JPH11292912A - Olefin polymerization catalyst and production of polyolefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyolefin with high melt tension, resin compatibility and bulk density. SOLUTION: This polyolefin is obtained by the following two steps: first, in the presence of a catalyst comprising (A) at least two kinds of compound selected from group 4 transition metal compounds each bearing cyclopentadienyl group and (B) (B-1) an aluminumoxy compound, (B-2) an ionic compound capable of converting the transition metal compounds to the corresponding cations through reaction therewith and (B-3) at least one kind of substance selected from clay, clay mineral and layered compounds of ion exchanging capability, at least one kind of compound selected from 2-20C α-olefins and cyclic olefins is prepolymerized in an amount of 0.01-2,000 g per g of the transition metal compounds to form a prepolymerization catalyst with an intrinsic viscosity [η]of 0.01-20 dL/g. Next, at least one kind of compound selected from 2-20C α-olefins, cyclic olefins and styrene-based monomers is polymerized or copolymerized in the presence of the above prepolymerization catalyst (plus an organoaluminum compound).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyolefin, and more particularly, to a method for producing a polyolefin having a high melt tension, excellent resin compatibility and a high bulk density at a low cost and efficiently. It is.

[0002]

2. Description of the Related Art Polyolefins are widely used in many fields, taking advantage of their excellent properties. However, in conventional polyolefins,
Melt tension and melt viscoelasticity were insufficient, and the parison was inferior in stability in large-size blow molding. Further, when the molecular weight is increased to improve the melt tension, the melt fluidity is lowered, and there is a problem that the method cannot be applied to molding of a complicated shape.

[0003] In the field of foamed moldings, demands for foamed moldings having heat resistance as well as weight reduction, heat insulation and vibration damping properties are increasing, and polypropylene foamed moldings are expected. In fact, polypropylene does not have sufficient melt tension, and it is difficult to obtain a sufficiently satisfactory foam molded article. In order to further expand the field of use of this polypropylene, it is necessary to improve the extrusion processability. Conventionally, various attempts have been made to improve the melt processability of polyolefins.For example, by improving the polymerization catalyst and polymerization recipe during the production of polyolefins and expanding the molecular weight distribution, the melt processability is improved. And a method of partially cross-linking a polyolefin to improve melt processability.

[0004] On the other hand, in the case of ethylene-based polymers, recently, despite the narrow molecular weight distribution due to the catalyst system combining a metallocene catalyst and aluminoxane, etc.
An ethylene polymer having an improved melt tension has been proposed (JP-A-4-213306). Also, for ethylene polymers produced by constrained geometric catalysts,
Similarly, it is disclosed that the melt tension is improved despite the narrow molecular weight distribution (JP-A-3-16308).
No. 8), suggesting the existence of long-chain branching. However, the improvement in extrusion processability due to the improvement in melt tension is still small. In the case of polystyrene resin,
Although the melt tension is higher than that of a polyethylene resin or a polypropylene resin, the performance is still insufficient in deep drawing sheet molding and the like.

In general, when a long-chain branch is introduced into a polymer chain, melt processing characteristics are improved by the branch. However, in a branched polymer having a branched chain composed of a monomer different from the main-chain polymer, a so-called composite made of a heterogeneous polymer is used. In the materials field,
It is possible to increase the dispersibility of the polymer by lowering the interfacial tension between different kinds of polymers, and to effectively impart incompatible physical properties such as impact strength and rigidity. In addition, since it has a microphase-separated structure, it can be applied to various elastomers. However, until now, in the polyolefin field,
There is a limit to the introduction of branches, which limits the development of applications. If this is possible, it is expected that the field of application will be greatly expanded due to the excellent mechanical properties and environmental compatibility represented by recyclability inherent to polyolefins.

Meanwhile, as a method for improving the melt tension of a polyolefin and improving the melt processing characteristics, there have been known (1) a method of mixing high-molecular-weight high-density polyethylene having a high melt tension (Japanese Patent Publication No. 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 a general polyolefin, (5) A method of increasing the melt tension by irradiating light to a general polyolefin in the presence of a crosslinking agent or a peroxide, (6) ) A method of grafting a radical polymerizable monomer such as styrene to a general polyolefin, and (7) a method of copolymerizing an olefin and a polyene (JP-A-5-194778, JP-A-5-1947).
No. 79) has been attempted.

However, in the 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 polyolefin, especially polypropylene, are not impaired. Absent. 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. Furthermore, the method (6) causes problems in the generation of gel and the production cost. In the method (7), the effect of improving the melt tension is small and the effect is not sufficient. There is also a concern about the occurrence of this.

[0008]

SUMMARY OF THE INVENTION The present invention provides a method for efficiently and inexpensively producing a polyolefin having high melt tension, excellent resin compatibility and high bulk density under such circumstances. The purpose is to do so.

The present inventors have conducted intensive studies to achieve the above object, and as a result, in the presence of a prepolymerized catalyst obtained by prepolymerizing an olefin in the presence of a specific catalyst,
By polymerizing or copolymerizing an α-olefin, cyclic olefin or styrene monomer, a polyolefin having properties such as high melt tension, excellent resin compatibility, and high bulk density can be obtained, and the object is achieved. I found to do. The present invention has been completed based on such findings.

That is, the present invention relates to (A) at least two transition metal compounds selected from Group 4 transition metal compounds having a cyclopentadienyl group, and (B) (B-1) aluminum oxy A compound, (B-2) an ionic compound which can be converted into a cation by reacting with the above transition metal compound, and (B-3) at least one selected from clay, clay mineral and ion-exchangeable layered compound. In the presence of a catalyst comprising at least one selected from α-olefins and cyclic olefins having 2 to 20 carbon atoms at a rate of 0.01 to 2000 g per 1 g of the transition metal compound, and an intrinsic viscosity [ η] is in the range of 0.01 to 20 deciliter / g. Further, the present invention provides an α-olefin having 2 to 20 carbon atoms in the presence of the prepolymerization catalyst or in the presence of an organic aluminum compound added to the prepolymerization catalyst,
An object of the present invention is to provide a method for producing a polyolefin, comprising polymerizing or copolymerizing at least one selected from a cyclic olefin and a styrene monomer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the production method of the present invention, a catalyst selected from (A) a transition metal compound belonging to Group 4 of the periodic table having a cyclopentadienyl group is used as a catalyst for prepolymerization. , (B) (B-1) an aluminum oxy compound, (B-2) (A) an ionic compound which can be converted into a cation by reacting with the above transition metal compound, and (B-
3) A material containing at least one selected from clay, clay minerals and ion-exchangeable layered compounds is used. Examples of the transition metal compound of Group 4 of the periodic table having an indenyl group of the component (A) include the following (A-
One type selected from component 1), component (A-2) and component (A-3) can be mentioned. Component (A-1): The component (A-1) is represented by the general formula (I)

[0012]

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[Wherein, R¹~ R⁶Are each independently water
An element atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or
Represents a halogen-containing hydrocarbon group having 1 to 20 carbon atoms;
^ThreeAnd R ^Four, R^FourAnd R^FiveAnd R^FiveAnd R⁶At least of
May be bonded to each other to form a ring;¹Passing
And X^TwoAre each independently a hydrogen atom, halogen atom or charcoal
Y represents a hydrocarbon group having a prime number of 1 to 20,¹Is two ligands
A hydrocarbon group having 1 to 20 carbon atoms
Element group, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, silicon
Containing group or germanium or tin containing group,
¹Represents titanium, zirconium or hafnium. 〕so
It is a transition metal compound represented.

