000, more preferably 1:10 to 1: 100
A range of 0 is desirable. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if the amount is too large, especially if it exceeds the above range, the organoaluminum compound will be wasted and the polymer If the amount is large and the amount is small, sufficient catalytic activity cannot be obtained, which may be undesirable.

Further, in the present invention, each catalyst component
It is possible to use at least one of them supported on a suitable carrier.
Wear. There is no particular limitation on the type of the carrier, and inorganic acids
Compound carrier, any other inorganic carrier and organic carrier
Can be used, especially from the point of morphology control
Inorganic oxide carriers or other inorganic carriers are preferred
No. As the inorganic oxide carrier, specifically, SiO 2_Two,
Al_TwoO_Three, MgO, ZrO_Two, TiO_Two, Fe
_TwoO_Three, B_TwoO_Three, CaO, ZnO, BaO, ThO_Two
And mixtures thereof such as silica alumina, zeolite
, Ferrite, glass fiber, and the like.
Among them, especially SiO 2_TwoOr Al_TwoO_ThreeIs preferred
New In addition, the above-mentioned inorganic oxide carrier contains a small amount of carbonate,
Acid salts, sulfates and the like may be contained. On the other hand,
MgCl as carrier_Two, Mg (OC_TwoH_Five) _TwoMa
General formula MgR represented by a cesium compound, etc.⁴⁰ _XX⁷
_yAnd magnesium salts represented by
Can be Where R⁴⁰Is an alkyl having 1 to 20 carbon atoms
Kill group, alkoxy group having 1 to 20 carbon atoms or 6 to carbon atoms
20 aryl groups, X⁷Is a halogen atom or carbon number 1
20 represents an alkyl group, x is 0 to 2, y is 0 to 2
And x + y = 2. Each R⁴⁰And each X⁷Each
They may be the same or different. In addition,
Polystyrene, styrene-divinyl vinyl
Nzen copolymer, polyethylene, polypropylene, substitution
Polymers and stars such as polystyrene and polyarylate
And carbon. In the present invention
The carrier used is MgCl_Two, MgCl (O
C_TwoH_Five), Mg (OC_TwoH_Five)_Two, SiO_Two, Al_TwoO
_ThreeAre preferred. The shape of the carrier depends on its type and manufacturing method.
The average particle size is usually 1 to 300 μm,
10 to 200 μm, more preferably 20 to 100 μm
μm. If the particle size is small, the fine powder in the polymer increases,
If the particle size is large, coarse particles in the polymer increase and the bulk density is low.
It may cause clogging of the bottom and hopper. Also, the carrier ratio table
Area is usually 1-1000m^Two/ G, preferably 50 to
500m^Two/ G, pore volume is usually 0.1 to 5 cm^Three/ G,
Preferably 0.3-3cm^Three/ G. Specific surface area or thin
If any of the pore volumes deviate from the above range, the catalytic activity will decrease.
May drop. The specific surface area and pore volume are
For example, from the volume of nitrogen gas adsorbed according to the BET method
(J. Am. Chem. Soc, No.
60, p. 309 (1983)). Further
The carrier is usually 100 to 1000 ° C., preferably
It is desirable to use it after firing at 130 to 800 ° C.

When at least one of the catalyst components is carried on the carrier, at least one of the catalyst components (A) and (B), preferably the catalyst components (A) and (B)
Supporting both catalyst components is morphology control,
It is desirable from the viewpoint of applicability to processes such as gas phase polymerization. The method of supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, a method of mixing at least one of the component (A) and the component (B) with the carrier, After treatment with an organoaluminum compound or a halogen-containing silicon compound,
A method of mixing with at least one of the component (A) and the component (B) in an inert solvent, a method of reacting a carrier with the component (A) or the component (B) and an organoaluminum compound or a halogen-containing silicon compound. A method in which the component (A) or the component (B) is supported on a carrier, and then mixed with the component (B) or the component (A).
A method in which the contact reactant with the component is mixed with the carrier, a method in which the carrier coexists in the contact reaction between the component (A) and the component (B), and the like can be used.

In the above and the above reactions,
An organoaluminum compound as the component (C) can be added. In the present invention, the weight ratio of the compound (B-1) to the carrier is preferably 1: 0.5.
１ ： 1: 1000, more preferably 1: 1 to 1:50, and the ratio of the component (B-2) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1 to 5: 1 by weight. Is preferably 1:10 to 1: 500.
When two or more catalyst components (B) are used as a mixture, it is desirable that the weight ratio of each component (B) to the carrier be within the above range. The ratio of the component (A) to the carrier is preferably in a weight ratio of 1: 5 to 1:10.
000, more preferably 1:10 to 1: 500.

The component (B) [component (B-1), (B-
2) Component] and carrier, or (A) Component and carrier
If the use ratio with the above deviates from the above range, the activity decreases
Sometimes. Used in the present invention thus prepared
The average particle size of the polymerization catalyst is usually 2 to 200 μm, preferably
Is 10 to 150 μm, particularly preferably 20 to 100 μm
And the specific surface area is usually 20 to 1000 m^Two/ G, good
Preferably 50-500m ^Two/ G. Average particle size is 2μ
m, the fine powder in the polymer may increase,
If it exceeds 200 μm, coarse particles in the polymer may increase.
There is. Specific surface area is 20m^Two/ G is less than
1000m^Two/ G exceeds polymerization
The bulk density of the body may decrease. Also, this polymerization catalyst
, The amount of transition metal in 100 g of the support is usually 0.0
It is preferably from 5 to 10 g, particularly preferably from 0.1 to 2 g.
If the amount of the transition metal is outside the above range, the activity may be low.
There is. By supporting on a carrier in this way, industrial
With high bulk density and excellent particle size distribution
Polymer can be obtained.

The contact of the component (A), the component (B) and, if necessary, the component (C) and / or the carrier is carried out in an inert gas such as nitrogen, pentane, hexane, heptane, toluene,
It may be performed in a hydrocarbon solvent such as cyclohexane. The contact temperature may range from -30 ° C to the boiling point of the solvent, preferably from -10 ° C to 100 ° C, and the contact time may be generally 30 seconds to 10 hours. After contact, the solid catalyst component may or may not be washed. In contact,
Any of the two different transition metal compounds in the component (A) may be used first, or may be used by mixing them in advance.

The catalyst thus obtained may be used for polymerization after the solvent is once distilled off and taken out as a solid, or may be used for polymerization as it is. Further, in the present invention, a catalyst can be generated by performing an operation of loading at least one of the component (A) and the component (B) on a carrier in a polymerization system. For example, the catalyst may be a catalyst obtained by adding at least one of the components (A) and (B), a carrier and, if necessary, the organoaluminum compound of the component (C) and prepolymerizing the olefin.
Eufin used in the prepolymerization includes ethylene and an α-olefin having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, and 4-methyl-1-.
Pentene, 1-hexene, 1-octene, 1-decene,
Examples thereof include 1-dodecene and 1-tetradecene. Among them, particularly preferred is a combination with ethylene, propylene or an α-olefin used in the polymerization of ethylene-propylene. As the inert hydrocarbon solvent, specifically, the same inert hydrocarbon solvent as used in the preparation of the solid catalyst component described above can be used. In the case of pre-polymerization, it is usually 10 ⁻⁶ to 2 × 10 in terms of transition metal.
^-2 mol / l (solvent), preferably 5 × 10 ^-5 to 1
0 ^-2 is used in an amount of moles / liter (solvent), carrier 1g
As a transition metal, methylaluminoxane (MAO)
) In the organoaluminum compound (Al / transition metal) is usually 10 to 5000, preferably 20 to 1,000. The ratio of the aluminum atom in the organoaluminum compound used as necessary to the aluminum atom in MAO is usually in the range of 0.02 to 3, preferably 0.05 to 1.5. The pre-polymerization temperature is -20 to 60C, preferably 0 to 5C.
0 ° C., and the prepolymerization time is 0.5 to 100 hours,
Preferably, it is about 1 to 50 hours. In the present invention, a catalyst obtained by prepolymerizing an olefin is preferable. 2. Method for Producing Olefin Polymer The method for producing an olefin polymer of the present invention comprises: (A) at least two transition metal compounds belonging to Group 4 of the periodic table; (B) an aluminum oxy compound (B-1); Compound (B) that can be converted to a cation by reacting with
-2) a multistage polymerization method for olefin polymerization in the presence of an olefin polymerization catalyst containing at least one compound selected from the group consisting of compounds comprising: This is a production method for polymerizing an olefin.

