JP2003201308A - Olefin polymerization catalyst and method for producing polyolefin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefin having a high melt tension, excellent resin compatibility, and a high bulk density. <P>SOLUTION: The polyolefin is produced by preliminarily polymerizing at least one kind selected from a 2-20C α-olefin and a cyclic olefin and at least one nonconjugated diene compound in the presence of a catalyst comprising (A) at least one kind selected from compounds of a group 4 transition metal in the periodic table composed of (A-1) of formula (I), (A-2) of formula (II), (A-3) of formula (III), and (A-4) of formula (IV) (wherein M<SP>1</SP>to M<SP>7</SP>are each titanium, zirconium or hafnium) and (B) at least one kind selected from (B-1) an aluminumoxy compound, (B-2) an ionic compound capable of reacting with the above compound of a transition metal to convert to a cation, and (B-3) clay, a clay material or an ion-exchangeable layer compound, and polymerizing or copolymerizing at least one kind selected from a 2-20C α-olefin, a cyclic olefin, and a styrenic monomer in the presence of the preliminarily polymerized catalyst or in the presence of the preliminarily polymerized catalyst to which an organoaluminum compound has been added. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyolefin, and more particularly to a method for efficiently and inexpensively producing a polyolefin having high melt tension, excellent resin compatibility and high bulk density. Is.

[0002]

2. Description of the Related Art Polyolefins are widely used in many fields due to their excellent properties. However, in conventional polyolefins,
The melt tension and melt viscoelasticity are insufficient, the phenomenon of drawdown is likely to occur, and the stability of the parison in large-scale blow molding is poor, so that it is difficult to manufacture a large-sized molded product.
Further, when the polymer is made to have a high molecular weight in order to improve the melt tension, there arises a problem that the melt fluidity is lowered and it cannot be applied to molding of a complicated shape.

Further, in the field of foamed molded articles, there is an increasing demand for foamed molded articles having heat resistance as well as weight reduction, heat insulation and vibration damping properties, and polypropylene-based foamed molded articles are expected. In the case of polypropylene, the melt tension is insufficient and it is difficult to obtain a sufficiently satisfactory foamed molded product. In order to further expand the field of application of this polypropylene, it is necessary to improve extrusion processability. Heretofore, various attempts have been made to improve the melt processability of polyolefins. For example, the melt processability is improved by improving the polymerization catalyst and the polymerization prescription during the production of the polyolefin and expanding its molecular weight distribution. A method of improving the melt processability by partially crosslinking the polyolefin has been attempted.

On the other hand, regarding the ethylene-based polymer, recently, an ethylene-based polymer having an improved melt tension has been proposed by a catalyst system in which a metallocene catalyst and an aluminoxane are combined, although the molecular weight distribution is narrow. (Japanese Patent Laid-Open No. 4-213306). It has also been disclosed that the ethylene-based polymer produced by the constrained geometry type catalyst has an improved melt tension despite its narrow molecular weight distribution (JP-A-3-163088). The presence of long chain branches has been suggested. However, improvement in extrusion processability due to improvement in melt tension is still small. Further, although the polystyrene-based resin has a higher melt tension than the polyethylene-based resin and the polypropylene-based 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 branching characteristics are improved by the branch, but in a branched polymer in which a branched chain is composed of a monomer different from the main chain polymer, a so-called composite of different polymers is used. In the field of materials,
It is possible to lower the interfacial tension between different kinds of polymers, enhance the dispersibility of the polymers, and effectively impart incompatible physical properties such as impact strength and rigidity. Further, since it has a micro phase separation structure, it can be applied to various elastomers. However, until now, in the field of polyolefins,
Since there are restrictions on the introduction of branching, there was a limit to the application development. If this becomes possible, it is expected that the field of application will greatly expand due to the excellent mechanical properties inherent to polyolefin and the environmental compatibility represented by recyclability.

By the way, as a method for improving the melt tension of a polyolefin to improve its melt processing characteristics, (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 melt tension by irradiating a general polyolefin with light, (5) A method of increasing melt tension by irradiating a general polyolefin with light in the presence of a crosslinking agent or a peroxide, (6) ) A method of grafting a radically polymerizable monomer such as styrene onto a general polyolefin, and (7) a method of copolymerizing an olefin and a polyene (JP-A-5-194778 and JP-A-5-1947).
79), (8) a method of polymerizing an olefin or the like in the presence of a prepolymerized catalyst obtained by prepolymerizing an olefin in the presence of a specific catalyst (JP 2000-38411 A).
Japanese Unexamined Patent Publication No. 9-235337), (9) A method using a catalyst obtained by prepolymerizing olefin and polyene (Japanese Unexamined Patent Publication No. 9-235337) and the like have been tried.

However, in the above methods (1) to (3), the inherent characteristics of polyolefin, especially polypropylene, are impaired because the elastic modulus, strength, and heat resistance of the component for increasing the melt tension are insufficient. Absent. or,
In the methods (4) and (5), it is difficult to control the cross-linking reaction that occurs as a side reaction, the appearance of gel and the mechanical properties are adversely affected by the generation of gel, and molding processability is arbitrarily adjusted. There is a problem that the control is limited and the control range is narrow. Further, in the method (6), problems such as generation of gel and production cost occur, and in the method (7), the effect of improving the melt tension is small and sufficient effect cannot be exhibited. Is also a concern. In the method (8), the reaction point efficiency is low and the effect of improving the melt tension is insufficient. In the method (9), the olefin and the polyene are prepolymerized, but it is difficult to control the reaction points, and there is a concern that gel may be generated.

[0008]

Under such circumstances, the present invention provides a method for efficiently and inexpensively producing a polyolefin having a high melt tension, a high resin compatibility and a high bulk density. That is the purpose.

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

That is, the present invention provides (A) the following (A-1),
At least one selected from transition metal compounds of Group 4 of the periodic table consisting of (A-2), (A-3) and (A-4), and (B) (B-1) aluminum oxy compound ,
(B-2) contains an ionic compound capable of reacting with the above transition metal compound and converting into a cation, and (B-3) at least one selected from clay, clay minerals and ion-exchange layered compounds 2 to 2 carbon atoms in the presence of
At least one selected from α-olefins and cyclic olefins of 0 and a non-conjugated diene compound were prepolymerized at a rate of 0.01 g to 50 kg per 1 g of the above transition metal compound, and measured in a tetralin solvent at 135 ° C. The intrinsic viscosity [η] is in the range of 0.1 to 20 deciliter / g, and the intrinsic viscosity [η] (deciliter / g) measured in a tetralin solvent at 135 ° C. is not conjugated with a terminal vinyl group per 1000 carbons. The product [η] × [C] with the sum [C] of the content of carbon-carbon double bonds derived from the diene compound is 0.
The present invention relates to a prepolymerization catalyst characterized by being in the range of 05 to 1.1. Further, the present invention is selected from α-olefins having 2 to 20 carbon atoms, cyclic olefins and styrenic monomers in the presence of the prepolymerization catalyst or in the presence of the prepolymerization catalyst to which an organoaluminum compound is added. The present invention also relates to a method for producing a polyolefin, which comprises polymerizing or copolymerizing at least one kind.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the production method of the present invention, (A) the following (A-1) and (A-
2), (A-3) and (A-4) Periodic Table No. 4
One selected from a group of transition metal compounds, (B)
(B-1) an aluminum oxy compound, (B-2) an ionic compound capable of reacting with the above transition metal compound to be converted into a cation, and (B-3) a clay, a clay mineral, or an ion-exchange layered compound The one containing at least one selected from the above is used. Examples of the transition metal compound of Group 4 of the periodic table having a cyclopentadienyl group as the component (A) include the following components (A-1), (A-2), (A-3) and (A-3). One of them may be selected from the component A-4). Component (A-1): The component (A-1) has the general formula (I).

[0012]

[Chemical 5]

[Wherein R ^{1 to} R ⁶ each independently represent 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, and R ³
And R ⁴ , at least one pair of R ⁴ and R ^5, and R ⁵ and R ⁶ may be bonded to each other to form a ring, and X ¹ and X ² are each independently a hydrogen atom, a halogen atom or a carbon atom. Number 1-2
0 represents a hydrocarbon group, Y ¹ is a divalent bridging group that bonds two ligands, and is a hydrocarbon group having 1 to 20 carbon atoms,
Halogen-containing hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group, germanium-containing group, tin-containing group, -O-, -CO
-, - S -, - SO 2 -, - Se -, - NR 18 -, - P
^{R 18 -, - P (O} ) R 18 -, - BR 18 - or -AlR ¹⁸
Represents-, R ¹⁸ represents a hydrogen atom, a halogen atom, or a carbon number of 1 to
20 shows a hydrocarbon group and a C1-C20 halogen-containing hydrocarbon group. M ¹ represents titanium, zirconium or hafnium. ] A transition metal compound represented by

The transition metal compound in which at least one of R ³ and R ⁴ , R ⁴ and R ⁵ and R ⁵ and R ⁶ forms a ring in the general formula (I) is known as a BASF type complex. It is a compound. In the general formula (I), R ^{1 to} R ⁶
Examples of the halogen atom include chlorine, bromine, fluorine and iodine atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert.
-Butyl group, n-hexyl group, n-decyl group, and other alkyl groups, phenyl group, 1-naphthyl group, 2-naphthyl group, and other aryl groups, benzyl group, and other aralkyl groups, and the like. Examples of the halogen-containing hydrocarbon group of to 20 include groups in which one or more hydrogen atoms of the above hydrocarbon group are substituted with a suitable halogen atom. This R ¹ ~ R
⁶ may be the same or different from each other, and
At least one set of adjacent groups, that is, R ³ and R ⁴ , R ⁴ and R ^5, and R ⁵ and R ⁶ must be bonded to each other to form a ring. Examples of the ring-forming indenyl group include, for example, a 4,5-benzoindenyl group,
Examples thereof include an α-acenaphthoindenyl group and an alkyl-substituted product thereof having 1 to 10 carbon atoms.

The halogen atom of X ¹ and X ² includes chlorine, bromine, fluorine and iodine atoms, each having 1 carbon atom.
As the hydrocarbon group of 20 to 20, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, te
Examples thereof include alkyl groups such as rt-butyl group and n-hexyl group, aryl groups such as phenyl group, and aralkyl groups such as benzyl group. X ¹ and X ² may be the same or different from each other. On the other hand, Y ¹ is a divalent group that bonds 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; Examples of the divalent halogen-containing hydrocarbon group include a chloroethylene group and a chloromethylene group. The divalent silicon-containing group may be, for example, a methylsilylene group,
Examples thereof include 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 the groups obtained by converting silicon into germanium or 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.