In the general formula (I), R ³ and R ⁴ , R ⁴
A transition metal compound in which at least one pair formed a ring of R ⁵ and R ⁵ and R ⁶ is a compound known as BASF type complex. In the general formula (I), R ¹
Examples of the halogen atom in R ⁶ include chlorine, bromine, fluorine and iodine atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-hexyl group, and an n-decyl group. Alkyl group, phenyl group, 1-naphthyl group, 2
-An aryl group such as a naphthyl group, an aralkyl group such as a benzyl group, and the like. As the halogen-containing hydrocarbon group having 1 to 20 carbon atoms, at least one hydrogen atom of the hydrocarbon group is a suitable halogen atom And a group substituted with R ^{1 to} R ⁶ may be the same or different from each other, and at least one of adjacent groups, ie, R ³ and R ⁴ , R ⁴ and R ^5, and R ⁵ and R ^6. The pairs need to be linked to each other to form a ring. Examples of such an indenyl group forming a ring include a 4,5-benzoindenyl group, an α-acenaphthoindenyl group, and an alkyl-substituted product having 1 to 10 carbon atoms.

The halogen atom in X ¹ and X ² includes chlorine, bromine, fluorine and iodine atoms.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group and n-hexyl group, and aryl groups such as phenyl group. And an aralkyl group such as a benzyl group. X ¹ and X ² may be the same or different. On the other hand, Y ¹ is a divalent group bonding two ligands, and among them, examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include a methylene group; a dimethylmethylene group; An ethylene group; a dimethyl-1,2-ethylene group; a 1,4-tetramethylene group; an alkylene group such as a 1,2-cyclopropylene group;
Examples include an arylalkylene group such as a diphenylmethylene group, and examples of the divalent halogen-containing hydrocarbon group having 1 to 20 carbon atoms include a chloroethylene group and a chloromethylene group. 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 ¹ are usually the same, but may be different depending on the case.

As the transition metal compound represented by the general formula (I) of the component (A-1), for example, JP-A-6-18
Compounds described in JP-A-4179 and JP-A-6-345809 can be exemplified. As a specific example, rac-dimethylsilanediyl-bis-1-
(2-methyl-4,5-benzoindenyl) -zirconium dichloride, rac-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-methyl-α-methyl-α-acenaphthoindenyl) -zirconium dichloride, rac-
Benzoindenyl- or acenaphthoindenyl-type compounds such as phenylmethylsilanediyl-bis-1- (2-methyl-α-acenaphthoindenyl) -zirconium dichloride, and zirconium in these compounds is replaced by titanium or hafnium And the like.

Further, the component (A-1) is a compound represented by the formula (I), wherein R ³ and R ⁴ , R ⁴ and R ^5, and R ⁵ and R ^5
The transition metal compound having an indenyl skeleton in which none of the groups forms a ring, or the corresponding 4,5,6,
It is a transition metal compound having a 7-tetrahydroindenyl skeleton. This transition metal compound is a compound known as a Hoechst complex. Examples of the transition metal compound of the component (A-1) include, for example, JP-A-4-26830.
No. 8, No. 5-306304, No. 6-1005
No. 79, 6-157661, 7-149
No. 815, No. 7-188318, No. 7-25
Compounds described in 8321 and the like can be mentioned.

As a specific example, dimethylsilanediyl-
Bis-1- (2-methyl-4-phenylindenyl)-
Zirconium dichloride, dimethylsilanediyl-bis-1- [2-methyl-4- (1-naphthyl) indenyl] -zirconium dichloride, dimethylsilanediyl-bis-1- (2-ethyl-4-phenylindenyl)
-Zirconium dichloride, dimethylsilanediyl-bis-1- [2-ethyl-4- (1-naphthyl) indenyl] zirconium dichloride, phenylmethylsilanediyl-bis-1- (2-methyl-4-phenylindenyl)- Zirconium dichloride, phenylmethylsilanediyl-bis-1- [2-methyl-4- (1-naphthyl) indenyl] -zirconium dichloride, phenylmethylsilanediyl-bis-1- (2-ethyl-4-phenylindenyl) -Zirconium dichloride, phenylmethylsilanediyl-bis-1- [2-ethyl-4-
Aryl-substituted products such as (1-naphthyl) indenyl] -zirconium dichloride, rac-dimethylsilylene-
Bis-1- (2-methyl-4-ethylindenyl) -zirconium dichloride, rac-dimethylsilylene-bis-1- (2-methyl-4-isopropylindenyl)
-Zirconium dichloride, rac-dimethylsilylene-bis-1- (2-methyl-4-tert-butylindenyl) -zirconium dichloride, rac-phenylmethylsilylene-bis-1- (2-methyl-4-isopropylindenyl) ) -Zirconium dichloride, rac-dimethylsilylene-bis-1- (2-ethyl-4-methylindenyl) -zirconium dichloride, rac-dimethylsilylene-bis-1- (2,4-dimethylindenyl) -zirconium dichloride 2,4-position substituents such as, rac-dimethylsilylene-bis-1- (2-methyl-4-ethylindenyl) -zirconium dimethyl,
rac-dimethylsilylene-bis-1- (4,7-dimethylindenyl) -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-dimethylindenyl) -zirconium dichloride, rac
4,7, such as -1,2-butanediyl-bis-1- (4,7-dimethylindenyl) -zirconium dichloride
-Position, 2,4,7-position or 3,4,7-position substituent, dimethylsilanediyl-bis-1- (2-methyl-4,6-
Diisopropylindenyl) -zirconium dichloride, phenylmethylsilanediyl-bis-1- (2-methyl-4,6-diisopropylindenyl) -zirconium dichloride, rac-dimethylsilanediyl-bis-1- (2-methyl-4 , 6-Diisopropylindenyl) -zirconium dichloride, rac-1,2-ethanediyl-bis-1- (2-methyl-4,6-diisopropylindenyl) -zirconium dichloride, rac
-Diphenylsilanediyl-bis-1- (2-methyl-
4,6-diisopropylindenyl) -zirconium dichloride, rac-phenylmethylsilanediyl-bis-1- (2-methyl-4,6-diisopropylindenyl) -zirconium dichloride, rac-dimethylsilanediyl-bis-1- 2,4,6-substituted product such as (2,4,6-trimethylindenyl) -zirconium dichloride, rac-dimethylsilanediyl-bis-1-
2,5,6-substituted product such as (2,5,6-trimethylindenyl) -zirconium dichloride, rac-dimethylsilylene-bis- (2-methyl-4,5,6,7-
Tetrahydro-1-indenyl) -zirconium dichloride, rac-ethylene-bis- (2-methyl-4,
5,6,7-tetrahydro-1-indenyl) -zirconium dichloride, rac-dimethylsilylene-bis-
(2-methyl-4,5,6,7-tetrahydro-1-indenyl) -zirconium dimethyl, rac-ethylene-bis (2-methyl-4,5,6,7-tetrahydro-
1-indenyl) -zirconium dimethyl, rac-ethylene-bis- (4,7-dimethyl-4,5,6,7-
Examples thereof include 4,5,6,7-tetrahydroindenyl compounds such as tetrahydro-1-indenyl) -zirconium dichloride, and those obtained by substituting zirconium in these compounds with titanium or hafnium. Component (A-2): Component (A-2) is represented by the general formula (II)

[0019]

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Wherein R ^{7 to} R ¹³ , R ¹⁵ , R ¹⁶ , X ³ and X ⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R ⁷ and R ⁸ may be bonded to each other to form a ring. R ¹⁴ and R ¹⁷ are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, and a nitrogen-containing group. Or a phosphorus-containing group. Y ² is a divalent group bonding two ligands, and is a hydrocarbon group having 1 to 20 carbon atoms,
20 halogen-containing hydrocarbon group, a silicon-containing group, a germanium-containing group, -O -, - CO -, - S -, - SO 2 -,
^{-NR 18 -, - PR 18 -} , - P (O) R 18 -, - BR 18
— Or —AlR ¹⁸ —, wherein R ¹⁸ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms. M ² represents titanium, zirconium or hafnium. ] It is a transition metal compound represented by these.