It is difficult to achieve the object when the polymerization is not a multi-stage polymerization or when there is at least one step of polymerizing an olefin without using hydrogen in the polymerization step. That is, if not multi-stage polymerization, the melt tension is high,
An olefin polymer having excellent moldability is not obtained, which is not preferable. In addition, if at least one step of polymerizing an olefin without using hydrogen in the polymerization step is performed, an olefin polymer having a terminal vinyl terminal cannot be obtained, and a graft reaction does not occur even in multi-stage polymerization, which is not preferable.

As the olefin polymerization catalyst used in the method for producing an olefin polymer of the present invention, the component (A) comprises the components (A-1) and (A-2) and the following components (A-3) to (A-
7) reacts with at least two kinds of transition metal compounds selected from the group of transition metal compounds of Group 4 of the periodic table, (B) aluminum oxy compound (B-1) and the above-mentioned transition metal compound to convert them into cations. Ionic compounds (B-
An olefin polymerization catalyst containing at least one selected from the compound group consisting of 2).

(A-1) and (A-2) are as described above. Hereinafter, (A-3) to (A-
7) will be described in detail. (A-3) A transition metal compound of Group 4 of the periodic table represented by the following general formula (3).

[0062]

Embedded image

[Wherein, M ¹ represents titanium, zirconium or hafnium. R ¹³ to R ¹⁸ each independently represent a hydrogen atom, a halogen atom, a halogen-containing hydrocarbon group of the hydrocarbon group or a C1-20 having 1 to 20 carbon atoms, R ¹⁵
And R ¹⁶ , at least one pair of R ¹⁶ and R ^17, and R ¹⁷ and R ¹⁸ may be bonded to each other to form a ring, and X ⁴ and X ⁵ each independently represent a hydrogen atom, a halogen atom or A hydrocarbon group having 1 to 20 carbon atoms, Y ³ is a divalent cross-linking group connecting two ligands, and is a hydrocarbon group having 1 to 20 carbon atoms; Hydrocarbon group, silicon-containing group, germanium-containing group, tin-containing group, -O-,
-CO -, - S -, - SO 2 -, - NR 12 -, - PR 12
-, - P (O) R 12 -, - BR 12 - or -AlR ¹² - indicates, R ¹² is a hydrogen atom, a halogen atom, C1-20
Or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms. In the general formula (3), a transition metal compound in which at least one of R ¹⁵ and R ¹⁶ , R ¹⁶ and R ^17, and R ¹⁷ and R ¹⁸ forms a ring is known as a BASF-type complex. Compound.

In the general formula (3), examples of the halogen atom among R ^{13 to} R ¹⁸ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, and an n-
Alkyl groups such as propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-hexyl group, n-decyl group, phenyl group, 1-naphthyl group,
Examples thereof include an aryl group such as 2-naphthyl group and an aralkyl group such as benzyl group. As the halogen-containing hydrocarbon group having 1 to 20 carbon atoms, at least one hydrogen atom of the above hydrocarbon group is a suitable halogen. Examples include a group substituted with an atom. R ^{13 to} R ¹⁸ may be the same or different from each other, and an adjacent group, ie, R ¹⁵
And R ¹⁶ , R ¹⁶ and R ^17, and R ¹⁷ and R ¹⁸ must be bonded to each other to form a ring. As the indenyl group forming such a ring,
Examples thereof include a 4,5-benzoindenyl group, an α-acenaphthoindenyl group and an alkyl-substituted product having 1 to 10 carbon atoms.

The halogen atom of X ⁴ and X ⁵ includes chlorine, bromine, fluorine and iodine. Examples of the hydrocarbon having 1 to 20 carbon atoms include methyl, ethyl and the like. And alkyl groups such as propyl group, isopropyl group, n-butyl group, tert-butyl group and n-hexyl group, aryl groups such as phenyl group, and aralkyl groups such as benzyl group. X ⁴ and X ⁵ may be the same or different. On the other hand, Y ³ is a divalent cross-linking group that binds two ligands, and examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include a methylene group; a dimethylmethylene group;
-Ethylene group; dimethyl-1,2-ethylene group; 1,4
-Tetramethylene group; alkylene groups such as 1,2-cyclopropylene group, arylalkylene groups such as diphenylmethylene group and the like. Examples of the divalent halogen-containing hydrocarbon group having 1 to 20 carbon atoms include chloroethylene group. , A chloromethylene group and the like. Examples of the divalent silicon-containing group include a methylsilylene group, a dimethylsilylene group, a diethylsilylene group, a diphenylsilylene group, and a methylphenylsilylene group. Further, examples of the germanium-containing group and the tin-containing group include groups obtained by converting silicon into germanium and tin in the above-mentioned silicon-containing group. The two ligands bonded by Y ³ are usually the same, but may be different depending on the case.

As the transition metal compound represented by the general formula (3), for example, JP-A-6-184179,
Compounds described in JP-A-6-345809 can be exemplified. As a specific example, rac-
Dimethylsilanediyl-bis-1- (2-methyl-4,
5-benzoindenyl) -zirconium dichloride, r
ac-phenylmethylsilanediyl-bis-1- (2-
Methyl-4,5-benzoindenyl) -zirconium dichloride, rac-ethanediyl-bis-1- (2-methyl-4,5-benzoindenyl) -zirconium dichloride, rac-butanediyl-bis-1- (2- Methyl-4,5-benzoindenyl) -zirconium dichloride, rac-dimethylsilanediyl-bis-1-
(4,5-benzoindenyl) -zirconium dichloride, rac-dimethylsilanediyl-bis-1- (2-
Benzoindenyl type such as methyl-α-methyl-α-acenaphthoindenyl) -zirconium dichloride, rac-phenylmethylsilanediyl-bis-1- (2-methyl-α-acenaphthoindenyl) -zirconium dichloride or Acenaphthoindenyl-type compounds and those obtained by substituting zirconium in these compounds with titanium or hafnium can be mentioned.

Further, in the general formula (3), R ¹⁵
And a transition metal compound having an indenyl skeleton in which any pair of R ¹⁶ , R ¹⁶ and R ¹⁷ and R ¹⁷ and R ¹⁸ does not form a ring, or a corresponding 4,5,6,7-tetrahydroindenyl skeleton. A transition metal compound having the same can also be used. This transition metal compound is a compound known as a Hoechst complex. As this transition metal compound,
For example, JP-A-4-268308 and 5-306
Nos. 304, 6-100579, 6-15
Nos. 7661 and 7-149815, 7-1
Compounds described in JP-A-88318 and JP-A-7-258321 can be exemplified.

