JP2003292518A - Catalytic component for olefin polymerization, olefin polymerization catalyst, method for producing olefin polymer and transition metal compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalytic component for olefin polymerization capable of obtaining in high yield a high-molecular weight and high-melting olefin polymer moldable by extrusion or injection, to provide an olefin polymerization catalyst comprising the catalytic component, to provide a method for producing an olefin polymer, and to provide a transition metal compound as the catalytic component. <P>SOLUTION: The catalytic component for olefin polymerization consists of the transition metal compound of general formula (I). The olefin polymerization catalyst comprises said catalytic component. The method for producing the olefin polymer using said catalyst is also provided. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel olefin polymerization catalyst component, an olefin polymerization catalyst containing the same, an olefin polymer production method using the same, and a transition metal compound used therein. More specifically, the present invention provides a highly active polymerization catalyst component capable of producing a high molecular weight and high melting point α-olefin polymer, a polymerization catalyst, a method for producing an α-olefin polymer using the catalyst, and the use thereof. It relates to a transition metal compound.

[0002]

2. Description of the Related Art The so-called Kaminsky catalyst, which is well known as a homogeneous catalyst for olefin polymerization, has a high polymerization activity and can produce a polymer having a sharp molecular weight distribution. Ethylene bis (indenyl) zirconium dichloride and ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride are known as transition metal compounds used for producing isotactic polyolefin with a Kaminsky catalyst. (For example, JP-A-61
No. 130314). However, in the case of using such a catalyst, generally, there is a problem that the molecular weight of the obtained polyolefin is small, and when low temperature polymerization is performed to increase the molecular weight, the polymerization activity of the catalyst is lowered.

Further, a method of using a hafnium compound instead of the zirconium compound has been proposed for the purpose of producing a high molecular weight polyolefin (Jou).
rnal of Molecular Catalys
is, 56 (1989), 237-247). However, this method has a problem that the polymerization activity of the catalyst is low. Furthermore, dimethylsilylene bis-substituted cyclopentadienyl zirconium dichloride and the like have been proposed (Japanese Patent Laid-Open No. 1-1301704, Polymer).
Preprints, Japan 39 (1990),
1614-1616, JP-A-3-12406),
Dimethylsilylenebis (indenyl) zirconium dichloride and the like have been proposed (Japanese Patent Laid-Open No. 63-295007).
Japanese Patent Laid-Open No. 1-275609). And, by using these compounds, it is possible to produce a polymer having a high stereoregularity and a high melting point in the polymerization at a relatively low temperature, but the stereoregularity and the melting point of the polymer obtained under the economically high temperature polymerization conditions. And low molecular weight.

Further, a compound is known in which an improvement is made to improve the isotacticity and the molecular weight of polypropylene by adding a substituent to the indenyl group which is a part of the ligand (see, for example, Japanese Patent Application Laid-Open No. Hei 10 (1999) -242242). 4-268307
JP-A-6-157661). Furthermore, transition metal compounds in which the sub-ring including the adjacent two carbon atoms of the conjugated five-membered ring is a ring having a number of members other than the six-membered ring are also known (for example, JP-A-4-275294, JP-A-6-265294). −
239914, JP-A-8-59724).

However, the above compounds have insufficient catalytic performance under highly economical high temperature polymerization conditions, and the catalyst system of these compounds is often soluble in the reaction medium. Therefore, the obtained olefin polymer has an extremely inferior particle shape such as an irregular particle shape and a low bulk density, and more fine powder. Therefore, when applied to slurry polymerization, gas phase polymerization, etc., there are many problems in the manufacturing process, such as difficulty in continuous and stable operation.

On the other hand, in order to solve the above problems, a catalyst in which a transition metal compound and / or organoaluminum is supported on an inorganic oxide (eg silica, alumina etc.) or an organic substance has also been proposed (eg Kai 61-
No. 108610, No. 60-135408, No. 61-296008, No. 3-74412, No. 3-74415). However, the polymers obtained by these catalysts contain a large amount of fine powders and coarse particles, and are not sufficient in terms of particle properties such as low bulk density, and further, the polymerization activity per solid component is low. However, there is a problem that the molecular weight and stereoregularity are lower than those of a system that does not use a carrier.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide an olefin polymer having a high molecular weight and a high melting point, which enables extrusion molding and injection molding, in a high yield. It is to provide a novel catalyst component for olefin polymerization, which comprises a novel transition metal compound that can be obtained. Another object of the present invention is to provide a catalyst for olefin polymerization using the above catalyst component and a method for producing an olefin polymer using the catalyst. It is still another object of the present invention to provide a novel catalyst component having a small performance deterioration when the catalyst component is supported on a carrier and used for improving process applicability.

[0008]

Means for Solving the Problems As a result of repeated studies on the ligand structure in order to solve the above problems, the present inventors have found that a phenyl group is present at a specific position of the ring structure fused to a conjugated 5-membered ring. And, a transition metal compound having a bulky substituent at its specific position solves the above problems as a catalyst component for olefin polymerization, and a catalyst in which a transition metal compound is used in combination with another cocatalyst or a carrier solves the above problems. And has reached the present invention.

That is, according to the first aspect of the present invention,
There is provided a catalyst component for olefin polymerization, which comprises a transition metal compound represented by the following general formula (I).

[0010]

[Chemical 3] (In the general formula (I), R ¹ , R ² , R ⁴ , and R ⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 7 carbon atoms. Or carbon number 1-6
Of the halogenated hydrocarbon group of R ³ and R ⁶ are bonded to a cyclopentadienyl ring to form a hydrocarbon ring of 5 to 10-membered hydrocarbon: R ⁴¹ and R ⁴² are each independently And a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, which substitutes a hydrogen atom of the condensed ring hydrocarbon bond portion of R ³ or R ⁶ , R ⁹ and R ¹² are
Each independently, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a halogenated hydrocarbon group having 1 to 6 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 7 carbon atoms: R ⁸ and R
¹¹ are each independently a silicon-containing hydrocarbon group having 3 to 9 carbon atoms, or a branched hydrocarbon group having 3 to 10 carbon atoms: R ⁷ and R ¹⁰ are each independently 1 to 1 carbon atoms; 3 hydrocarbon groups, halogenated hydrocarbons having 1 to 3 carbon atoms, halogen atoms: j and k are integers from 0 to 8 (when j or k is 2 or more, R ^{41 s} or R ^{42 s);}
They may be bonded to each other at any position to form a ring structure. ): M and n are integers from 0 to 3 (when m or n is 2 or more, R ^{9 s} or R ^{12 s} may be bonded at any position to form a ring structure): Q is Bridging groups connecting two cyclopentadienyl rings: X and Y
Are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms,
The oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, the amino group or the nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms: M each represents a transition metal of Group 4 of the periodic table. )

Further, according to a second aspect of the present invention, there is provided an olefin polymerization catalyst characterized by comprising the following component (A), component (B) and optional component (C) as constituent components. It Component (A): Olefin polymerization catalyst component according to the first invention Component (B): Aluminum oxy compound, ionic compound capable of reacting with component (A) to convert component (A) into a cation Alternatively, a component (C) selected from the group consisting of Lewis acids: fine particle carrier

Further, according to a third aspect of the present invention, there is provided an olefin polymerization catalyst characterized by comprising the following components (A), (B) and optional components (C) as constituent components. It Component (A): Catalyst component for olefin polymerization according to the first invention Component (D): A component selected from the group consisting of ion-exchangeable layer compounds excluding silicates or inorganic silicates Component (E): Organoaluminum compound

According to the fourth aspect of the present invention, the second aspect
Or in the presence of the olefin polymerization catalyst according to the invention of 3,
There is provided a method for producing an olefin polymer, which comprises polymerizing an olefin or copolymerizing with an olefin.

According to a fifth aspect of the present invention, there is provided a transition metal compound represented by the following general formula (I).

[0015]

[Chemical 4] (In the general formula (I), R ¹ , R ² , R ⁴ , and R ⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 7 carbon atoms. Or carbon number 1-6
Of the halogenated hydrocarbon group of R ³ and R ⁶ are bonded to a cyclopentadienyl ring to form a hydrocarbon ring of 5 to 10-membered hydrocarbon: R ⁴¹ and R ⁴² are each independently And a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, which substitutes a hydrogen atom of the condensed ring hydrocarbon bond portion of R ³ or R ⁶ , R ⁹ and R ¹² are
Each independently, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a halogenated hydrocarbon group having 1 to 6 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 7 carbon atoms: R ⁸ and R
¹¹ are each independently a silicon-containing hydrocarbon group having 3 to 9 carbon atoms, or a branched hydrocarbon group having 3 to 10 carbon atoms: R ⁷ and R ¹⁰ are each independently 1 to 1 carbon atoms; 3 hydrocarbon groups, halogenated hydrocarbons having 1 to 3 carbon atoms, halogen atoms: j and k are integers from 0 to 8 (when j or k is 2 or more, R ^{41 s} or R ^{42 s);}
They may be bonded to each other at any position to form a ring structure. ): M and n are integers from 0 to 3 (when m or n is 2 or more, R ^{9 s} or R ^{12 s} may be bonded at any position to form a ring structure): Q is Bridging groups connecting two cyclopentadienyl rings: X and Y
Are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms,
The oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, the amino group or the nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms: M each represents a transition metal of Group 4 of the periodic table. )

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
First, the transition metal compound used for the olefin polymerization catalyst component of the present invention will be described. The transition metal compound of the present invention is represented by the following general formula (I).

[0017]

[Chemical 5]

The transition metal compound of the present invention naturally comprises a five-membered ring ligand having the substituents R ¹ , R ² and R ³ and a five-membered ring ligand having the substituents R ⁴ , R ⁵ and R ^6. With respect to the relative position of the ring ligand via the bonding group Q,
It includes a compound (a) which is asymmetric with respect to a plane containing M, X and Y and a compound (b) which is symmetrical. However,
In order to produce a high molecular weight and high melting point α-olefin polymer, the above compound (a), that is, two five-membered ring ligands facing each other across a plane containing M, X and Y are used. It is preferable to use a compound that does not have a mirror image of the substance with respect to the plane.

In the general formula (I), R ¹ , R ² , R ⁴ and R ⁵
Are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a silicon-containing hydrocarbon group having 1 to 7 carbon atoms, or a halogenated hydrocarbon group having 1 to 6 carbon atoms. Specific examples of the hydrocarbon group having 1 to 6 carbon atoms include methyl,
Ethyl, n-propyl, i-propyl, n-butyl, i
-Butyl, s-butyl, t-butyl, n-pentyl, n
Preferred examples include alkyl groups such as hexyl, cyclopropyl, cyclopentyl, cyclohexyl, alkenyl groups such as vinyl, propenyl, cyclohexenyl, and phenyl groups.

Specific examples of the silicon-containing hydrocarbon group having 1 to 7 carbon atoms include trialkylsilyl groups such as trimethylsilyl, triethylsilyl and t-butyldimethylsilyl, and alkylsilylalkyl groups such as bis (trimethylsilyl) methyl. And the like are preferable.

In the above-mentioned halogenated hydrocarbon group having 1 to 6 carbon atoms, the halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The above-mentioned halogenated hydrocarbon group is a compound in which, when the halogen atom is, for example, a fluorine atom, a fluorine atom is substituted at any position of the above-mentioned hydrocarbon group. Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2,2. 1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 2
-, 3-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl, 2-, 3-, 4-bromophenyl, 2,
4-, 3,5-, 2,6-, 2,5-difluorophenyl, 2,4-, 3,5-, 2,6-, 2,5-dichlorophenyl, 2,4,6-trifluorophenyl , 2,
4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl and the like can be mentioned. (Note that
In the present specification, some of the substituents mentioned as examples of the substituents are omitted. For example, the above-mentioned "2--3
"-, 4-fluorophenyl" means that three compounds of "2-fluorophenyl", "3-fluorophenyl" and "4-fluorophenyl" are mentioned. )

Among these, as R ¹ and R ⁴ ,
A hydrocarbon group having 1 to 6 carbon atoms is preferable, particularly methyl,
An alkyl group having 1 to 6 carbon atoms such as ethyl, propyl and butyl is preferable, and a hydrogen atom is particularly preferable as R ² and R ⁵ .

In the general formula (I), R ³ and R ⁶ represent a hydrocarbon bond portion which is bonded to the cyclopentadienyl ring to form a 5- to 10-membered hydrocarbon ring structure. What is characteristic of the present invention is that it has a substituted phenyl at the 4-position of the ring fused to the cyclopentadienyl ring as shown in the above general formula, and as long as such structural characteristics are not impaired, the hydrocarbon bonding group R ^{The 3} and R ⁶ groups can be any.