This transition metal compound is a single-bridge type complex.
You. In the general formula (II), R⁷~ R¹³, R^Fifteen, R
¹⁶, X^ThreeAnd X^FourAmong the halogen atoms are salts
Elemental, bromine, fluorine and iodine atoms. Carbon number 1
Examples of the hydrocarbon group of No. 20 to No. 20 include a methyl group, ethyl
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).
C) silyl group, etc., and as the oxygen-containing group,
And ethoxy and ethoxy groups.
Examples include thiol groups and sulfonic acid groups.
Examples of the silicon-containing group include a dimethylamino group,
Phosphorus-containing groups include phenylphosphine groups and the like
Can be Also, R⁷And R⁸Fluorine binding to each other
May form a ring such as R¹⁴, R¹⁷As a specific example of
The above R ⁷~ R¹³From hydrogen sources
And groups excluding offspring. R⁷, R⁸As a hydrogen source
And an alkyl group having 6 or less carbon atoms are preferable.
, Methyl, ethyl, isopropyl, cyclohexyl
A sil group is more preferred, and a hydrogen atom is even more preferred. Ma
R⁹, R¹², R¹⁴ And R¹⁷As for carbon number 6 or less
The following alkyl groups are preferred, methyl, ethyl, iso
A propyl group and a cyclohexyl group are more preferred.
A ropyl group is more preferred. R^Ten, R¹¹, R¹³, R ^Fifteen 
And R¹⁶Is preferably a hydrogen atom. X^Three, X^Fourage
Halogen, methyl, ethyl, propyl
Is preferred.

Specific examples of Y ² 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 these, methylene,
Ethylene, ethylidene and isopropylidene are preferred from the viewpoint of achieving the object of the present invention. M ² represents titanium, zirconium or hafnium, with hafnium being particularly preferred.

Specific examples of the transition metal compound represented by the general formula (II) include 1,2-ethanediyl (1-
(4,7-diisopropylindenyl)) (2- (4,4
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-diisopropylindenyl) hafnium dichloride, and the like, and the like. Examples include, but are not limited to, compounds obtained by substituting hafnium in a compound with zirconium or titanium.The transition metal compound represented by the general formula (II) may be, for example, Application for Japanese Patent Application No. 09
-296612. Component (A-3): Component (A-3) is represented by the general formula (III)

[0024]

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[Wherein, M^ThreeIs titanium, zirconium or
Indicates hafnium, E¹And E^TwoAre each substituted cyclo
Pentadienyl group, indenyl group, substituted indenyl group,
Heterocyclopentadienyl group, substituted heterocyclopen
Tadienyl group, amide group, phosphide group, hydrocarbon group and
A ligand selected from the group consisting of¹Passing
And A^TwoForm a cross-linked structure through
They may be the same or different, X^FiveIs σ connectivity
A ligand of X^FiveIf there are multiple Xs ^FiveIs the same
Same or different, other X^Five, E¹, E^TwoOr
Y^ThreeAnd may be crosslinked. Y^ThreeRepresents a Lewis base,
Y^ThreeIf there is more than one,^TwoAre the same but different
May be other Y^Three, E¹, E^TwoOr X^FiveCross-linked with
A¹And A^TwoIs carbonized with 1 or more carbon atoms
Shows bridging groups consisting of hydrogen groups, which are identical and
May also be different. q is an integer of 1 to 5 [(M^Threeof
(Valence) -2], and r represents an integer of 0 to 3. 〕so
Transition metal compound (hereinafter referred to as a double-bridged complex)
Sometimes. ).

In the general formula (III), M ³ represents titanium, zirconium or hafnium, but zirconium and hafnium are preferred. E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group (-N <), and a phosphide, respectively, as described above. Group (-P <), hydrocarbon group [>
CR-,> C <] and a silicon-containing group [>SiR-,> Si
<] (Where 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 doing. E ¹ and E ² may be the same or different. As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferred.

Also, X^ThreeΣ-binding ligand tool represented by
Examples of the body include a halogen atom, a hydrocarbon having 1 to 20 carbon atoms.
Element group, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, C1-20 amide group, carbon
A silicon-containing group having 1 to 20 carbon atoms, a phosphide having 1 to 20 carbon atoms
Group, a sulfide group having 1 to 20 carbon atoms, and a sulfide group having 1 to 20 carbon atoms
Acyl groups and the like. This X^ThreeIf there are multiple
Multiple X^ThreeMay be the same or different, and other X^Three,
E¹, E^TwoOr Y^TwoAnd may be crosslinked. On the other hand, Y^Three
Specific examples of Lewis bases represented by
-Tels, phosphines, thioethers, etc.
be able to. This Y^ThreeIf there is more than one,^ThreeIs
May be the same or different, other Y^ThreeAnd E¹, E^Twoor
Is X ^FiveAnd may be crosslinked. Next, A¹And A^TwoIndicated by
As a crosslinking group comprising a hydrocarbon group having 1 or more carbon atoms
Is, for example, the general formula

[0028]

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(R ¹⁸ and R ¹⁹ 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 (III),
^{When 1} and E ² are a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group, the bond of the cross-linking group of A ¹ and A ² is (1,1 ′) (2,2 ′) double cross-linking type. And (1,2 ′) (2,1 ′) double cross-linking type. Among the transition metal compounds represented by the general formula (III), the general formula (III-a)

[0030]

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A transition metal compound having a double-bridged biscyclopentadienyl derivative represented by the following formula as a ligand is preferred. In the above general formula (III-a), M ³ , A ¹ ,
A ² , q and r are the same as above. X ⁶ represents a σ-bonding ligand, and when X ⁶ there is a plurality, the plurality of X ⁶ may be the same or different, may be crosslinked with other X ⁶ or Y ^4. Specific examples of X ⁶ include compounds represented by the general formula (III)
It includes the same as those of the exemplified in the description of X ^5. Y ⁴ represents a Lewis base, if Y ⁴ is more, the plurality of Y ⁴ may be the same or different, the other Y
³ or X ⁴ and may be crosslinked. Specific examples of Y ⁴ include the same as those exemplified in the description of Y ^{3 in} the general formula (III). R ^{20 to} R ²⁵ 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 required to be a hydrogen atom. R ^{20 to} R ²⁵ 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 (III) 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. Of course, it is not limited to these.

In the present invention, the catalyst used for the prepolymerization is
As the transition metal compound of the component (A), preferably, the component (A-1) (BASF type complex or Hoechst type complex), the component (A-2) (single crosslinked type complex) and (A-3)
At least two kinds selected from the components (double-crosslinked type complex) are used, and a combination of a zirconium compound-hafnium compound, a zirconium compound-zirconium compound, and a hafnium compound-hafnium compound is particularly preferable.

As a preferred example of such a combination,
Mono-bridged zirconium complex-mono-bridged hafnium complex,
BASF zirconium complex-BASF hafnium complex, Hoechst zirconium complex-Hoechst hafnium complex, single bridge zirconium complex-BASF hafnium complex, single bridge zirconium complex-Hoechst hafnium complex, BASF zirconium complex-single bridge Hafnium complex, Hoechst-type zirconium complex-single-bridged hafnium complex, BASF-type zirconium complex-double-bridged hafnium complex, Hoechst-type zirconium complex-double-bridged hafnium complex, single-bridged 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 catalyst, double-bridged zirconium Complex-single-bridged hafnium complex, single-bridged zirconium complex-single-bridged zirconium complex, BASF
-Type zirconium complex-BASF-type zirconium complex, Hoechst-type zirconium complex-Hoechst-type zirconium complex, BASF-type zirconium complex-single-bridged zirconium complex, Hoechst-type zirconium complex-single-bridged zirconium complex, BASF-type zirconium complex-double-bridged type Zirconium complex, Hoechst-type zirconium complex-double-bridged zirconium complex, double-bridged zirconium complex-single-bridged zirconium complex, double-bridged zirconium complex-double-bridged zirconium complex, single-bridged hafnium complex-single-bridged -Type hafnium complex, BASF-type hafnium complex-BASF-type hafnium complex, Hoechst-type hafnium complex-Hoechst-type hafnium complex, BASF-type hafnium complex-single-bridge type hafnium complex, Hoechst-type hafnium complex-single -Type hafnium complex, BASF-type hafnium complex-double-bridged hafnium complex, Hoechst-type hafnium complex-double-bridged hafnium complex, double-bridged hafnium complex-single-bridged hafnium complex, double-bridged hafnium complex-double Crosslinked hafnium complexes and the like can be mentioned.