As a specific example, dimethylsilanediyl-
Bis-1- (2-methyl-4-phenylindenyl)-
Zirconium dichloride, dimethylsilanediyl-bis
-1- [2-methyl-4- (1-naphthyl) indeni
] -Zirconium dichloride, dimethylsilanediyl
-Bis-1- (2-ethyl-4-phenylindenyl)
-Zirconium dichloride, dimethylsilanediyl-bi
S-1- [2-ethyl-4- (1-naphthyl) indeni
Ru] zirconium dichloride, phenylmethylsilanedi
Il-bis-1- (2-methyl-4-phenylindenyl)
Le) -zirconium dichloride, phenylmethylsilane
Diyl-bis-1- [2-methyl-4- (1-naphthy
Ru) indenyl] -zirconium dichloride, phenyl
Methylsilanediyl-bis-1- (2-ethyl-4-f
Enylindenyl) -zirconium dichloride, phenyl
Methylsilanediyl-bis-1- [2-ethyl-4-
(1-Naphthyl) indenyl] -zirconium dichloride
Aryl-substituted products such as rac-dimethylsilylene-
Bis-1- (2-methyl-4-ethylindenyl) -di
Ruconium dichloride, rac-dimethylsilylene-bi
S-1- (2-methyl-4-isopropylindenyl)
-Zirconium dichloride, rac-dimethylsilylene
-Bis-1- (2-methyl-4-tert-butylindenyl)
Le) -zirconium dichloride, rac-phenylmethyl
Rusilylene-bis-1- (2-methyl-4-isopropyl)
Ruindenyl) -zirconium dichloride, rac-di
Methylsilylene-bis-1- (2-ethyl-4-methyl
Indenyl) -zirconium dichloride, rac-dim
Tylsilylene-bis-1- (2,4-dimethylindeni
) -Zirconium dichloride, rac-dimethylsilicone
Len-bis-1- (2-methyl-4-ethylindeni
B) 2,4-substituted products such as -zirconium dimethyl,
rac-dimethylsilylene-bis-1- (4,7-dimethyl
Tylindenyl) -zirconium dichloride, rac-
1,2-ethanediyl-bis-1- (2-methyl-4,
7-dimethylindenyl) -zirconium dichloride,
rac-dimethylsilylene-bis-1- (3,4,7-
Trimethylindenyl) -zirconium dichloride, r
ac-1,2-ethanediyl-bis-1- (4,7-di
Methylindenyl) -zirconium dichloride, rac
-1,2-butanediyl-bis-1- (4,7-dimethyl
4,7, such as ruindenyl) -zirconium dichloride
-Position, 2,4,7-position or 3,4,7-position substitution,
Tylsilanediyl-bis-1- (2-methyl-4,6-
Diisopropylindenyl) -zirconium dichloride
, Phenylmethylsilanediyl-bis-1- (2-meth
Tyl-4,6-diisopropylindenyl) -zirconi
Um dichloride, rac-dimethylsilanediyl-bis
-1- (2-methyl-4,6-diisopropylindeni
Ru) -zirconium dichloride, rac-1,2-eta
Ndiyl-bis-1- (2-methyl-4,6-diisoprop
Ropylindenyl) -zirconium dichloride, rac
-Diphenylsilanediyl-bis-1- (2-methyl-
4,6-diisopropylindenyl) -zirconiumdi
Chloride, rac-phenylmethylsilanediyl-bis
-1- (2-methyl-4,6-diisopropylindeni
Ru) -zirconium dichloride, rac-dimethylsila
Ndiyl-bis-1- (2,4,6-trimethylindene
2,4,6-position such as nyl) -zirconium dichloride
Substituted product, rac-dimethylsilanediyl-bis-1-
(2,5,6-trimethylindenyl) -zirconium
2,5,6-substituted products such as dichloride, rac-dim
Tylsilylene-bis- (2-methyl-4,5,6,7-
Tetrahydro-1-indenyl) -zirconium dichloro
Lido, rac-ethylene-bis- (2-methyl-4,
5,6,7-tetrahydro-1-indenyl) -zirco
Numium dichloride, rac-dimethylsilylene-bis-
(2-methyl-4,5,6,7-tetrahydro-1-i
Ndenyl) -zirconium dimethyl, rac-ethylene
-Bis (2-methyl-4,5,6,7-tetrahydro-
1-indenyl) -zirconium dimethyl, rac-d
Tylene-bis- (4,7-dimethyl-4,5,6,7-
Tetrahydro-1-indenyl) -zirconium dichloro
4,5,6,7-tetrahydroindenylation such as lido
And zirconium in these compounds
List those substituted with titanium or hafnium
Can be. As the component (A-3), two or more
They may be used together. (A-4) Group 4 of the periodic table represented by the following general formula (4)
Transition metal compounds. (R¹⁹ _FiveC_Five)_mM¹X¹ _4-m... (4) [where, M¹Is titanium, zirconium or hafnium
And R¹⁹ _Five C_FiveIs a hydrocarbon-substituted cyclopentadiene
Group, X¹Represents a hydrogen atom, a halogen atom or a carbon number of 1 to 2
And 0 represents a hydrocarbon group. m shows the integer of 2-4. 5 pieces
R¹⁹May be the same or different. m R¹⁹ _FiveC
_FiveMay be the same or different. (4-m) X¹
May be the same or different. In the compound (A) used in the present invention, the compound represented by the above formula (4)
Middle R¹⁹Or X¹The hydrocarbon group represented by is particularly limited.
Although not specified, for example, an alkyl group having 1 to 20 carbon atoms,
Group, arylalkyl group, alkylaryl group, etc.
Preferred examples are given. Here, carbon number 1-20
Examples of the alkyl group include a methyl group, an ethyl group,
Propyl group, isopropyl group, butyl group, isobutyl group,
t-butyl group, amyl group, hexyl group, heptyl group,
Octyl, nonyl, capryl, undecyl, lau
Ryl, tridecyl, myristyl, pentadecyl
Group, cetyl group, heptadecyl group, stearyl group, nonade
Examples include a sil group and an eicosyl group. Carbon number
1 to 20 aryl groups and arylalkyl groups include
Examples include phenyl, benzyl, phenethyl and the like.
Can be C1-C20 alkylaryl group
For example, a p-tolyl group, pn-butylphenyl
And the like. In addition, in the above equation (4),
And m is preferably 1 or 2, especially 2.
As the compound of the formula (4), specifically, for example, [(C
H_Three)_FiveC_Five]_TwoHf (CH_TwoPh)_Two, [(CH_Three)
_FiveC_Five]_TwoZr (CH_TwoPh)_Two, [(CH_Three)
_FiveC_Five] HfPh_Three, [(CH_Three)_FiveC_Five] ZrP
h_Three, [(CH_Three)_FiveC₆]_TwoHf (C₆H_Four-P-C
H_Three)_Two, [(CH _Three)_FiveC_Five]_TwoZr (C₆H_Four-P
-CH_Three)_Two, [(CH_Three)_FiveC_Five]_TwoHf (C
H_Three)_Two, [(CH_Three)_FiveC_Five]_TwoZr (CH_Three)_Two,
[(C_TwoH_Five) C _Five]_TwoHf (CH_Three)_Two, [(C_TwoH
_Five)_FiveC_Five]_TwoZr (CH_Three)_Two, [(NC_ThreeH₇)_Five
C_Five]_TwoHf (CH_Three)_Two, [(NC_ThreeH₇)_FiveC_Five]
_TwoZr (CH_Three)_Two, [(CH_Three)_FiveC_Five]_TwoHfH
(CH_Three), [(CH_Three)_FiveC_Five]_TwoZrH (C
H_Three), [(C_TwoH_Five)_FiveC_Five]_TwoHfH (CH_Three),
[(C_TwoH_Five)_FiveC_Five]_TwoZrH (CH_Three), [(C_Three
H₇)_FiveC_Five]_TwoHfH (CH_Three), [(C_ThreeH₇)_Five
C_Five]_TwoZrH (CH_Three), [(CH_Three)_FiveC_Five]_TwoH
f (H)_Two, [(CH_Three)_FiveC_Five]_TwoZr (H)_Two,
[(C_TwoH_Five) (CH_Three)_FourC_Five]_TwoHf (C
H_Three)_Two, [(C_TwoH_Five) (CH_Three)_FourC_Five]_TwoZr
(CH_Three)_Two, [(NC_ThreeH₇) (CH_Three)_FourC_Five]_Two
Hf (CH_Three)_Two, [(NC_ThreeH₇) (CH_Three)
_FourC_Five]_TwoZr (CH_Three)_Two, [(NC_FourH₉) (CH
_Three)_FourC_Five] _TwoHf (CH_Three)_Two, [(NC_FourH₉)
(CH_Three)_FourC_Five]_TwoZr (CH_Three)_Two, [(CH_Three)
_FiveC_Five]_TwoHfC1_Two, [(CH_Three)_FiveC_Five]_TwoZrC
1_Two, [(CH_Three)_FiveC_Five]_TwoHfH (Cl), [(C
H_Three)_FiveC_Five]_TwoZrH (Cl), or the like is preferably used.
[(CH_Three)_FiveC_Five]_TwoH
f (CH_TwoPh)_Two, [(CH_Three)_FiveC_Five]_TwoZr (C
H_TwoPh)_Two([(CH_Three)_FiveC_Five]_TwoHf (CH_Three)
_Two, [(CH_Three)_FiveC_Five]_TwoZr (CH_Three)_Two, [(C
H_Three)_FiveC_Five]_TwoHfH (CH_Three), [(CH_Three)_FiveC
_Five]_TwoZrH (CH _Three), [(CH_Three)_FiveC_Five]_TwoHf
(H)_Two, [(CH_Three)_FiveC_Five]_TwoZr (H)_Two,
[(C_TwoH_Five) (CH_Three)_FourC_Five]_TwoHf (C
H_Three)_Two, [(C_TwoH_Five) (CH_Three)_FourC_Five]_TwoZr
(CH_Three)_Two, [(NC_ThreeH₇) (CH_Three)_FourC_Five]
_TwoHf (CH_Three)_Two, [(NC_ThreeH₇) (CH_Three)_FourC
_Five]_TwoZr (CH_Three) _Two, [(NC_FourH₉) (CH_Three)
_FourC_Five]_TwoZr (CH_Three)_Two, [(CH_Three)_FiveC_Five]_Two
ZrCl_Two, [(CH_Three)_FiveC_Five]_TwoZrHCl,
[(CH_Three)_FiveC_Five]_TwoHfCl_Two, [(CH_Three)_FiveC
_Five]_TwoPentaalkylcyclopentadi such as HfHCl
Enyl compounds are preferred, especially hafnium compounds,
Conium compounds are preferred. As the component (A-4),
Two or more types may be used in combination. (A-5) of group 4 of the periodic table represented by the following general formula (5)
Transition metal compounds. Cp_TwoM¹R²⁰ _aR^{twenty one} _b... (5) [where, M¹Represents a transition metal of Group 4 of the periodic table, and Cp
Is a cyclopentadieel group, a substituted cyclopentadiee
Group, indenyl group, substituted indenyl group, tetrahydro
Indenyl group, substituted tetrahydroindenyl group, fluoro
Cyclic unsaturated carbon such as enyl or substituted fluorenyl
It represents a hydrogen group or a chain unsaturated hydrocarbon group. R ²⁰, R
^{twenty one}Are independently σ-binding ligands, chelating properties
A ligand such as a ligand or a Lewis base;²⁰, R^{twenty one}Is
It may combine with each other to form a ring. a and b are respectively
An integer of 0 to 2 is independently shown. In addition, substituted cyclopentadiene
The number of substituents of the enyl group is 1 to 5, and
The number and types of the substituents on the tadienyl group are the same.
Or different. However, one cyclopentane
When the number of substituents of the dienyl group is 5, the other cyclo is
The number of substituents of the pentadienyl group is 1 to 4. In the general formula (5), M¹Is the fourth member of the periodic table
Metals, such as titanium, zirconium or hafnium
I can do it. Cp is a cyclopentadieel group, substituted cycle
Rontadiel, indenyl, substituted indenyl
Group, tetrahydroindenyl group, substituted tetrahydroin
Denenyl group, fluorenyl group or substituted fluorenyl group, etc.
Represents a cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group.
You. R²⁰, R^{twenty one}Are independently σ-binding ligands,
A chelating ligand, a ligand such as a Lewis base,
Specific examples of the σ-binding ligand include a hydrogen atom, oxygen
Atom, halogen atom, alkyl group having 1 to 20 carbon atoms, charcoal
Alkoxy group having 1 to 20 primes, aryl having 6 to 20 carbons
Group, alkylaryl group or arylalkyl
Group, acyloxy group having 1 to 20 carbon atoms, allyl group, substitution
Examples include an allyl group and a substituent containing a silicon atom.
Acetylacetonate is a chelating ligand.
Examples include black ink and substituted acetylacetonate groups.
R²⁰, R^{twenty one}May combine with each other to form a ring. a,
b shows the integer of 0-2 each independently. Also, the replacement
The number of substituents of the cloantadienyl group is 1 to 5,
Number of substituents on cyclopentadienyl group of
The classes may be the same or different. However, one of
When the number of substituents of the cyclopentadienyl group is 5,
The other cyclopentadienyl group has 1 to 4 substituents.
You. The substituent is not particularly limited.
The transition metal compound of Group 4 of the periodic table represented by the general formula (4)
R shown in¹⁹And the same.