The bond portions R ³ and R ⁶ are preferably saturated or unsaturated divalent hydrocarbon bond groups having 2 to 8 carbon atoms, and specific examples thereof include dimethylene, trimethylene, tetramethylene and pentamethylene. , A divalent saturated hydrocarbon group such as hexamethylene, ethylene, propenylene, 2-propen-1-ylidene, 1-butenylene, 2
-Butenylene, 1,3-butadienylene, 1-pentenylene, 2-pentenylene, 1,3-pentadienylene,
1,4-pentadienylene, 1-hexenylene, 2-hexenylene, 3-hexenylene, 1,3-hexadienylene, 1,4-hexadienylene, 1,5-hexadienylene, 2,4-hexadienylene, 2,5-hexadienylene, 1, Divalent unsaturated hydrocarbon groups such as 3,5-hexatrienylene are preferred, and among these, particularly preferred are 2-propen-1-ylidene, 1,3-butadienylene and the like having 3 to 5 carbon atoms. Is a divalent unsaturated hydrocarbon, and a 1,3-butadienylene group is a more preferable bonding group.

In the general formula (I), R ⁴¹ and R ⁴² are each independently a substituent for substituting the hydrogen atom of the condensed ring hydrocarbon bond portion of R ³ or R ⁶ and having 1 to 8 carbon atoms. A hydrocarbon group or a halogen hydrocarbon group having 1 to 8 carbon atoms is shown.
Specific preferred examples of the hydrocarbon group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, i-propyl,
n-butyl, i-butyl, s-butyl, t-butyl, n
-Alkyl groups such as pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl and methylcyclohexyl, alkenyl groups such as vinyl, propenyl, butenyl and cyclohexenyl, arylalkyl groups such as benzyl and phenylethyl, aryls such as trans-styryl Examples thereof include alkenyl groups, aryl groups such as phenyl, tolyl, dimethylphenyl and ethylphenyl.

In the halogenated hydrocarbon group having 1 to 8 carbon atoms, the halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The above-mentioned halogenated hydrocarbon group is a compound in which, when the halogen atom is, for example, a fluorine atom, a fluorine atom is substituted at any position of the above-mentioned hydrocarbon group. Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2,2. 1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 2
-, 3-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl, 2-, 3-, 4-bromophenyl, 2,
4-, 3,5-, 2,6-, 2,5-difluorophenyl, 2,4-, 3,5-, 2,6-, 2,5-dichlorophenyl, 2,4,6-trifluorophenyl , 2,
4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl and the like can be mentioned. These R
⁴¹ and R ⁴² are preferably alkyl groups having 1 to 6 carbon atoms.

In the general formula (I), R ⁹ and R ¹² are each independently a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms,
Halogenated hydrocarbon group having 1 to 6 carbon atoms, or 1 carbon atom
~ 7 of silicon-containing hydrocarbons.

Preferred specific examples of the hydrocarbon group having 1 to 6 carbon atoms are methyl, ethyl, n-propyl and i.
-Propyl, n-butyl, i-butyl, s-butyl, t
-Butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl and other alkyl groups,
Preferable examples include an alkenyl group such as vinyl, propenyl, cyclohexenyl, and a phenyl group.

In the above halogenated hydrocarbon group having 1 to 6 carbon atoms, the halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The above-mentioned halogenated hydrocarbon group is a compound in which, when the halogen atom is, for example, a fluorine atom, a fluorine atom is substituted at any position of the above-mentioned hydrocarbon group. Specific examples thereof include 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 2
-, 3-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl, 2-, 3-, 4-bromophenyl, 2,
4-, 3,5-, 2,6-, 2,5-difluorophenyl, 2,4-, 3,5-, 2,6-, 2,5-dichlorophenyl, 2,4,6-trifluorophenyl , 2,
4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl and the like can be mentioned.

Specific examples of the silicon-containing hydrocarbon group having 1 to 7 carbon atoms include trialkylsilyl groups such as trimethylsilyl, triethylsilyl and t-butyldimethylsilyl, and alkylsilylalkyl groups such as bis (trimethylsilyl) methyl. And the like are preferable.

Among these, a methyl group, an ethyl group,
Propyl group, alkyl group having 1 to 4 carbon atoms such as i-propyl group, silicon-containing hydrocarbon group such as alkylated silyl group such as trimethylsilyl and triethylsilyl, or fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloro A halogenated alkyl group having 1 to 3 carbon atoms such as methyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, and iodomethyl is preferable, and a hydrogen atom or a carbon number such as a methyl group, an ethyl group, a propyl group, and an i-propyl group. Alkyl groups of 1-3 are more preferred.

As R ⁸ and R ^{11 at} the para position of the phenyl group bonded to the 4-position of the condensed ring with cyclopentadienyl, which is a feature of the present invention, a silicon-containing hydrocarbon group having 3 to 9 carbon atoms, carbon It has a hydrocarbon group having a branch of several 3 to 10.

Specific examples of the silicon-containing hydrocarbon group having 3 to 9 carbon atoms include trimethylsilyl, triethylsilyl, isopropyldimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl, cyclotrimethylenemethylsilyl, cyclohexyldimethylsilyl and the like. Preferred examples thereof include trialkylsilyl groups, and alkylsilylalkyl groups such as trimethylsilylmethyl and bis (trimethylsilyl) methyl.

Specific examples of the branched hydrocarbon group having 3 to 10 carbon atoms include isopropyl, i-butyl,
s-Butyl, t-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 3,3-dimethylbutyl, 1, 2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylpentyl, 2,2- Dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 2,3-dimethylpentyl, 2,4-
Examples thereof include dimethylpentyl and 3,4-dimethylpentyl.

Among these, isopropyl group, t-butyl group, 1,1-dimethylpropyl group and the like having 3 to 6 carbon atoms.
A branched alkyl group, or trimethylsilyl,
Trialkylsilyl groups such as triethylsilyl and t-butyldimethylsilyl are preferred, and t-butyl groups and 1,1-
An alkyl group having a branch at the α-position such as a dimethylpropyl group or a trialkylsilyl group is particularly preferable.

[0036] In the present invention, has a ^{R 7, R 10} at the adjacent position to the ^{R 8, R 11, R 7} , R 10 is 1 to carbon atoms
3 represents a hydrocarbon group, a halogen-containing hydrocarbon group having 1 to 3 carbon atoms, and a halogen atom.

Specific examples of preferable hydrocarbon groups having 1 to 3 carbon atoms include methyl, ethyl, n-propyl and i.
Examples include alkyl groups such as propyl. Carbon number 1
Specific examples of the halogen-containing hydrocarbon group of ~ 3 include fluoromethyl, difluoromethyl, trifluoromethyl,
Chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2,2
Alkyl halides such as 1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, and pentafluoropropyl are preferred. Preferable examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, alkyl groups such as methyl group and ethyl group, trifluoromethyl group,
C1 halogenated alkyl group such as chloromethyl group,
Alternatively, chlorine atom is preferable.

In the general formula (I), j and k are integers from 0 to 8. When j and k are 2 or more, R
^41's or R ^42's may be linked to each other to form a new ring structure. It is preferably an integer of 0 to 2, and more preferably 0. In general formula (I), m and n are integers from 0 to 8. When m and n are 2 or more, R ^{9 s} or R ^{12 s} may be linked to each other to form a new ring structure. Preferably 0 and 1
And 0 is more preferable.

In the general formula (I), Q is a bridging group connecting two cyclopentadienyl rings. It is well known that metallocene transition metal compound-based olefin polymerization catalysts bond the two cyclopentadienyl rings with a bonding group, and various kinds of bonding groups can be similarly used in the present invention. Specific examples of Q include methylene,
Methylmethylene, dimethylmethylene, 1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene,
Alkylene groups such as 1,2-cyclohexylene and 1,4-cyclohexylene, (methyl) (phenyl) methylene,
Arylalkylene groups such as diphenylmethylene, silylene groups, methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, and other alkylsilylene groups, methyl (phenyl) ) (Alkyl) (aryl) silylene groups such as silylene and methyl (tolyl) silylene, arylsilylene groups such as diphenylsilylene,
Preferable examples include an alkyloligosilylene group such as tetramethyldisilylene, and a germanium group obtained by substituting germanium for silicon, an alkylgermylene group, an (alkyl) (aryl) germylene group, an arylgermylene group, and the like. When two hydrocarbon groups are present on the above silylene group, oligosilylene group or germylene group, they may be bonded to each other to form a ring structure.

Of these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is more preferable, and an alkylsilylene group, (alkyl) (aryl) ) A silylene group or an arylsilylene group, an alkylgermylene group, an (alkyl) (aryl) germylene group, and an arylgermylene group are more preferable, and an alkylsilylene group and an alkylgermylene group are particularly preferable.

In the general formula (I), X and Y are groups that coordinate with the transition metal M, and such groups are well known in the metallocene complex. Specifically, each of them is independently a hydrogen atom or a halogen. Atoms, hydrocarbon groups having 1 to 20 carbon atoms, 1 to carbon atoms
20 shows a halogenated hydrocarbon group, a C1-C20 silicon-containing hydrocarbon group, a C1-C20 oxygen-containing hydrocarbon group, an amino group, or a C1-C20 nitrogen-containing hydrocarbon group. As the above halogen atom, a fluorine atom,
Examples thereof include chlorine atom, bromine atom and iodine atom.

Specific examples of the above hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl and n-. Alkyl groups such as pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl and methylcyclohexyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, arylalkyl groups such as benzyl, phenylethyl and phenylpropyl, aryls such as trans-styryl Alkenyl group, phenyl, tolyl,
Examples of the aryl group include dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl, 2-naphthyl, acenaphthyl, phenanthryl, anthryl and the like.

Specific examples of the above-mentioned oxygen-containing hydrocarbon group having 1 to 20 carbon atoms include alkoxy groups such as methoxy, ethoxy, propoxy, cyclopropoxy and butoxy, and allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy. And arylalkoxy groups such as phenylmethoxy and naphthylmethoxy, and oxygen-containing heterocyclic groups such as furyl groups.

Specific examples of the above-mentioned nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms include methylamino, dimethylamino,
Alkylamino groups such as ethylamino and diethylamino,
Arylamino groups such as phenylamino and diphenylamino, (alkyl) such as (methyl) (phenyl) amino
Examples thereof include (aryl) amino groups, nitrogen-containing heterocyclic groups such as pyrazolyl, and indolyl.

In the above halogenated hydrocarbon group having 1 to 20 carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. And
When the halogen atom is, for example, a fluorine atom, the above halogenated hydrocarbon group is a compound in which a fluorine atom is substituted at any position of the above hydrocarbon group. 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, 2- , 3-, 4-fluorophenyl, 2
-, 3-, 4-chlorophenyl, 2-, 3-, 4-bromophenyl, 2,4-, 3,5-, 2,6-, 2,5-
Difluorophenyl, 2,4-, 3,5-, 2,6-,
2,5-dichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, 4-fluoronaphthyl, 4-chloronaphthyl, 2,4-difluoronaphthyl, hepta Fluoro-1-naphthyl, heptachloro-1-naphthyl, 2-, 3-, 4-trifluoromethylphenyl, 2-, 3-, 4-trichloromethylphenyl, 2,4-, 3,5-, 2,6 -, 2,5-bis (trifluoromethyl) phenyl, 2,4-, 3,5-,
2,6-, 2,5-bis (trichloromethyl) phenyl, 2,4,6-tris (trifluoromethyl) phenyl, 4-trifluoromethylnaphthyl, 4-trichloromethylnaphthyl, 2,4-bis (tri Fluoromethyl)
Examples thereof include naphthyl group.

Specific examples of the silicon-containing hydrocarbon group having 1 to 20 carbon atoms include trialkylsilylmethyl groups such as trimethylsilylmethyl and triethylsilylmethyl,
Examples thereof include di (alkyl) (aryl) silylmethyl groups such as dimethylphenylsilylmethyl, diethylphenylsilylmethyl and dimethyltolylsilylmethyl. As X and Y, 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 a halogen atom and 1 to 20 carbon atoms are preferable.
And a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms are more preferable, and a chlorine atom, a methyl group, an i-butyl group, a phenyl group, a benzyl group, a dimethylamino group or a diethylamino group is particularly preferable.

In the general formula (I), M represents a transition metal of Group 4 of the periodic table, preferably titanium, zirconium or hafnium, particularly preferably zirconium or hafnium.

The transition metal compound of the present invention can be synthesized by any method as to the mode of substitution or bonding. A typical synthetic route is as shown in the following reaction formula. H ₂ R ^a and H ₂ R ^b in the reaction formula each have the following structures.