When a combination of a zirconium compound and a hafnium compound is used as the transition metal compound of the component (A), the content of the zirconium compound in the mixed transition metal compound is preferably 1 to 99 mol%, more preferably 2
The range is from 95 to 95 mol%, more preferably from 5 to 90 mol%, particularly preferably from 10 to 80 mol%.

In the catalyst used as the prepolymerization catalyst in the present invention, (B-1) an aluminum oxy compound and (B-2) an ionic compound which can be converted to a cation by reacting with the transition metal compound as the component (B). And (B-3)
At least one selected from clay, clay minerals and ion-exchange layered compounds is used. The aluminum oxy compound of the component (B-1) is represented by the general formula (IV)

[0037]

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(Wherein R ²⁶ 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 R ²⁶ may be the same or different. Aluminoxane represented by general formula (V):

[0039]

Embedded image

(Wherein R ²⁶ and w are the same as those in formula (IV)). 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 of dissolving an organoaluminum compound in an organic solvent and bringing it into contact with water, a method of adding an organoaluminum compound initially during polymerization and then adding water, and a method of crystal water contained in a metal salt or the like 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 toluene-insoluble.

These aluminum oxy compounds may be used alone or in combination of two or more.
On the other hand, as the component (B-2), any compound can be used as long as it is an ionic compound that can be converted into a cation by reacting with the transition metal compound, and particularly, a polymerization active site can be formed efficiently. , The following general formula (VI),
(VII) ([L ¹ -R ²⁷ ] ^{h +} ) _a ([Z] ^- ) _b ... (VI) ([L ² ] ^{h +} ) _a ([Z] ^- ) _b ... (VII) (However , L ² is ^{M 5, R 28 R 29 M} 6, R 30 3 C or R ³¹
It is an M ^6. [Wherein L ¹ is a Lewis base and [Z] ⁻ is
Non-coordinating anion [Z ^{1] -} or [Z ^{2] -,} wherein [Z ^{1] -} anion in which a plurality of groups are bonded to the element, i.e. ^{[M 4 G 1 G 2 ··· G} f ] ( Here, M ⁴ is an element belonging to Groups 5 to 15 of the periodic table, preferably 13 to 1 of the periodic table.
Shows Group 5 elements. G ^{1 to} G ^f each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon atom having 2 to 4 carbon atoms.
0 dialkylamino group, C1-C20 alkoxy group, C6-C20 aryl group, C6-C20 aryloxy group, C7-C40 alkylaryl group, C7-C40 Arylalkyl group, 1 to 1 carbon atoms
A halogen-substituted hydrocarbon group of 20; an acyloxy group of 1 to 20 carbon atoms; an organic metalloid group; or a heteroatom-containing hydrocarbon group of 2 to 20 carbon atoms. 2 out of G ^{1 to} G ^f
One or more may form a ring. f is [(center metal M
⁴ ) +1]. ), [Z ² ] ^-
A conjugate base of a Bronsted acid alone or a combination of a Bronsted acid and a Lewis acid having _a logarithm (pKa) of the reciprocal of the acid dissociation constant of −10 or less, or a conjugate base generally defined as a superstrong acid is shown. Further, a Lewis base may be coordinated. R ²⁷ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms, and R ²⁸ and R ²⁹ each represent a cyclopentadienyl group, A cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ³⁰ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ³¹ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. h is an ionic valence of [L ¹ -R ²⁷ ] and [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (h × a). M ⁵ are those containing a periodic table Group 1～3,11～13,17 element, M ⁶ represents a periodic table 7-12 group element. ] Can be suitably used.

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 ²⁷ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ²⁸ and R ²⁹ include cyclopentadienyl group, methylcyclopentane Examples thereof include a dienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Specific examples of R ³⁰ include a phenyl group, a p-tolyl group, a p-methoxyphenyl group and the like, and specific examples of R ³¹ include a tetraphenylporphine, phthalocyanine, allyl, methallyl and the like. . Specific examples of M ⁵ include Li, Na, K, Ag, Cu, Br, I, and I _3. Specific examples of M ⁶ include Mn, F
e, Co, Ni, Zn and the like.

[Z ¹ ] ⁻ , that is, [M ⁴ G ¹ G
² ... G ^f ], B and A are specific examples of M ^4.
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, hydrocarbon groups such as phenoxy
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, 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 C
O ₂ ) ^- , hexafluoroantimony anion (SbF ₆ )
^-, fluorosulfonic acid anion (FSO ₃₎ ^-, chlorosulfonic acid anion (ClSO ₃₎ ^-, fluorosulfonic acid anion / antimony pentafluoride (FSO ₃ / S
bF 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 compound (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, tetraphenylporphyrin manganese tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, silver hexafluorophosphate, Kisafuruoro arsenic, silver perchlorate, silver trifluoroacetate, and the like of silver trifluoromethanesulfonate.

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. As the component (B-3), clay, clay mineral or ion-exchange layered compound is used. Clay is an aggregate of fine hydrated silicate minerals, and is a substance that produces plasticity when mixed with an appropriate amount of water, exhibits rigidity when dried, and sinters when baked at high temperatures. Also,
Clay mineral refers to a hydrated silicate that is a main component of clay. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and means a compound whose contained ions are exchangeable. Most clay minerals are ion-exchangeable layered compounds. These are not limited to natural products,
It may be artificially synthesized. Examples of the ion-exchange layered compound include, for example, an ion-forming compound having a layered crystal structure such as a hexagonal close-packing type, an antimony type, a cadmium chloride type, and a cadmium iodide type.

Specific examples of the component (B-13) include kaolin, bentonite, Kibushi clay, gairome clay, allophane, hysingelite, pyrophyllite, talc, plum group, montmorillonite group, vermiculite, ryokudeite group, and palygorskite. , Nacrite, dickite, halloysite and the like. As the component (B-3), a pore volume having a radius of 20 ° or more measured by a mercury intrusion method is preferably 0.1 ml / g or more, particularly preferably 0.3 to 5 ml / g or more. It is also preferable to carry out a chemical treatment from the viewpoint of removing impurities from the clay or changing the structure and function. Here, the chemical treatment refers to both surface treatment for removing impurities attached to the surface and treatment for affecting the crystal structure of clay. In particular,
Acid treatment, alkali treatment, salt treatment, organic matter embedding, and the like are included. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as aluminum, iron and magnesium in the crystal structure. The alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and organic treatment, an ionic complex, a molecular complex, an organic complex, etc. are formed, and the surface area, interlayer distance, etc. Can be changed. By utilizing the ion exchange property and replacing the exchangeable ions in the layers with another bulky ion, it is possible to obtain an interlayer material in which the layers are expanded. Still further, it is also possible to secure a polymerization reaction field where the main catalyst is present between the layers.