When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. The two Cp may be the same or different from each other. Examples of the substituted cyclopentadienyl group in the above formula (5) include a methylcyclopentadienyl group, an ethylcyclopentadienyl group; an isopropylcyclopentadienyl group; a 1,2-dimethylcyclopentadienyl group; Cyclopentadienyl group:
1,3-dimethylcyclopentadienyl group: 1,2,3
-Trimethylcyclopentadienyl group; 1,2,4-trimethylcyclopentadienyl group; pentamethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group and the like. Specific examples of R ²⁰ and R ²¹ in the above formula (5) include, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom as a halogen atom, a methyl group, an ethyl group as an alkyl group having 1 to 20 carbon atoms, n
A propyl group, an isopropyl group, an n-butyl group, an octyl group, a 2-ethylhexyl group, a C1-20 alkoxy group such as a methkin group, an ethkin group, a propoxy group,
A butoxy group, a phenoquine group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, such as a phenyl group, a tolyl group, a xylyl group, a benzyl group;
Examples of the acyloxy group having 1 to 20 carbon atoms include a heptadecylcarbonyloxy group, and examples of the substituent containing a silicon atom include a trimethylsilyl group and a (trimethylsilyl) methyl group.

Examples of the compound represented by the general formula (5) include bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, and bis (cyclopentadienyl) diethyl zirconium. Cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydride Zirconium, bis (methylcyclopentadienyl) dimethyl zirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, (cyclopentane Enyl) (pentamethylcyclopentadienyl) such dichlorozirconium, further in these, the compound zirconium is replaced with titanium or hafnium and the like. The component (A-5) may be used in combination of two or more kinds. (A-6) A transition metal compound of Group 4 of the periodic table represented by the following general formula (6). ^{_{CpM 1 R 20 a R 21 b}} R 22 c ··· (6) wherein, M ¹ is shown a periodic table group IV transition metal, Cp is cyclo preventor cyclopentadienyl group, a substituted cycloalkyl preventor cyclopentadienyl group, It represents a cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as an indel group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group. R ²⁰ , R ²¹ , R
Each independently σ bonding ligand ^22, chelate ligand, showed the ligand such as a Lewis base, R ^20, R ^21, R
Two or more of ²² may combine with each other to form a ring.
a, b, and c each independently represent an integer of 0 to 2. M in the transition metal compound represented by the general formula (6)
¹ , Cp, R ²⁰ , R ²¹ , a, and b are as described in the general formula (5). R ²² is the aforementioned R
²⁰ and R ²¹ each independently represent a σ-binding ligand, a chelating ligand, or a ligand such as a Lewis base. Specific examples thereof are the same as those of R ²⁰ and R ²¹ . Things.

Examples of the compound represented by the general formula (6) include (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, and (pentamethylcyclopentadienyl) Tribenzylzirconium, (pentamethylcyclopentadienyl) trichlorozirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cycloventazi) (Enyl) tribenzylzirconium, (cyclopentadienyl) trichlorozirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium , (Methylcyclopentadienyl) trimethylzirconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopesitadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) ) Dimethyl (methoxy) zirconium, (dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium, Methylcyclopentadienyl) trichlorozirconium and the like, and furthermore, compounds in which zirconium is replaced by titanium or hafnium. It is. (A-
6) Two or more types of components may be used in combination. (A-7) A transition metal compound of Group 4 of the periodic table represented by the following general formula (7).

[0072]

Embedded image

[Wherein, M¹Is titanium, zirconium or
Represents a hafnium atom, and Cp is cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, tetrahydroindenyl group, substituted tetra
Hydroindenyl, fluorenyl or substituted fluor
Cyclic unsaturated hydrocarbon group such as an n-yl group or chain unsaturated carbon
Shows a hydrogen group. X⁶Is hydrogen atom, halogen atom, carbon number
An alkyl group having 1 to 20, an aryl group having 6 to 20 carbon atoms,
Alkylaryl group or arylalkyl group or charcoal
It represents an alkoxy group having a prime number of 1 to 20. Z is SiR^{twenty three} _Two,
CR^{twenty three} _Two, SiR^{twenty three} _TwoSiR^{twenty three} _Two, CR^{twenty three} _TwoCR^{twenty three} _Two,
CR^{twenty three} _TwoCR^{twenty three} _TwoCR^{twenty three} _Two, CR^{twenty three}= CR^{twenty three}, CR^{twenty three} _Two
SiR^{twenty three} _TwoOr GeR^{twenty three} _TwoAnd Y^ThreeIs -N (R^{twenty four})
-, -O-, -S- or -P (R^{twenty four})-. R above
^{twenty three}Is hydrogen or an alkyl having up to 20 non-hydrogen atoms
Le, aryl, silyl, halogenated alkyl, halogen
Selected from aryl halide groups and combinations thereof.
R^{twenty four}Is alkyl having 1 to 10 carbons or 6 carbons
10 to 10 aryl groups, or 1 or more aryl groups
R on^{twenty three}Form a linked ring system of up to 30 non-hydrogen atoms with
You may. w represents 1 or 2. Specific examples of the compound represented by the general formula (7) include:
(Tertiary butylamide) (tetramethyl-η^Five-Cyclo
(Pentadienyl) -1,2-ethanediyl zirconium
Dichloride: (tert-butylamide) (tetramethyl-
η^Five-Cyclopentadienyl) -1,2-ethanediyl
Titanium dichloride; (methylamide) (tetramethyl-
η^Five-Cyclopentadienyl) -1,2-ethanediyl
Zirconium dichloride: (methylamide) (tetrame
Chill-η^Five-Cyclopentadieel) -1.2-ethane
Diyl titanium dichloride; (ethylamide) (tetrame
Chill-η^Five-Cyclopentadienyl) -methylene titanium
Dichloride: (tertiary butylamido) dimethyl (tetra
Methyl-η^Five-Cyclopentadienyl) silanetitaniumdi
Chloride: (tert-butylamido) dimethyl (tetrame
Chill-η^Five-Cyclopentadienyl) silane zirconium
Mudibenzyl; (benzylamido) dimethyl- (tetra
Methyl-η^Five-Cyclopentadienyl) silane titanium dik
Chloride; (phenyl phosphide) dimethyl (tetramethe)
Le-η^Five-Cyclopentadienyl) silane zirconium
Dibenzyl and the like. The component (A-7) has two types.
It may be used in combination of more than one.