[0049]

[Chemical 6] (R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ ,
R ¹⁰ , R ¹¹ , R ¹² , R ⁴¹ , R ⁴² and j,
k, m, and n are as defined in the general formula (I). )

H_TwoR^a+ N-C_FourH₉Li → HR^aLi
+ C_FourH₁₀ H_TwoR^b+ N-C_FourH₉Li → HR^bLi + C_FourH₁₀ HR^aLi + HR^bLi + QCl_Two→ HR^a-Q-HR
^b+ 2LiCl HR^a-Q-HR^b+ 2n-C_FourH₉Li → LiRa-
Q-LiRb + 2C_FourH₁₀ LiR^a-Q-LiR^b+ HfCl_Four→ (R^a-Q-R
^b) HfCl_Two+ 2LiCl

Further, the above-mentioned HR ^a Li and HR ^b Li
The formation of a metal salt of a cyclopentadienyl compound as described above is known, and for example, it can be synthesized by a method involving an addition reaction of an aryl group or the like, as described in the examples of EP 6974418. Good. Specifically, an aryllithium compound and an azulene compound are reacted in an inert solvent to form a lithium salt of a dihydroazurenyl compound. Phenyllithium, naphthyllithium, fluoronaphthyllithium, biphenylyllithium, fluorobiphenylyllithium and the like are used as the aryllithium compound. Further, as the inert solvent, hexane,
Benzene, toluene, diethyl ether, tetrahydrofuran, a mixed solvent thereof or the like is used.

Specific preferred examples of the transition metal compound of the present invention are shown in the table below. The three-dimensional structure means both a compound having asymmetry and a compound having symmetry as used in the present invention. In addition, for the understanding of the structure of the compound, the structural formula and the name of the hafnium dichloride described in the compound (IV) are shown below. Of course, instead of hafnium, titanium or zirconium, and instead of dichloride, other X and Y may be used. Certain compounds are also based on the intent. The compound of this structural formula is dichloro {1,1′-dimethylsilylenebis [2-methyl-4- (4-trimethylsilyl-3
-Chlorophenyl) -4H-azurenyl]} hafnium.

[0053]

[Chemical 7]

Preferred specific compound names are listed below with the intention of exemplifying M, X and Y as in the above (1) dichloro {1,1'-dimethylsilylene bis [2].
-Methyl-4- (4-trimethylsilyl-3-chlorophenyl) -4H-azurenyl]} hafnium (2) dichloro {1,1'-dimethylmethylenebis [2
-Methyl-4- (4-trimethylsilyl-3-chlorophenyl) -4H-azurenyl]} hafnium (3) dichloro {1,1'-dimethylgermylenebis [2-methyl-4- (4-trimethylsilyl-3-chlorophenyl) ) -4H-azurenyl]} hafnium (4) dichloro {1,1'-ethylenebis [2-methyl-4- (4-trimethylsilyl-3-chlorophenyl))
-4H-azurenyl]} hafnium (5) dichloro {1,1 '-(methyl) (phenyl) silylenebis [2-methyl-4- (4-trimethylsilyl-3-chlorophenyl) -4H-azurenyl]} hafnium

(6) Dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-
3-chlorophenyl) -4H-azurenyl]} hafnium (7) dichloro {1,1'-dimethylmethylenebis [2
-Ethyl-4- (4-trimethylsilyl-3-chlorophenyl) -4H-azurenyl]} hafnium (8) dichloro {1,1'-dimethylgermylenebis [2-ethyl-4- (4-trimethylsilyl-3-chlorophenyl) ) -4H-azurenyl]} hafnium (9) dichloro {1,1'-ethylenebis [2-ethyl-4- (4-trimethylsilyl-3-chlorophenyl))
-4H-azurenyl]} hafnium (10) dichloro {1,1 '-(methyl) (phenyl)
Silylenebis [2-ethyl-4- (4-trimethylsilyl-3-chlorophenyl) -4H-azurenyl]} hafnium

(11) Dichloro {1,1'-dimethylsilylenebis [2-n-propyl-4- (4-trimethylsilyl-3-chlorophenyl) -4H-azurenyl]}
Hafnium (12) dichloro {1,1'-dimethylgermylene bis [2-n-propyl-4- (4-trimethylsilyl-3
-Chlorophenyl) -4H-azurenyl]} hafnium (13) dichloro {1,1'-dimethylsilylenebis [2-i-propyl-4- (4-trimethylsilyl-3)
-Chlorophenyl) -4H-azurenyl]} hafnium (14) dichloro {1,1'-dimethylgermylene bis [2-i-propyl-4- (4-trimethylsilyl-3)
-Chlorophenyl) -4H-azurenyl]} hafnium (15) dichloro {1,1'-dimethylsilylenebis [2-phenyl-4- (4-trimethylsilyl-3-chlorophenyl) -4H-azurenyl]} hafnium (16) dichloro {1,1'-Dimethylgermylene bis [2-phenyl-4- (4-trimethylsilyl-3-chlorophenyl) -4H-azurenyl]} hafnium

(17) Dichloro {1,1'-dimethylsilylenebis [2-methyl-4- (4-trimethylsilyl-3-methylphenyl) -4H-azulenyl]} hafnium (18) dichloro {1,1'- Dimethylgermylene bis [2-methyl-4- (4-trimethylsilyl-3-methylphenyl) -4H-azurenyl]} hafnium (19) dichloro {1,1'-ethylenebis [2-methyl-4- (4- Trimethylsilyl-3-methylphenyl) -4H-azurenyl]} hafnium (20) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-3-methylphenyl) -4H-azurenyl]} Hafnium (21) dichloro {1,1'-dimethylgermylene bis [2-ethyl-4- (4-trimethylsilyl-3-me] Ruphenyl) -4H-azurenyl]} hafnium (22) dichloro {1,1′-ethylenebis [2-ethyl-4- (4-trimethylsilyl-3-methylphenyl) -4H-azurenyl]} hafnium (23) dichloro { 1,1′-Dimethylsilylenebis [2-n-propyl-4- (4-trimethylsilyl-3
-Methylphenyl) -4H-azurenyl]} hafnium (24) dichloro {1,1'-dimethylgermylenebis [2-n-propyl-4- (4-trimethylsilyl-3)
-Methylphenyl) -4H-azurenyl]} hafnium (25) dichloro {1,1'-ethylenebis [2-n-
Propyl-4- (4-trimethylsilyl-3-methylphenyl) -4H-azurenyl]} hafnium (26) dichloro {1,1'-dimethylsilylenebis [2-i-propyl-4- (4-trimethylsilyl-3)
-Methylphenyl) -4H-azurenyl]} hafnium (27) dichloro {1,1'-dimethylgermylenebis [2-i-propyl-4- (4-trimethylsilyl-3)
-Methylphenyl) -4H-azurenyl]} hafnium (28) dichloro {1,1'-ethylenebis [2-i-
Propyl-4- (4-trimethylsilyl-3-methylphenyl) -4H-azulenyl]} hafnium

(29) Dichloro {1,1'-dimethylsilylenebis [2-methyl-4- (4-trimethylsilyl-3-ethylphenyl) -4H-azulenyl]} hafnium (30) dichloro {1,1'- Dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-3-ethylphenyl) -4H-azurenyl]} hafnium (31) dichloro {1,1'-dimethylsilylenebis [2-n-propyl-4- ( 4-trimethylsilyl-3
-Ethylphenyl) -4H-azurenyl]} hafnium (32) dichloro {1,1'-dimethylsilylenebis [2-methyl-4- (4-trimethylsilyl-3-trifluoromethylphenyl) -4H-azurenyl]} hafnium (33) Dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-3-trifluoromethylphenyl) -4H-azulenyl]} hafnium (34) dichloro {1,1'-dimethyl Silylene bis [2-n-propyl-4- (4-trimethylsilyl-3
-Trifluoromethylphenyl) -4H-azurenyl]} hafnium

(35) Dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-3-fluorophenyl) -4H-azulenyl]} hafnium (36) dichloro {1,1'- Dimethylsilylene bis [2-ethyl-4- (4-trimethylsilyl-3-n-
Propylphenyl) -4H-azurenyl]} hafnium (37) Dichloro {1,1'-dimethylsilylene bis [2-ethyl-4- (4-triethylsilyl-3-chlorophenyl) -4H-azurenyl]} hafnium (38) Dichloro {1,1'-dimethylsilylene bis [2-ethyl-4- (4-dimethylphenylsilyl-3
-Chlorophenyl) -4H-azurenyl]} hafnium (39) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-i-propyldimethylsilyl-3-chlorophenyl) -4H-azurenyl]} hafnium (40) Dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (4-t-butyldimethylsilyl-
3-Chlorophenyl) -4H-azurenyl]} hafnium (41) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-cyclotrimethylenemethylsilyl-3-chlorophenyl) -4H-azurenyl]} Hafnium (42) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-cyclohexyldimethylsilyl-3-chlorophenyl) -4H-azulenyl]} hafnium (43) dichloro {1,1'-dimethyl Silylene bis [2-ethyl-4- (4-trimethylsilylmethyl-3
-Chlorophenyl) -4H-azurenyl]} hafnium

(44) Dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-triethylsilyl-3-methylphenyl) -4H-azulenyl]} hafnium (45) dichloro {1,1 ' -Dimethylsilylene bis [2-ethyl-4- (4-dimethylphenylsilyl-3
-Methylphenyl) -4H-azurenyl]} hafnium (46) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-dimethyl-i-propylsilyl-3-methylphenyl) -4H-azurenyl ] Hafnium (47) dichloro {1,1′-dimethylsilylene bis [2-ethyl-4- (4-t-butyldimethylsilyl-
3-Methylphenyl) -4H-azurenyl]} hafnium (48) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-cyclotrimethylenemethylsilyl-3-methylphenyl) -4H-azurenyl ] Hafnium (49) dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (4-cyclohexyldimethylsilyl-3-methylphenyl) -4H-azurenyl]} hafnium (50) dichloro {1,1 '-Dimethylsilylenebis [2-ethyl-4- (4-trimethylsilylmethyl-3
-Methylphenyl) -4H-azurenyl]} hafnium

(51) Dichloro {1,1'-dimethylsilylenebis [2-methyl-4- (4-t-butyl-3-)
Chlorophenyl) -4H-azurenyl]} hafnium (52) dichloro {1,1′-dimethylgermylene bis [2-methyl-4- (4-t-butyl-3-chlorophenyl) -4H-azurenyl]} hafnium (53 ) Dichloro {1,1'-ethylenebis [2-methyl-4- (4-t-butyl-3-chlorophenyl) -4
H-azurenyl]} hafnium (54) dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-chlorophenyl) -4H-azurenyl]} hafnium (55) dichloro {1 , 1'-Dimethylgermylene bis [2-ethyl-4- (4-t-butyl-3-chlorophenyl) -4H-azurenyl]} hafnium (56) dichloro {1,1'-ethylenebis [2-ethyl- 4- (4-t-butyl-3-chlorophenyl) -4
H-azurenyl]} hafnium (57) dichloro {1,1′-dimethylsilylene bis [2-n-propyl-4- (4-t-butyl-3-chlorophenyl) -4H-azurenyl]} hafnium (58) dichloro {1,1'-Dimethylsilylenebis [2-i-propyl-4- (4-t-butyl-3-chlorophenyl) -4H-azurenyl]} hafnium (59) dichloro {1,1'-dimethylsilylenebis [ 2-Phenyl-4- (4-t-butyl-3-chlorophenyl) -4H-azulenyl]} hafnium

(60) Dichloro {1,1'-dimethylsilylenebis [2-methyl-4- (4-t-butyl-3-)
Fluorophenyl) -4H-azurenyl]} hafnium (61) dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-fluorophenyl) -4H-azurenyl]} hafnium ( 62) Dichloro {1,1'-dimethylgermylene bis [2-ethyl-4- (4-t-butyl-3-chlorophenyl) -4H-azurenyl]} hafnium (63) dichloro {1,1'-ethylenebis [2-Ethyl-4- (4-t-butyl-3-chlorophenyl) -4
H-azurenyl]} hafnium (64) dichloro {1,1′-dimethylsilylene bis [2-n-propyl-4- (4-t-butyl-3-chlorophenyl) -4H-azurenyl]} hafnium (65) dichloro {1,1'-Dimethylsilylenebis [2-methyl-4- (4-t-butyl-3-trifluoromethylphenyl) -4H-azurenyl]} hafnium (66) dichloro {1,1'-dimethylsilylenebis [2-Ethyl-4- (4-t-butyl-3-trifluoromethylphenyl) -4H-azurenyl]} hafnium (67) dichloro {1,1'-dimethylsilylenebis [2-n-propyl-4-] (4-t-Butyl-3-trifluoromethylphenyl) -4H-azurenyl]} hafnium (68) dichloro {1,1'-dimethylgermylenebis [[ -Ethyl-4- (4-t-butyl-3-trifluoromethylphenyl) -4H-azurenyl]} hafnium (69) dichloro {1,1'-ethylenebis [2-ethyl-4- (4-t- Butyl-3-trifluoromethylphenyl) -4H-azurenyl]} hafnium