The above-mentioned component (B-3) may be used as it is, or may be newly added and adsorbed water.
Alternatively, ripened and dehydrated ones may be used. (B
-3) As the component, preferred are clay or clay mineral, and most preferred is montmorillonite.
The component (B-13) is preferably treated with a silane compound and / or an organoaluminum compound. This treatment may improve activity. Examples of the silane compound include trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride, tert-butyldimethylsilyl chloride, te
Trialkylsilyl chlorides such as rt-butyldiphenylsilyl chloride and phenethyldimethylsilyl chloride, dimethylsilyl dichloride, diethylsilyl dichloride, diisopropylsilyl dichloride, bisdiphenethylsilyl dichloride, methylphenethylsilyl dichloride, diphenylsilyl dichloride, dimesitylsilyl Dialkylsilyl dichlorides such as dichloride and ditolylsilyl dichloride, methylsilyl trichloride, ethylsilyl trichloride, isopropylsilyl trichloride, phenylsilyl trichloride, mesitylsilyl trichloride, tolysilyl trichloride, phenethylsilyl trichloride and the like Alkylsilyl trichlorides, halides in which the above-mentioned chloride portion is replaced with another halogen element, bis Trimethylsilyl) amine, bis (triethylsilyl) amine, bis (triisopropylsilyl) amine, bis (dimethylethylsilyl) amine, bis (diethylmethylsilyl) amine, bis (dimethylphenylsilyl) amine, bis (dimethyltolylsilyl) amine , Bis (dimethylmesitylsilyl) amine, silylamines such as N, N-dimethylaminotrimethylsilane, (diethylamino) trimethylsilane, N- (trimethylsilyl) imidazole, and polysilanols commonly used as peralkylpolysiloxypolyol , Tris (trimethylsiloxy) silanol and other silanols, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N- (trimethylsilyl) acetamide Amide, bis (trimethylsilyl) urea, silylamides inclined such trimethylsilyl diphenylurea, linear siloxanes such as 1,3-dichlorotetramethyldisiloxane, cyclic siloxanes such as pentamethyl cyclopentane siloxane,
Tetraalkylsilanes such as dimethyldiphenylsilane, diethyldiphenylsilane, diisopropyldiphenylsilane, etc., trimethylsilane, triethylsilane, triisopropylsilane, tri-t-butylsilane, triphenylsilane, tolylsilane, trimesitylsilane, methyldiphenylsilane, Examples thereof include trialkylsilanes such as dinaphthylmethylsilane and bis (diphenyl) methylsilane, and inorganic silicon compounds such as silicon tetrachloride and silicon tetrabromide. Of these, preferred are silylamines, and more preferred are trialkylsilane chlorides. One of the silane compounds may be used from among these, but in some cases, two or more of them can be used in any combination.

Further, the organoaluminum compound used for the treatment of the component (B-3) is not particularly limited. A linear aluminoxane represented by the general formula (IV) or a cyclic aluminoxane represented by the general formula (V) or an aggregate of the cyclic aluminoxane can be preferably used. In terms of shellfish,
Trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-t-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum methoxide, diethylaluminum methoxide, dimethylaluminum hydroxide, diethylaluminum Alkyl aluminum and dimethyl aluminum hydride containing halogen, alkoxy group or hydroxyl group such as hydroxide,
Hydrogen atom-containing alkylaluminums such as diisobutylaluminum hydride; and aluminoxanes such as methylaluminoxane, ethylaluminoxane and isobutylaluminoxane. Of these, trimethylaluminum and triisobutylaluminum are particularly preferred. The organoaluminum compound used in the treatment of the component (B-3) may be used alone or in combination of two or more.

The proportions of the silane compound and the organoaluminum compound used in the treatment of the component (B-3) are not particularly limited, but when the component (B-13) is a clay or a clay mineral, the (B-3) 3) For 1 mol of hydroxyl group in the component,
Normally 0.1 to 10000 silicon atoms in the silane compound
0 mol, preferably in a ratio of 0.5 to 10000 mol, and when using an organoaluminide, aluminum atoms in the organoaluminum compound are usually 0.1 to 0.1 mol.
It is used in a proportion of 100,000 mol, preferably 0.5 to 10,000 mol. When the component (B-3) is other than clay or clay mineral, 1 g of the component (B-3)
At a ratio of 0.001 to 100 g of silicon atoms in the silane-based compound, and when an organoaluminum compound is used, the aluminum atom in the organoaluminum compound is 0.001 g.
It is preferable to use it at a ratio of 001 to 100 g. If the ratio is outside the above range, the polymerization activity may decrease.
The treatment of the component (B-3) may be performed in an inert gas such as nitrogen or a hydrocarbon such as pentane, hexane, toluene, or xylene. Furthermore, this treatment can be carried out at a polymerization temperature, and it is preferable that the treatment be carried out at a temperature between -30 ° C and the boiling point of the solvent used, particularly between room temperature and the boiling point of the solvent used.

In the polymerization catalyst of the present invention, component (B-1), component (B-2),
The component (B-3) may be used alone, or may be used in combination. The proportions of the (A) catalyst component and the (B) catalyst component in the prepolymerized catalyst are as follows:
When the compound (B-1) is used as the catalyst component (B), the molar ratio is preferably in the range of 1: 1 to 1:10 ⁶ , more preferably 1:10 to 1:10 ^4. If the ratio is out of the range, the catalyst cost per unit weight polymer increases, which is not practical. When the compound (B-2) is used, the molar ratio is preferably from 10: 1 to 1:10.
0, more preferably in the range of 2: 1 to 1:10. If the ratio is outside this range, the cost of the catalyst per unit weight of polymer increases, which is not practical. Also, (B-
3) When clay or clay mineral is used as the compound,
The molar ratio of the hydroxyl group in the catalyst component (A) to the hydroxyl group in the catalyst component (B) is preferably 1: 0.1 to 1: 100,000, and more preferably 1: 0.5 to 1: 10000. Further, when an ion-exchange layered compound is used as the compound (B-3), the ratio of the catalyst component (A) to the catalyst component (B) is preferably 1: 1 to 1: 100,000 by weight. If the ratio is outside this range, the cost of the catalyst per unit weight of polymer increases, which is not practical.

Further, the catalyst used for the prepolymerization in the present invention may contain the above-mentioned components (A) and (B) as the main components.
(B) component and (C) organoaluminum compound and / or
Alternatively, it may contain a carrier as a main component.
This carrier is preferably used when the catalyst does not contain the component (B-3) as the component (B).

Here, the organoaluminum compound of the component (C) is represented by the following general formula (VIII): R ³² _v AlQ _3-v ... (VIII) (where R ³² is an alkyl group having 1 to 10 carbon atoms) , Q is a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms.
And v is an integer of 1 to 3). Specific examples of the compound represented by the general formula (VIII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride ,
Examples thereof include diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride. Preferred are trimethylaluminum, triethylaluminum and triisobutylaluminum. These organoaluminum compounds may be used alone or in combination of two or more. Also, (A)
The molar ratio of the catalyst component and the optionally used (C) organoaluminum compound is preferably 1: 1 to 1
1: 20000, more preferably 1: 5 to 1: 200
0, more preferably 1:10 to 1: 1000. By using the organoaluminum compound, the polymerization activity per 1 g of the transition metal compound can be improved. However, if the amount is too large, especially if it is out of the above range, the organoaluminum compound will be wasted and a large amount will be contained in the polymer. When the amount is small, sufficient catalytic activity cannot be obtained, which may be undesirable.

In the present invention, at least one of the catalyst components can be used by being supported on a suitable carrier.
The type of the carrier of the component (C) is not particularly limited, and any of an inorganic oxide carrier, other inorganic carriers and organic carriers can be used. Other inorganic carriers are preferred. As the inorganic oxide carrier, specifically, Si
O ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe
₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂
And mixtures thereof, for example, silica alumina, zeolite, ferrite, glass fiber and the like.
Among them, SiO ₂ or Al ₂ O ₃ is particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate, or the like.