Regarding the olefin polymerization catalyst used in the method for producing an olefin polymer of the present invention, the component (A)
At least two components selected from the above-mentioned component (A-1) (hetero-cross-linked complex), component (A-2) (double-cross-linked complex) and component (A-3) (BASF-type complex and Hoechst-type complex). It is preferable to achieve the object of the present invention that different kinds of transition metal compounds are used. Particularly preferred is a case of two types of transition metal compounds belonging to Group 4 of the periodic table consisting of one selected from the component (A-1) and one selected from the component (A-2). As the transition metal of Group 4 of the periodic table, hafnium is preferable for achieving the object, a combination of a hafnium compound and another transition metal compound is preferable, and a combination of a hafnium compound and a zirconium compound is more preferable. is there.

As a preferable example of such a combination,
Hoechst zirconium complex-Hoechst hafnium complex, BASF zirconium complex-BASF hafnium complex, Hoechst zirconium complex-BASF hafnium complex, BASF zirconium complex-Hoechst hafnium complex, BASF zirconium complex-double crosslinked hafnium Complex, Hoechst-type zirconium complex-double-bridged hafnium complex, double-bridged zirconium complex-double-bridged hafnium complex, double-bridged zirconium complex-BASF-type hafnium catalyst, double-bridged zirconium complex-Hoechst-type hafnium Complex, Hetero-bridged zirconium complex-Hetero-bridged hafnium complex, Hetero-bridged zirconium complex-BASF-type hafnium complex, Hetero-bridged zirconium complex-Double-bridged hafnium complex, Hetero-bridged zirconium complex- Text type zirconium complex, cross bridged hafnium complexes -BASF type zirconium complex, different crosslinked hafnium complex - double crosslinked zirconium complexes, different crosslinked hafnium complexes - such as Hoechst-type zirconium complex. Examples of particularly preferred combinations include:
Hetero-bridged zirconium complex-double-bridged hafnium complex, hetero-bridged hafnium complex-double-bridged zirconium complex.

When a combination of a hafnium compound and another transition metal compound is used as the transition metal compound of the component (A), the content of the hafnium compound in the mixed transition metal compound is preferably from 1.0 to 99. 9 mol%, more preferably 5.0 to 99.0 mol%, even more preferably 25.
0 to 95.0 mol%, particularly preferably 50.0 to 90.
The range is 0 mol%.

Next, the component (B) will be described.
The component (B) [the components (B-1) and (B-2)] is the same as the component 1. Component (B) in the olefin polymerization catalyst [(B-
1) and (B-2) component]. Further, the olefin polymerization catalyst used in the method for producing an olefin polymer of the present invention includes the above-mentioned 1. As in the case of the olefin polymerization catalyst, the component (A) and the component (B), and if necessary, the (C) organoaluminum compound may be used. You may. These specific contents are described in 1. above. Same as the olefin polymerization catalyst.

The polymerization method of the multistage polymerization in the method for producing an olefin polymer of the present invention may be any of a batch type and a continuous type, and may be a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, Any method can be adopted from among polymerization methods and the like. Examples of the polymerization solvent used for carrying out slurry polymerization or solution polymerization include, for example, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, cyclopentane, cyclohexane and methylcyclohexane. Alicyclic hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and chloroform. These solvents may be used alone or as a mixture of two or more.

In the first stage of the multi-stage polymerization, it is preferable to produce an olefin polymer having an intrinsic viscosity of 0.01 dl / g to 20 dl / g, more preferably 0.05 dl / g to 10 dl / g. g of olefin polymer. In the second stage, it is preferable to produce an olefin polymer having an intrinsic viscosity of 0.5 dl / g to 10 dl / g, more preferably an olefin polymer having an intrinsic viscosity of 1.0 dl / g to 5 dl / g. Is to manufacture. The weight ratio of the first stage to the second stage olefin polymer (first stage / second stage) is usually 0.1.
It is from 0.01 to 95% by weight, preferably from 0.5 to 90% by weight, particularly preferably from 1.0 to 85% by weight.

Regarding the polymerization conditions, the polymerization temperature is usually-
The range is 50 to 200C, preferably -20 to 150C, more preferably 0 to 120C. The polymerization pressure is usually 0 to 200 kg / cm ² G, preferably 0.1 to 150 kg / cm ² G.
kg / cm ² G, more preferably 0.2 to 100 kg /
cm ² G. The polymerization time is usually 10
The range is from seconds to 5 hours, preferably from 30 seconds to 3 hours, and more preferably from 1 minute to 2 hours. In order to obtain an olefin polymer having a terminal vinyl in at least one polymerization step, it is necessary not to use hydrogen. In the multistage polymerization, it is preferable that the polymerization conditions of the first stage and the second stage are different. Further, the amount of the polymerization catalyst used is such that the molar ratio of the raw material monomer / the component (A) is preferably 1 to 1.
It is preferable to select 10 ⁸ , more preferably 100 to 10 ⁷ .

The limiting viscosity (control of the molecular weight) of the produced propylene polymer is controlled by controlling the proportion of each component of the polymerization catalyst, the amount of the polymerization catalyst used, the polymerization temperature, the polymerization pressure, and the chain transfer agent such as hydrogen. By appropriately selecting in the above range,
Just do it. The olefin is not particularly limited, and examples thereof include ethylene and α-olefins having 3 to 20 carbon atoms. Of these, ethylene and propylene are preferred. Particularly preferred is propylene. Examples of the α-olefin include propylene, 1-butene, 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-
Α such as 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane, etc.
-Halogen substitution α such as olefins, hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene and 3,4-dichloro-1-butene; -Cyclic olefins such as olefin, cyclopentene, cyclohexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 5-benzylnorbornene, and styrenes such as styrene and 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-dimethylstyrene, 2,5
Alkylstyrenes such as -dimethylstyrene and 3,5-dimethylstyrene, alkoxystyrenes such as p-methoxystyrene, o-methoxystyrene and m-methoxystyrene, p-chlorostyrene, m-chlorostyrene, o
-Chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene,
halogenated styrenes such as m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene,
Further, trimethylsilyl styrene, vinyl benzoate, divinyl benzene and the like can be mentioned. In the present invention, the above olefins may be used alone or in combination of two or more. When two or more olefins are brought into contact, the above olefins can be arbitrarily combined. Further, in the present invention, it may be copolymerized. The monomer or comonomer in the copolymer may be appropriately selected from the above olefins or other monomers. As other monomers, for example, chain diolefins such as butadiene, isoprene, 1,4-pentadiene and 1,5-hexadiene, norbornene,
1,4,5,8-dimethano-1,2,3,4,4a,
Polycyclic olefins such as 5,8,8a-octahydronaphthalene and 2-norbornene; norbornadiene;
-Ethylidene norbornene, 5-vinyl norbornene,
Examples thereof include cyclic diolefins such as dicyclopentadiene and unsaturated esters such as ethyl acrylate and methyl methacrylate.