(70) Dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-)
Chloromethylphenyl) -4H-azurenyl]} hafnium (71) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-methyl-5)
-Fluorophenyl) -4H-azurenyl]} hafnium (72) dichloro {1,1'-dimethylsilylene bis [2-ethyl-4- (4-t-butyl-3-chloro-5]
-Methylphenyl) -4H-azurenyl]} hafnium (73) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-methylphenyl) -4H-azurenyl]} hafnium (74) Dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-ethylphenyl) -4H-azulenyl]} hafnium (75) dichloro {1,1'-dimethyl Silylenebis [2-ethyl-4- (4-t-butyl-3-n-propylphenyl) -4H-azurenyl]} hafnium (76) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4-] (4-t-Butyl-3-i-propylphenyl) -4H-azulenyl]} hafnium

(77) Dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-i-propyl-3)
-Methylphenyl) -4H-azurenyl]} hafnium (78) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-i-propyl-3-ethylphenyl) -4H-azurenyl]} hafnium (79) Dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-i-propyl-3-chloromethylphenyl) -4H-azulenyl]} hafnium (80) dichloro {1,1'- Dimethylsilylenebis [2-ethyl-4- (4-i-propyl-3-chlorophenyl) -4H-azurenyl]} hafnium (81) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4 -I-Propyl-3-trifluoromethylphenyl) -4H-azurenyl]} hafnium (82) dichloro {1,1'-dimethylsilylenebis [2 Ethyl-4- (4-i-propyl-3-fluorophenyl) -4H-azurenyl]} hafnium (83) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-i-butyl- 3-Methylphenyl) -4H-azurenyl]} hafnium (84) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-i-butyl-3-ethylphenyl) -4H-azurenyl]} Hafnium (85) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-i-butyl-3-chloromethylphenyl) -4H-azulenyl]} hafnium (86) dichloro {1,1 ' -Dimethylsilylene bis [2-ethyl-4- (4-i-butyl-3-chlorophenyl) -4H-azurenyl]} hafnium (87) dichloro {1,1'-dimethyl Rylene bis [2-ethyl-4- (4-i-butyl-3-trifluoromethylphenyl) -4H-azurenyl]} hafnium (88) dichloro {1,1'-dimethylsilylene bis [2-ethyl-4- ( 4-i-butyl-3-fluorophenyl) -4H-azulenyl]} hafnium

(89) Dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-s-butyl-3-)
Methylphenyl) -4H-azurenyl]} hafnium (90) dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (4-s-butyl-3-ethylphenyl) -4H-azurenyl]} hafnium ( 91) Dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-s-butyl-3-chloromethylphenyl) -4H-azulenyl]} hafnium (92) dichloro {1,1'-dimethyl Silylenebis [2-ethyl-4- (4-s-butyl-3-chlorophenyl) -4H-azurenyl]} hafnium (93) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4- s-Butyl-3-trifluoromethylphenyl) -4H-azurenyl]} hafnium (94) dichloro {1,1'-dimethylsilylenebis [2-ethyl- -(4-s-Butyl-3-fluorophenyl) -4H-azurenyl]} hafnium (95) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4- (1-methyl-1-- Ethylpropyl) -3-methylphenyl) -4H-azurenyl]} hafnium (96) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4- (1-methyl-1-ethylpropyl)- 3-Ethylphenyl) -4H-azurenyl]} hafnium (97) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4- (1-methyl-1-ethylpropyl) -3-chloromethyl] Phenyl) -4H-azurenyl]} hafnium (98) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4- (1-methyl-1-ethylpropyl) -3] Chlorophenyl) -4H- azulenyl]} hafnium (99) dichloro {1,1'-dimethylsilylene-bis [2-ethyl-4- (4- (1-methyl-1-ethyl -
Propyl) -3-trifluoromethylphenyl) -4H
-Azurenyl]} hafnium (100) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4- (1-methyl-1-ethylpropyl) -3-fluorophenyl) -4H-azurenyl]} hafnium

(101) Dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3)
-Chlorophenyl) -4H-azurenyl] [2-ethyl-4- (4-t-butyl-3-chlorophenyl) -indenyl]} hafnium (102) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4] -(4-t-Butyl-3-chlorophenyl) -4H-azurenyl] [2-ethyl-4- (4-
Chlorophenyl) -indenyl]} hafnium (103) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-trifluoromethylphenyl) -4H-azurenyl] [2-ethyl -4- (4-t-Butyl-3-trifluoromethylphenyl) -indenyl]} hafnium (104) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3) -Trifluoromethylphenyl) -4H-azurenyl] [2-ethyl-4- (4-chlorophenyl) -indenyl]} hafnium (105) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4 -T-Butyl-3-methylphenyl) -4H-azurenyl] [2-ethyl-4- (4-
t-Butyl-3-methylphenyl) -indenyl]} hafnium (106) dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-methylphenyl) -4H-azurenyl ] [2-Ethyl-4- (4-
Chlorophenyl) -indenyl]} hafnium (107) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-ethylphenyl) -4H-azurenyl] [2-ethyl-4 -(4-
t-Butyl-3-ethylphenyl) -indenyl]} hafnium (108) dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-ethylphenyl) -4H-azurenyl ] [2-Ethyl-4- (4-
Chlorophenyl) -indenyl]} hafnium (109) dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-3-chlorophenyl) -4H-azurenyl] [2-ethyl-4-
(4-Trimethylsilyl-3-chlorophenyl) -indenyl]} hafnium (110) dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-3-chlorophenyl) -4H-azurenyl] [2 -Ethyl-4-
(4-Chlorophenyl) -indenyl]} hafnium (111) dichloro {1,1'-dimethylsilylene bis [2-ethyl-4- (4-trimethylsilyl-3-trifluoromethylphenyl) -4H-azurenyl] [2-
Ethyl-4- (4-trimethylsilyl-3-trifluoromethylphenyl) -indenyl]} hafnium (112) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-3-trifluoro) Methylphenyl) -4H-azurenyl] [2-
Ethyl-4- (4-chlorophenyl) -indenyl]}
Hafnium (113) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-3-methylphenyl) -4H-azulenyl] [2-ethyl-4-
(4-Trimethylsilyl-3-methylphenyl) -indenyl]} hafnium (114) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-3-methylphenyl) -4H-azurenyl] [2-ethyl-4-
(4-Chlorophenyl) -indenyl]} hafnium (115) dichloro {1,1′-dimethylsilylene bis [2-ethyl-4- (4-trimethylsilyl-3-ethylphenyl) -4H-azurenyl] [2-ethyl- 4-
(4-Trimethylsilyl-3-ethylphenyl) -indenyl]} hafnium (116) dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-3-ethylphenyl) -4H-azurenyl] [2-ethyl-4-
(4-Chlorophenyl) -indenyl]} hafnium (117) dichloro {1,1'-dimethylsilylene bis [2-ethyl-4- (4-trimethylsilyl-3-ethylphenyl) -4H-azurenyl] [2-ethyl- 4-
(4-Chlorophenyl) -4H-azurenyl]} hafnium (118) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-3-methylphenyl) -4H-azurenyl] [2- Ethyl-4-
(4-Chlorophenyl) -4H-azurenyl]} hafnium (119) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-3-trifluoromethylphenyl) -4H-azurenyl] [ 2-
Ethyl-4- (4-chlorophenyl) -4H-azurenyl]} hafnium (120) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-3-chlorophenyl) -4H-azurenyl] [2-ethyl-4-
(4-Chlorophenyl) -4H-azurenyl]} hafnium (121) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-3-fluorophenyl) -4H-azurenyl] [2- Ethyl-4
-(4-Chlorophenyl) -4H-azurenyl]} hafnium (122) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-ethylphenyl) -4H-azurenyl] [2-ethyl-4- (4-
Chlorophenyl) -4H-azurenyl]} hafnium (123) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-methylphenyl) -4H-azurenyl] [2-ethyl -4- (4-
Chlorophenyl) -4H-azurenyl]} hafnium (124) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-trifluoromethylphenyl) -4H-azurenyl] [2 -Ethyl-4- (4-chlorophenyl) -4H-azurenyl]}
Hafnium (125) dichloro {1,1'-dimethylsilylene bis [2-ethyl-4- (4-t-butyl-3-chlorophenyl) -4H-azurenyl] [2-ethyl-4- (4-
Chlorophenyl) -4H-azurenyl]} hafnium (126) dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-fluorophenyl) -4H-azurenyl] [2-ethyl -4- (4
-Chlorophenyl) -4H-azurenyl]} hafnium

As described above, in the above compound, one or both of the two chlorine atoms corresponding to the X and Y moieties of the general formula (I) is a hydrogen atom, a fluorine atom, a bromine atom,
Examples thereof include compounds substituted for iodine atom, methyl group, phenyl group, fluorophenyl group, benzyl group, methoxy group, dimethylamino group, diethylamino group and the like. It is also equivalent to the compounds in which the central metal (M) of the above-exemplified compounds is replaced by titanium or zirconium instead of hafnium.

The olefin polymerization catalyst component comprising the transition metal compound of the present invention can be used in an olefin polymerization catalyst. For example, the olefin polymerization catalyst component described below containing the olefin polymerization catalyst component as the component (A). It is preferable to use as a polymerization catalyst for the catalyst (1) for olefin polymerization and the catalyst (2) for olefin polymerization.

The olefin polymerization catalyst (1) which is the second invention of the present invention will be explained. The olefin polymerization catalyst (1) comprises a component (A), a component (B) and an optional component (C).
It is a catalyst containing. The component (B) is selected from the group consisting of an aluminumoxy compound, an ionic compound capable of reacting with the component (A) and converting the component (A) into a cation, or a Lewis acid, and an optional component ( C) is
It is a fine particle carrier. It should be noted that some of the above Lewis acids can be understood as ionic compounds capable of reacting with the component (A) and converting the component (A) into a cation. Therefore, the compounds belonging to both the above-mentioned Lewis acid and ionic compound shall belong to either one.

Specific examples of the above aluminum oxy compound include the following general formula (V), (VI) or (VI)
Examples thereof include compounds represented by I).

[0071]

[Chemical 8]

The above general formulas (V), (VI) and (V)
In II), R ³⁴ is a hydrogen atom or a hydrocarbon residue, preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms.
The hydrocarbon residue of is shown. Further, the plurality of R ³⁴ may be the same or different. Also, p is 0 to 40,
It is preferably an integer of 2 to 30.

The compounds represented by the general formulas (V) and (VI) are compounds also called alumoxane, and are obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminum with water. Specifically, (a) methylalumoxane, ethylalumoxane, propylalumoxane, butylalumoxane, isobutylalumoxane, and (b) two kinds of trialkylaluminum obtained from one kind of trialkylaluminum and water. Methyl ethyl alumoxane, methyl butyl alumoxane, methyl isobutyl alumoxane, etc. which are obtained from water are exemplified. Of these, methylalumoxane or methylisobutylalumoxane is preferable.

The above alumoxanes can be used in combination in each group and between each group. The alumoxane can be prepared under various known conditions. Specifically, the following methods can be exemplified. (A) A method in which a trialkylaluminum is directly reacted with water in the presence of a suitable organic solvent such as toluene, benzene or ether. (B) A method of reacting a trialkylaluminum with a salt hydrate having water of crystallization, for example, copper sulfate or aluminum sulfate hydrate. (C) A method of reacting trialkylaluminum with moisture impregnated in silica gel or the like. (D) A method in which trimethylaluminum and triisobutylaluminum are mixed and then directly reacted with water in the presence of a suitable organic solvent such as toluene, benzene or ether.

(E) A method in which a mixture of trimethylaluminum and triisobutylaluminum and a salt hydrate having water of crystallization, for example, a hydrate of copper sulfate or aluminum sulfate are reacted by heating. (F) A method in which silica gel or the like is impregnated with water, treated with triisobutylaluminum, and then additionally treated with trimethylaluminum. (G) A method of synthesizing methylalumoxane and isobutylalumoxane by a known method, mixing a predetermined amount of these two components, and reacting by heating. (H) A method in which a salt having water of crystallization such as copper sulfate pentahydrate and trimethylaluminum are added to an aromatic hydrocarbon solvent such as benzene or toluene and reacted under a temperature condition of about -40 to 40 ° C.

The amount of water used in the above reaction is usually 0.5 to 1.5 in terms of molar ratio to trimethylaluminum. The methylalumoxane obtained by the above method is a linear or cyclic organoaluminum polymer.