Examples of the transition metal compound represented by the general formula (I) of the component (A-1) include, for example, JP-A-6-18.
The compounds described in JP-A No. 4179 and JP-A No. 6-15809 can be mentioned. 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-phenylmethylsilanediyl-bis-1- (2-methyl-α-acenaphthoindenyl) -zirconium dichloride, etc. Examples thereof include benzoindenyl type or acenaphthoindenyl type compounds, and compounds obtained by substituting zirconium with titanium or hafnium in these compounds.

Further, the component (A-1) is an indenyl in which, in the general formula (I), neither R ³ and R ⁴ , R ⁴ and R ⁵ nor R ⁵ and R ⁶ form a ring. A transition metal compound having a skeleton or a corresponding transition metal compound having a 4,5,6,7-tetrahydroindenyl skeleton. This transition metal compound is a compound known as a Hoechst complex. Examples of the transition metal compound as the component (A-1) include, for example, JP-A-4-268308, JP-A-5-306304, and JP-A-6-100.
Examples thereof include the compounds described in JP-A No. 579, JP-A-6-157661, JP-A-7-149815, JP-A-7-188318, and JP-A-7-258321.

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 compounds 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, rac-dimethylsilylene-bis-1- (2-methyl-4-ethylindenyl)-
2,4-position substitution products such as 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- (1,7-trimethylindenyl) -zirconium dichloride, rac-1,2
4,7- such as -ethanediyl-bis-1- (4,7-dimethylindenyl) -zirconium dichloride, rac-1,2-butanediyl-bis-1- (4,7-dimethylindenyl) -zirconium dichloride Rank 2,
4,7-position or 1,7-position substitution product, 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, ra
c-Phenylmethylsilanediyl-bis-1- (2-methyl-4,6-diisopropylindenyl) -zirconium dichloride, rac-dimethylsilanediyl-bis-1- (2,4,6-trimethylindenyl)- Zirconium dichloride, etc. substituted 2,4-, 6-position, rac-
2, such as dimethylsilanediyl-bis-1- (2,5,6-trimethylindenyl) -zirconium dichloride,
Substituted 5,6-position, 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 , Ra
c-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,
4,5,6, such as 7-dimethyl-4,5,6,7-tetrahydro-1-indenyl) -zirconium dichloride,
Examples thereof include 7-tetrahydroindenyl compounds and the like, and compounds in which zirconium in these compounds is replaced with titanium or hafnium. Component (A-2): Component (A-2) has the general formula (II)

[0019]

[Chemical 6]

[In the formula, R ^{7 to} R ¹³ , R ¹⁵ , R ¹⁶ , X ³ and X ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. A halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group,
It represents a nitrogen-containing group or a phosphorus-containing group, and R ⁷ and R ⁸ may combine with 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, a nitrogen-containing group. Alternatively, it represents a phosphorus-containing group.
Y ² is a divalent bridging group connecting two ligands,
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 -, - CO -, - S -, - SO 2 -, -
^{Se -, - NR 18 -,} - PR 18 -, - P (O) R 18 -,
Represents —BR ¹⁸ — or —AlR ¹⁸ —, R ¹⁸ is a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
~ 20 halogen-containing hydrocarbon groups. M ² represents titanium, zirconium or hafnium. ] It is a transition metal compound represented by.

This transition metal compound is a single cross-linking complex.
It In the general formula (II), R⁷~ R¹³, R¹⁵, R
¹⁶, X³And X^FourThe halogen atom is chlorine,
Examples include bromine, fluorine and iodine atoms. Having 1 to 20 carbon atoms
As the hydrocarbon group, for example, methyl group, ethyl group, n-
Propyl group, isopropyl group, n-butyl group, isobutyl
Group, tert-butyl group, n-hexyl group, n-decyl group
Group such as alkyl group, phenyl group, 1-naphthyl group, 2
-Aryl groups such as naphthyl groups, aralkyl groups such as benzyl groups
Group containing hydrogen, etc., and a halogen-containing carbon having 1 to 20 carbon atoms
As the hydrogenated group, the above hydrocarbon water such as trifluoromethyl
Substitution of one or more hydrogen atoms of elementary groups with appropriate halogen atoms
Groups mentioned above. As a silicon-containing group, trimethyl
Rusilyl group, dimethyl (tert-butyl) silyl group, etc.
Examples of the oxygen-containing group include a methoxy group and an ethoxy group.
Si groups and the like, as the sulfur-containing group, a thiol group,
Examples of the nitrogen-containing group include a sulfonic acid group and the like.
Examples of the phosphorus-containing group include methyl.
Examples thereof include a phosphine group and a phenylphosphine group.
Also, R⁷And R⁸Combine with each other to form a ring such as fluorene
You may. R¹⁴, R ¹⁷As specific examples of R,⁷~
R¹³Groups excluding hydrogen atoms from those listed in
To be R⁷, R⁸As a hydrogen atom and 6 or less carbon atoms
The alkyl group of is preferably a hydrogen atom, a methyl group or ethyl.
Group, isopropyl group, cyclohexyl group are more preferable.
However, a hydrogen atom is more preferable. Also, R⁹, R¹², R¹⁴Over
And R¹⁷For, an alkyl group having 6 or less carbon atoms is preferable.
, Methyl group, ethyl group, isopropyl group, cyclohexyl
A sil group is more preferable, and an isopropyl group is further preferable.
Yes. R^Ten, R¹¹, R¹³, R¹⁵And R¹⁶As a hydrogen atom
Is preferred. X³And X^FourAs a halogen atom,
A tyl group, an ethyl group and a propyl group are preferred.

Specific examples of Y ² include methylene, ethylene, ethylidene, isopropylidene, cyclohexylidene, 1,2-cyclohexylene, dimethylsilylene, tetramethyldisilyne, dimethylgermylene and 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-), sulfur (-)
S-) and the like, and among these, methylene, ethylene, ethylidene and isopropylidene are preferable from the viewpoint of ease of synthesis and yield. 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,
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 Examples thereof include compounds in which hafnium in the compound is replaced with zirconium or titanium, but are not limited thereto.The transition metal compound represented by the general formula (II) is, for example, Japanese Patent Application Laid-Open No. 11-
It can be manufactured by the method described in Japanese Patent No. 130807. Component (A-3): The component (A-3) has the general formula (III)

[0024]

[Chemical 7]

[Wherein M³Is titanium, zirconium or
Indicates hafnium, E¹And E²Is a substituted cyclope
Interdienyl group, indenyl group, substituted indenyl group,
Telocyclopentadienyl group, substituted heterocyclopenta
Dienyl group, amide group, phosphide group, hydrocarbon group and
A ligand selected from silicon-containing groups, wherein¹as well as
A²Form a cross-linking structure via
, Which may be the same or different, X^FiveIs a sigma bond
Show the child, X^FiveIf there are multiple^FiveAre the same but different
May be other X^Five, E¹, E²Or Y³Cross-linked with
May be. Y ³Represents a Lewis base, Y³There are multiple
If more than one Y²Can be the same or different, other
Y³, E¹, E²Or X^FiveMay be crosslinked with A¹as well as
A²Is a divalent bridging group linking two ligands,
Hydrocarbon group having 1 to 20 carbon atoms, halogen having 1 to 20 carbon atoms
-Containing hydrocarbon group, silicon-containing group, germanium-containing group,
Tin-containing group, -O-, -CO-, -S-, -SO₂-,-
Se-, -NR¹⁸-,-PR¹⁸-, -P (O) R¹⁸-,
-BR¹⁸-Or-AlR¹⁸-Indicates R¹⁸Is a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
~ 20 halogen-containing hydrocarbon radicals, which are
May be the same or different. q is an integer from 1 to 5
[(M³Valence of 2) -2], and r is an integer of 0 to 3
Show. ] A transition metal compound represented by
Sometimes referred to as a complex. ).

In the above general formula (III), M ³ represents titanium, zirconium or hafnium, and zirconium and hafnium are preferable. E ¹ and E ² are each a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group (-
N <), phosphide group (-P <), hydrocarbon group [> CR
-,> C <] and silicon-containing groups [>SiR-,> Si <]
(Provided that R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms or a hetero atom-containing group), and a cross-linked structure is formed via A ¹ and A ^2. There is.
Further, E ¹ and E ² may be the same or different from each other.
As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable.

Specific examples of the σ-bonding 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 carbon atom having 6 to 20 carbon atoms. Aryloxy group, C1-C20 amide group, C1-C20 silicon-containing group, C1-C20 phosphide group, C1-C20 sulfide group, C1-C20 acyl group, etc. Is mentioned. If this X ³ there is a plurality, the plurality of X ³ may be the same or different, the other X ^3,
It may be crosslinked with E ¹ , E ² or Y ² . On the other hand, specific examples of the Lewis base represented by Y ³ include amines, ethers, phosphines, thioethers and the like. If the Y ³ there is a plurality, the plurality of Y ³ may be the same or different, may be crosslinked with other Y ^3, E ^1, E ² or X ^5. Next, at least one of the crosslinking groups represented by A ¹ and A ² is preferably a crosslinking group composed of a hydrocarbon group having 1 or more carbon atoms. Examples of such a crosslinking group include those represented by the general formula

[0028]

[Chemical 8]

(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 from each other, or may be bonded to each other to form a ring structure. .E represents an integer of 1 to 4), and specific examples thereof include a methylene group, an ethylene group, an ethylidene group, a propylidene group, an isopropylidene group, a cyclohexylidene group, 1, Examples thereof include a 2-cyclohexylene group and a vinylidene group (CH ₂ ═C =). Of these, a methylene group, an ethylene group and an isopropylidene group are preferable. This A ¹ and A
^{The two} may be the same or different from each other. This general formula
In the transition metal compound represented by (III), E ¹ and E ²
Is a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group, the bonds of the bridging groups of A ¹ and A ² may be (1,1 ′) (2,2 ′) double bridging type. Well, it may be a (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]

[Chemical 9]

A transition metal compound having a double-bridged biscyclopentadienyl derivative represented by the formula as a ligand is preferable. 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 are the same as those exemplified in the description of X ^{5 in} the general formula (III). Y
⁴ represents a Lewis base, and when there are plural Y ⁴ , plural Y ⁴
May be the same or different and may be crosslinked with another Y ³ or X ⁴ . As a specific example of Y ⁴ , general formula (II
The same as those exemplified in the description of Y ³ in I) can be mentioned. 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 having 1 to 20 carbon atoms, a silicon-containing group or a hetero atom-containing group, and at least one of them. One must not be a hydrogen atom. R ^{20 to} R ²⁵ may be the same or different from each other, and adjacent groups may be bonded to each other to form a ring.