The (C) organoaluminum compound optionally used in the production method of the present invention includes a chain aluminoxane represented by the general formula (8), a cyclic aluminoxane represented by the formula (9), An alkyl group-containing aluminum compound represented by the formula (12) is given. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-t-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum methoxide, diethylaluminum methoxide, dimethyl Aluminum hydroxide, halogen aluminum such as diethylaluminum hydroxide, alkylaluminum containing alkoxy group or hydroxyl group, alkylaluminum containing hydrogen atom such as dimethylaluminum hydride, diisobutylaluminum hydride, aluminoxane such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, etc. Yes, among these, especially trimethyl aluminum Rui triisobutylaluminum are preferred. The amount of the organoaluminum compound is usually selected such that the molar ratio of the transition metal in the above (A) to aluminum in the organoaluminum compound is 1: 0 to 10,000.

The method for producing the olefin polymer of the present invention is as follows. The obtained olefin polymer, typically, a propylene-based polymer has a terminal vinyl selectivity (indicating the proportion of the terminal vinyl group) of 15% or more. Preferably, there is. More preferably, it is 20% or more, more preferably 30% or more, particularly preferably 35% or more, and most preferably 45%.
That is all. Further, a method of producing an olefin polymer having a terminal vinyl selectivity of 15% or more in the first-stage polymerization is preferred. The terminal vinyl selectivity was determined by ¹ H-NMR.
And a method by IR. For example, as a measuring method by IR, the following method can be mentioned.

The terminal vinyl selectivity per molecule is calculated based on the measurement results of an infrared absorption spectrum according to the following method. That is, the olefin polymer is reduced to about 100
μm film, 907c with infrared altimeter
The transmittance of the peak at m ^-1 is measured, the number of terminal vinyl groups per 1000 carbon atoms is calculated, and the terminal vinyl selectivity per molecule is calculated. The calculation is performed according to the following formula (see “Polymer Handbook”, edited by The Chemical Society of Japan, page 240).

N _1000c = 1.41 × log (I ₀ / I) × (1 / (DT)) n _chain = n _1000c × Mn / 14000 In the formula, each symbol indicates the following content. n _1000c : number of terminal vinyl groups per 1000 carbon atoms n _chain : terminal vinyl selectivity per molecule I ₀ : transmittance at baseline I: transmittance at 907 cm ^-1 D: density of polymer (g / cm ³ ) T: film thickness (mm) M: number average molecular weight

[0086]

EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. First, a method for evaluating a polymer in the present invention will be described. (1) Intrinsic viscosity [η] (d) at 135 ° C. in decalin solvent
1 / g) was measured. (2) The bulk density was measured according to JIS K6721. (3) Melt tension MS is Capillograph 1 manufactured by Toyo Seiki Co., Ltd.
B was measured under the following conditions.

Capillary: 2.095 mm in diameter, 8.0 mm in length Cylinder diameter: 9.6 mm Cylinder extrusion speed: 10 mm / min Winding speed: 3.14 m / min Temperature: 230 ° C. [Example 1] Olefin polymerization catalyst (1) Preparation of carrier SiO_Two(P-10 manufactured by Fuji Silysia Chemical Ltd.) 70 g
Was dried at 140 ° C. for 15 hours under a slight nitrogen flow. Dry
Dry S1O_TwoWeighed 22.0 g and dehydrated toluene 200 ml
It was put in. Temperature to 40 ° C with stirring under nitrogen atmosphere
And then add triisobutylaluminum
Toluene solution (lmol / 1) converted to aluminum atoms
And 0.5 mmol was added dropwise. After reacting for 5 hours, dehydrate
Wash twice with 200 ml of toluene by the decantation method
Purified. The washing temperature was 40 ° C. After washing,
Similarly, 250 ml of dehydrated toluene was charged. (2) Preparation of aluminum oxy compound Methylaluminoxane as aluminum oxy compound
Was used. Toluene solution of methylaluminoxane 1.0
Liter (1.5mo1 / 1, Albemarle
Methyl aluminum (14.5% by weight) under reduced pressure (2
0 mmHg) and the solvent was distilled off at 60 ° C. In this state,
After holding for 4 hours, the temperature was lowered to room temperature and dried up
Methylaluminoxane was obtained. This dry up methyl
Add dehydrated toluene to the aluminoxane, redissolve it,
Return to the volume before distilling off the solvent, ¹By H-NMR
Determination of trimethylaluminum in tilluminoxane
The result was 3.6% by weight. In addition, fluorescent X-rays (IC
P) The result of measuring the total aluminum content by the method 1.32.
Mol / l. Then, this solution is
The mixture was allowed to stand, and insoluble components were allowed to settle. After this, the supernatant is
5 Filter under a nitrogen stream with a glass filter
And recover the solution as an aluminum oxy compound.
Methylalumoxane (a) was obtained. Concentration by ICP method
Was 1.06. By the above measurement, the organic aluminum
Is 10.9% by weight and the insoluble component is 17.3% by weight.
Removed. (3) Preparation of supported methylaluminoxane S1O prepared in (1) above_TwoOf toluene slurry
Under stirring and a nitrogen atmosphere, the temperature was controlled at 0 ° C. this
The soluble methylaluminoxane solution prepared in (2) above
A wave of 200 ml was dropped over 60 minutes. After dropping,
Raise the temperature to room temperature and react for 30 minutes.
The temperature rose. In this state, the reaction was continued for 3 hours. End of reaction
Thereafter, the temperature is lowered to 60 ° C., and while maintaining this temperature, dehydration is performed.
Twice with 200 ml of toluene, followed by dehydrated heptane 2
Washed twice with 00 ml. After drying under reduced pressure at 50 ° C
32.8 g of Si0_TwoSupported methylaluminoxane
Obtained. Again, 186 ml of dehydrated heptane was charged and S1O
_TwoPrepare heptane slurry of supported methylaluminoxane
did. (4) Preparation of metallocene-supported catalyst After replacing 200 ml of Schlenk with dry nitrogen, nitrogen
80 ml of dry heptane in an atmosphere, MA on silica
Add 10 mmol of O in terms of aluminum atom and add at room temperature
Stirred. Rac-SiMe_Two[2-Me-4
-Ph-lnd]_TwoZrC1_TwoLml of toluene solution of
(Equivalent to 25 micromol as zirconium atom)
After dripping, carry out the supporting reaction with stirring for 20 minutes.
Was. The supported catalyst turns orange and the catalyst slurry becomes static.
And the color unique to the zirconium compound is completely
The zirconium compound was supported
It was confirmed. Furthermore, rac-SiMe_Two[2-Me
-4-Ph-lnd]_TwoHfC1_Two1m of toluene solution of
l (equivalent to 25 micromoles as hafnium atom)
After dripping, carry out the supporting reaction for 40 minutes with stirring.
Metallocene-supporting catalyst containing two transition metal compounds
A slurry of the medium was obtained. [Example 2] Production of polypropylene (1) Preparation of prepolymerized catalyst Removed to a 1.6-liter stainless steel pressure-resistant autoclave
Water heptane 400ml, triisobutylaluminum
0.5 mmol was added, and the mixture was stirred for 10 minutes. to this,
Slurry of metallocene-supported catalyst obtained in (4) of Example 1
As the sum of zirconium and hafnium atoms
Icromol equivalent was introduced. While adjusting the temperature to 25 ° C
6 kg / cm of propylene^TwoPressurize to G pressure 3
Feeded continuously for hours. After the reaction, remove propylene.
The mixture was removed by pressure and nitrogen replacement to obtain a prepolymerized catalyst. (2) Production of polypropylene Dehydration in a 1.6-liter stainless steel pressure-resistant autoclave
Heptane 400 ml, triisobutylaluminum 0.
5 mmol was added and the mixture was stirred for 10 minutes. to this,
Convert the prepolymerized catalyst prepared in (1) into zirconium atoms
And the equivalent of 5 micromol was introduced. Polymerization temperature while stirring
Temperature to 80 ° C., and the polymerization pressure of propylene is increased to 1.0.
kg / cm^TwoContinuously supply the monomer so that it becomes G
Polymerization was performed for 200 minutes [first-stage polymerization]. After polymerization
The pressure was released and sampling was partially performed.