On the other hand, as a carrier other than the above, MgC
_{l 2, Mg (OC 2 H} 5) such as magnesium compounds and their complex salts represented by the general formula MgR ³³ _{X X} ⁷ _y represented by magnesium compounds such as ₂ can be cited.
Here, R ³³ is an alkyl group having 1 to 20 carbon atoms and 1 carbon atom.
X 20 is an alkoxy group or an aryl group having 6 to 20 carbon atoms, X ⁷ is a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, y is 0 to 2, and x + y
= 2. Each R ³³ and each X ⁷ may be the same or different. Examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, polypropylene, substituted polystyrene, and polyarylate, starch, and carbon. The carrier used in the present invention includes MgCl ₂ , MgCl (OC ₂ H ₅ ),
Mg (OC ₂ H ₅ ) ₂ , SiO ₂ , Al ₂ O _{3 and the} like are preferable. The properties of the carrier vary depending on the type and manufacturing method, but the average particle size is usually 1 to 300 μm, preferably 10 to 300 μm.
２００200 μm, more preferably 20-100 μm. If the particle size is small, fine powder in the polymer increases, and if the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of a hopper. The specific surface area of the carrier is
Usually 1 to 1000 m ² / g, preferably 50 to 500 m
^The pore volume is usually 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g.

If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method (see J. Am. Chem. Soc, Vol. 60, p. 309 (1983)). Further, it is desirable that the above-mentioned carrier is used after being calcined usually at 150 to 1000 ° C, preferably 200 to 800 ° C. When at least one of the catalyst components is supported on the carrier, at least one of the catalyst components (A) and (B) is preferably (A)
Supporting both the catalyst component and the (B) catalyst component
Desirable in terms of morphology control, applicability to processes such as gas phase polymerization, and the like.

The method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, at least one of the component (A) and the component (B) is mixed with the carrier. Method, a method in which a carrier is treated with an organoaluminum compound or a halogen-containing silicon compound, and then mixed with at least one of the component (A) and the component (B) in an inert solvent. Or a method of reacting both with an organoaluminum compound or a halogen-containing silicon compound,
After supporting the component (A) or the component (B) on a carrier,
A method of mixing the component (B) or the component (A), a method of mixing a contact reaction product of the component (A) and the component (B) with a carrier,
In the contact reaction between the component (A) and the component (B), a method in which a carrier is allowed to coexist may be used. In the above and the above reactions, an organoaluminum compound as the component (C) may be added.

The catalyst thus obtained may be subjected to solvent distillation once, taken out as a solid, and then used for prepolymerization, or may be used for prepolymerization as it is. In the present invention, the component (A) is usually contained in an amount of 10 g per 1 g of the carrier.
^-6 to 10 ^-2 mol, preferably 3 × 10 ^-6 to 10 ^-3 mol. The component (B) relative to the component (A) [(B-1) component, (B-2) component, (B-3) component]
Is as described above.

The component (B) [component (B-1), (B-
If the proportion of the component (2), the component (B-3)] and the carrier or the proportion of the component (A) and the carrier is outside the above range, the activity may be reduced. The average particle size of the catalyst thus prepared is usually 2 to 500 μm, preferably 10 to 400 μm, particularly preferably 20 to 200 μm.
And the specific surface area is usually 20 to 1000 m ² / g, preferably 50 to 500 m ² / g. Average particle size is 2μ
m, the fine powder in the polymer may increase,
If it exceeds 500 μm, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. By supporting on a carrier in this manner, an industrially advantageous polyolefin having a high bulk density and an excellent particle size distribution can be obtained.

The prepolymerized catalyst of the present invention is produced by first polymerizing at least one selected from α-olefins having 2 to 20 carbon atoms and cyclic olefins in the presence of the catalyst. Here, as the α-olefin having 2 to 20 carbon atoms, ethylene, propylene, 1-butene, 1
-Pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1
-Eicosene and the like, and examples of the cyclic olefin include cyclopentene, cycloheptene, norbornene,
5-ethyl-2-norbornene, tetracyclododecene, and the like. The polymerization method may be any of a batch type and a continuous type, and any method can be adopted from a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method 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 the like. Examples include alicyclic hydrocarbons such as methylcyclohexane, 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. Regarding the polymerization conditions, the polymerization temperature is usually in the range of -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 it is in the range of 0.1 to 150 kg / cm ² G, more preferably 0.2 to 100 kg / cm ² G. The polymerization time is usually in the range of 10 seconds to 40 hours, preferably 30 seconds to 30 hours, more preferably 1 minute to 10 hours. Furthermore, the amount of catalyst, the raw material monomer / component (A) molar ratio is preferably 1 to 10 ^8, advantageously chosen so that more preferably 100 to 10 ^7.

In the present invention, a polymerization catalyst can be produced by carrying out the operation of loading at least one of the component (A) and the component (B) on a carrier in a polymerization system. For example, the components (A) and (B), a carrier and, if necessary, the above-mentioned organoaluminum compound are added, and 0.1 to 50 kg / cm ^{2 of} an olefin is added.
For about 1 minute to 40 hours to form catalyst particles. The control of the intrinsic viscosity (control of the molecular weight) of the prepolymerized catalyst produced by the prepolymerization and the target polyolefin 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, etc. in the above range. It can be carried out by appropriately selecting within.

The prepolymerized catalyst obtained by such prepolymerization has an intrinsic viscosity [η] of 0.1 to 20 deciliters / liter.
g to 0.01 to 2 per gram of the transition metal compound.
000 g. The intrinsic viscosity [η] is measured at a temperature of 135 ° C. in a tetralin solvent. When the intrinsic viscosity [η] is less than 0.01 deciliter / g,
A polyolefin obtained by polymerizing or copolymerizing an α-olefin or the like using this prepolymerization catalyst is inferior in melt processability and has insufficient mechanical strength. High viscosity, lowers melt processability. From the viewpoint of the balance between the melt processability and the mechanical strength of the polyolefin, the intrinsic viscosity [η] is 0.05 to 20 deciliters / liter.
g, particularly preferably in the range of 0.1 to 18 deciliter / g.

The prepolymerized catalyst obtained by the prepolymerization is as follows:
(A) 0.01 to 200 per gram of the transition metal compound of the component.
0 g, but 0.1 to 150 g / g of the transition metal compound.
g is preferable, and 1 to 120 g is particularly preferable.

The prepolymerized catalyst produced by the above prepolymerization is a state in which the polymer is attached around the catalytically active component, and the reaction mixture after the prepolymerization contains the polymer and the catalyst. ing. In the present invention, the polymer and the catalyst (in other words, the catalyst to which the polymer is attached) are referred to as a prepolymerization catalyst. In the production method of the present invention, in the presence of the pre-polymerization catalyst or in the presence of an organic aluminum compound as required,
Polyolefins can be obtained by polymerizing or copolymerizing at least one selected from α-olefins, cyclic olefins and styrene monomers of Nos. 20 to 20. Here, as the organoaluminum compound, the same compounds as described above can be used. (A) The usage ratio of the catalyst component and the optional organoaluminum compound is as follows:
When the prepolymerization catalyst does not contain an organoaluminum compound, the molar ratio is preferably from 1: 1 to 1: 2.
0000, more preferably 1: 5 to 1: 2000, further preferably 1:10 to 1: 1000. When the prepolymerized catalyst contains an organoaluminum compound, the amount varies depending on the amount used, but the organoaluminum compound is not used at all, or the molar ratio of the transition metal compound to the organoaluminum compound in the prepolymerized catalyst is changed. By using an organoaluminum compound in the range of 1: 0.5 to 1: 10000, more preferably 1: 2 to 1: 8000, the polymerization activity per transition metal can be improved. In particular, when the amount is outside the above range, the organoaluminum compound is wasted, and a large amount remains in the polymer. When the amount is small, sufficient catalytic activity cannot be obtained, which is not preferable.