In the transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand, the ligands are (1,1 ′) (2,2 ′) double-bridged and (1,2). ')
Any of (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 (3,3
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 the like, and those obtained by substituting zirconium with titanium or hafnium in these compounds.
Of course, it is not limited to these. Component (A-4): The component (A-4) has the general formula (IV)

[0033]

[Chemical 10]

[In the formula, M ⁷ represents titanium, zirconium or hafnium, and R ³⁴ and R ³⁷ each independently represent a hydrocarbon group having 3 to 10 carbon atoms or a silicon-containing hydrocarbon group having 2 to 18 carbon atoms. And R ³⁵ and R ³⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms.
18 is a silicon-containing hydrocarbon group, and R ³⁶ and R ³⁹ are each independently a divalent saturated or unsaturated hydrocarbon group having 3 to 10 carbon atoms which forms a condensed ring with the 5-membered ring to which it is bonded. Indicates a group. R ⁴⁰ and R ⁴¹ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a phosphorus-containing hydrocarbon group. . s and t each independently represent an integer of 0-20. J is at least one hydrocarbon group having 1 to 20 carbon atoms that bonds two five-membered rings, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group. An alkylene group having a hydrogen group,
Or at least one hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a silylene group having a phosphorus-containing hydrocarbon group, or, At least one carbon number 1-20
And a germylene group having a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, and a phosphorus-containing hydrocarbon group. X ⁸ and Y ⁵ are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 2.
A hydrocarbon group having 0, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group and a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms are shown. ] It is a transition metal compound represented by.

In the general formula (IV), the substituent R ³⁴ ,
A five-membered ring ligand having R ³⁵ and R ³⁶ , and a substituent R ³⁷ ,
Include compounds in which the five-membered ring ligand having R ³⁸ and R ³⁹ is asymmetric with respect to the plane containing M ⁷ , X ⁸ and Y ⁵ in terms of relative position via the group J, and compounds which are symmetrical . However, in order to produce a highly active, high molecular weight, and high melting point α-olefin polymer, a five-membered ring ligand having substituents R ³⁴ , R ³⁵ , and R ³⁶ , and a substituent R ³⁷ , The five-membered ring ligands having R ³⁸ and R ³⁹ are asymmetric with respect to the plane containing M ⁷ , X ⁸ and Y ⁵ in terms of relative position via the group J, in other words M ⁷ , X ⁸ And a compound containing two five-membered ring ligands opposed to each other with the plane containing Y ⁵ sandwiched between the two planes does not have a mirror image with respect to the plane.

As described above, R ³⁴ and R ³⁷ are each independently a hydrocarbon group having 3 to 10 carbon atoms or a silicon-containing hydrocarbon group having 2 to 18 carbon atoms, and R ³⁵ and R ³⁸ are each independently. , A hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 18 carbon atoms.

More specifically, R ³⁴ , R ³⁵ , R ³⁷ , R
³⁸ is each independently (a) a hydrogen atom, (b) a hydrocarbon group having 1 to 10 carbon atoms, for example, methyl, ethyl, n-
Propyl, i-propyl, n-butyl, i-butyl, s
ec-butyl, tert-butyl, n-pentyl, n-
Alkyl groups such as hexyl, cyclopropyl, cyclopentyl, cyclohexyl and methylcyclohexyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl,
Arylalkyl such as benzyl, phenylethyl and phenylpropyl, arylalkenyl group such as trans-styryl, phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, α-naphthyl, β-
An aryl group such as naphthyl, (c) a silicon-containing hydrocarbon group having 1 to 18 carbon atoms, for example, a trialkylsilyl group such as trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, a triarylsilyl group such as triphenylsilyl, (Alkyl) such as dimethylphenylsilyl
An (aryl) silyl group and an alkylsilylalkyl group such as bis (trimethylsilyl) methyl. Of these, R ³⁴ and R ³⁷ are hydrocarbon groups having up to 3 to 10 carbon atoms such as isopropyl, tert-butyl, cyclopropyl, phenyl, cyclopentyl, or 2 carbon atoms such as dimethylsilyl, trimethylsilyl, diethylsilyl and the like. ~
Eighteen silicon-containing hydrocarbon groups are used.

R ³⁶ and R ³⁹ are each independently a divalent carbon atom having 3 to 3 carbon atoms which forms a condensed ring with the five-membered ring to which it is bonded.
10 saturated or unsaturated hydrocarbon groups are shown. Therefore, the fused ring is a 5- to 12-membered ring. Preferably R ³⁶ and R ³⁹
At least one of them forms a condensed ring composed of a 7 to 12 membered ring. At this time, at least one of the condensed rings is 7 to 10
It is preferably a membered ring, and both of the condensed rings are 7-1.
It is more preferably a 0-membered ring.

Specific examples of such R ³⁶ and R ³⁹ are as follows. Divalent saturated hydrocarbon groups such as trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, propenylene, 2-butenylene, 1,3-butadienylene, 1-pentenylene, 2
-Pentenylene, 1,3-pentadienylene, 1,4-
Pentadienylene, 1-hexanylene, 2-hexanylene, 3-hexanylene, 1,3-hexadienylene,
Examples thereof include divalent unsaturated hydrocarbon groups such as 1,4-hexadienylene, 1,5-hexadienylene, 2,4-hexadienylene, 2,5-hexadienylene, and 1,3,5-hexatrinylene. Of these, pentamethylene, 1,3-pentadienylene, 1,4-pentadienylene, and 1,3,5-hexatrinylene are preferable, and
3-Pentadienylene and 1,4-pentadienylene are particularly preferable.

R ⁴⁰ and R ⁴¹ each independently have 1 to 2 carbon atoms.
0 hydrocarbon group or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group,
Indicates a phosphorus-containing hydrocarbon group. More specifically, (a) carbon number 1
20 hydrocarbon groups, for example methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, se
alkyl groups such as c-butyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl and methylcyclohexyl, vinyl,
Alkenyl groups such as propenyl and cyclohexenyl, arylalkyl such as benzyl, phenylethyl and phenylpropyl, arylalkenyl groups such as trans-styryl, phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, α-naphthyl, β-naphthyl. And aryl groups such as acenaphthylenyl, phenanthrenyl, anthracenyl, and the like. Of these, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, ter
Preferred are alkyl groups having 1 to 4 carbon atoms such as t-butyl and cyclopropyl, and aryl groups having 6 to 20 carbon atoms such as phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, α-naphthyl and β-naphthyl.

Other groups for R ⁴⁰ and R ⁴¹ include (b) halogen-containing hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups, nitrogen-containing hydrocarbon groups and phosphorus-containing hydrocarbon groups. . Examples of the halogen atom constituting the halogen-containing hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As the halogen-containing hydrocarbon group having 1 to 20 carbon atoms, for example, when a fluorine atom is used as the halogen atom, a compound in which the fluorine atom is substituted at any position of the above-mentioned hydrocarbon group having 1 to 20 carbon atoms. Is. Specifically, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2,2,2.
1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 1,1-difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, o- Or, m- or p-fluorophenyl, o- or m- or p-chlorophenyl, o- or m- or p-bromophenyl, 2,4- or 3,
5-or 2,6- or 2,5-difluorophenyl,
2,4- or 3,5-or 2,6- or 2,5-dichlorophenyl, 2,4,6-trifluorophenyl,
2,4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, 4-fluoronaphthyl,
4-chloronaphthyl, 2,4-difluoronaphthyl, heptafluoro-α-naphthyl, heptachloro-α-naphthyl, o- or m- or p-trifluoromethylphenyl, o- or m- or p-trichloromethyl Phenyl, 2,4- or 3,5-or 2,6- or 2,5
-Di-trifluoromethylphenyl, 2,4-, or
3,5-or 2,6- or 2,5-di-trichloromethylphenyl, 2,4,6-tri-trifluoromethylphenyl, 4-trifluoromethylnaphthyl, 4-trichloromethylnaphthyl, 2,4 -Di-trifluoromethyl naphthyl group and the like.

Of these, a fluorine-containing hydrocarbon group or a chlorine-containing hydrocarbon group is preferable, and o-, m- or p-
A fluorophenyl group, or an o-, m- or p-chlorophenyl group, or an o-, m- or p-trifluoromethylphenyl group is particularly preferable.

As the oxygen-containing hydrocarbon group, methoxy,
Ethoxy, propoxy, phenoxy, ethoxyethyl,
Furyl, methoxyphenyl and methyl cellosolve groups are exemplified. Examples of the nitrogen-containing hydrocarbon group include dimethylamino, diethylamino, pyridyl, indolyl, carbazolyl, dimethylaminophenyl and quinolyl groups. Examples of the phosphorus-containing hydrocarbon group include dimethylphosphino, diphenylphosphino and dimethylphosphinoethyl groups.

S and t each independently represent an integer of 0-20. Preferably, s and t are 0-5. Here, when s or t, or both s and t are integers of 2 to 20, a plurality of groups R ⁴⁰ (R ⁴¹ ) may be the same or different from each other. When s and t are 2 or more, these groups may be linked to form a new ring structure.

J is at least one hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having oxygen, and a hydrocarbon group having nitrogen, which bond two five-membered rings. An alkylene group having a phosphorus-containing hydrocarbon group, or at least one hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, phosphorus A silylene group having a hydrocarbon group or at least one carbon number of 1 to 2
A germylene group having a hydrocarbon group of 0, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group and a phosphorus-containing hydrocarbon group is shown.

As the cross-linking group containing a hydrocarbon group, J
Examples of methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene and the like. Alkylene group; arylalkylene group such as (methyl) (phenyl) methylene and diphenylmethylene; silylene group; methylsilylene;
Alkylsilylene groups such as dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, and (alkyl) (methyl (phenyl) silylene, methyl (tolyl) silylene, etc. Aryl) silylene group; arylsilylene group such as diphenylsilylene; alkyloligosilylene group such as tetramethyldisilylene; germylene group; silicon of silylene group having divalent hydrocarbon group having 1 to 20 carbon atoms described above to germanium Examples thereof include a substituted alkylgermylene group; (alkyl) (aryl) germylene group; and arylgermylene group. Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms,
Alternatively, a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group, (alkyl) (aryl) silylene group or arylsilylene group is particularly preferable.

Examples of the halogen atom which constitutes the halogen-containing hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Specifically, (fluoromethyl) methylmethylene, (difluoromethyl) methylmethylene,
(Trifluoromethyl) methylmethylene, (4-fluorophenyl) methylmethylene, ditrifluoromethylmethylene, 1,2-ditrifluoromethylethylene, (fluoromethyl) methylsilylene, (chloromethyl) methylsilylene, di (chloromethyl) Silylene, di (trifluoromethyl) silylene, (1,1,1-trifluoropropyl) methylsilylene, (2-fluorophenyl)
Methylsilylene, (3-fluorophenyl) methylsilylene, (4-fluorophenyl) methylsilylene, (2
-Chlorophenyl) methylsilylene, (3-chlorophenyl) methylsilylene, (4-chlorophenyl) methylsilylene, (2-trifluoromethylphenyl) methylsilylene, (3-trifluoromethylphenyl) methylsilylene, (3-trifluoromethyl) (Phenyl) methylsilylene, (4-trifluoromethylphenyl) methylsilylene, (3,5-difluorophenyl) methylsilylene, (2,4,6-trifluorophenyl) methylsilylene, (4-fluorophenyl) ethylsilylene,
(4-chlorophenyl) ethylsilylene, (4-fluorophenyl) (chloromethyl) silylene, di (4-fluorophenyl) silylene, di (4-chlorophenyl) silylene, and a germylene group obtained by replacing silicon in the silylene group with germanium. Etc. can be mentioned.