The compound represented by the general formula (VII) is a compound of one kind of trialkylaluminum or two or more kinds of trialkylaluminum and an alkylboronic acid represented by the following general formula (VIII): 1: 1 (molar ratio)
It can be obtained by the reaction of. General formula (VIII)
In the formula, R ³⁵ has 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
6 represents a hydrocarbon residue or a halogenated hydrocarbon group. R ³⁵ B (OH) ₂ (VIII)

Specifically, the following reaction products can be exemplified. (A) Trimethylaluminum and methylboronic acid 2:
1 reaction product (b) triisobutylaluminum and methylboronic acid 2: 1 reaction product (c) trimethylaluminum, triisobutylaluminum and methylboronic acid 1: 1: 1 reaction product (d) trimethylaluminum and ethylboronic acid 2: 1:
1 reaction product (e) of triethylaluminum and butylboronic acid 2:
1 reaction product

Further, examples of the ionic compound capable of reacting with the component (A) to convert the component (A) into a cation include compounds represented by the general formula (IX). [K] ^{e +} [Z] ^e- (IX)

In the general formula (IX), K is a cation component, and examples thereof include carbonium cation, tropylium cation, ammonium cation, oxonium cation, sulfonium cation and phosphonium cation. In addition, cations of metals that are themselves easily reduced, cations of organic metals, and the like are also included. Specific examples of the above cations include triphenyl carbonium,
Diphenylcarbonium, cycloheptatrienium,
Indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, dicyclohexylammonium, triphenylphosphonium, trimethylphosphonium, tris (dimethylphenyl) phosphonium, tris (methylphenyl) phosphonium,
Triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion,
Gold ion, platinum ion, copper ion, palladium ion,
Examples include mercury ions and ferrocenium ions.

In the above general formula (IX), Z is an anion component, and the component (A) is a component (generally a non-coordinating component) which becomes a counter anion with respect to the converted cation species. As Z, for example, an organic boron compound anion,
Organic aluminum compound anions, organic gallium compound anions, organic phosphorus compound anions, organic arsenic compound anions, organic antimony compound anions, and the like,
Specifically, the following anions are listed.

(A) Tetraphenylboron, tetrakis (3,4,5-trifluorophenyl) boron, tetrakis {3,5-bis (trifluoromethyl) phenyl}
Boron, tetrakis {3,5-di (t-butyl) phenyl} boron, tetrakis (pentafluorophenyl) boron, etc. (b) tetraphenylaluminum, tetrakis (3,3)
4,5-trifluorophenyl) aluminum, tetrakis {3,5-bis (trifluoromethyl) phenyl}
Aluminum, tetrakis (3,5-di (t-butyl))
(Phenyl) aluminum, tetrakis (pentafluorophenyl) aluminum, etc.

(C) Tetraphenylgallium, tetrakis (3,4,5-trifluorophenyl) gallium, tetrakis {3,5-bis (trifluoromethyl) phenyl} gallium, tetrakis {3,5-di (t- Butyl)
Phenyl} gallium, tetrakis (pentafluorophenyl) gallium, etc. (d) Tetraphenylphosphorus, tetrakis (pentafluorophenyl) phosphorus, etc. (e) Tetraphenylarsenic, tetrakis (pentafluorophenyl) arsenic, etc. (f) Tetraphenylantimony, tetrakis (Pentafluorophenyl) antimony, etc. (g) Decaborate, undecaborate, carbadodecaborate, decachlorodecaborate, etc.

Examples of Lewis acids, particularly Lewis acids capable of converting the component (A) into cations, include various organic boron compounds, metal halogen compounds, solid acids and the like. Specific examples thereof include the following compounds. Is mentioned.

(A) Triphenylboron, tris (3,
Organoboron compounds such as 5-difluorophenyl) boron and tris (pentafluorophenyl) boron (b) Aluminum chloride, aluminum bromide, aluminum iodide, magnesium chloride, magnesium bromide, magnesium iodide, magnesium chloride bromide, chloride Metal halide compounds such as magnesium iodide, magnesium bromide iodide, magnesium chloride hydride, magnesium chloride hydroxide, magnesium bromide hydroxide, magnesium chloride alkoxide, magnesium bromide (c) Alumina, solid acids such as silica-alumina

In the olefin polymerization catalyst (1) of the present invention, the fine particle carrier as the optional component (C) is made of an inorganic or organic compound, and usually has a particle diameter of 5 μm to 5 mm, preferably 10 μm to 2 mm. Carrier.

As the above-mentioned inorganic carrier, for example, SiO
₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B
₂ O ₃ , oxides such as ZnO, SiO ₂ —MgO, SiO
_{2 -Al 2 O 3, SiO 2} -TiO 2, SiO 2 -Cr
Examples thereof include composite oxides such as ₂ O ₃ and SiO ₂ —Al ₂ O ₃ —MgO.

Examples of the above organic carrier include (co) polymers of α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, styrene, divinylbenzene and the like. Examples thereof include fine particle carriers of porous polymers composed of (co) polymers of aromatic unsaturated hydrocarbons. The specific surface area of these fine particles is usually 20 to 1000 m ² / g, preferably 50 to 700 m.
² / g, and the pore volume is usually 0.1 cm ² / g or more, preferably 0.3 cm ² / g, more preferably 0.1.
It is 8 cm ² / g or more.

The olefin polymerization catalyst (1) of the present invention is
As an optional component other than the fine particle carrier, for example, active hydrogen-containing compounds such as H ₂ O, methanol, ethanol and butanol, electron donating compounds such as ethers, esters and amines, phenyl borate, dimethylmethoxyaluminum,
It can include alkoxy containing compounds such as phenyl phosphite, tetraethoxysilane, diphenyldimethoxysilane.

As optional components other than the above, tri-lower alkylaluminum such as trimethylaluminum, triethylaluminum and triisobutylaluminum, halogen-containing alkylaluminum such as diethylaluminum chloride, diisobutylaluminum chloride and methylaluminum sesquichloride, diethylaluminum. Alkyl aluminum hydride such as hydride,
Examples thereof include alkoxy-containing alkyl aluminum such as diethyl aluminum ethoxide and dimethyl aluminum butoxide, and aryloxy-containing alkyl aluminum such as diethyl aluminum phenoxide.

In the olefin polymerization catalyst (1) of the present invention, the ionic compound or Lewis acid capable of reacting with the aluminum oxy compound, the component (A) to convert the component (A) into a cation is a component ( As B), besides being used individually, these three components can be used in an appropriate combination. One or more of the above lower alkylaluminums, halogen-containing alkylaluminums, alkylaluminum hydrides, alkoxy-containing alkylaluminums, aryloxy-containing alkylaluminums, which are optional components, are aluminumoxy compounds, ionic compounds or It is preferably contained in the olefin polymerization catalyst (1) in combination with a Lewis acid.

The olefin polymerization catalyst (1) of the present invention is
It can be prepared by bringing the above-mentioned components (A) and (B) into contact with each other in the presence or absence of the monomer to be polymerized inside or outside the polymerization tank. That is, the components (A) and (B) and, if necessary, the component (C) and the like may be separately introduced into the polymerization tank, or the components (A) and (B) may be preliminarily contacted with each other and then added to the polymerization tank. May be introduced. Alternatively, the mixture of the components (A) and (B) may be impregnated in the component (C) and then introduced into the polymerization tank.

The above components may be brought into contact with each other in an inert gas such as nitrogen or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene or xylene. The contact temperature is in the range of −20 ° C. to the boiling point of the solvent, in particular,
Temperatures in the range of room temperature to the boiling point of the solvent are preferred. The catalyst thus prepared may be used without washing after preparation, or may be used after washing. Furthermore, after the preparation, new components may be used in combination if necessary.

Further, the components (A), (B) and the component (C)
It is also possible to carry out so-called pre-polymerization in which a part of the olefin is polymerized by allowing a monomer to be polymerized to exist when it is previously contacted. That is, prior to polymerization, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4
It is also possible to preliminarily polymerize an olefin such as -methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like, and use the washed preliminarily polymerized product as a catalyst. This prepolymerization is preferably carried out under a mild condition in an inert solvent.
It is usually 0.01 to 1000 g, preferably 0.
It is preferable to carry out so as to produce 1 to 100 g of the polymer.

The amounts of components (A) and (B) used are arbitrary. For example, in the case of solvent polymerization, the amount of component (A) used is
As a transition metal atom, usually 10 ⁻⁷ to 10 ² mmol /
L, preferably in the range of 10 ^{−4 to 1} mmol / L. In the case of an aluminum oxy compound, the Al / transition metal molar ratio is usually 10 to 10 ⁵ , preferably 100 to 2.
× 10 ^4, more preferably is in the range of 100 to 10 ^4. On the other hand, when an ionic compound or a Lewis acid is used as the component (B), the molar ratio of these to the transition metal is usually 0.1 to 1000, preferably 0.5 to 10.
The range is 0, more preferably 1 to 50.

The olefin polymerization catalyst (2), which is the third invention of the present invention, will be explained. The olefin polymerization catalyst (2) comprises a component (A), a component (D) and an optional component (E).
It is a catalyst containing. The component (D) is selected from the group consisting of ion-exchange layered compounds excluding silicates or inorganic silicates, and the optional component (E) is an organoaluminum compound.

As the ion-exchangeable layered compound excluding the silicate of the above component (D), there are ionic crystalline compounds having a layered crystal structure such as hexagonal closest packing type, antimony type, CdCl ₂ type and CdI ₂ type. Specific examples thereof include α-Zr (HAsO ₄ ) ₂ · H ₂ O and α-Z.
_{r (HPO 4) 2, α} -Zr (KPO 4) 2 · 3H
₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAs
O ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O,
γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ
-Ti _{(NH 4} PO ₄₎ polyvalent metal crystalline acid salts of such 2 · _{H 2} O and the like.

The above ion-exchangeable layered compound may be subjected to salt treatment and / or acid treatment, if necessary, and then used. The ion-exchangeable layered compound excluding silicate, which is not subjected to salt treatment or acid treatment, is a compound having a crystal structure in which planes constituted by ionic bonds and the like are stacked in parallel with each other with weak bonding forces, It is possible to exchange the contained ions.

Examples of the above-mentioned inorganic silicate include clay, clay mineral, zeolite, diatomaceous earth and the like. They are,
Synthetic products may be used, or naturally occurring minerals may be used. Specific examples of clay and clay minerals include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite, and anoxite, halloysites such as metahalloysite, halloysite, chrysotile, lizardite, serpentine such as antigorite. Stone family, montmorillonite, sauconite, beidellite,
Smectites such as nontronite, saponite, hectorite, vermiculite minerals such as vermiculite,
Examples include mica minerals such as illite, sericite, glauconite, attapulgite, sepiolite, palygorskite, bentonite, kibushi clay, gyrome clay, hisingelite, pyrophyllite, and ryokdee stones. These may form a mixed layer. Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, and the like.

Among the above inorganic silicates, the kaolin group,
Halosite, serpentine, smectite, vermiculite mineral, mica mineral, synthetic mica, synthetic hectorite, synthetic saponite or synthetic teniolite is preferable, and smectite, vermiculite mineral, synthetic mica, synthetic hectorite, synthetic saponite or synthetic teniolite is further used. preferable. These may be used as they are without any particular treatment, or may be used after treatments such as ball milling and sieving. Moreover, you may use it individually or may mix and use 2 or more types.

The above-mentioned inorganic silicate can be subjected to salt treatment and / or acid treatment to change the solid acid strength, if necessary. In addition, in the salt treatment, the surface area and the interlayer distance can be changed by forming an ionic complex, a molecular complex, an organic derivative and the like. That is, by utilizing the ion exchanging property and substituting the exchangeable ion between the layers with another large bulky ion, it is possible to obtain a layered substance in a state where the layers are expanded.

The ion-exchangeable layered compound and the inorganic silicate may be used untreated, but the exchangeable metal cations contained therein are the cations and ions dissociated from the salts and / or acids shown below. It is preferable to replace it. The salt used for the above-mentioned ion exchange is a compound containing a cation containing at least one atom selected from the group consisting of atoms of Groups 1 to 14 of the Periodic Table, preferably from atoms of the Groups 1 to 14 of the Periodic Table. A compound comprising a cation containing at least one atom selected from the group consisting of: and an anion derived from at least one atom or group selected from the group consisting of a halogen atom, an inorganic acid and an organic acid. And more preferably, a cation containing at least one atom selected from the group consisting of atoms of Groups 2 to 14 of the Periodic Table, Cl, Br, I, F, PO ₄ , SO ₄ , and NO ₃ ,
CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ C
OCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (C
10 ₄ ) ₂ , O (SO ₄ ), OH, O ₂ Cl ₂ , OCl
₃ , at least one anion selected from the group consisting of OOCH and OOCCH ₂ CH ₃ . Also, two or more of these salts may be used at the same time.