Next, the polymerization temperature was lowered to 70 ° C., and the monomers were continuously supplied so that the polymerization pressure of propylene became 7.0 kg / cm ² G, and the polymerization was carried out for 200 minutes. After the polymerization was completed, the pressure was released and the polypropylene was recovered.
g. The obtained polypropylene was measured according to the above-described polymer evaluation method. The results obtained are shown in Table 1. Example 3 Production of Propylene Copolymer A reaction was started in the same manner as in Example 2, and the first-stage polymerization was completed. Thereafter, the polymerization temperature was set to 50 ° C., the flow rate ratio of propylene / ethylene was kept constant at 10 / 0.5, and the polymerization pressure was set to 7
The polymerization was carried out for 60 minutes by continuously supplying the monomer so as to obtain kg / cm ² G. After the completion of the polymerization, the pressure was released and the copolymer was recovered, and it was 180 g. The measurement was performed in the same manner as in Example 2, and the obtained results are shown in Table 1. Example 4 Production of Propylene Copolymer In a 1.6-liter stainless steel autoclave, 400 ml of dehydrated heptane and 0.1 ml of triisobutylaluminum were added.
5 mmol was added and the mixture was stirred for 10 minutes. To this, 10 micromoles of the catalyst prepared in Example 1- (4) was added as a sum of zirconium atoms and hafnium atoms. The polymerization temperature was raised to 70 ° C. while stirring, the flow ratio of propylene / ethylene was kept constant at 10 / 0.2, and the monomer was continuously supplied so that the polymerization pressure became 1.0 kg / cm ² G. Polymerization was performed for 60 minutes [first-stage polymerization]. After the completion of the polymerization, the pressure was released and sampling was partially performed. Next, the polymerization temperature was lowered to 50 ° C., the flow rate ratio of propylene / ethylene was kept constant at 10 / 0.5, and the monomer was continuously supplied so that the polymerization pressure was 7.0 kg / cm ² G, for 60 minutes. Polymerization was performed. After the polymerization was completed, the pressure was released, and the propylene copolymer was recovered. The measurement was performed in the same manner as in Example 2, and the obtained results are shown in Table 1. Example 5 Production of Propylene Copolymer A reaction was started and the first-stage polymerization was completed in the same manner as in Example 4. Next, the polymerization temperature was lowered to 70 ° C., and monomers were continuously supplied so that the polymerization pressure of propylene became 7.0 kg / cm ² G, and polymerization was carried out for 200 minutes. After the polymerization was completed, the pressure was released and the polypropylene was recovered, and it was 157 g. The measurement was performed in the same manner as in Example 2, and the obtained results are shown in Table 1. Example 6 Production of Propylene Copolymer A propylene copolymer was prepared in the same manner as in Example 3 except that the catalyst prepared in Example 1- (4) was used in an amount of 10 μmol as the sum of zirconium atoms and hafnium atoms. Was manufactured. The measurement was performed in the same manner as in Example 2, and the obtained results are shown in Table 1. Example 7 Preparation of Catalyst Component In Example 1- (4), the metallocene catalyst component used first was rac- (1,2′-ethylene) (2,1′-
Ethylene) -bis (indenyl) zirconium dichloride was added with a metallocene catalyst component to be used next as rac- (1,
A supported catalyst was prepared in the same manner as in Example 1- (4) except that the catalyst was changed to 2'-ethylene) (2,1'-ethylene) -bis (indenyl) hafnium dichloride. Example 8 Preparation of Catalyst Component In Example 1- (4), the metallocene catalyst component used first was rac- (1,2′-ethylene) (2,1 ′).
Example except that the metallocene catalyst component to be used next was changed to rac-dimethylsilanediyl-bis-1- (2-methyl-4-phenylindenyl) hafnium dichloride for -ethylene) -bis (indenyl) zirconium dichloride. A supported catalyst was prepared in the same manner as in 1- (4). Example 9 Preparation of Catalyst Component In Example 1- (4), the metallocene catalyst component used first was rac- (1,2′-ethylene) (2,1 ′).
-Ethylene) -bis (indenyl) zirconium dichloride and metallocene catalyst component to be used next are 1,2-ethanediyl (1- (4,7-diisopropylindenyl))
Example 1- (4) except that (2- (4,7-diisopropylindenyl)) hafnium dichloride was used.
And a supported catalyst was prepared. Example 10 Production of Polypropylene A polypropylene was obtained in the same manner as in Example 2, except that the catalyst obtained in Example 7 was used as the metallocene-supported catalyst. Table 2 shows the measurement results obtained in the same manner as in Example 2.
It was shown to. Example 11 Production of Polypropylene A polypropylene was obtained in the same manner as in Example 2 except that the catalyst obtained in Example 8 was used as the metallocene-supported catalyst. Table 2 shows the measurement results obtained in the same manner as in Example 2.
It was shown to. Example 12 Production of Polypropylene A polypropylene was obtained in the same manner as in Example 2 except that the catalyst obtained in Example 9 was used as the metallocene-supported catalyst. Table 2 shows the measurement results obtained in the same manner as in Example 2.
It was shown to. Comparative Example 1 Example 6 of JP-A-6-179776
The polymerization of propylene was carried out in the presence of hydrogen using the catalyst species described in 1) as follows.

400 ml of dehydrated heptane and 5 mmol (in terms of aluminoxane) of methylaluminoxane (1.5 mol / l, manufactured by Albemarle, containing 14.5% by weight of triethylaluminum) were added to a 1.6-liter stainless steel autoclave and stirred for 10 minutes. did. 0.5 micromol of racemic-dimethylsilyl-bis (2-methyl-1-indenyl) zirconium dichloride and 2.68 micromol of racemic-dimethylsilyl-bis (indenyl) hafnium dichloride were added thereto. The temperature of the reaction mixture was set to 40 ° C., and hydrogen was added thereto at a gauge pressure of 0.04 g.
5 kg / cm ² G was introduced. In addition, 8k of propylene
The polypropylene was continuously supplied at a pressure of g / cm ² G for 60 minutes to produce polypropylene. After completion of the polymerization, the polypropylene was recovered to obtain 80 g. The measurement was performed in the same manner as in Example 2, and the obtained results are shown in Table 2.

[0090]

[Table 1]

[0091]

[Table 2]

[0092]

Industrial Applicability According to the present invention, an olefin which has a high melt tension and is excellent in molding processability, and which can efficiently produce an olefin polymer which is particularly preferably used for molding large-sized blow molding, thick foams, sheets and the like. A polymerization catalyst and a method for producing an olefin polymer are provided.

Continued on the front page F term (reference) 4J028 AA02A AB00A AB01A AC01A AC09A AC10A AC27A AC28A BA00A BA01B BA02B BB00A BB01B BB02B BC12B BC15B BC16B BC17B BC19B BC25B BC27B CA16A CA16B CA27 CA26 CA27 CA27 CA26 CA27 CA29B CA29C CB08A CB08B CB08C CB09A CB09B CB09C CB35A CB35B CB35C CB36A CB36B CB36C DA01 DA02 DA03 DA04 DA05 DA06 EA02 EB02 EB04 EC03 EB05 EB02 EB17 EB02 EB14 EB05

Claims (9)