Examples of the cross-linking group having an oxygen-containing hydrocarbon group include phenoxymethylsilylene, methoxyphenylmethylsilylene, ethoxyethylmethylsilylene, dimethoxyphenylsilylene and diethoxyethylsilylene groups,
Examples include various substituted germylene groups. Examples of the nitrogen-containing hydrocarbon group-containing crosslinking group include diethylaminoethylmethylsilylene, dimethylaminophenylmethylsilylene, dipyridylsilylene, and the like. Examples of the phosphorus-containing hydrocarbon group-containing cross-linking group include diphenylphosphinoethylmethylsilylene and bis (dimethylphosphinomethyl) silylene groups.

X ⁸ and Y ⁵ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms.
20 halogen-containing hydrocarbon groups, C 1-20 oxygen-containing hydrocarbon groups, amino groups, C 1-20 nitrogen-containing hydrocarbon groups, specifically hydrogen atoms; fluorine atoms, chlorine atoms, Halogen atom such as bromine atom and iodine atom; R above
⁴⁰ , a hydrocarbon group having 1 to 20 carbon atoms similar to R ⁴¹ or a halogen-containing hydrocarbon group; an alkoxy group such as methoxy, ethoxy, propoxy, cyclopropoxy and butoxy, and an allyloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy. Group, an arylalkoxy group such as phenylmethoxy, naphthylmethoxy, etc., having 1 to 2 carbon atoms
Oxygen-containing hydrocarbon group of 0; amino group; alkylamino group such as methylamino, dimethylamino, ethylamino, diethylamino, arylamino group such as phenylamino, diphenylamino, (alkyl) such as (methyl) (phenyl) amino 1-20 carbon atoms such as (aryl) amino groups
The nitrogen-containing hydrocarbon group of can be mentioned. Among these, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms are preferable, and further, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and carbon. The nitrogen-containing hydrocarbon group of the number 1 to 20 is preferable,
In particular, chlorine atom, methyl group, i-butyl group, phenyl group,
Dimethylamino group and diethylamino group are preferred.

The catalyst used for the prepolymerization in the present invention is
The transition metal compound of the component (A) is preferably the component (A-1) (BASF-type complex or Hoechst-type complex), the component (A-2) (single cross-linking complex), and the component (A-3) ( At least one selected from the group consisting of double-bridged complex) and the component (A-4) (azurenyl complex) is used. Compounds are preferred.

In the catalyst used for prepolymerization in the present invention, as the component (B), (B-1) an aluminum oxy compound, (B-2) an ionic compound capable of reacting with the above transition metal compound and converting into a cation, and (B-3) At least one selected from clay, clay minerals, and ion-exchange layered compounds is used. As the aluminum oxy compound of the component (B-1), a compound represented by the general formula (V)

[0053]

[Chemical 11]

(Wherein R ²⁶ is an alkyl group, an alkenyl group or an 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. Incidentally, each R ²⁶ may be the same or different. ) A chain aluminoxane represented by

[0055]

[Chemical 12]

(In the formula, R ²⁶ and w are the same as those in the above-mentioned general formula (V).) A cyclic aluminoxane represented by the formula can be given. Examples of the method for producing the aluminoxane include a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor 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 then brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization, and water is added later, water of crystallization contained in a metal salt, etc. There are a method of reacting water adsorbed on an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water. The aluminoxane may be insoluble in toluene.

These aluminum oxy compounds are one type
They may be used, or two or more kinds may be used in combination.
On the other hand, as the component (B-2), the transition metal compound and
Any ionic compound that can react and convert to a cation
However, any of these can be used, but polymerization is particularly efficient.
From the viewpoint that an active site can be formed, the following general formula (VII),
(VIII)   ([L¹-R²⁷]^{2h +})_a([Z]^-)_b    ... (VII)   ([L²]^{h +})_a([Z]^-)_b              ... (VIII) (However, L²Is M^Five, R²⁸R²⁹M⁶, R³⁰ ₃C or R³¹M⁶
Is. ) [(VI), (VII) in the formula, L¹Is a Lewis base, [Z]^-Is
Non-coordinating anion [Z¹] ^-Or [Z²]^-,here
[Z¹]^-Is an anion in which multiple groups are bound to an element, ie
[M^FourG¹G²... G^f] (Where M^FourIs Periodic Table No. 5
~ Group 15 element, preferably Group 13 ~ 15 element of the Periodic Table
Indicates. G¹~ G^fAre hydrogen atom, halogen atom,
C1-C20 alkyl group, C2-C40 dial
Kiramino group, alkoxy group having 1 to 20 carbon atoms, carbon number
6-20 aryl group, C6-C20 aryl group
Si group, C7-C40 alkylaryl group, C7
~ 40 arylalkyl group, C1-20 halogen
Substituted hydrocarbon group, an acyloxy group having 1 to 20 carbon atoms,
Organic metalloid group or hetero atom containing 2 to 20 carbon atoms
Indicates a hydrocarbon group. G¹~ G^fTwo or more of them form a ring
May be made. f is [(central metal M^FourValence) +
1] is an integer. ), [Z²]^-Is the reciprocal of the acid dissociation constant
Logarithm of (pK_a) Is -10 or less Bronsted acid alone
Or a conjugated salt of a combination of Bronsted acid and Lewis acid
Group, or a conjugated base commonly defined as a superacid
You Also, a Lewis base may be coordinated. Also, R²⁷Is
Hydrogen atom, alkyl group having 1 to 20 carbon atoms, 6 to 2 carbon atoms
0 aryl group, alkylaryl group or arylar
R represents a kill group²⁸And R²⁹Are each cyclopentadi
Enyl group, substituted cyclopentadienyl group, indenyl group
Or a fluorenyl group, R³⁰Is alkyl having 1 to 20 carbons
Group, aryl group, alkylaryl group or arylalkyl
Indicates a kill group. R³¹Is tetraphenylporphyrin, lid
Macrocyclic ligands such as cyanonin are shown. h is [L¹−
R²⁷], [L²], An integer of 1 to 3 and a is 1
The above integer, b = (h × a). M^FiveIs the periodic table
Group 1 to 3 elements, 11 to 13 and 17 elements are included,
M⁶Indicates an element belonging to groups 7 to 12 of the periodic table. ]]
What is suitable can be used.

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, triethylphosphine , Phosphines such as triphenylphosphine and diphenylphosphine, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, nitriles such as acetonitrile and benzonitrile.

Specific examples of R ²⁷ include hydrogen, methyl group, ethyl group, benzyl group and trityl group, and specific examples of R ²⁸ and R ²⁹ include cyclopentadienyl group and methylcyclopenta group. Examples thereof include a dienyl group, an ethylcyclopentadienyl group and a pentamethylcyclopentadienyl group. Specific examples of R ³⁰ include phenyl group, p-tolyl group, p-methoxyphenyl group and the like, and specific examples of R ³¹ include tetraphenylporphine, phthalocyanine, allyl, methallyl and the like. .. Further, as a specific example of M ⁵ , Li,
Na, K, Ag, Cu, Br, I, I _{3 and the} like can be mentioned, and specific examples of M ⁶ include Mn, Fe, Co and N.
i, Zn, etc. can be mentioned.

[Z ¹ ] ^- , that is, [M ⁴ G ¹ G ² ...
G ^f ], specific examples of M ⁴ include B, Al, Si,
P, As, Sb, etc., preferably B and Al are mentioned. Specific examples of G ¹ and G ^{2 to} G ^f include a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group and a phenoxy group as an alkoxy group or an aryloxy group. As a hydrocarbon group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
n-octyl group, n-eicosyl group, phenyl group, p-
Tolyl group, benzyl group, 4-tert-butylphenyl group, 3,5-dimethylphenyl group, etc., fluorine, chlorine, bromine, iodine as a halogen atom, p-fluorophenyl group as a hetero atom-containing hydrocarbon group, 3, 5, -Difluorophenyl group, pentachlorophenyl group, 1,5-trifluorophenyl group, pentafluorophenyl group, 3,5-
Examples of organic metalloid groups such as bis (trifluoromethyl) phenyl group and bis (trimethylsilyl) methyl group include pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, diphenylboron and the like.

The non-coordinating anion, ie, pKa, is -1.
0 following Bronsted acid alone or Bronsted the slashed.nsted acid and Lewis acid combined conjugate base [Z ^{2] -} trifluoromethanesulfonic acid anion (CF ₃ S Specific examples of
O ₃ ) ^- , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl)
Amide, perchlorate anion (ClO ₄ ) ^- , trifluoroacetate anion (CF ₃ CO ₂ ) ^- , hexafluoroantimony anion (SbF ₆ ) ^- , fluorosulfonate anion (FSO ₃ ) ^- , chlorosulfonate anion (ClSO)
₃₎ ^-, fluorosulfonic acid anion / antimony pentafluoride (FSO ₃ / SbF ₅₎ ^-, fluorosulfonic acid anion / 5- fluoride arsenic (FSO ₃ / AsF ₅₎ ^-, trifluoromethanesulfonic acid / 5-fluoride Antimony oxide (CF
₃ SO ₃ / SbF ₅₎ ^-, and the like.

Specific examples of such a component (B-2) compound include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate and tetraphenylboric acid. 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) Acid triethylammonium, tetrakis (pentafluorophenyl) borate tri-n-butylammonium, tetrakis (pentafluorophenyl) borate triphenylammonium, tetrakis (pentafluorophenyl) borate tetra-n-butylammonium, tetrakis (pentafluorophenyl) borate Tetraethylammonium, tetrakis (pentafluorophenyl) benzyl benzyl (tri-n-butyl) 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, tetrakis (pentafluorophenyl) methyl borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) benzyl borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) methyl borate (4-cyanopyridinium), tetrakis ( Pentafluorophenyl) borate triphenylphosphonium, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] dimethyl borate Nilinium, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1′-dimethylferro) (Cenium)
, Tetrakis (pentafluorophenyl) decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl)
Trityl borate, tetrakis (pentafluorophenyl)
Lithium borate, tetrakis (pentafluorophenyl)
Sodium borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, silver trifluoromethanesulfonate, etc. be able to.