As the α-olefin and cyclic olefin having 2 to 20 carbon atoms, the same as described above can be mentioned. The styrene monomer includes styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,
2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,5-trimethylstyrene, 2,4,6-
Alkyl styrenes such as trimethyl styrene and pt-butyl styrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-
Examples thereof include halogenated styrenes such as bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, and o-methyl-p-fluorostyrene.

The polymerization mode and the polymerization conditions can be the same as in the above-mentioned preliminary polymerization. Further, an olefin block copolymer can also be produced by a block copolymerization method under reaction conditions different from those of the preliminary polymerization. In this case, the different reaction conditions are, for example, using a prepolymerization catalyst, first producing a homopolymer of polypropylene, and then, in the next reaction step, ethylene, an α-olefin having 4 to 20 carbon atoms, a cyclic olefin, and styrene. By copolymerizing a monomer selected from and propylene and in the same manner as described above, ethylene, an α-olefin having 4 to 20 carbon atoms,
After copolymerizing propylene with a monomer selected from a cyclic olefin and styrene, the charge composition of the monomer is changed in the next step to produce a block copolymer having a changed copolymer composition, etc. Yes, refers to performing a polymerization reaction in two or more steps by changing the monomer species, polymerization temperature, pressure, time, and monomer charge composition.

The melting point of the polyolefin obtained by the method of the present invention is usually 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and further preferably 80 to 160 ° C.
Range. The melting point is a value measured by the following method. That is, the temperature was raised from room temperature to 200 ° C. at a rate of 10 ° C./min using a differential scanning calorimeter (DSC200 manufactured by Seiko Instruments Inc.), and the temperature was maintained at 200 ° C. for 3 minutes. Cool down to 30 ° C in minutes. After maintaining at 30 ° C. for 5 minutes, the temperature is raised at 10 ° C./min, and the melting peak temperature that appears at that time is defined as the melting point. This polyolefin has a melt index MI of 0.00.
Those in the range of 5 to 1000 g / 10 minutes are preferred.
If the MI is less than 0.005 g / 10 min, the melt fluidity is insufficient, and if it exceeds 1000 g / 10 min, the mechanical properties are significantly reduced, which is not preferable. From the viewpoint of balance between melt fluidity and mechanical properties, a more preferable MI is 0.01 to
800 g / 10 min, especially 0.05 to 600 g
A range of / 10 minutes is preferred. Note that this MI is AST
230 ° C, load according to MD1238-T65
It is a value measured under the condition of 2.16 kg.

The melt tension MS (g) of the above polyolefin
Is the melt tension MS (g) measured at a temperature of 230 ° C.
And the intrinsic viscosity [η] (deciliter / g) measured at a temperature of 135 ° C. in a tetralin solvent preferably satisfies the following relationship: logMS ≧ 3.17 × log [η] −0.68 (1) . logMS is "3.17
× log [η] −0.68 ”, the melt processability is poor, and the object of the present invention cannot be achieved. From the viewpoint of melt processability, more preferably logMS ≧ 3.17 × log [η] −0.57, more preferably logMS ≧ 3.17 × log [η] −0.46, particularly preferably logMS ≧ 3.17 × log [η] −0.35. The melt tension MS is a value measured using a Capillograph manufactured by Toyo Seiki Co., Ltd. under the following conditions. Capillary: diameter 2.095 mm, length 8.0 mm, inflow angle 90 degrees Cylinder diameter: 9.0 mm Cylinder extrusion speed: 10 mm / min Winding speed: 3.14 m / min Temperature: 230 ° C. A mixture of Irganox 1010 and BHT at a weight ratio of 1: 1 was previously added as an antioxidant at 4000 ppm by weight.

The polyolefin has a bulk density of 0.2 to 0.2.
5 g / cc is preferred, and 0.3 to 0.5 g / cc is particularly preferred. The bulk density was determined in accordance with JIS K6721.

[0072]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Preparation Example 1 Preparation of n-heptane suspension of silica-supported methylaluminoxane SiO ₂ (P-10, manufactured by Fuji Silysia Chemical Ltd.)
27.1 g was heated at 200 ° C. for 2 hours under a nitrogen stream to obtain 25.9 g of dry silica. The dried silica was put into 400 ml of toluene cooled to −78 ° C. in a dry ice / methanol bath, and stirred while stirring.
145.5 ml of a 1.5 mol / l methylaluminoxane toluene solution was dropped by a dropping funnel over 1.0 hour. After leaving this condition for 4.0 hours, -7
The temperature was raised from 8 ° C. to 20 ° C. in 6.0 hours, and left in this state for 4.0 hours. Then, from 20 ° C to 80 ° C, 1.
The temperature was raised in 0 hour and left at 80 ° C. for 4.0 hours to complete the reaction between silica and methylaluminoxane.

The suspension was filtered at 60 ° C., and the solid obtained was diluted with 400 ml of toluene at 60 ° C.
Washing was performed twice, again at 60 ° C., with 400 ml of n-hexane. Wash the solid at 60 ° C
After drying under reduced pressure for 4.0 hours, 33.69 g of methylaluminoxane supported on silica was obtained. The supported amount of methylaluminoxane was 23.12% by weight. The total amount of the silica-supported methylaluminoxane thus obtained was added to n
Adding heptane to a total volume of 500 ml,
A suspension having a methylaluminoxane concentration of 0.27 mol / liter was prepared.

Preparation Example 2 Preparation of Silica-Supported Metallocene Catalyst 9.26 ml (2.5 mmol of methylaluminoxane) of the silica-supported methylaluminoxane suspension obtained in Preparation Example 1 was collected in a dry nitrogen purged vessel, and charged with n- 20 ml of heptane was added and stirred. To this suspension, rac-dimethylsilanediyl-
Bis-1- (2-methyl-4-phenylindenyl) zirconium dichloride [rac-Me ₂ Si (2-Me
-4-PhInd) ₂ ZrCl ₂ ] in 5 μmol toluene solution, rac-dimethylsilanediyl-bis-1
-(2-methyl-4-phenylindenyl) hafnium dichloride [rac-Me ₂ Si (2-Me-4-Ph
5 μmol of a toluene solution of [Ind) ₂ HfCl ₂ ] was added, and the mixture was stirred at room temperature for 0.5 hour. Thereafter, the stirring was stopped, and the solid catalyst component was allowed to settle. It was confirmed that the precipitated solid catalyst component was pale yellow and the solution was colorless and transparent. Thus, a silica-supported metallocene catalyst was prepared.

Example 1 Production of polypropylene-based prepolymerized catalyst A 1.4-liter stainless steel pressure-resistant autoclave equipped with a stirrer was heated to 80 ° C, dried sufficiently under reduced pressure, and then returned to atmospheric pressure with dry nitrogen. 400 ml of dry deoxygenated n-heptane and 0.5 ml of triisobutylaluminum (toluene solution) under a stream of dry nitrogen.
Then, the mixture was stirred at 500 rpm for 10 minutes.
The silica-supported metallocene catalyst prepared in Preparation Example 2 was added thereto (zirconium compound and hafnium compound in total of 10 μmol), and propylene was continuously supplied at 8.0 kg / cm ² G while controlling at 30 ° C. Then, preliminary polymerization was carried out for 90 minutes to obtain polypropylene (preliminary polymerization catalyst). After the completion of the prepolymerization, the unreacted propylene was depressurized, and the unreacted propylene was removed with nitrogen. A portion of the obtained polypropylene was sampled under a nitrogen atmosphere, and the amount of pre-polymerization (the amount of polypropylene obtained by pre-polymerization) was determined.
And 27.9 g per 1 g of the metallocene catalyst supported on silica.
Met. The intrinsic viscosity [η] of the polypropylene obtained by the preliminary polymerization was 3.3 deciliter / g.
The solid portion of the prepolymerized catalyst obtained by the prepolymerization was separated from the liquid portion by decantation, and stored as a slurry of 100 ml of dry deoxygenated n-heptane.