The acid used for the above ion exchange is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid, and two or more of them may be used at the same time. As a method of combining the salt treatment and the acid treatment, a method of performing the acid treatment after performing the salt treatment, a method of performing the salt treatment after performing the acid treatment, a method of simultaneously performing the salt treatment and the acid treatment,
There is a method of performing salt treatment and acid treatment at the same time after performing salt treatment. In addition to the effect of ion exchange and removal of surface impurities, the acid treatment has a crystalline structure of Al, Fe, M.
It has an effect of eluting a part of cations such as g and Li.

The treatment conditions with salts and acids are not particularly limited. However, normally the salt and acid concentrations will be less than 0.
1 to 30% by weight, the treatment temperature is from room temperature to the boiling point of the solvent used, and the treatment time is 5 minutes to 24 hours. Further, salts and acids are generally used as an aqueous solution.

When the above-mentioned salt treatment and / or acid treatment is carried out, the shape may be controlled by crushing or granulating before, during or after the treatment. Further, other chemical treatments such as alkali treatment, organic compound treatment, and organic metal treatment may be used together. The component (D) thus obtained has a pore volume of 0.1 c or more measured with a mercury penetration method and having a radius of 20 Å or more.
It is preferably c / g or more, particularly 0.3 to 5 cc / g. When such component (D) is treated in an aqueous solution,
Includes adsorbed water and interlayer water. Here, the adsorbed water is water adsorbed on the surface of the ion-exchange layered compound or the inorganic silicate or on the crystal fracture surface, and the interlayer water is water existing between the crystal layers.

In the present invention, the component (D) is preferably used after removing the adsorbed water and interlayer water as described above. The dehydration method is not particularly limited, but heat dehydration,
Methods such as heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. The heating temperature is
The temperature range is set so that adsorbed water and interlayer water do not remain,
The temperature is usually 100 ° C. or higher, preferably 150 ° C. or higher, but high temperature conditions that cause structural destruction are not preferable. The heating time is 0.5 hours or longer, preferably 1 hour or longer. At that time, the weight loss of the component (D) after dehydration and drying is preferably 3% by weight or less as a value when sucked for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg. In the present invention, when the component (D) whose weight loss is adjusted to 3% by weight or less is used, even when the component (D) is brought into contact with the essential component (A) and the optional component (E) described later, the same weight loss is achieved. It is preferable to handle so that the state is maintained.

In the olefin polymerization catalyst (2) of the present invention, an example of the organoaluminum compound as the optional component (E) is represented by the following general formula (X). AlR ³⁶ _a P _3-a (X)

In the general formula (X), R ³⁶ has 1 to 2 carbon atoms.
0 represents a hydrocarbon group, P represents hydrogen, halogen, an alkoxy group or a siloxy group, and a represents a number greater than 0 and 3 or less. Specific examples of the organoaluminum compound represented by the general formula (X) include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum,
Examples thereof include halogen- or alkoxy-containing alkylaluminums such as diethylaluminum monochloride and diethylaluminum monomethoxide. Among these,
Trialkylaluminum is preferred. In the olefin polymerization catalyst (2) of the present invention, as the component (E),
In addition to the organoaluminum compound represented by the general formula (X), aluminoxanes such as methylaluminoxane can be used. Further, the above organoaluminum compound and aluminoxane can be used in combination.

The olefin polymerization catalyst (2) of the present invention is
It can be prepared by the same method as in the case of the olefin polymerization catalyst (1). At this time, the method of contacting the component (A) and the component (D) with the optional component (E) is not particularly limited, but the following method can be exemplified.

(1) Method of contacting component (A) with component (D) (2) Method of contacting component (A) with component (D) and then adding optional component (E) (3) Method for adding component (D) after contacting component (A) with optional component (E) (4) Adding component (A) after contacting component (D) with optional component (E) Method (5) The components (A), (D) and (E) are brought into contact with each other at the same time.

This contact may be carried out not only during the preparation of the catalyst but also during the prepolymerization with the olefin or during the polymerization of the olefin. During or after the contact of each of the above components, a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or alumina may coexist or contact.

The above components may be contacted with each other in an inert gas such as nitrogen or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene or xylene. The contacting is carried out at a temperature between −20 ° C. and the boiling point of the solvent, and particularly preferably at a temperature between room temperature and the boiling point of the solvent.

The amounts of the above components used are as follows.
That is, the component (A) is usually 10 ^{−4 to} 10 mmol, preferably 10 ^{−3 to 5} mm per 1 g of the component (D).
and the component (E) is usually 0.01 to 10 ⁴ mm.
ol, preferably 0.1 to 100 mmol. The atomic ratio of the transition metal in the component (A) to the aluminum in the component (E) is usually 1: 0.01 to 10 ⁶ , preferably 1: 0.1 to 10 ⁵ . The catalyst thus prepared may be used without washing after preparation, or may be used after washing. Moreover, you may newly combine and use the arbitrary component (E) as needed. At this time, the amount of the optional component (E) used is 1 to 10 ⁴ , preferably 1 to 10 in terms of atomic ratio of aluminum in the optional component (E) to the transition metal in the component (A). Selected to be ⁴ .

Next, a method for producing an olefin polymer according to the fourth aspect of the present invention will be described. In the present invention, the catalyst of the present invention and the olefin are brought into contact with each other to carry out polymerization or copolymerization. The olefin polymerization catalyst (1) or (2) of the present invention is applied not only to solvent polymerization using a solvent, but also to liquid phase solvent-free polymerization, gas phase polymerization, and melt polymerization substantially without using a solvent. To be done. The polymerization method is
Either continuous polymerization or batch polymerization may be used.

Solvents for solvent polymerization include hexane, heptane, pentane, cyclohexane, benzene,
An inert saturated aliphatic or aromatic hydrocarbon such as toluene is used alone or as a mixture. The polymerization temperature is usually -78 to 250 ° C, preferably -20 to 100 ° C. The olefin pressure of the reaction system is not particularly limited, but is preferably in the range of normal pressure to 2000 kgf / cm ² G, more preferably normal pressure to 50 kgf / cm ² G.
Also, the molecular weight can be adjusted by a known means such as selection of temperature or pressure or introduction of hydrogen.

As the starting olefin, an α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms is used, and specific examples thereof include ethylene, propylene and 1
-Butene, 4-methyl-1-pentene, 1-hexene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like can be mentioned. The catalyst of the present invention is preferably used for the polymerization of α-olefins having 3 to 10 carbon atoms, particularly propylene, for the purpose of stereoregular polymerization.

The catalyst of the present invention can also be applied to the above-mentioned α-olefins or copolymerization of α-olefins with other monomers. Examples of the other monomer copolymerizable with α-olefin include butadiene and 1,4-
Hexadiene, 1,5-hexadiene, 7-methyl-
1,6-octadiene, 1,8-nonadiene, 1,9-
Included are conjugated and non-conjugated dienes such as decadiene, and cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, norbornene and dicyclopentadiene. In the polymerization, so-called multi-stage polymerization in which conditions are changed in multiple stages, for example, so-called block copolymerization in which propylene is polymerized in the first stage and ethylene and propylene are copolymerized in the second stage, is also possible.

By using the transition metal compound of the present invention as a catalyst component for olefin polymerization, effects such as high melting point, high molecular weight and low MFR of the obtained polymer can be achieved, as shown in Examples described later. It The reason for this is not clear, but it can be estimated as follows. That is, the substituent R ⁷ and / or R ⁸ in the transition metal compound of the present invention is the R to which it is bonded.
^{Since 3} and / or R ⁶ forms a condensed ring having 7 or more members, it occupies a steric configuration with a certain angle from the condensed ring plane formed by the 5-membered ring portion and R ³ and / or R ^6. . Moreover, the substituents R ⁷ and R ⁸ are sterically bulky as compared with the unsubstituted phenyl group and form appropriate steric hindrance and shape. As a result, it is presumed that the action of regulating the growth direction of the polymer chain and the coordination direction of the monomer is enhanced, the stereoregularity of the produced polymer is improved, and a polymer having a high melting point is obtained.

[0119]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to the following examples without departing from the gist thereof. In the following examples, the catalyst synthesis step and the polymerization step were all performed in a purified nitrogen atmosphere, and the solvent was dehydrated with MS-4A and then deaerated by bubbling with purified nitrogen. In addition, the activity per solid catalyst component is expressed as the catalytic activity (unit: g-polymer / g-solid · time), and the activity per complex component is expressed as the complex activity (unit: g-polymer / g-complex · time). .

(1) Measurement of MFR: To 6 g of the polymer was added 6 g of an acetone solution (0.6% by weight) of a heat stabilizer (BHT). Then, after drying the above-mentioned polymer, it was filled in a melt indexer (230 ° C.) and left under a condition of 2.16 kg load for 5 minutes. Then, measure the extruded amount of the polymer and convert it into the amount per 10 minutes.
The value of (2) Measurement of melting point: DSC ("TA200" manufactured by DuPont)
Type 0 ”) was used, and the temperature was raised and lowered once from 20 to 200 ° C. at 10 ° C./minute, and then measured during the second heating.

Comparative Example 1 Synthesis of dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilylphenyl) -4H-azulenyl]} hafnium (1) Synthesis of ligand p-dibromobenzene (10.0 g) was dissolved in diethyl ether (100 ml), and a hexane solution of n-butyllithium (1.54M, 27.6 ml) was added dropwise at -78 ° C. After stirring at that temperature for 10 minutes, the cooling bath was removed and 2.
After stirring for 5 hours, the mixture was cooled again, and trimethylsilyl chloride (5.65 ml) was added dropwise at -78 ° C. After removing the cooling bath and stirring for 2.5 hours, the reaction solution was poured into saturated saline and extracted with diethyl ether, and the organic layer was dried over magnesium sulfate. The residue (11 g) obtained by distilling off the solvent was purified by silica gel column chromatography (eluting solvent: n-hexane: ethyl acetate = 100: 1) to obtain 4
-Trimethylsilyl bromobenzene (9.3 g) was obtained (yield 96%). ¹ H-NMR (CDCl ₃ ) δ 0.25 (s, 9
H), 7.38 (d, J = 1.8 Hz, 2H),
7.47 (d, J = 1.8 Hz, 2H).

The 4-trimethylsilylbromobenzene (2.59 g) obtained above was dissolved in a mixed solvent of hexane (30 ml) and diethyl ether (30 ml), and -7
Cooled to 8 ° C. A pentane solution of t-butyllithium (1.51M, 14.9 ml) was added dropwise at -78 ° C.
After stirring at -78 ° C for 10 minutes, the temperature of the reaction solution was gradually raised to 0 ° C. When the temperature of the reaction solution reached 0 ° C, 2-ethylazulene (1.59 g) was added all at once,
Stir for 1.5 hours. After cooling to −5 ° C. again, tetrahydrofuran (30 ml), N-methylimidazole (3
0 μl) was added, and dimethylsilyl dichloride (0.62 ml) was added dropwise at −5 ° C. After removing the cooling bath and stirring for 1.5 hours, the reaction solution was poured into a saturated saline solution and extracted with diethyl ether. The organic layer was dried over magnesium sulfate and the solvent was distilled off. The obtained crude purified product (3.7 g) was subjected to silica gel column chromatography (elution solvent: n-
The desired ligand (1.81 g) was obtained by purification with hexane: ethyl acetate = 65: 1 (yield 53%).

(2) Synthesis of complex The above ligand (1.63 g) was converted into diethyl ether (15
ml), cooled to −78 ° C., and added with n-hexane solution of n-butyllithium (1.57 M, 3.1 ml).
78 ° C. was added dropwise. After stirring at -78 ° C for 10 minutes, the cooling bath was removed and the mixture was stirred for 2 hours. After adding toluene (110 ml), the mixture was cooled to −78 ° C. again, hafnium tetrachloride (0.78 g) was added, and the mixture was stirred at that temperature for 10 minutes. Then, the cooling bath was removed and the mixture was stirred overnight, and the reaction solution was concentrated to about 1/2. The concentrate was transferred onto a G3 frit, the solid on the frit was further washed with toluene, and the filtrate was concentrated to give a brown powder. N-Hexane was added to this brown powder, and the mixture was stirred and allowed to stand, and the supernatant was removed. After performing the same operation, the powder was washed with ethanol several times. Then, the suspension was washed with n-hexane and dried. Further, by washing with a mixed solvent of n-hexane and diethyl ether, the target dichloro {1,1 '
-Dimethylsilylene bis [2-ethyl-4- (4-trimethylsilylphenyl) -4H-azulenyl]} hafnium racemate (0.31 g) was obtained (yield 15%). ¹ H-NMR (CDCl ₃ ) δ 0.26-0.3
(M, 18H), 0.99 (s, 6H), 1.05
(T, J = 6.9 Hz, 6H), 2.4-2.6
(M, 2H), 2.6-2.8 (m, 2H), 5.
30 (d, J = 3.6 Hz, 2H), 5.85-6.
2 (m, 6H), 5.98 (s, 2H), 6.78
(D, J = 11.7 Hz, 2H), 7.35 (d, J
= 9.0 Hz, 4H), 7.49 (d, J = 9.0H)
z, 4H), 7.4-7.6 (m, 2H)

(3) Polymerization of propylene with methylalumoxane as a cocatalyst Into a stirring autoclave having an internal volume of 1 L, 8 mmol of methylalumoxane (“MMAO” manufactured by Tosoh Akzo Co., Ltd.) was added.
(Al atom conversion) was introduced. On the other hand, 0.68 mg of the above racemate was diluted with toluene and introduced into a catalyst feeder equipped with a rupturable plate. Then, after introducing 700 ml of propylene into the autoclave, the rupture disc was cut at room temperature,
The temperature was raised to 0 ° C. and a polymerization operation was performed for 30 minutes to obtain 95 g of a polymer. The complex activity was 28 × 10 ⁴ . Polypropylene has an MFR of 0.11 g / 10 minutes and a melting point of 159.
It was 2 ° C.

(4) Polymerization of propylene with clay mineral as co-catalyst (a) Chemical treatment of clay mineral Magnesium sulfate heptahydrate (133 g), sulfuric acid (10
9 g) in ion-exchanged water (660 ml),
Commercially available granulated montmorillonite (100 g, manufactured by Mizusawa Chemical Co., Inc., Benclay SL) was dispersed, heated to 100 ° C. in 2 hours, and maintained at that temperature for 2 hours. Then, it cooled to room temperature over 1 hour. The slurry was filtered and the cake was collected. Pure water (3 L) was added to re-slurry and then filtered. This operation was repeated twice more. The collected cake was dried overnight at 110 ° C. under a nitrogen atmosphere. As a result, 80 g of a chemically treated carrier was obtained. This chemically treated montmorillonite 400 mg has a concentration of 0.5 mol /
1.6 ml of toluene solution of L triethylaluminum
Was added and the mixture was stirred at room temperature for 1 hour. Then, it wash | cleaned by toluene and 33 mg / mL montmorillonite-toluene slurry was obtained.

(B) 0.25 mm of triisobutylaluminum (manufactured by Tosoh Akzo Co.) in a stirring autoclave having an internal volume of 1 L.
ol (Al atom conversion) was introduced. On the other hand, the complex (1.27 mg, 1.39 μmol) obtained in Comparative Example 1 (2) was diluted with toluene and introduced into a catalyst feeder equipped with a rupture plate, and further obtained in Comparative Example 1 (4). Clay slurry (1.5 mL) and triisobutylaluminum (0.015 mmol, Al atom conversion) were introduced.
After putting propylene (700 mL) in the autoclave, cut the rupture plate at room temperature, raise the temperature to 80 ° C.,
Polymerization was performed for minutes to obtain polypropylene (151.5 g). The complex activity was 24 × 10 ⁴ , and the catalyst activity was 6,100. The MFR of polypropylene is 0.45g / 10
Min, melting point was 157.4 ° C.

Example 1 Dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (3-chloro-4-t-butylphenyl) -4H]
-Azulenyl]} hafnium synthesis (1) 4-t-butyl-3-chloro-bromobenzene synthesis 4-t-butyl-3-bromo-nitrobenzene (35.
75 g, 0.139 mol) (Recueil, 196)
0, 79, 1022. Synthetic) and cuprous chloride (1
38.0 g, 1.44 mol of α-picoline (200
The suspension was heated at 130 ° C. for 10 hours, cooled, and extracted with hexane. The organic phase is diluted with dilute hydrochloric acid and saturated NaHCO _3.
The extract was washed with an aqueous solution and saturated brine, dried over magnesium sulfate, and concentrated. The obtained crude product was suspended and washed with hexane to give 4-t-butyl-3-chloro-nitrobenzene (23.66 g, 0.111 mol, 73.7% yield).
was gotten. 4-t-butyl-3-chloro-nitrobenzene (18.33 g, 85.8 mmol) and iron powder (1
4.44 g, 0.259 mol) of ethanol / water (2
The suspension (8 ml / 10 ml) was refluxed. A mixed solution of hydrochloric acid (1 ml) and 50% ethanol (4.3 ml) was added dropwise to the suspension. After refluxing for 5 hours, the precipitate was filtered off. The filtrate was treated with 6N sulfuric acid and a saturated NaHCO ₃ aqueous solution, washed with saturated saline, dried over magnesium sulfate, and concentrated. By distilling the crude product, 4-t-
Butyl-3-chloroaniline (13.88 g, 75.5)
mmol, 88.0% yield) was obtained.

4-t-butyl-3-chloroaniline (1
3.73 g, 72.1 mmol) with 48% HBr water added dropwise
The white suspension was cooled to 0 ° C. There Na
NO _Two(4.97 g, 72.0 mmol) in water (3
(7 ml) was slowly added dropwise, and the mixture was stirred at 0 ° C for 1 hour.
It was CuBr (95.2mmo) cooled to 0 ° C
1) HBr solution (30 ml) was slowly added dropwise. drop
After the bottom was finished, the mixed solution was stirred at 50 ° C. for 30 minutes. A
The organic matter is extracted with tell, and the extract is saturated NaHCO 3.
_ThreeAfter washing with magnesium sulfate, wash with saturated saline
Dried and concentrated. Target by distilling the crude product
Compound (7.49 g, 30.2 mmol, 41.9% yield
Rate) was obtained.

(2) Dimethylsilylene bis {2-ethyl-4- (4-t-butyl-3-chlorophenyl) -1,
Synthesis of 4-dihydroazulene 4-t-butyl-3-chlorobromobenzene (5.0
g, 20.2 mmol) of diethyl ether (150 m
l) The solution was added with a solution of t-butyllithium in n-pentane (27.5 ml, 40.4 mmol, 1.47 N).
The mixture was added dropwise at 78 ° C and stirred for 0.5 hours. The temperature was gradually raised to 0 ° C., and 2-ethylazulene (2.68 g,
(17.2 mmol) was added and the mixture was stirred at room temperature for 3 hours. n
-Hexane (30 ml) was added and the supernatant was removed by decantation. Furthermore, this operation was repeated once again. Tetrahydrofuran (90 ml) was added to the obtained yellow precipitate at 0 ° C. Then, N-methylimidazole (0.02 ml) and dimethyldichlorosilane (1.0
3 ml, 8.49 mmol) was added, the temperature was raised to room temperature, and the mixture was stirred for 1.5 hours. After this, distilled water was added, and after liquid separation, the organic phase was washed with saturated saline, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product of the desired product. Then, it was purified using column chromatography (silica gel manufactured by Merck & Co., Ltd., methylene chloride / n-hexane) to obtain the desired product (3.55 g, 60% yield).

(3) Synthesis of dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-t-butyl-3-chlorophenyl) -4H-azulenyl]} hafnium Then, obtained above. The resulting product (2.1 g) was dissolved in diethyl ether (10 ml), and n-hexane solution of n-butyllithium (3.8 ml, 5.93 mm) was added at -78 ° C.
ol, 1.56 N) was added dropwise, the temperature was gradually raised, and the mixture was stirred at 0 ° C. for 1 hour. Further, toluene (80 ml) was added, the mixture was cooled to -78 ° C, and hafnium tetrachloride (0.95
g, 3.97 mmol) was added, the temperature was gradually raised, and the mixture was stirred at room temperature for one day. The solvent was distilled off from the obtained slurry under reduced pressure, and the mixture was extracted with hexane. The extract solution was concentrated to dryness and washed with hexane at low temperature to obtain a meso-racemic mixture. 0.3 g of the resulting mixture was added to dichloromethane 15
It was dissolved in ml and irradiated with 10 spectra using a high pressure mercury lamp (100 W). The solvent was distilled off from this solution under reduced pressure, washing with hexane was repeated, and further washing with ether was performed to obtain the target dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (4-t-butyl). -3-chlorophenylyl)
-4H-azulenyl]} hafnium racemate 0.09
g was obtained. ¹ H-NMR (CDCl ₃ ) δ 1.00 (s, 6
H, SiMe ₂ ), 1.05 (t, J = 5.6 Hz,
_{6H, 2-CH 2 CH 3} ), 1.47 (s, 18H,
tBu), 2.4-2.5 (m, 2H, 2-CHHC
_{H 3), 2.6-2.7 (m,} 2H, 2-CHHCH
₃ ), 4.99 (d, J = 3.0 Hz, 2H, 4-
H), 5.8-6.1 (m, 6H), 6.78.
(D, J = 11.7 Hz, 2H), 7.2-7.6
(M, 12H)

(4) Polymerization of propylene with methylalumoxane as a cocatalyst Methylalumoxane (“MMAO” manufactured by Tosoh Akzo Co., Ltd.) (8.0 mm) was placed in a stirring autoclave having an internal volume of 2 L.
ol, Al atom conversion) was introduced. On the other hand, the above racemate (0.7 mg) was diluted with toluene and introduced into a catalyst feeder with a rupturable plate. Then, after introducing propylene (1400 mL) into the autoclave, the rupture plate was cut at room temperature, the temperature was raised to 70 ° C., and the polymerization operation was performed for 1 hour.
Polypropylene (29 g) was obtained. Complex activity is 4.1x
It was 10 ⁴ . The Tm of polypropylene is 162.7.
C., MFR was 0.04 g / 10 minutes.

(5) Polymerization of propylene with clay mineral as co-catalyst (a) Chemical treatment of clay mineral Magnesium sulfate heptahydrate (133 g), sulfuric acid (10
9 g) in ion-exchanged water (660 ml),
Commercially available granulated montmorillonite (100 g, manufactured by Mizusawa Chemical Co., Inc., Benclay SL) was dispersed, heated to 100 ° C. in 2 hours, and maintained at that temperature for 2 hours. Then, it cooled to room temperature over 1 hour. The slurry was filtered and the cake was collected. Pure water (3 L) was added to re-slurry and then filtered. This operation was repeated twice more. The collected cake was dried overnight at 110 ° C. under a nitrogen atmosphere. As a result, 80 g of a chemically treated carrier was obtained. This chemically treated montmorillonite 400 mg has a concentration of 0.5 mol /
1.6 mL of toluene solution of triethylaluminum
Was added and the mixture was stirred at room temperature for 1 hour. Then, it wash | cleaned by toluene and 33 mg / mL montmorillonite-toluene slurry was obtained.

(B) In a stirring autoclave having a polymerization internal volume of 2 L, triisobutylaluminum (manufactured by Tosoh Akzo) (0.25 mmo)
l) (Al atom conversion) was introduced. On the other hand, the catalyst (0.8 m) obtained in Example 1 (3) was added to the catalyst feeder equipped with a rupturable plate.
g) was diluted with toluene and introduced, and further, the above slurry containing montmorillonite (50 mg) and triisobutylaluminum (0.015 mmol, converted to Al atoms) were introduced. Then, propylene (1400 mL) was introduced into the autoclave, the rupture disc was cut at room temperature,
The temperature was raised to 80 ° C. and polymerization was carried out for 1 hour to obtain polypropylene (60.3 g). The catalyst activity was 1,200 and the complex activity was 4.3 × 10 ⁴ . The polypropylene had a Tm of 160.1 ° C. and an MFR of 0.5 g / 10 minutes.

Example 2 Synthesis of dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (3-chloro-4-trimethylsilylphenyl) -4H-azulenyl]} hafnium (1) 3-chloro-4 -Synthesis of trimethylsilylphenyl 3-chloro-4-iodo-bromobenzene (3.1 g)
Was dissolved in diethyl ether (100 ml), and the temperature was -78 ° C.
Solution of n-butyllithium in hexane (1.59M,
6.1 ml) was added dropwise. After stirring at that temperature for 30 minutes,
Trifluoromethanesulfonic acid trimethylsilyl (3.
(77 ml, 17.4 mmol) was added dropwise and stirred for 1 hour. After completion of the reaction, water was added little by little under an ice bath and then extracted with ether. The organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The target product (2.3 g) was obtained by purifying the obtained crude product twice by column chromatography (silica gel, hexane manufactured by Merck) (yield 90).
%). ¹ H-NMR (CDCl ₃ ) δ 0.35 (s, 9
H, TMS), 7.3-7.4 (m, 2H, aro
m), 7.50 (s, 1H, arm)

(2) Synthesis of Ligand The 3-chloro-4-trimethylsilyl-bromobenzene obtained in the above (1) was dissolved in a mixed solvent of hexane (50 ml) and diethyl ether (50 ml) to prepare t-butyl. Lithium pentane solution (1.51M, 11.6ml)
Was added dropwise at -78 ° C. After stirring at -78 ° C for 30 minutes, the temperature was raised to 0 ° C, and 2-ethylazulene (1.29
g) was added all at once and then the temperature was raised to room temperature immediately and the mixture was stirred for 1 hour. Tetrahydrofuran (50 ml) and N-methylimidazole (0.02 ml) were added, and dimethylsilyl dichloride (0.42 ml) was added dropwise at -5 ° C. After stirring at that temperature for 1.5 hours, distilled water was added to the reaction solution,
It was extracted with diethyl ether. The organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained crude product was subjected to column chromatography (Merck silica gel,
Hexane / methylene chloride) and dimethylsilylene bis {2-ethyl-4- (3-chloro-4-trimethylbenzene) -1,4-dihydroazulene} (2.5 g)
Was obtained (yield 98%).

(3) Synthesis of complex The ligand (2.5 g) obtained in the above (2) was dissolved in diethyl ether (15 ml), and n-butyllithium n was prepared.
-Hexane solution (1.59M, 4.3 ml) at -78 ° C
It was dripped at. The temperature was raised to 0 ° C., the mixture was stirred for 1 hour, toluene (120 ml) was added, the mixture was cooled to −78 ° C. again, and hafnium tetrachloride (1.09 g) was added. The temperature was raised slowly and the mixture was stirred at room temperature for 6 hours. The resulting reaction solution was once concentrated, extracted with hexane, and concentrated again to dryness.
The solid was further extracted with hexane at -78 ° C. Desired dichloro {1,1'-dimethylsilylene bis [2-
A mixture of ethyl-4- (3-chloro-4-trimethylsilylphenyl) -4H-azurenyl]} hafnium was obtained.

(4) Polymerization of Propylene with Methylalumoxane as a Cocatalyst The compound obtained in Example 2 (3) was used instead of the racemic compound obtained in Example 1 (3). The same operation as in Example 1 (3) was performed except that the complex mixture (3 mg) was used to obtain 42.3 g of polypropylene. The catalytic activity was 4.2 × 10 ⁴ . The Tm of polypropylene is 16
The temperature was 1.4 ° C. and the MFR was 0.08 g / 10 minutes.

(5) Polymerization of Propylene with Clay Mineral as Cocatalyst In Example 1 (5), instead of the racemic compound obtained in Example 1 (3), the complex mixture obtained in Example 2 (3) (6
The same operation as in Example 1 (5) was carried out except that (mg) was used to obtain 91 g of polypropylene. Complex activity is 7.9
The catalyst activity was × 10 ⁴ , and the catalytic activity was 1,820. Polypropylene has an MFR of 0.26 g / 10 minutes and a melting point of 160.7
It was ℃.

Example 3 Synthesis of dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-trimethylsilyl-3-methyl-phenyl) -4H-azulenyl]} hafnium: (1) Ligand Synthesis of 4-iodo-3-methyl-bromobenzene (6.3 g)
Was dissolved in diethyl ether (100 ml), and the temperature was -78 ° C.
Solution of n-butyllithium in n-hexane (1.56
M, 13.6 ml) was added dropwise. After stirring at that temperature for 30 minutes, trimethylsilyl chloride (4.0 ml, 3 ml
(1.8 mmol) was added dropwise, the temperature was raised to 0 ° C., and the mixture was stirred for 1 hour. After completion of the reaction, water was added, the mixture was extracted with ether, and the organic phase was dried over magnesium sulfate. The target product (5.0 g) was obtained by refine | purifying the crude product obtained by distilling a solvent off by column chromatography (Silica gel by Merck & Co., hexane) (yield 97%). ¹ H-NMR (CDCl ₃ ) δ 2.42 (s, 3
H), 7.3-7.4 (m3H)

(2) Synthesis of ligand 4-Trimethylsilyl-3-methyl-bromobenzene (3.0 g, 12.3 mmol) was added to hexane (30 m).
1) and diethyl ether (90 ml) dissolved in a mixed solvent, and a solution of t-butyllithium in pentane (1.47 M,
16.8 mL) was added dropwise at -78 ° C. 30 at -78 ° C
After stirring for 1 minute, the temperature was raised to 0 ° C., 2-ethylazulene (1.7 g, 10.9 mmol) was added all at once, the temperature was immediately raised to room temperature and the mixture was stirred for 1 hour. Further, tetrahydrofuran (40 ml) and N-methylimidazole (0.
02 mL) was added, dimethyldichlorosilane (0.67 mL) was added at -5 ° C, and the mixture was stirred for 1.5 hours. After that, water was added thereto for liquid separation, the organic layer was dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained composition organism was purified by column chromatography (silica gel manufactured by Merck & Co., Inc., n-hexane / methylene chloride), and the target dimethylsilylenebis {2-ethyl-4- (4-trimethylsilyl-
3-Methylphenyl) -1,4-dihydroazulene}
(2.7 g, yield 71%) was obtained.

(3) Synthesis of Complex Next, the ligand (2.7 g, 3.9 mmo) obtained above was used.
l) was dissolved in diethyl ether (15 ml) and n-butyllithium solution in n-hexane (1.56M, 5.0
ml) was added dropwise at -78 ° C. After stirring at -78 ° C for 1 hour, the temperature was raised to 0 ° C and the mixture was stirred for 1 hour. After adding toluene (120 ml) there, it cooled to -78 degreeC again, and hafnium tetrachloride (1.24 g, 3.9 mmo).
1) was added, then the temperature was gradually raised, and the mixture was stirred at room temperature overnight. The obtained reaction solution was concentrated once, extracted with hexane and concentrated again. When the product is further dissolved in hexane and cooled to 0 ° C., the racemic complex precipitates. Therefore, the supernatant is removed, and ether is extracted from the supernatant to obtain the target dichloro {1,1′-dimethylsilylenebis {2-ethyl-4- (4- Trimethylsilyl-3-methylphenyl) -4H-azurenyl}
A hafnium racemate (0.1 g) was obtained. ¹ H-NMR (CDCl ₃ ) δ 0.31 (s, 18
H, TMS), 0.99 (s, 6H, SiMe ₂ ),
1.03 (t, J = 5.5 Hz, 6H, 2-CH ₂ C
_{H 3), 2.5-2.6 (m,} 2H, 2-CHHCH
₃ ), 2.7-2.8 (m, 2H, 2-CHHC
H ₃ ), 5.02 (d, J = 2.7 Hz, 2H, 4-
H), 5.8-6.1 (m, 6H), 5.99.
(S, 2H), 6.75 (d, J = 8.73 Hz, 2
H), 7.1-7.5 (m, 12H)

(4) Using methylalumoxane as a cocatalyst
Polymerization of propylene In Example 1 (4), the lath obtained in Example 1 (3) was used.
Racemic body obtained in Example 3 (3) instead of the semimeric body
Same as Example 1 (4) except that (0.75 mg) was used.
The same operation was performed to obtain 50 g of polypropylene. Complex activity
Is 11.2 × 10 ^FourMet. The Tm of polypropylene is
It was 160.9 ° C. and MFR was 0.05 g / 10 minutes.

(5) Polymerization of Propylene with Clay Mineral as Promoter In Example 1 (5), the racemic body obtained in Example 3 (3) instead of the racemic body obtained in Example 1 (3). (1.
The same operation as in Example 1 (5) was performed except that 4 mg) was used, to obtain 31.7 g of polypropylene. The complex activity was 2.2 × 10 ⁴ , the catalyst activity was 600, the MFR of polypropylene was 0.5 g / 10 min, and the melting point was 158.9 ° C.

[0144]

EFFECT OF THE INVENTION When a novel transition metal compound of the present invention, an olefin polymerization catalyst component using the same, and an olefin polymerization catalyst are used to polymerize olefins, the growth direction of polymer chains and the coordination direction of monomers are regulated. The action is enhanced, the stereoregularity of the produced polymer is improved, and thus a polymer having a high melting point can be obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Fumihiko Shimizu             1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa             Within Mitsubishi Chemical Corporation (72) Inventor Nao Urata             3-3-1 Chuo 8-chome, Ami Town, Inashiki District, Ibaraki Prefecture             Within Mitsubishi Chemical Corporation F-term (reference) 4H049 VN01 VN07 VP01 VP02 VQ06                       VQ84 VR24 VU14 VW01                 4H050 AA01 AA03 AB40                 4J128 AA01 AB00 AB01 AC01 AC10                       AC28 AD06 AD07 AD08 AD11                       AD13 AD19 BA00A BA01B                       BB00A BB00B BB01B BC11B                       BC12B BC13B BC15B BC16B                       BC25B CA15C CA16C CA18C                       CA19C CA25C CA30C CA32C                       CA54C CB08C CB09C CB23C                       CB42C CB62C CB88C CB91C                       CB92C CB95C CB97C CB98C                       EB01 EB02 EB04 EB05 EB07                       EB09 EB10 EB13 EB15 EB18                       GA05 GA12 GA19 GB01

Claims (5)

[Claims] 1. An olefin polymerization catalyst component comprising a transition metal compound represented by the following general formula (I). [Chemical 1] (In the general formula (I), R ¹ , R ² , R ⁴ , and R ⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 7 carbon atoms. Or carbon number 1-6
Of the halogenated hydrocarbon group of R ³ and R ⁶ are bonded to a cyclopentadienyl ring to form a hydrocarbon ring of 5 to 10-membered hydrocarbon: R ⁴¹ and R ⁴² are each independently And a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, which substitutes a hydrogen atom of the condensed ring hydrocarbon bond portion of R ³ or R ⁶ , R ⁹ and R ¹² are
Each independently, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a halogenated hydrocarbon group having 1 to 6 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 7 carbon atoms: R ⁸ and R
¹¹ are each independently a silicon-containing hydrocarbon group having 3 to 9 carbon atoms, or a branched hydrocarbon group having 3 to 10 carbon atoms: R ⁷ and R ¹⁰ are each independently 1 to 1 carbon atoms; 3 hydrocarbon groups, halogenated hydrocarbons having 1 to 3 carbon atoms, halogen atoms: j and k are integers from 0 to 8 (when j or k is 2 or more, R ^{41 s} or R ^{42 s);}
They may be bonded to each other at any position to form a ring structure. ): M and n are integers from 0 to 3 (when m or n is 2 or more, R ^{9 s} or R ^{12 s} may be bonded at any position to form a ring structure): Q is Bridging groups connecting two cyclopentadienyl rings: X and Y
Are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms,
The oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, the amino group or the nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms: M each represents a transition metal of Group 4 of the periodic table. ) 2. An olefin polymerization catalyst comprising the following component (A), component (B) and optional component (C) as constituent components. Component (A): Catalyst component for olefin polymerization according to claim 1, Component (B): Aluminum oxy compound, ionic compound capable of reacting with Component (A) to convert Component (A) into cation, or Component (C) selected from the group consisting of Lewis acids: fine particle carrier 3. An olefin polymerization catalyst comprising the following component (A), component (B), and optional component (C) as constituent components. Component (A): Catalyst component for olefin polymerization according to claim 1 Component (D): A component selected from the group consisting of ion-exchangeable layer compounds excluding silicates or inorganic silicates Component (E): Organoaluminum compound 4. A method for producing an olefin polymer, which comprises polymerizing an olefin or copolymerizing it with another olefin in the presence of the catalyst for olefin polymerization according to claim 2 or 3. 5. A transition metal compound represented by the following general formula (I). [Chemical 2] (In the general formula (I), R ¹ , R ² , R ⁴ , and R ⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 7 carbon atoms. Or carbon number 1-6
Of the halogenated hydrocarbon group of R ³ and R ⁶ are bonded to a cyclopentadienyl ring to form a hydrocarbon ring of 5 to 10-membered hydrocarbon: R ⁴¹ and R ⁴² are each independently And a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, which substitutes a hydrogen atom of the condensed ring hydrocarbon bond portion of R ³ or R ⁶ , R ⁹ and R ¹² are
Each independently, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a halogenated hydrocarbon group having 1 to 6 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 7 carbon atoms: R ⁸ and R
¹¹ are each independently a silicon-containing hydrocarbon group having 3 to 9 carbon atoms, or a branched hydrocarbon group having 3 to 10 carbon atoms: R ⁷ and R ¹⁰ are each independently 1 to 1 carbon atoms; 3 hydrocarbon groups, halogenated hydrocarbons having 1 to 3 carbon atoms, halogen atoms: j and k are integers from 0 to 8 (when j or k is 2 or more, R ^{41 s} or R ^{42 s);}
They may be bonded to each other at any position to form a ring structure. ): M and n are integers from 0 to 3 (when m or n is 2 or more, R ^{9 s} or R ^{12 s} may be bonded at any position to form a ring structure): Q is Bridging groups connecting two cyclopentadienyl rings: X and Y
Are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms,
The oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, the amino group or the nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms: M each represents a transition metal of Group 4 of the periodic table. )