[Claims] (A) The following (A-1) and (A-2)
Selected from the group of transition metal compounds of Group 4 of the Periodic Table
At least two transition metal compounds, (B) aluminum
Reaction with oxy compound (B-1) and the above transition metal compound
Ionic compound (B-2) that can be converted to a cation by
At least one selected from the group consisting of
An olefin polymerization catalyst. (A-1) of the group 4 of the periodic table represented by the following general formula (1)
Transition metal compound[Where M¹Is titanium, zirconium or hafnium
Show. R¹~ R¹¹, X¹And X^TwoAre each independently water
An element atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
C1-C20 halogen-containing hydrocarbon group, silicon-containing
Group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group
Represents a group, R^ThreeAnd R^FourAnd R⁸And R⁹Joined to each other
To form a ring. X¹And X^TwoIs German
A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group, a silicon-containing group, an acid
Oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups
Show. Y¹Is a divalent bridging group connecting the two ligands
Thus, a hydrocarbon group having 1 to 20 carbon atoms,
Halogen containing hydrocarbon group, silicon containing group, germanium containing
Organic group, tin-containing group, -O-, -CO-, -S-, -SO
_Two-, -NR¹²-, -PR¹²-, -P (O) R¹²−, −
BR¹²-Or-AlR¹²-Indicates R¹²Is a hydrogen atom,
A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or 1 carbon atom
And -20 to 20 halogen-containing hydrocarbon groups. (A-2) of the periodic table 4 group represented by the following general formula (2)
Transition metal compound｛Where M¹Represents titanium, zirconium or hafnium
Show, E¹And E^TwoIs cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, heterocyclopentadienyl group,
Telocyclopentadienyl group, amide group, phosphide
Ligands selected from groups, hydrocarbon groups and silicon-containing groups
And A¹And A^TwoTo form a crosslinked structure via
And they may be the same or different
, X^ThreeRepresents a σ-binding ligand, and X^ThreeWhere there are multiple
Multiple X^ThreeMay be the same or different, and other X
^Three, E¹, E^TwoOr Y^TwoAnd may be crosslinked. Y^TwoIs
Lewis base, Y^TwoIf there is more than one,^TwoIs
May be the same or different, other Y^Two, E¹, E^Twoor
Is X ^ThreeMay be cross-linked with A¹And A^TwoIs two
A divalent crosslinking group that binds a ligand, and has 1 to 20 carbon atoms
Hydrocarbon groups, halogen-containing hydrocarbons having 1 to 20 carbon atoms
Group, silicon-containing group, germanium-containing group, tin-containing group,-
O-, -CO-, -S-, -SO_Two-, -NR¹²−, −
PR¹²-, -P (O) R¹²-, -BR¹²-Or-AlR
¹²-Indicates R¹²Is hydrogen atom, halogen atom, carbon number 1
Containing 20 to 20 hydrocarbon groups or 1 to 20 carbon atoms
Show hydrocarbon radicals, which are identical or different
May be. q is an integer of 1 to 5 [(M¹Valence) −
2], and r represents an integer of 0 to 3. ｝ (A) at least two transition metal compounds of Group 4 of the periodic table, (B) an aluminum oxy compound (B
Olefin in the presence of an olefin polymerization catalyst comprising at least one compound selected from the group consisting of -1) and an ionic compound (B-2) that can be converted to a cation by reacting with the transition metal compound. Is a multistage polymerization method, wherein at least one polymerization step is performed without using hydrogen to polymerize an olefin. 3. The olefin polymerization catalyst according to claim 2,
(A) Component is (A-1), (A-2) in Claim 1.
And periodic table 4 group consisting of the following (A-3) to (A-7)
At least two transitions selected from the group of transition metal compounds
3. The olefin polymer according to claim 2, which is a transfer metal compound.
Production method. (A-3) of the group 4 of the periodic table represented by the following general formula (3)
Transition metal compound[Where M¹Is titanium, zirconium or hafnium
Show. R¹³~ R¹⁸Are independently a hydrogen atom and a halogen
Atom, hydrocarbon group having 1 to 20 carbon atoms or 1 to 2 carbon atoms
0 represents a halogen-containing hydrocarbon group;^FifteenAnd R¹⁶, R¹⁶
And R¹⁷And R¹⁷And R¹⁸At least one pair of
To form a ring, and X^FourAnd X^FiveEach
Each independently represents a hydrogen atom, a halogen atom or a group having 1 to 20 carbon atoms;
Y represents a hydrocarbon group;^ThreeIs a divalent linking two ligands
A hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group, a silicon-containing group,
Rumanium-containing group, tin-containing group, -O-, -CO-,-
S-, -SO_Two-, -NR¹²-, -PR¹²-, -P
(O) R¹²-, -BR¹²-Or-AlR¹²-Indicates R
¹²Is a hydrogen atom, a halogen atom, a hydrocarbon having 1 to 20 carbon atoms
A hydrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms.
You. (A-4) group 4 of the periodic table represented by the following general formula (4)
Transition metal compound (R¹⁹ _FiveC_Five)_mM¹X¹ _4-m... (4) [where, M¹Represents titanium, zirconium or hafnium
And R¹⁹ _FiveC_FiveIs a hydrocarbon-substituted cyclopentadiene
Group, X¹Represents a hydrogen atom, a halogen atom or a carbon number of 1 to 2
And 0 represents a hydrocarbon group. m shows the integer of 2-4. 5 pieces
R¹⁹May be the same or different. m R¹⁹ _FiveC
_FiveMay be the same or different. (4-m) X¹
May be the same or different. (A-5) of group 4 of the periodic table represented by the following general formula (5)
Transition metal compound Cp_TwoM¹R²⁰ _aR^{twenty one} _b・ (5) [where M¹Represents a transition metal of Group 4 of the periodic table, and Cp
Is a cyclopentadienyl group, a substituted cyclopentadienyl
Group, indenyl group, substituted indenyl group, tetrahydro
Indenyl group, substituted tetrahydroindenyl group, fluoro
Cyclic unsaturated carbon such as enyl or substituted fluorenyl
It represents a hydrogen group or a chain unsaturated hydrocarbon group. R ²⁰, R
^{twenty one}Are independently σ-binding ligands, chelating properties
A ligand such as a ligand or a Lewis base;²⁰, R^{twenty one}Is
It may combine with each other to form a ring. a and b are respectively
An integer of 0 to 2 is independently shown. In addition, substituted cyclopentadiene
The number of substituents of the enyl group is 1 to 5, and
The number and types of the substituents on the tadienyl group are the same.
Or different. However, one cyclopentane
When the number of substituents of the dienyl group is 5, the other cyclo is
The number of substituents of the pentadienyl group is 1 to 4. (A-6) of the periodic table 4 group represented by the following general formula (6)
Transition metal compound CpM¹R²⁰ _aR^{twenty one} _bR^{twenty two} _c... (6) [where, M¹Represents a transition metal of Group 4 of the periodic table, and Cp represents
Cyclobentadenyl, substituted cyclobentadenyl
Group, indenyl group, substituted indenyl group, tetrahydroi
Ndenyl group, substituted tetrahydroindenyl group, fluor
Cyclic unsaturated hydrocarbon such as nyl group or substituted fluorenyl group
And represents an unsaturated group or a chain unsaturated hydrocarbon group. R²⁰, R^{twenty one}, R
^{twenty two}Are independently σ-binding ligands and chelating ligands.
A ligand such as a ligand or a Lewis base;²⁰, R^{twenty one},
R^{twenty two}And two or more of which may combine with each other to form a ring
No. a, b, and c each independently represent an integer of 0 to 2
You. (A-7) of the periodic table 4 group represented by the following general formula (7)
Transition metal compound[Where M¹Is a titanium, zirconium or hafnium source
Cp is a cyclopentadienyl group, a substituted cyclo
Pentadienyl group, indenyl group, substituted indenyl group,
Tetrahydroindenyl group, substituted tetrahydroindenyl
Ring such as phenyl group, fluorenyl group or substituted fluorenyl group
It represents a linear unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group.
X⁶Is a hydrogen atom, a halogen atom, an alkyl having 1 to 20 carbon atoms.
Kill group, aryl group having 6 to 20 carbon atoms, alkyl aryl
Or an arylalkyl group or a group having 1 to 20 carbon atoms.
Shows an alkoxy group. Z is SiR^{twenty three} _Two, CR^{twenty three} _Two, Si
R^{twenty three} _TwoSiR^{twenty three} _Two, CR^{twenty three} _TwoCR^{twenty three} _Two, CR^{twenty three} _TwoCR^{twenty three}
_TwoCR^{twenty three} _Two, CR^{twenty three}= CR^{twenty three}, CR^{twenty three} _TwoSiR^{twenty three} _TwoOr
GeR^{twenty three} _TwoAnd Y^ThreeIs -N (R^{twenty four})-,-O-,-
S- or -P (R^{twenty four})-. R above^{twenty three}Is a hydrogen atom or
Represents an alkyl, aryl having up to 20 non-hydrogen atoms,
Silyl, alkyl halide, aryl halide and
And a group selected from the group consisting of^{twenty four}Is the carbon number
Alkyl having 1 to 10 or aryl having 6 to 10 carbon atoms
Or one or more R^{twenty three}And 30
Up to a non-hydrogen bonded ring system. w is 1
Or 2. ] 4. The method for producing an olefin polymer according to claim 2, wherein the olefin polymerization catalyst according to claim 2 is the olefin polymerization catalyst according to claim 1. 5. The method for producing an olefin polymer according to claim 2, wherein at least one of the transition metal compounds belonging to Group 4 of the periodic table as the component (A) is a hafnium compound. 6. The olefin polymer according to claim 2, wherein the olefin polymerization catalyst contains (C) an organoaluminum compound in addition to the components (A) and (B). Production method. 7. The process for producing an olefin polymer according to claim 2, wherein at least one of component (A) and / or at least one of component (B) in the olefin polymerization catalyst is supported on a carrier. . 8. The method for producing an olefin polymer according to claim 2, wherein the olefin polymerization catalyst is obtained by prepolymerization of an olefin. 9. The process for producing an olefin polymer according to claim 2, wherein the terminal vinyl selectivity of the obtained olefin polymer is 15% or more.