As the component (B-2), one type of ionic compound capable of reacting with the transition metal compound of the component (A) and converting into a cation may be used, or two or more types may be used in combination. Good. As the component (B-3), clay, clay mineral, or an ion-exchange layered compound is used. Clay is an aggregate of fine hydrous silicate minerals, and it is a substance that produces plasticity when kneaded with an appropriate amount of water, exhibits rigidity when dried, and sinters when baked at high temperature. Further, the clay mineral means a hydrous silicate which is a main component of clay.
The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with weak bonding forces, and the ions contained therein are exchangeable. Most clay minerals are ion-exchangeable layered compounds. These are not limited to naturally occurring ones, but may be artificially synthesized ones. Examples of the ion-exchangeable layered compound include an ion-consolidating compound having a layered crystal structure such as a hexagonal closest 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, gyrome clay, allophane, hissingelite, pyrophyllite, talc, pummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite. , Nacrite, dickite, halloysite and the like. As the component (B-3), the volume of pores having a radius of 20 Å or more measured by mercury porosimetry is 0.1 ml / g or more, and particularly 0.3 to 5
It is preferably milliliter / g or more. It is also preferable to perform chemical treatment from the viewpoint of removing impurities in 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. Specific examples include acid treatment, alkali treatment, salt treatment, organic substance treatment and the like. The acid treatment not only removes impurities on the surface but also increases the surface area by eluting cations such as aluminum, iron and magnesium in the crystal structure. Alkali treatment destroys the crystal structure of clay, resulting in a change in clay structure.Salt treatment or organic treatment forms ionic complex, molecular complex, organic complex, etc. Can be changed. It is also possible to obtain an interlayer material in which the interlayer is expanded by utilizing the ion-exchange property and substituting the exchangeable ion of the layer with another bulky ion. It is also possible to secure a polymerization reaction field in which the main catalyst exists in the layers.

The above-mentioned component (B-3) may be used as it is, or may be used after newly adsorbing water.
Alternatively, the one that has been subjected to the aging and dehydration treatment may be used. (B-
As the component 3), preferred is clay or clay mineral, and most preferred is montmorillonite. (B
Component (3) is preferably treated with a silane compound and / or an organoaluminum compound. This treatment may improve activity. Examples of the silane-based compound include trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride, tert-butyldimethylsilyl chloride, and ter.
Trialkylsilyl chlorides such as t-butyldiphenylsilyl chloride, phenethyldimethylsilyl chloride, dimethylsilyldichloride, diethylsilyldichloride, diisopropylsilyldichloride, bisdiphenethylsilyldichloride, methylphenethylsilyldichloride, diphenylsilyldichloride, dimesitylsilyl Dialkyl silyl dichlorides such as dichloride and ditolyl silyl dichloride, methyl silyl trichloride, ethyl silyl trichloride, isopropyl silyl trichloride, phenyl silyl trichloride, mesityl silyl trichloride, tolyl silyl trichloride, phenethyl silyl trichloride, etc. Alkylsilyl trichlorides, and halides in which the above-mentioned chloride moieties are replaced with other halogen elements, bis ( Limethylsilyl) amine, bis (triethylsilyl) amine, bis (triisopropylsilyl) amine, bis (dimethylethylsilyl) amine, bis (diethylmethylsilyl) amine, bis (dimethylphenylsilyl) amine, bis (dimethyltolylsilyl) amine , Bis (dimethylmesitylsilyl) amine, N, N-dimethylaminotrimethylsilane, (diethylamino) trimethylsilane, silylamines such as N- (trimethylsilyl) imidazole, and polysilanols commonly known as peralkylpolysiloxypolyols. , Silanols such as tris (trimethylsiloxy) silanol, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N- (trimethylsilyl) acetate Bromide, 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, trimethylsilane, triethylsilane, triisopropylsilane, tri-tert-butylsilane, triphenylsilane, tritolylsilane, 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, silylamines are preferable, and trialkylsilane chlorides are more preferable. The silane-based compound may be used alone from these, but in some cases, two or more kinds may be used in arbitrary combination.

Further, the organoaluminum compound used for the treatment of the component (B-3) is not particularly limited. The linear aluminoxane represented by the general formula (V) or the cyclic aluminoxane represented by the general formula (VI) or an aggregate of the cyclic aluminoxane can be preferably used. In terms of shell, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum,
Trialkyl aluminum such as tri-tert-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum methoxide, diethylaluminum methoxide, dimethylaluminium hydroxide, halogen, alkoxy group or hydroxyl group-containing alkyl such as diethylaluminum hydroxide. Examples thereof include hydrogen atom-containing alkylaluminums such as aluminum, dimethylaluminum hydride and diisobutylaluminum hydride, aluminoxanes such as methylaluminoxane, ethylaluminoxane and isobutylaluminoxane. Of these, trimethylaluminum or triisobutylaluminum is particularly preferable.
The organoaluminum compound used for the treatment of the component (B-3) may be used alone or in combination of two or more.

The ratio of the silane compound and the organoaluminum compound used for the treatment of the component (B-3) is not particularly limited, but when the component (B-13) is clay or clay mineral, ) The silicon atom in the silane compound is usually 0.1 to 100,000 per 1 mol of the hydroxyl group in the component).
The amount of aluminum atom in the organoaluminum compound is usually 0.1 to 0.1 mol, preferably 0.5 to 10000 mol.
It is used in a ratio of 100,000 mol, preferably 0.5 to 10,000 mol. Further, when the component (B-3) is other than clay or clay mineral, for 1 g of the component (B-3),
The silicon atom in the silane-based compound is preferably 0.001 to 100 g, and when an organoaluminum compound is used, the aluminum atom in the organoaluminum compound is preferably 0.001 to 100 g. If the ratio is out of 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 in a hydrocarbon such as pentane, hexane, toluene, xylene. Furthermore, this treatment can be carried out not only at the polymerization temperature but also preferably 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, as the component (B), the component (B-1), the component (B-2),
The component (B-3) may be used alone or in combination. The use ratio of the (A) catalyst component and the (B) catalyst component in this prepolymerization catalyst is
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 it deviates from the range, the catalyst cost per unit weight polymer becomes high, which is not practical. When the compound (B-2) is used, the molar ratio is preferably 10: 1 to 1:10.
The range of 0, more preferably 2: 1 to 1:10 is desirable. When it deviates from this range, the catalyst cost per unit weight polymer becomes high, which is not practical. Also, (B-
3) When clay, clay mineral, or ion-exchange layered compound is used as the compound, relative to 1 g of the catalyst component (B),
The catalyst component (A) is preferably in the range of 0.01 to 100 μmol, more preferably 0.1 to 100 μmol. If it deviates from this range, the catalyst cost per unit weight polymer becomes high, which is not practical.

Further, the prepolymerization medium in the present invention may contain the above-mentioned components (A) and (B) as the main components, or the components (A), (B) and It may contain (C) an organoaluminum compound and / or 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 as the component (C) is represented by the general formula (IX) R ³² _v AlQ _3-v (IX) (wherein 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, or 6 to 20 carbon atoms.
Is an aryl group or a halogen atom, and v is an integer of 1 to 3). Specific examples of the compound represented by the general formula (VIII) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride. ,
Diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride and the like can be mentioned. These organoaluminum compounds may be used alone or in combination of two or more. or,
The molar ratio of the (A) catalyst component to the organoaluminum compound used as desired is preferably 1: 1 to 1: 1.
1: 20000, more preferably 1: 5 to 1: 200
The range of 0, more preferably 1:10 to 1: 1000 is desirable. By using an organoaluminum compound,
It is possible to improve the polymerization activity per transition metal, but when it is too much, especially when it deviates from the above range, the organoaluminum compound is wasted, and a large amount remains in the polymer, and when it is small, it is sufficient. In some cases, the catalytic activity cannot be obtained, which is not preferable.

In the present invention, at least one of the catalyst components can be used by supporting it on a suitable carrier.
The type of carrier of the component (C) is not particularly limited, and any of an inorganic oxide carrier, an inorganic carrier other than that, and an organic carrier can be used. In particular, from the viewpoint of morphology control, the inorganic oxide carrier or the carrier Other inorganic carriers are preferred. As the inorganic oxide carrier, specifically, SiO 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 such as silica alumina, zeolite, ferrite,
Examples thereof include glass fiber. Of these, 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
l₂, Mg (OC₂H_Five)₂Replace with magnesium compounds, etc.
General formula represented MgR³³ _xX⁷ _yRepresented by magnesium
Examples thereof include compounds and their complex salts. Where R
³³Is an alkyl group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms.
Rucoxy group or aryl group having 6 to 20 carbon atoms, X⁷Ha
A logen 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 ³³And each X⁷Can be the same or different
You can have it. Further, as the organic carrier, polystyrene,
Styrene-divinylbenzene copolymer, polyethylene,
Polypropylene, substituted polystyrene, polyarylate, etc.
Examples of polymers include starch, carbon, etc.
It As the carrier used in the present invention, MgCl 2
₂, MgCl (OC₂H_Five), Mg (OC₂H_Five)₂, SiO
₂, Al₂O₃Etc. are preferred. The nature of the carrier is its type
And, depending on the production method, the average particle size is usually 1 to 300 μm.
m, preferably 10 to 200 μm, more preferably 20
˜100 μm. If the particle size is small, the fine powder in the polymer
When the particle size increases, the coarse particles in the polymer increase and the bulk
This will cause a decrease in density and clogging of the hopper. Also, the carrier
Has a specific surface area of usually 1 to 1000 m²/ G, preferably
50-500m²/ G, pore volume is usually 0.1-5 cm³
/ G, preferably 0.3-3 cm³/ G.

If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. still,
The specific surface area and the pore volume can be obtained from the volume of nitrogen gas adsorbed according to the BET method (JA, for example).
m. Chem. Soc, Volume 60, Page 309 (1
983))). Furthermore, when the carrier is an inorganic carrier,
Usually 150 to 1000 ° C, preferably 200 to 800 ° C
It is desirable to use it after firing. When at least one catalyst component is supported on the carrier, at least one of (A) catalyst component and (B) catalyst component, preferably both (A) catalyst component and (B) catalyst component, is supported. It is desirable from the standpoint of applicability to processes such as morphology control and 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, but for example, at least one of the component (A) and the component (B) is mixed with the carrier. Method, method of treating carrier with organoaluminum compound or halogen-containing silicon compound and then mixing with at least one of component (A) and component (B) in inert solvent, carrier and component (A) or component (B) 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 with 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 of allowing a carrier to coexist can be used. In addition, the organoaluminum compound of the component (C) may be added in the above reactions and.

The catalyst thus obtained may be used for prepolymerization after the solvent has been distilled off and taken out as a solid, or may be used for prepolymerization as it is. In the present invention, the component (A) is usually 10 per 1 g of the carrier.
It is used in an amount of ⁻⁶ to 10 ⁻² mol, preferably 3 × 10 ⁻⁶ to 10 ⁻³ mol. Further, the component (B) with respect to the component (A) [component (B-1), component (B-2), component (B-3)]
The use ratio of is as described above.

Component (B) [Component (B-1), (B-
When the ratio of the component (2), the component (B-3)] to the carrier or the ratio of the component (A) to the carrier deviates from the above range, the activity may decrease. 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.
The specific surface area is usually 20 to 1000 m ² / g, preferably 50 to 500 m ² / g. Average particle size is 2μ
If it is less than m, fine powder in the polymer may increase,
If it exceeds 600 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 way, a polyolefin having a high bulk density and an excellent particle size distribution which is industrially advantageous can be obtained.

In the prepolymerization catalyst of the present invention, at least one selected from α-olefins having 2 to 20 carbon atoms and cyclic olefins and a non-conjugated diene compound are polymerized (prepolymerization) in the presence of the catalyst. It is manufactured by
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 can be mentioned, and as the cyclic olefin, cyclopentene, cycloheptene, norbornene, 5-ethyl-2-norbornene, tetracyclodone Examples include decene.

Examples of the non-conjugated diene compound include compounds formed from at least two residues of the same or different types selected from α-olefin residues, styrene residues and cyclic olefin residues, and cyclic diene compounds. A polyfunctional monomer selected from the above is preferably used. As the non-conjugated diene compound, a compound having 7 or more carbon atoms is preferable. Non-conjugated dienes having less than 7 carbon atoms, such as 1,5-hexadiene, easily cause a cyclization reaction, and the efficiency of introducing a carbon-carbon double bond into the polymer chain is not high. On the other hand, the carbon number is 2
Non-conjugated dienes of more than 0 have low flowability per se and are troublesome to handle. Further, it is difficult to remove unreacted substances from the produced polymer, which causes odor, which is not preferable. For these reasons, a non-conjugated diene having 7 or more carbon atoms is preferable, and a non-conjugated diene having 7 to 20 carbon atoms is particularly preferable. Examples of such polyfunctional monomers include linear or branched acyclic diene compounds, monocyclic alicyclic diene compounds, polycyclic alicyclic diene compounds, cycloalkenyl-substituted alkenes, and aromatic rings. Examples thereof include a diene compound having a diene compound having an α-olefin residue and a styrene residue in one molecule. Among these,
From the viewpoint of excellent reactivity, an acyclic diene compound, particularly a linear acyclic diene compound is preferable.

Examples of the linear or branched acyclic diene compound include 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene,
1,9-decadiene, 1,11-dodecadiene, 2-methyl-1,4-pentadiene, 2-methyl-1,5-hexadiene, 3-ethyl-1,7-octadiene and the like, monocyclic alicyclic ring Examples of the diene compound include 1,
3-cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, 1,5-cyclododecadiene, 1,2-divinylcyclohexane, 1,3-
Examples include divinylcyclohexane and the like.

As the polycyclic alicyclic diene compound, for example, dicyclopentadiene, norbornadiene, tetrahydroindene, methyltetrahydroindene, 5-methyl-2,5-norbornadiene, further alkenyl,
Norbornenes of alkylidene, cycloalkenyl and cycloalkylidene, for example 5-methylidene-2
-Norbornene, 5-ethylidene-2-norbornene,
5-isopropylidene-2-norbornene, 5-vinylnorbornene, 5- (3-butenyl) norbornene, 5
-(3-Cyclopentenyl) -2-norbornene, 5-
Cyclohexylidene-2-norbornene and formula

[0081]

[Chemical 13]

Examples thereof include compounds represented by: Examples of the cycloalkenyl-substituted alkenes include allylcyclohexene, vinylcyclooctene, allylcyclodecene, vinylcyclododecene, and the like. Examples of the diene compound having an aromatic ring include p-divinylbenzene, m-divinylbenzene, and the like. o-divinylbenzene, di- (p-vinylphenyl) methane, 1,3-bis (p-
Examples thereof include vinylphenyl) propane and 1,5-bis (p-vinylphenyl) pentane.

Examples of the diene compound having an α-olefin residue and a styrene residue in one molecule include p- (2
-Propenyl) styrene, m- (2-propenyl) styrene, p- (3-butenyl) styrene, m- (3-butenyl) styrene, o- (3-butenyl) styrene, p-
(4-Pentenyl) styrene, m- (4-pentenyl)
Styrene, o- (4-pentenyl) styrene, p- (7
-Octenyl) styrene, p- (1-methyl-3-butenyl) styrene, p- (2-methyl-3-butenyl) styrene, m- (2-methyl-3-butenyl) styrene,
o- (2-methyl-3-butenyl) styrene, p- (3
-Methyl-3-butenyl) styrene, p- (2-ethyl-4-pentenyl) styrene, p- (3-butenyl)-
α-methylstyrene, m- (3-butenyl) -α-methylstyrene, o- (3-butenyl) -α-methylstyrene, 4-vinyl-4 ′-(3-butenyl) biphenyl,
4-vinyl-3 '-(3-butenyl) biphenyl, 4-
Vinyl-4 '-(4-pentenyl) biphenyl, 4-vinyl-2'-(4-pentenyl) biphenyl, 4-vinyl-4 '-(2-methyl-3-butenyl) biphenyl and the like can be mentioned. These diolefins may be used alone or in combination of two or more.

The prepolymerization may be carried out batchwise or continuously, and may be carried out by any method selected from slurry polymerization method, gas phase polymerization method, bulk polymerization method, solution polymerization method and the like. Can be adopted. The polymerization solvent used when carrying out the slurry polymerization or solution polymerization, for example, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, cyclohexane, methylcyclohexane, etc. Alicyclic hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, ethylene chloride, chlorobenzene,
Examples thereof include halogenated hydrocarbons such as dichloromethane and chloroform. These solvents may be used alone,
You may use it in mixture of 2 or more types. Regarding the prepolymerization conditions, the polymerization temperature is usually in the range of -50 to 200 ° C, preferably -20 to 150 ° C, more preferably 0 to 120 ° C. Polymerization pressure is usually 0.098 to 19.71MP
a, preferably 0.11 to 14.81 MPa, more preferably 0.12 to 9.91 MPa. The polymerization time is usually 10 seconds to 2 hours, preferably 30 seconds to
It is in the range of 1 hour, more preferably 1 to 30 minutes. 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 10 ⁸ , more preferably 10
It is advantageous to choose between 0 and 10 ⁷ . If the prepolymerization amount is 0.01 g or less per 1 g of the transition metal compound, it is insufficient. This is because the particle shape of the polyolefin particles obtained by the main polymerization performed after the preliminary polymerization is deteriorated and the effect of improving the physical properties such as melt tension and compatibility cannot be sufficiently obtained. On the other hand, when the amount of the preliminary polymerization exceeds 50 kg, the activity in the main polymerization which follows the preliminary polymerization becomes insufficient, and the particle shape of the obtained polyolefin particles deteriorates. A suitable prepolymerization amount is in the range of 0.1 g to 20 kg per transition metal compound.

In the present invention, the polymerization catalyst can be produced by carrying out the operation of loading at least one of the component (A) and the component (B) on the carrier in the polymerization system. For example, the component (A) and the component (B), a carrier and, if necessary, the organoaluminum compound are added, and the olefin and the non-conjugated diene compound are added in an amount of 0.12 to 9.91 MPa, 0.
A method of preliminarily polymerizing at 120 ° C for about 1 to 30 minutes to generate catalyst particles can be used. When a catalyst supported on a carrier is used, the amount of preliminary polymerization is not sufficient if it is 0.01 g or less per 1 g of the total amount of the carrier, the component (A) and the component (B). This is because the particle shape of the polyolefin particles obtained by the main polymerization performed after the preliminary polymerization may be deteriorated or the physical properties such as melt tension and compatibility may not be sufficiently improved. On the other hand, the amount of preliminary polymerization is 200
If it exceeds 0 g, the activity in the main polymerization performed after the preliminary polymerization may be insufficient, and the particle shape of the obtained polyolefin particles may be deteriorated. In particular, a suitable amount of prepolymerization is the total amount of the carrier, the component (A) and the component (B) of 1
It is in the range of 0.1 to 500 g per g.

The intrinsic viscosity [η] of the prepolymerized catalyst produced by the prepolymerization is controlled by adjusting the ratio of each component of the polymerization catalyst, the amount of the polymerization catalyst used, the prepolymerization temperature, the prepolymerization pressure, etc.
It can be performed by appropriately selecting within the above range. A method of using hydrogen as a chain transfer agent to reduce the intrinsic viscosity [η] is generally used, but since a reaction point consisting of a terminal vinyl group and a carbon-carbon double bond derived from a non-conjugated diene compound is lost, The use of hydrogen should be kept low. The intrinsic viscosity [η] is measured at 135 ° C in a tetralin solvent. [Η] of the prepolymerization catalyst is 0.05 to 20 deciliter / g, preferably 0.08 to 15 deciliter / g, and more preferably 0.1 to 10 deciliter / g. When it is less than 0.05 deciliter / g, the balance of melt tension, compatibilizing ability and mechanical strength of the polymer obtained by the main polymerization is insufficient, and when it exceeds 20 deciliter, melt processability is deteriorated.

The sum [C] of the content of the terminal vinyl group per 1000 carbons and the content of the carbon-carbon double bond derived from the non-conjugated diene compound depends on the production efficiency of the terminal vinyl of the catalyst used and the amount of the non-conjugated diene compound added. In addition to the control, it can be controlled by appropriately selecting the prepolymerization conditions such as the polymerization temperature, the polymerization pressure and the polymerization time within the above range. Especially when the polymerization is carried out by a palindrome, if the prepolymerization time is lengthened, [C]
It should be stopped in a short time because it decreases.

Here, the sum [C] of the contents of the terminal vinyl group and the carbon-carbon double bond derived from the non-conjugated diene compound per 1000 carbons can be calculated as follows. (1) When the non-conjugated diene compound is a linear or branched acyclic diene compound: It is calculated based on the measurement result of the infrared absorption spectrum by the following method. That is, the above polymer was formed into a film having a thickness of about 100 μm by hot pressing, and the peak transmittance at 907 cm ⁻¹ was measured by an infrared spectrophotometer.
Reference method [See "Polymer Analysis Handbook" edited by The Japan Society for Analytical Chemistry, Asakura Shoten, 1985, p. 240]
It is calculated from the following formula based on [C] = 1.14 × log (I./I) × (1 / (D
XT)) In the formula, each symbol has the following contents. [C]; Number of carbon-carbon double bonds derived from terminal vinyl group and non-conjugated diene compound (pieces / 1000 carbons) I. Transmittance at baseline I; transmittance at 907 cm ^-1 D; polymer density (g / cm ³ ) T; film thickness (mm) (2) non-conjugated diene compound other than the above (1) In the case of using, the terminal vinyl group and the α-olefinic carbon-carbon double bond derived from the non-conjugated diene compound can be calculated as in the above (1). The other carbon-carbon double bonds are measured by nuclear magnetic resonance spectroscopy by a conventional method per 1000 carbon atoms in the main chain, that is, the monomer repeating unit 5
It is calculated as the number per 00. The sum of the measured values calculated in this way is defined as [C]. [C] of the prepolymerization catalyst is 0.001 to 25/1000 carbons, preferably 0.0015 to 20/1000 carbons, and more preferably 0.002 to 10/1000 carbons. 0.00
If it is 1 or less, the reaction point for the main polymerization (hereinafter referred to as the main polymerization) subsequent to the preliminary polymerization is insufficient, and the melt tension, compatibilizing ability, and mechanical strength of the polymer obtained by the main polymerization are balanced. If it exceeds 25, a crosslinking reaction is likely to occur, and the melt processability of the polymer obtained by the main polymerization is deteriorated.
In the above polymer, the intrinsic viscosity [η] (deciliter / g) measured at 135 ° C in a tetralin solvent was 100
The product [η] × [C] of the terminal vinyl group per 0 carbon and the sum [C] of the number (content) of carbon-carbon double bonds derived from the non-conjugated diene compound is 0.05 to 1.1, Preferably 0.0
6 to 1.1, more preferably 0.07 to 1.0.

The prepolymerization catalyst produced by the above-mentioned prepolymerization is in 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 this prepolymerization catalyst or in the presence of an organoaluminum compound if necessary, the number of carbon atoms is 2 to
A polyolefin can be obtained by polymerizing or copolymerizing at least one selected from 20 α-olefins, cyclic olefins and styrene-based monomers. Here, as the organoaluminum compound, the same ones as described above can be used. When the prepolymerization catalyst does not contain the organoaluminum compound, the molar ratio of the (A) catalyst component to the organoaluminum compound optionally used is preferably 1: 1 to 1: 20000 by molar ratio. It is preferably 1: 5 to 1: 2000, more preferably 1:10 to 1: 1.
A range of 1000 is desirable. Further, when the prepolymerization catalyst is a substance containing an organoaluminum compound, depending on the amount used, no organoaluminum compound is used, or a transition metal compound and an organoaluminum compound in the prepolymerization catalyst are used. The molar ratio is 1: 0.5 to 1:10
It is possible to improve the polymerization activity per transition metal by using an organoaluminum compound in the range of 000, and more preferably in the range of 1: 2 to 1: 8000. The aluminum compound is wasted and remains in a large amount in the polymer, and when it is small, sufficient catalytic activity cannot be obtained, which is not preferable in some cases.

Examples of the α-olefin having 2 to 20 carbon atoms and the cyclic olefin include the same ones as described above. or,
Styrene-based monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,
4-dimethylstyrene, 2,5-dimethylstyrene, 1
-Dimethylstyrene, 3,5-dimethylstyrene, 2,
Alkyl styrenes such as 4,5-trimethylstyrene, 2,4,6-trimethylstyrene, p-tert-butylstyrene, p-chlorostyrene, m-chlorostyrene,
o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o
Examples thereof include halogenated styrene such as methyl-p-fluorostyrene.

The type of polymerization and the polymerization conditions can be the same as those used in the preliminary polymerization. Also, the block copolymerization method can be used to produce an olefin block copolymer under reaction conditions different from those in the prepolymerization. in this case,
The different reaction conditions include, for example, using a prepolymerization catalyst,
First, after producing a homopolymer of polypropylene, in the next reaction step, a monomer selected from ethylene, an α-olefin having 4 to 20 carbon atoms, a cyclic olefin, and styrene is copolymerized with propylene, and In the same manner as above, after copolymerizing a monomer selected from ethylene, an α-olefin having 4 to 20 carbon atoms, a cyclic olefin and styrene with propylene, the composition of the charged monomer is changed in the next step. , Producing a block copolymer having a changed copolymer composition, monomer species, polymerization temperature, pressure,
It refers to carrying out the polymerization reaction in two or more steps by changing the composition of the charged monomers and the time.

The melting point of the polyolefin obtained by the method of the present invention is usually 50 ° C. or higher, preferably 70 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 90 to 160 ° C. The melting point is a value measured by the following method. That is, using a differential scanning calorimeter [DSC7 type manufactured by Perkin Elmer Co., Ltd.], 4
Increase the temperature from 0 ℃ to 220 ℃ at a rate of 320 ℃ / min.
After holding at 20 ° C for 3 minutes, the temperature is lowered to 0 ° C at 10 ° C / minute. After holding at 0 ° C. for 3 minutes, the temperature is raised at 10 ° C./minute, and the temperature of the melting peak appearing at that time is taken as the melting point. This polyolefin has a melt index MI of 0.0
Those in the range of 05 to 1000 g / 10 minutes are preferable. 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 deteriorated, which is not preferable. From the viewpoint of the balance of melt fluidity and mechanical properties, etc., a more preferable MI is in the range of 0.01 to 800 g / 10 minutes, particularly 0.0
A range of 5 to 600 g / 10 minutes is preferable. This MI
Complies with ASTM D1238-T65, temperature 23
It is a value measured under the conditions of 0 ° C. and a load of 2.16 kg.
Further, when the intrinsic viscosity [η] of the above polyolefin is less than 0.1 deciliter / g, the melt processability is poor and the mechanical strength is insufficient, and when it exceeds 20 deciliter / g, the melt viscosity is high and the melt processing is difficult. Sex decreases. From the viewpoint of the balance between melt processability and mechanical strength, etc., [η] is preferably 0.4 to 10.0 deciliter / g, and particularly preferably 0.6 to 8.0 deciliter / g.

Melt tension MS (g) of the above polyolefin
Is 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 satisfy the relationship of the formula logMS ≧ 3.17 × log [η] −0.46 (1). . logMS shows "3.1
If it is smaller than the value of 7 × log [η] −0.46 ”, the melt processability may be poor and the object of the present invention may not be achieved. From the viewpoint of melt processability, logMS ≧ 3.17 × log [η] −0.35 is more preferable. The melt tension MS is a value measured using the 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 prepared as an antioxidant.
000 weight ppm was added.

The bulk density of the above polyolefin is 0.3 g.
/ Cc or more, preferably 0.35 g / c
c is preferred. The bulk density was determined according to JIS K6721.

[0095]

EXAMPLES 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 silica supported methylaluminoxane n- heptane suspension prepared silica (Si0 ₂₎ [Fuji Silysia Chemical Ltd., trade name:
27.3 g of P-10] was dried under reduced pressure at 200 ° C. for 2 hours to obtain 26.0 g of dried silica. This dried silica was put into 400 ml of toluene cooled to -78 ° C in a dry ice / methanol bath, and 150 ml of 1.5 mol / l methylaluminoxane toluene solution was added dropwise thereto over 1 hour while stirring. It was dripped with a funnel. After leaving this state for 4 hours, -7
The temperature was raised from 8 ° C. to 20 ° C. over 6 hours, and further left in this state for 4 hours. Then, the temperature was raised from 20 ° C. to 80 ° C. in 1 hour and left at 80 ° C. for 4 hours to complete the reaction between silica and aluminoxane. The suspension was filtered at 60 ° C. and the solid obtained was washed at 60 ° C.
2 times with 0 ml of toluene, and further at 60 ° C., 4
It was washed twice with 00 ml of n-hexane. The solid substance after washing was dried under reduced pressure at 60 ° C. for 4 hours to give silica-supported methylaluminoxane 32.6.
g was obtained. The supported amount of methylaluminoxane was 20.2% by weight. To the total amount of silica-supported methylaluminoxane thus obtained, n-heptane was added to make the total volume 500 ml, to prepare a suspension having a methylaluminoxane concentration of 0.23 mol / l.

Preparation Example 2 Preparation of silica-supported metallocene catalyst 10.9 ml of the silica-supported methylaluminoxane suspension obtained in Preparation Example 1 (methylaluminoxane 2.
(5 mmol) was collected in a dry nitrogen-substituted container, 20 ml of n-heptane was added, and the mixture was stirred. To this suspension, a transition metal compound, rac- dimethylsilanediylbis - bis-1- (2-methyl-4-phenyl-indenyl) hafnium dichloride [rac-Me ₂ Si (2-
Me-4-PhInd) ₂ HfC1 ₂ ] in toluene solution 1
0 micromol was added and stirred at room temperature for 15 minutes. Then, stirring was stopped, the solid catalyst component was allowed to settle, and 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 prepolymerization catalyst A 1.4 liter stainless steel pressure autoclave equipped with a stirrer was heated to 80 ° C. and sufficiently dried under reduced pressure.
The atmosphere was returned to atmospheric pressure with dry nitrogen, and 400 ml of dry deoxygenated n-heptane, triisobutylaluminum as an n-heptane solution in an amount of 0.5 mmol, and 1,7-octadiene in an amount of 0.5 mmol were added to the autoclave under a dry nitrogen stream. It was charged and stirred at 500 rpm for 10 minutes. The silica-supported metallocene catalyst prepared in Preparation Example 2 was added thereto (10 μmol of hafnium compound), and 5
Preliminary polymerization was carried out for 30 minutes while controlling the temperature to 0 ° C. and continuously supplying propylene so as to obtain 1.0 kg / cm ² G. After the prepolymerization was completed, the unreacted propylene was depressurized, and the unreacted propylene was removed by nitrogen. A part of the obtained polypropylene was sampled in a nitrogen atmosphere and the amount of prepolymerization (the amount of polypropylene obtained by prepolymerization)
Was calculated to be 6.8 kg per 1 g of the transition metal compound.
And 17.0 g per 1 g of silica-supported metallocene catalyst.
It was g. In addition, the intrinsic viscosity [η] of polypropylene obtained by prepolymerization is 1.53 deciliter (dl) / g.
Met. The number [C] of carbon-carbon double bonds derived from the terminal vinyl group and 1,7-octadiene per 1000 carbons of this polypropylene was 0.15, and [η] × [C] was 0.23. . The produced prepolymerized catalyst was extracted under a nitrogen atmosphere, the solid component was separated from the liquid portion by decantation, and the resulting mixture was added with 100 ml of n-heptane to obtain 2 parts.
After washing twice, it was stored as a slurry of n-heptane.

Example 2 Production of polypropylene prepolymerized catalyst A prepolymerized catalyst was produced in the same manner as in Example 1 except that 1.0 mmol of 1,7-octadiene was added. The results are shown in Table 1.

Example 3 Production of Polypropylene Prepolymerized Catalyst A prepolymerized catalyst was produced in the same manner as in Example 1 except that 1,9-decadiene was added instead of 1,7-octadiene. The results are shown in Table 1.

Comparative Example 1 Preparation of polypropylene prepolymerization catalyst Example 1 except that 1,7-octadiene was not used
A prepolymerized catalyst was produced in the same manner as in. The results are shown in Table 1.

Comparative Example 2 A prepolymerization catalyst was produced in the same manner as in Example 1 except that the prepolymerization time was 2 hours. The polypropylene obtained by this prepolymerization contained a gel insoluble in the 135 ° C. tetralin solvent. The results are shown in Table 1.

[0102]

[Table 1]

Example 4 Production of Polypropylene Using Prepolymerized Catalyst A 1.4 liter stainless steel pressure autoclave equipped with a stirrer was heated to 80 ° C., sufficiently dried under reduced pressure, and then returned to atmospheric pressure with dry nitrogen, 400 ml of dry deoxygenated n-heptane and 0.5 mmol of a solution of triisobutylaluminum in n-heptane were added to this autoclave under a stream of dry nitrogen, and the mixture was stirred at 500 rpm for 10 minutes. 100 ml (9 μmol in terms of hafnium atom) of the prepolymerized catalyst prepared in Example 1 was added to this, and the temperature was raised to 80 ° C. Propylene was continuously supplied thereto at 0.88 MPa to carry out polymerization for 120 minutes. After the reaction is completed, the unreacted propylene is depressurized,
The catalyst was deactivated with a large amount of methanol, filtered and dried to obtain 56 g of polypropylene. This polypropylene had an intrinsic viscosity [η] of 2.65 dl / g, a melting point of 144 ° C., a bulk density of 0.41 g / cc, and a melt tension of 10.5 g.

Comparative Example 3 Production of Polypropylene Using Prepolymerization Catalyst Polymerization was carried out in the same manner as in Example 4 except that the prepolymerization catalyst prepared in Comparative Example 1 was used. The results are shown in Table 2.

[0105]

[Table 2]

[0106]

EFFECTS OF THE INVENTION According to the present invention, a polyolefin having a high melt tension, excellent resin compatibility, and high bulk density can be produced efficiently at low cost.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J028 AA01A AB00A AC01A AC02A                       AC23A BA02B BB02B BC18B                       BC24B BC25B CB94B CB94C                       CB97B CB97C DA01 DA02                       DA03 DA04 DA06 DA09 EA01                       EB02 EB03 EB07 EB21 GA04                       GA09 GA19

Claims (5)

[Claims] 1. (A) The following (A-1), (A-2),
Transition of Group 4 of the Periodic Table consisting of (A-3) and (A-4)
At least one selected from the metal transfer compounds, (A-1) General formula (I) [Chemical 1] [In the formula, R¹~ R⁶Are hydrogen atom and halogen
Hydrogen atom, hydrocarbon group having 1 to 20 carbon atoms or 1 to 2 carbon atoms
0 represents a halogen-containing hydrocarbon group, R³And R^Four, R^FourWhen
R^FiveAnd R^FiveAnd R⁶At least one set of
To form a ring, and X¹And X²Each independently
Hydrogen atom, halogen atom or hydrocarbon having 1 to 20 carbon atoms
Group, Y¹Is a divalent bridging group linking two ligands
And a hydrocarbon group having 1 to 20 carbon atoms and 1 to 2 carbon atoms
0 halogen-containing hydrocarbon groups, silicon-containing groups, germanium
Group containing group, tin containing group, -O-, -CO-, -S-, -S
O₂-, -Se-, -NR¹⁸-,-PR¹⁸-, -P
(O) R¹⁸-, -BR¹⁸-Or-AlR¹⁸-Indicates R
¹⁸Is a hydrogen atom, a halogen atom, a hydrocarbon having 1 to 20 carbon atoms
Indicates an elementary group or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms
You M¹Indicates titanium, zirconium or hafnium
You ] The transition metal compound represented by, (A-2) General formula
(II) [Chemical 2] [In the formula, R⁷~ R¹³, R¹⁵, R¹⁶, X³And X^FourIs it
Each independently has a hydrogen atom, a halogen atom, and 1 to 20 carbon atoms.
Hydrocarbon group, halogen-containing hydrocarbon having 1 to 20 carbon atoms
Group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group
Or a phosphorus-containing group, R⁷And R⁸Are joined together to form a ring
May be done. R¹⁴, R¹⁷Are independently halogen
Atom, hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
Halogen-containing hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur
A yellow-containing group, a nitrogen-containing group or a phosphorus-containing group is shown. Y²Is two
A divalent bridging group that binds the ligand of
20 hydrocarbon groups, halogen containing carbon atoms having 1 to 20 carbon atoms
Hydrogen group, silicon-containing group, germanium-containing group, tin-containing group,
-O-, -CO-, -S-, -SO₂-, -Se-,-
NR¹⁸-,-PR¹⁸-, -P (O) R¹⁸-, -BR¹⁸−
Or-AlR¹⁸-Indicates R¹⁸Is hydrogen atom, halogen atom
Child, hydrocarbon group having 1 to 20 carbon atoms, ha group having 1 to 20 carbon atoms
A logen-containing hydrocarbon group is shown. M²Is titanium, zirconi
Indicates um or hafnium. ] A transition metal compound represented by
Thing, (A-3) general formula (III) [Chemical 3] [In the formula, M³Is titanium, zirconium or hafnium
Show, E¹And E²Are each substituted cyclopentadienyl
Group, indenyl group, substituted indenyl group, heterocyclope
Entadienyl group, substituted heterocyclopentadienyl group,
Of amide group, phosphide group, hydrocarbon group and silicon-containing group
A ligand selected from¹And A²Through
Form a bridge structure, and they may be the same or different
May be X^FiveRepresents a σ-bonding ligand, X^FiveBut
If there are multiple, multiple X^FiveCan be the same or different
Ku, other X^Five, E¹, E²Or Y³And may be crosslinked.
Y ³Represents a Lewis base, Y³If there is more than one, more than one Y
²Can be the same or different, other Y³, E¹, E²or
Is X^FiveMay be crosslinked with A¹And A²Has two configurations
A divalent bridging group for binding a child, having 1 to 20 carbon atoms
Hydrocarbon group, halogen-containing hydrocarbon having 1 to 20 carbon atoms
Group, silicon-containing group, germanium-containing group, tin-containing group, -O
-, -CO-, -S-, -SO₂-, -Se-, -NR
¹⁸-,-PR¹⁸-, -P (O) R¹⁸-, -BR¹⁸-Or
-AlR¹⁸-Indicates R¹⁸Is a hydrogen atom, a halogen atom,
Hydrocarbon group having 1 to 20 carbon atoms, halogen having 1 to 20 carbon atoms
Group containing hydrocarbon groups, which may be the same or different from each other.
You may q is an integer of 1 to 5 [(M³The atom of
Valence) -2], and r represents an integer of 0 to 3. ]]
Transition metal compound and (A-4) general formula (IV) [Chemical 4] [In the formula, M⁷Is titanium, zirconium or hafnium
Show, R³⁴And R³⁷Each independently has 3 to 10 carbon atoms.
Hydrocarbon group or silicon-containing hydrocarbon group having 2 to 18 carbon atoms
And R³⁵, R³⁸Are each independently a hydrogen atom or charcoal.
Hydrocarbon group having 1 to 10 carbon atoms or silicon containing 1 to 18 carbon atoms
R is a hydrocarbon group³⁶, R³⁹Each independently,
A divalent carbon that forms a condensed ring with the five-membered ring to which it binds
It represents a saturated or unsaturated hydrocarbon group having a prime number of 3 to 10.
R⁴⁰, R⁴¹Are independently hydrocarbons having 1 to 20 carbon atoms
Group or halogen-containing hydrocarbon group having 1 to 20 carbon atoms, oxygen
Hydrocarbon group containing, nitrogen containing hydrocarbon group, phosphorus containing hydrocarbon
Indicates a group. s and t each independently represent an integer of 0 to 20.
You J is at least one carbon linking two five-membered rings
Hydrocarbon group having 1 to 20 carbon atoms, halogen containing 1 to 20 carbon atoms
Hydrocarbon group, Oxygen-containing hydrocarbon group, Nitrogen-containing hydrocarbon
Group, an alkylene group having a phosphorus-containing hydrocarbon group, or a small amount
At least one hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 carbon atoms
20 halogen-containing hydrocarbon groups, oxygen-containing hydrocarbon groups,
Silicone containing nitrogen-containing hydrocarbon group and phosphorus-containing hydrocarbon group
Group, or at least one hydrocarbon having 1 to 20 carbon atoms
Elementary group, C1-C20 halogen-containing hydrocarbon group, oxygen
Hydrocarbon group containing, nitrogen containing hydrocarbon group, phosphorus containing hydrocarbon
A germylene group having a group is shown. X⁸And Y^FiveAre each
Independently hydrogen atom, halogen atom, carbonization of 1 to 20 carbon atoms
Hydrogen group, halogen-containing hydrocarbon group having 1 to 20 carbon atoms, charcoal
Oxygen-containing hydrocarbon group having a prime number of 1 to 20, amino group, carbon number
1 to 20 nitrogen-containing hydrocarbon groups are shown. ] Transition represented by
Metal transfer compound, (B) (B-1) aluminum oxydation
Compound (B-2) reacts with the above transition metal compound to give a cation.
An ionic compound that can be converted into a silane, and (B-3) clay,
Selected from clay minerals and ion-exchange layered compounds
Carbon number in the presence of a catalyst containing at least one
Selected from 2 to 20 α-olefins and cyclic olefins
At least one of the
0.01 g to 50 kg per 1 g of the metal transfer compound
Prepolymerized, measured in tetralin solvent at 135 ° C
With an intrinsic viscosity [η] of 0.1 to 20 deciliter / g
And the pole measured in a tetralin solvent at 135 ° C.
Viscosity limit [η] (deciliter / g) and 1000 carbon equivalent
Terminal vinyl group and carbon derived from non-conjugated diene compound
Product [η] × [C] with the sum of carbon double bond contents [C]
Reserve in the range of 0.05 to 1.1
Polymerization catalyst. 2. The prepolymerization catalyst according to claim 1, wherein the catalyst used in the prepolymerization further contains (C) an organoaluminum compound and / or a carrier. 3. At least one of the component (A) or the component (B) is supported on a carrier, and 0.01 to 2000 g of a prepolymerization catalyst is added per 1 g of the total amount of the carrier, the component (A) and the component (B). The prepolymerization catalyst according to claim 1, which is obtained by 4. The prepolymerization catalyst according to claim 1, wherein the non-conjugated diene compound is a compound having 7 or more carbon atoms. 5. An α-olefin or a cyclic olefin having 2 to 20 carbon atoms in the presence of the prepolymerization catalyst according to any one of claims 1 to 4 or in the presence of an organoaluminum compound added to the prepolymerization catalyst. And a method for producing a polyolefin, which comprises polymerizing or copolymerizing at least one selected from styrene-based monomers.