Example 2 Production of Polypropylene Using Preliminary Polymerization Catalyst A 1.4-liter stainless steel pressure-resistant autoclave equipped with a stirrer was heated to 80 ° C., sufficiently dried under reduced pressure, and then returned to atmospheric pressure with dry nitrogen. 300 ml of dry deoxygenated n-heptane and 0.5 ml of triisobutylaluminum (toluene solution) were placed in an autoclave under a stream of dry nitrogen.
Then, the mixture was stirred at 500 rpm for 10 minutes.
100 ml of the prepolymerized catalyst prepared in Example 1 (corresponding to 9 micromol in terms of zirconium and hafnium atoms) was added thereto, and the temperature was raised to 70 ° C. Propylene was continuously supplied at 8.0 kg / cm ² G, and 30
The polymerization was carried out for minutes. After completion of the reaction, unreacted propylene was depressurized, the catalyst was deactivated with a large amount of methanol, and filtered and dried to obtain 189 g of polypropylene. For this polypropylene, the melt index MI, intrinsic viscosity [η], melt tension MS, melting point Tm, and bulk density were determined and evaluated according to the methods described in the specification text. The results are shown in Table 1.

Example 3 Production of polyethylene-based prepolymerization catalyst A polyethylene (prepolymerization catalyst) was produced in the same manner as in Example 1, except that propylene was changed to ethylene and the polymerization time was changed to 45 minutes. A portion of the obtained polyethylene was sampled under a nitrogen atmosphere, and the amount of prepolymerization (the amount of polyethylene obtained by prepolymerization) was determined. Met. The intrinsic viscosity [η] of the polyethylene obtained by the preliminary polymerization was 3.3 deciliters / g. The solid portion of the prepolymerized catalyst obtained by the prepolymerization was separated from the liquid portion by decantation, and stored as a slurry of 100 ml of dry deoxygenated n-heptane.

Example 4 Production of an ethylene-propylene copolymer using a prepolymerization catalyst An ethylene-propylene copolymer was prepared in the same manner as in Example 2 except that the one prepared in Example 3 was used as a prepolymerization medium. Was produced.

[0079]

[Table 1]

[0080]

According to the present invention, a polyolefin having high melt tension, excellent resin compatibility, and high bulk density can be produced inexpensively and efficiently.

Claims (7)

[Claims] (A) at least two transition metal compounds selected from Group 4 of the periodic table having a cyclopentadienyl group, (B) (B-1) an aluminum oxy compound, (B) -2) an ionic compound that can be converted to a cation by reacting with the transition metal compound, and (B-3) a clay;
C2 in the presence of a catalyst containing at least one selected from clay minerals and ion-exchange layered compounds
At least one selected from α-olefins and cyclic olefins of 0.2 to 0.2 per g of the transition metal compound.
A prepolymerized catalyst obtained by prepolymerizing at a rate of from 01 to 2000 g and having an intrinsic viscosity [η] in a range of from 0.01 to 20 deciliter / g. 2. The catalyst used in the prepolymerization further comprises (C)
The prepolymerized catalyst according to claim 1, which contains an organic aluminum compound and / or a carrier. 3. The prepolymerized catalyst according to claim 1, wherein at least one of the component (A) and the component (B) is supported on a carrier. 4. The method according to claim 1, wherein the transition metal compound as the component (A) is (A-
1) General formula (I)[Wherein, R¹~ R⁶Are independently a hydrogen atom and a halo
Gen atom, hydrocarbon group having 1 to 20 carbon atoms or 1 to carbon atoms
20 represents a halogen-containing hydrocarbon group;^ThreeAnd R ^Four, R
^FourAnd R^FiveAnd R^FiveAnd R⁶At least one pair of
May be bonded to form a ring;¹And X^TwoIs it
Each independently represents a hydrogen atom, a halogen atom or a carbon number of 1 to 20;
Y represents a hydrocarbon group of¹Is the two that binds the two ligands
A hydrocarbon group having 1 to 20 carbon atoms,
1 to 20 halogen-containing hydrocarbon groups, silicon-containing groups or
Represents a rumanium or tin-containing group;¹Is titanium,
Indicates zirconium or hafnium. ]
Metal compound, (A-2) general formula (II)[Wherein, R⁷~ R¹³, R^Fifteen, R¹⁶, X^ThreeAnd X^FourIs
Each independently a hydrogen atom, a halogen atom, a carbon number of 1 to 20
Hydrocarbon groups, halogen-containing hydrocarbons having 1 to 20 carbon atoms
Group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing
A group or a phosphorus-containing group;⁷And R⁸Joined to each other
To form a ring. R¹⁴, R¹⁷Are independent of each other
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
To 20 halogen-containing hydrocarbon groups, silicon-containing groups, and oxygen-containing
Indicates a group containing, sulfur-containing, nitrogen-containing or phosphorus-containing group.
You. Y^TwoIs a divalent group linking two ligands,
C1-C20 hydrocarbon group, C1-C20 halogen
Hydrocarbon-containing groups, silicon-containing groups, germanium-containing groups,
-O-, -CO-, -S-, -SO_Two-, -NR¹⁸−,
-PR¹⁸-, -P (O) R¹⁸-, -BR¹⁸-Or -Al
R¹⁸-Indicates R¹⁸Is hydrogen atom, halogen atom, carbon number
Contains 1 to 20 hydrocarbon groups and 1 to 20 carbon atoms
Shows a hydrocarbon group. M^TwoIs titanium, zirconium or ha
Indicates funium. The transition metal compound represented by, and
(A-3) General formula (III)[Where M^ThreeIs titanium, zirconium or hafnium
Show, E¹And E^TwoAre each substituted cyclopentadienyl
Group, indenyl group, substituted indenyl group, heterocyclo
Pentadienyl group, substituted heterocyclopentadienyl
Group, amide group, phosphide group, hydrocarbon group and silicon-containing
A ligand selected from the group¹And A^TwoThrough
To form a crosslinked structure, and they
May be one or different, X^FiveRepresents a σ-binding ligand
X^FiveIf there are multiple Xs ^FiveAre the same but different
Other X^Five, E¹, E^TwoOr Y^ThreeAnd crosslink
It may be. Y^ThreeRepresents a Lewis base;^ThreeIs multiple
If there is more than one Y^TwoMay be the same or different,
Other Y^Three, E¹, E^TwoOr X^FiveMay be cross-linked,
A¹And A^TwoIs from a hydrocarbon group having 1 or more carbon atoms
Which are the same or different
May be. q is an integer of 1 to 5 [(M^ThreeValence) −
2], and r represents an integer of 0 to 3. ] Represented by
Claims are at least two selected from metal transfer compounds
The prepolymerized catalyst according to any one of 1 to 3, above. 5. The transition metal compound as the component (A) is a combination selected from a zirconium compound-hafnium compound, a zirconium compound-zirconium compound and a hafnium compound-hafnium compound. The prepolymerized catalyst according to any one of the above. 6. An olefin polymerization catalyst comprising the prepolymerized catalyst according to claim 1 and an organoaluminum compound. 7. An α-olefin having 2 to 20 carbon atoms, a cyclic olefin and a styrene monomer in the presence of the prepolymerized catalyst according to claim 1 or in the presence of an organic aluminum compound added to the prepolymerized catalyst. A method for producing a polyolefin, comprising polymerizing or copolymerizing at least one selected from the group consisting of: