JP2002194016A - Metallocene compound, catalyst for olefin polymerization containing the same, and method for producing olefin polymer using the catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a metallocene compound excellent in the synthetic cost which can produce an olefin polymer with high molecular weight and significant high controlled stereoregularity, and to provide a metallocen catalyst containing the compound, and a method for producing the olefin polymer using the catalyst. SOLUTION: The metallocene compound has the formula: Q(C5H4-mR1m)(C5 H4-nR2n)MXY [wherein (C5H4-mR1m) and (C5H4-nR2n) are each a cyclopentadienyl group; C5H4-m and C5H4-n are each a cyclopentadienyl ring; among a linkage group represented by R1m and R2n, among a linkage group bound to a ring formed by a pair of R1 and that formed by a pair of R2 or other linkage groups, at least one linkage group is a hetero aromatic group having a hetero aromatic ring, and the linkage group is a 1-20C hydrocarbon group or a silicon-containing hydrocarbon group].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel metallocene compound useful as a catalyst component for olefin polymerization, and more particularly to a specific metallocene compound having a specific heteroaromatic group. Further, the present invention relates to an olefin polymerization catalyst containing the metallocene compound and a method for producing an olefin polymer using the same.

[0002]

2. Description of the Related Art Instead of the Ziegler-Natta catalyst conventionally used in the polymerization of olefins, π-electron donating groups such as unsubstituted or substituted cyclopentadienyl groups, unsubstituted or substituted Coordinating a polydentate compound containing an unsubstituted or substituted cycloalkadienyl group such as a substituted indenyl group, an unsubstituted or substituted tetrahydroindenyl group, an unsubstituted or substituted fluorenyl group. Some metallocene compounds, which are complex compounds, have begun to be used.

Particularly in recent years, various metallocene compounds having higher olefin polymerization activity per mole of transition metal atom have been proposed. For example, a chiral metallocene compound in which a polydentate compound in which two substituted cycloalkadienyl groups are cross-linked with a divalent linking group is coordinated to a transition metal atom has been proposed (J. Am. . Chem. Soc. 199
8, 120, 11316-11322). It has been reported that an α-olefin polymer having 3 or more carbon atoms, particularly a propylene polymer, which is polymerized by using the compound as a catalyst has a high stereoregularity.

[0004] Further, development of metallocene compounds having high polymerization activity in olefin polymerization has been continued. Various metallocene compounds having a heteroatom introduced as a substituent bonded to the cycloalkadienyl ring or an atom constituting the ring itself of the cycloalkadiene ring have been proposed.

[0005] For example, JP-A-7-258282 discloses a metallocene compound in which the 2-position of an indenyl group is substituted by a saturated group containing a hetero atom such as a nitrogen atom, a phosphorus atom, an arsenic atom, an antimony atom, a bismuth atom and the like. Specifically, a metallocene compound in which two 2-pyrrolidino-1-indenes are crosslinked with a divalent linking group and coordinated to a transition metal atom is disclosed.

JP-A-8-183814 discloses a metallocene compound in which the 4-position of an indenyl group is substituted by a 1-pyrrolyl group, a 1-indolyl group, etc., specifically, two 4- (1-indolyl) compounds. ) A chiral metallocene compound in which 2-methylindene is crosslinked with a divalent linking group and this is coordinated with a transition metal atom is disclosed.

Further, J. Am. Chem. Soc. 1998, 120, 1
0786-10787 discloses a metallocene compound in which two heteroatom-containing cycloalkadienes obtained by condensing a thiophene ring or a pyrrole ring with a cyclopentadiene ring are crosslinked with a divalent linking group, and this is coordinated to a transition metal atom. It has been disclosed. JP-A-8-333379 discloses a metallocene compound having a pyridyl group, a quinolyl group, or the like as a substituent.

In general, these metallocene compounds have been developed mainly for obtaining a high-molecular-weight olefin polymer and for making it possible to highly control the stereoregularity of the obtained olefin polymer.

However, T.I. Production of propylene / ethylene copolymers using metallocene catalysts, as reported by Sugano on pages 31-53 of "SPO '99 (1999)", generally results in an increase in the amount of ethylene copolymerized. The molecular weight of the obtained copolymer is lower than the molecular weight of the propylene homopolymer. For this reason, development of a metallocene compound capable of producing a propylene / ethylene copolymer having a sufficiently high molecular weight even when the ethylene content is high has been desired.

On the other hand, as an olefin polymer having controlled stereoregularity, for example, Japanese Patent Application Laid-Open No. Hei 10-273507 discloses (A) ¹³ C-NMR nuclear magnetic field of a propylene unit chain composed of a head-to-tail bond. Resonance spectrum method ( ¹³ C-N
The isotactic triad fraction measured by MR) is 9
(B) measured by ¹³ C-NMR,
The proportion of the position irregular units based on the 2,1-insertion of the propylene monomer in the total propylene insertion is 0.5 to 2.0 mo
1%, and the proportion of the position irregular units based on the 1,3-insertion of the propylene monomer is 0.06 to 0.4 mol.
% (C) weight average molecular weight M measured by gel permeation chromatography (GPC).
High stereoregularity propylene polymers have been reported that satisfy w in the range of 10,000 to 1,000,000.

Japanese Patent Application Laid-Open No. H11-171925 discloses that the fraction of (A) a propylene unit chain composed of a head-to-tail bond has an isotactic triad fraction of 98% or more as measured by ¹³ C-NMR. B) Measured by ¹³ C-NMR,
The proportion of regio-irregular units based on 2,1-insertion of propylene monomer in all propylene insertions is 0.03 mol% or less, and the proportion of regio-irregular units based on 1,3-insertion of propylene monomer is 0.06 mol% As described above, (C) the weight average molecular weight is 10,000 to 1,000,000,
(D) A highly stereoregular propylene polymer having a melting point of 160 ° C. or higher has been reported.

Further, JP-A-7-145212 discloses that (A) the triad tacticity of a propylene unit chain composed of a head-to-tail bond measured by ¹³ C-NMR is 90.0% or more; (B) The proportion of regio-irregular units based on the 2,1-insertion of the propylene monomer in the total propylene insertion measured by ¹³ C-NMR is 0.7 mol% or more, and Based on the proportion of position irregular units is 0.05 mol% or less,
(C) The intrinsic viscosity measured in decalin at 135 ° C. is 0.
High rigidity and high heat resistance propylene polymers in the range of 1 to 12 dl / g have been reported.

Japanese Unexamined Patent Publication (Kokai) No. 7-149832 discloses that (A) comprises 95 to 99.5 mol% of a propylene unit and 0.5 to 5 mol% of an ethylene unit;
¹³ C-NMR of a propylene unit chain consisting of a tail bond
The triad tacticity measured in step (c) is 90.0% or more, and the proportion of regio-irregular units based on the 2,1-insertion of the propylene monomer in the total propylene insertion measured by (C) ¹³ C-NMR is 0%. 0.5 mol% or more and the proportion of regio-irregular units based on 1,3-insertion of the propylene monomer is 0.05 mol% or less, and (D) the intrinsic viscosity measured at 135 ° C. in decalin is 0.1 to 0.1 mol%. Highly rigid and heat-resistant propylene copolymers in the range of 12 dl / g have been reported.

However, when a propylene polymer is produced using a metallocene compound as a catalyst, a heterogeneous bond caused by a 2,1 insertion reaction of a propylene monomer in the propylene polymer and a heterogeneous bond caused by a 1,3 insertion reaction in the propylene polymer. It has been considered difficult to produce propylene polymers whose stereoregularity is very highly controlled such that the bonds are both less than 0.05 mol%.

[0015]

DISCLOSURE OF THE INVENTION The present invention relates to a metallocene compound capable of producing an olefin polymer having a high molecular weight and extremely high stereoregularity, a metallocene catalyst containing the metallocene compound, and a metallocene catalyst containing the same. An object of the present invention is to provide a method for producing an olefin polymer using Further, the present invention provides a metallocene compound having a high polymerization activity and a high polymerization yield, a metallocene compound having an excellent synthesis cost capable of producing an olefin polymer having a high molecular weight and a very high degree of stereoregularity. It is an object of the present invention to provide a metallocene catalyst containing the same and a method for producing an olefin polymer using the same.

[0016]

Means for Solving the Problems In order to achieve the above object, the present inventors examined the relationship between the structure of the metallocene compound and the molecular weight and stereoregularity of the obtained olefin polymer. It has been found that the object of the present invention can be achieved by using a specific metallocene compound having an aromatic group, and the present invention has been completed.

That is, the present invention is described below.

(1) A metallocene compound represented by the following general formula (1). _{Q (C 5 H 4-m} R 1 m) (C 5 H 4-n R 2 n) MXY (1) ( Incidentally, in the _{formula, (C 5 H 4-m} R 1 m) and (C ₅ H _{4 -n} R ² _n)
Represents a cyclopentadienyl group, and C ₅ H _4-m and C ₅
H _4-n represents a cyclopentadienyl ring. m represents an integer of 1 to 3, and n represents an integer of 2 or 3 independently of m. R ¹ and R ² are C ₅ H _4-m and C
It is a bonding group bonded to ₅ H _4-n and independently represents a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group or a heteroaromatic group. Each of R ¹ _m and each of R ² _n may be the same or different from each other. The heteroaromatic group has a heteroaromatic ring and, if necessary, at least one bonding group bonded to the ring, and the bonding group is a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon. Group. A pair of R ² out of R ² _n are bonded to each other to form at least one ring. When m is an integer of 2 or 3, one pair of R ¹ of R ¹ _m is bonded to each other to form at least one ring independently of the ring formed by the pair of R ^2. Is also good. The pair of R
^The ring formed by ¹ and the ring formed by the pair of R ² may have, independently of each other, at least one bonding group bonded to the ring, and the bonding group has 1 to 20 carbon atoms. , A silicon-containing hydrocarbon group or a heteroaromatic group. The heteroaromatic group has a heteroaromatic ring and, if necessary, at least one bonding group bonded to the aromatic ring, wherein the bonding group is a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing group. It is a hydrocarbon group. However, the bonding group represented by R ¹ _m and R ² _n and the pair of R ¹
And at least one of the bonding groups or groups bonded to the ring formed by the pair of R ² and the ring formed by the pair of R ² is a heteroaromatic group, and the heteroaromatic group is a heteroaromatic group. It has a ring and at least one bonding group bonded to the heteroaromatic ring, and the bonding group is a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group. Q represents (C ₅ H _4-m R ¹ _m ) and (C ₅ H
_4-n R ² _n ) is a divalent hydrocarbon group, an unsubstituted silylene group, a hydrocarbon-substituted silylene group,
³ is a boron compound having a ₂ NB structure. Where R ³
Is a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group or a heteroaromatic group. M represents a titanium atom, a zirconium atom or a hafnium atom. X and Y may be the same or different and represent a hydrogen atom, a halogen atom or a hydrocarbon group. )

[0019] (2) n is an integer 3, bonded to a pair of forming at least one ring other than R ² together R ²
Is a heteroaromatic group, wherein the heteroaromatic group has a heteroaromatic ring and at least one bonding group bonded to the heteroaromatic ring, and the bonding group has 1 to 1 carbon atoms. 2
The metallocene compound according to (1), which is a hydrocarbon group of 0 or a silicon-containing hydrocarbon group.

[0020] (3) n is an integer 3, bonded to a pair of forming at least one ring other than R ² together R ²
Is bonded to the 2-position of the cyclopentadienyl ring C ₅ H _4-n. (1) or (2).

(4) The metallocene compound is represented by R ¹ and R ²
And / or the difference in their position of attachment to the cyclopentadienyl ring,
The metallocene compound according to any one of (1) to (3), wherein the metallocene compound has a structure having no symmetry plane including

(5) bonding groups represented by R ¹ _m and R ² _n ;
And at least one of a bonding group or a bonding group bonded to the ring formed by the pair of R ¹ and the ring formed by the pair of R ² is a heteroaromatic group; The group has a heteroaromatic ring and at least one bonding group bonded to the heteroaromatic ring, and the bonding group is a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group. And the heteroaromatic ring is 2
-The metallocene compound according to any one of (1) to (4), which is a furyl ring, a 2-thienyl ring, a 2-benzofuryl ring, or a 2-benzothienyl ring.

(6) bonding groups represented by R ¹ _m and R ² _n ;
And at least one of a bonding group or a bonding group bonded to a ring formed by the pair of R ¹ and a ring formed by the pair of R ² is a 2- (5-methyl) -furyl group , A 2- (5-t-butyl) -furyl group,
2- (5-trimethylsilyl) -furyl group, 2- (5-
Phenyl) -furyl group, 2- (5-methyl) -thienyl group, 2- (5-t-butyl) -thienyl group, 2- (5-
Trimethylsilyl) -thienyl group, 2- (5-phenyl) -thienyl group, 2- (4,5-dimethyl) -furyl group, 2- (4,5-dimethyl) -thienyl group, 2-benzofuryl group, or 2 -The metallocene compound according to (5), which is a benzothienyl group.

(7) The metallocene compound is dimethylsilylenebis (2- (2- (5-methyl) -furyl) -indenyl) zirconium dichloride or dimethylsilylenebis (2- (2- (5-t-butyl)- Furyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl)
-Indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -furyl)-
Indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -thienyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -thienyl)-
Indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -thienyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -thienyl) -indenyl) zirconium dichloride Dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-
Butyl) -furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-trimethylsilyl) -furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylene Bis (2- (2- (5-methyl) -thienyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2
-(5-t-butyl) -thienyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -thienyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylene Bis (2- (2- (5-phenyl) -thienyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-methyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -furyl) -4-phenyl-dihydroazulenyl ) Zirconium dichloride, dimethylsilylenebis (2- (2-
(5-trimethylsilyl) -furyl) -4-phenyl-
Dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2-
(5-methyl) -thienyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -thienyl)
-4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-
Trimethylsilyl) -thienyl) -4-phenyl-dihydroazulenyl) zirconium dichloride or dimethylsilylenebis (2- (2- (5-phenyl) -thienyl) -4-phenyl-dihydroazulenyl) zirconium dichloride ( 6) The metallocene compound according to the above.

(8) Any one of the above items (1) to (7)
An olefin polymerization catalyst comprising the metallocene compound described in the above item, an activating compound, and optionally an organoaluminum compound.

(9) Any one of the above items (1) to (7)
9. An olefin polymerization catalyst comprising an organoaluminum compound, a metallocene compound according to item 1, an activating compound, a particulate carrier, and a supported catalyst component produced using an organoaluminum compound, if desired.

(10) A supported type produced by using the metallocene compound, the ion-exchange layered compound or the inorganic silicate described in any one of the above items (1) to (7) and, if desired, an organic aluminum compound. An olefin polymerization catalyst containing a catalyst component and an organoaluminum compound.

(11) A method for producing an olefin polymer using the olefin polymerization catalyst according to any one of the above items (8) to (10).

(12) The olefin polymer is a propylene homopolymer or a propylene / olefin copolymer of propylene containing at least 50% by weight of propylene units based on the weight of the copolymer and olefins other than propylene. (11) The method for producing an olefin polymer according to the above (11).

(13) With respect to the total number of propylene units constituting the olefin polymer, the number of moles of propylene units due to the 2,1-insertion reaction of the propylene monomer and the 1,3-insertion reaction of the propylene monomer (12) The ratio of the number of moles of the propylene unit caused by the above is less than 0.05 mol% in each case.
The method for producing an olefin polymer according to the above item.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The metallocene compound of the present invention is a metallocene compound represented by the following general formula (1). _{Q (C 5 H 4-m} R 1 m) (C 5 H 4-n R 2 n) MXY (1) Incidentally, in the formula _{(1), (C 5 H} 4-m R 1 m) and (C ₅ H _4-n R
² _n ) represents a cyclopentadienyl group, and C ₅ H _4-m and C _5
5 H _4-n represents a cyclopentadienyl ring. m is 1-3
And an integer of 3 is preferred. n is
Independently of m, an integer of 2 or 3 is shown, and an integer of 3 is preferred.

R ¹ and R ² are bonding groups bonded to C ₅ H _4-m and C ₅ H _4-n , respectively, and independently of each other,
A hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group,
Alternatively, it represents a heteroaromatic group. Each of R ¹ _m and each of R ² _n may be the same or different from each other.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-butyl group, an isobutyl group and a t-
Examples thereof include a butyl group, an n-hexyl group, an n-octyl group, a cyclohexyl group, and a phenyl group, and preferred are a methyl group, a t-butyl group, and a phenyl group.

A preferred example of the silicon-containing hydrocarbon group having 1 to 20 carbon atoms is a trimethylsilyl group.

The heteroaromatic group has a heteroaromatic ring and, if desired, at least one bonding group bonded to the ring.

As the heteroaromatic ring, those having a monocyclic or polycyclic structure can be used, but a monocyclic or bicyclic heteroaromatic ring is preferred, and a monocyclic heteroaromatic ring is particularly preferred. .

[0037] The heteroatom in the heteroaromatic ring is not particularly limited. Preferred is a heteroaromatic ring containing an oxygen atom or a sulfur atom as a heteroatom, and a heteroaromatic ring containing an oxygen atom is particularly preferred. Specifically preferred aromatic rings are furyl, thienyl, benzofuryl or benzothienyl rings,
More preferred are 2-furyl ring, 2-thienyl ring and 2
-A benzofuryl ring or a 2-benzothienyl ring, and particularly preferred is a 2-furyl ring.

If desired, the bonding group which may be bonded to the heteroaromatic ring is a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group. The hydrocarbon group and silicon-containing hydrocarbon group having 1 to 20 carbon atoms, C ₅ H _4-m and C ₅ H same hydrocarbon group and a silicon-containing hydrocarbon as mentioned above as a coupling group attached to _4-n Groups.

The heteroaromatic group preferably has a heteroaromatic ring and at least one bonding group bonded to the ring. Specifically, the heteroaromatic ring is a furyl ring, a thienyl ring, a benzofuryl ring or a benzothienyl ring, and at least one bonding group bonded to the ring is a methyl group, an ethyl group, an n-butyl group, an isobutyl group. And a heteroaromatic group such as a t-butyl group, a phenyl group or a trimethylsilyl group. Further preferably, the heteroaromatic ring is a 2-furyl ring, a 2-thienyl ring, a 2-benzofuryl ring or a 2-benzothienyl ring, and at least one bonding group bonded to the ring is a methyl group, t
-A heteroaromatic group which is a butyl group, a phenyl group or a trimethylsilyl group. Specifically, a 2- (5-methyl) -furyl group, a 2- (5-t-butyl) -furyl group, a 2- (5-trimethylsilyl) -furyl group,
(5-phenyl) -furyl group, 2- (5-methyl) -thienyl group, 2- (5-t-butyl) -thienyl group, 2-
(5-trimethylsilyl) -thienyl group, 2- (5-phenyl) -thienyl group, 2- (4,5-dimethyl) -furyl group, 2- (4,5-dimethyl) -thienyl group, 2-
Examples thereof include a benzofuryl group and a 2-benzothienyl group.

A pair of R ² out of R ² _n are bonded to each other to form a monocyclic or polycyclic ring. The number of rings is not particularly limited, but is preferably 1 to 5, and particularly preferably 1 or 2. The monocyclic or polycyclic ring formed by combining the pair of R ² is a cyclopentadienyl ring C ₅ H _4-n
Preferred as a ring structure to be composed with, an indenyl ring, a tetrahydroindenyl ring, a benzoindenyl ring,
A dihydroazulenyl ring or a cyclopentaphenanthrene ring is more preferable, and an indenyl ring, a benzoindenyl ring and a dihydroazulenyl ring are more preferable.

[0041] when m is 2 or 3, R ¹ a pair of the R ¹ _m is bonded to each other, independently of the ring where the pair of R ² to form, at least one ring (i.e. mono- Or polycyclic). The monocyclic or polycyclic ring formed by the pair of R ¹ bonded to each other is preferably a ring structure formed together with a cyclopentadienyl ring C ₅ H _4-m , for example, an indenyl ring, a tetrahydroindenyl ring, a benzoindenyl ring. A ring, a dihydroazulenyl ring or a cyclopentaphenanthrene ring, and more preferably an indenyl ring, a benzoindenyl ring or a dihydroazulenyl ring.

The ring formed by the pair of R ¹ and the ring formed by the pair of R ² may be the same or different.
The ring structure composed of a ring formed by a pair of R ¹ and C ₅ H _4-m is an indenyl ring, a benzoindenyl ring, or a dihydroazulenyl ring, and a ring formed by a pair of R ² and C 5 _The ring structure composed of ₅ H _4-n is preferably an indenyl ring, a benzoindenyl ring, or a dihydroazulenyl ring. More preferred are a ring structure composed of a ring formed by a pair of R ¹ and C ₅ H _4-m ,
^The ring structure composed of the ring formed by ² and C ₅ H _4-n is a metallocene compound in which both are an indenyl ring, a benzoindenyl ring, or a dihydroazulenyl ring.

The ring formed by the pair of R ¹ and the ring formed by the pair of R ² may independently have at least one bonding group bonded to each ring. At least one bonding group bonded to each ring is a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group or a heteroaromatic group.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-butyl group, an isobutyl group and a t-
Examples thereof include a butyl group, an n-hexyl group, an n-octyl group, a cyclohexyl group, and a phenyl group, and preferred are a methyl group, a t-butyl group, and a phenyl group.

A preferred example of the silicon-containing hydrocarbon group having 1 to 20 carbon atoms is a trimethylsilyl group.

The heteroaromatic group has a heteroaromatic ring and, if desired, at least one bonding group bonded to the ring.

As the heteroaromatic ring, those having a monocyclic or polycyclic structure can be used, but a monocyclic or bicyclic heteroaromatic ring is preferred, and a monocyclic heteroaromatic ring is particularly preferred. .

The hetero atom of the heteroaromatic ring is not particularly limited. Preferred is a heteroaromatic ring containing an oxygen atom or a sulfur atom as a hetero atom. Particularly preferred are heteroaromatic rings containing an oxygen atom as a heteroatom. More specifically, preferred examples of the heteroaromatic ring include a furyl ring, a thienyl ring, a benzofuryl ring and a benzothienyl ring, and more preferred are a 2-furyl ring, a 2-thienyl ring, a 2-benzofuryl ring and a 2-benzofuryl ring. A benzothienyl ring, and particularly preferred is a 2-furyl ring.

If desired, the bonding group which may be bonded to the heteroaromatic ring is a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group. The hydrocarbon group and silicon-containing hydrocarbon group having 1 to 20 carbon atoms may include the same as those exemplified above as binding group attached to the C ₅ H _4-m and C ₅ H _4-n .

The heteroaromatic group preferably has a heteroaromatic ring and at least one bonding group bonded to the ring. Specifically, the heteroaromatic ring is a furyl ring, a thienyl ring, a benzofuryl ring or a benzothienyl ring, and at least one bonding group bonded to the ring is a methyl group, an ethyl group, an n-butyl group, an isobutyl group. And a heteroaromatic group such as a t-butyl group, a phenyl group or a trimethylsilyl group. Further preferably, the heteroaromatic ring is a 2-furyl ring, a 2-thienyl ring, a 2-benzofuryl ring or a 2-benzothienyl ring, and at least one bonding group bonded to the ring is a methyl group, t
A heteroaromatic group which is a -butyl group, a phenyl group or a trimethylsilyl group, and specifically, a 2- (5-methyl) -furyl group, a 2- (5-t-butyl) -furyl group, a 2- ( 5-trimethylsilyl) -furyl group, 2-
(5-phenyl) -furyl group, 2- (5-methyl) -thienyl group, 2- (5-t-butyl) -thienyl group, 2-
(5-trimethylsilyl) -thienyl group, 2- (5-phenyl) -thienyl group, 2- (4,5-dimethyl) -furyl group, 2- (4,5-dimethyl) -thienyl group, 2-
Examples thereof include a benzofuryl group and a 2-benzothienyl group.

In the metallocene compound of the present invention, R
¹ _m and bonding groups group represented by R ² _n, as well as at least one ring and the pair of the pair of R ¹ to form R ²
Is at least one of the bonding groups or bonding groups bonded to at least one ring formed by the heteroaromatic ring and the heteroaromatic ring described above, which has at least one bonding group bonded to the ring. Group.

Q is (C ₅ H _4-m R ¹ _m ) and (C ₅ H _4-m R ¹ _m )
_4-n R ² _n ) is a divalent hydrocarbon group, an unsubstituted silylene group, a hydrocarbon-substituted silylene group,
³ is a boron compound having a ₂ NB structure. Where R ³
Is a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group or a heteroaromatic group. As Q, specifically, a methylene group, an ethylene group, a dimethylsilylene group,
Diphenylsilylene group, dimethylamidoborane group, diisopropylamidoborane group, bis (trimethylsilane)
An amidoborane group can be exemplified, but a dimethylsilylene group is preferred.

M represents a titanium atom, a zirconium atom or a hafnium atom, and is preferably a zirconium atom.

X and Y each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group.

The metallonecene compound of the present invention is characterized in that n is 3
An integer, C_FiveH_4-nR^Two _n, A pair of R^TwoAre each other
To form at least one ring (monocyclic or polycyclic)
Forming the pair of R^TwoR other than^TwoBut heteroaromatic
Before having a ring and at least one linking group attached to the ring
It is preferably the heteroaromatic group described above. A pair of R ^Two
And the ring formed by_FiveH_4-nAs a ring structure composed of
Preferred is the indenyl ring, tetrahydroindenyl
Ring, benzoindenyl ring, dihydroazulenyl ring or
Is a cyclopentaphenanthrene ring, more preferably
Are indenyl ring, benzoindenyl ring, dihydroa
It is a zulenyl ring.

[0056] Further, the metallocene compounds of the present invention, n is an integer of 3, the ^{_{C 5 H 4-n R 2}} n, forms at least one ring one pair of R ² are bonded to each other , R ² other than the R ² of the pair is a cyclopentadienyl ring C ₅ H
_It is preferably bonded to the 2-position of _4-n . A ring structure composed of at least one ring formed by a pair of R ² and C ₅ H _4-n is preferably an indenyl ring, a tetrahydroindenyl ring, a benzoindenyl ring, a dihydroazulenyl ring or cyclopentane. A phenanthrene ring is more preferable, and an indenyl ring, a benzoindenyl ring and a dihydroazulenyl ring are more preferable.

It is particularly preferred that both n and m are integers of 3
And C_FiveH_4-nR^Two _nAnd C_FiveH_4-mR ¹ _mIn, one pair
R^TwoAnd a pair of R¹Are connected to each other
And forming at least one ring, the pair of R^TwoLess than
Outside R^TwoAnd the pair of R¹R other than¹Are each cyclo
Pentadienyl ring C_FiveH_4-nAnd C_FiveH_4-m2-position position
Is a metallocene compound bonded to

The pair of R ² other than R ² and the pair of R ¹ other than R ¹ are a heteroaromatic ring and at least one R ¹ bonded to the ring.
It is preferably a heteroaromatic group as described above having two linking groups.

Further, the metallocene compound of the present invention further has a symmetric plane containing M depending on at least one of the difference of R ¹ and R ^{2 and} the difference of their bonding position to the cyclopentadienyl ring. It is preferable to form a structure that does not exist.

Further, the metallocene compound of the present invention further comprises a bonding group represented by R ¹ _m and R ² _n , and a ring formed by the pair of R ¹ and a ring formed by the pair of R ^2. At least one of a bonding group or group of bonding groups
One bonding group is a heteroaromatic ring, and a heteroaromatic group having a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group bonded to the heteroaromatic ring, wherein the heteroaromatic ring is A metallocene compound which is a 2,2-furyl ring, a 2-thienyl ring, a 2-benzofuryl ring, or a 2-benzothienyl ring is preferable.

Further, the metallocene compound of the present invention further comprises a group of bonding groups represented by R ¹ _m and R ² _n , and a ring formed by the pair of R ¹ and a ring formed by the pair of R ^2. At least one of the bonding groups or bonding groups to be bonded is a 2- (5-methyl) -furyl group,
(5-t-butyl) -furyl group, 2- (5-trimethylsilyl) -furyl group, 2- (5-phenyl) -furyl group, 2- (5-methyl) -thienyl group, 2- (5-t −
Butyl) -thienyl group, 2- (5-trimethylsilyl)
-Thienyl group, 2- (5-phenyl) -thienyl group, 2
-(4,5-dimethyl) -furyl group, 2- (4,5-dimethyl) -thienyl group, 2-benzofuryl group, or
Metallocene compounds that are 2-benzothienyl groups are preferred.

Non-limiting examples of the metallocene compounds of the present invention include dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -furyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl)) -Furyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -indenyl) zirconium dichloride, dimethylamidoboranebis (2- (2-
(5-methyl) -furyl) -indenyl) zirconium dichloride, diisopropylamidoboranebis (2-
(2- (5-methyl) -furyl) -indenyl) zirconium dichloride, bis (trimethylsilyl) amidoboranebis (2- (2- (5-methyl) -furyl) -indenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -thienyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -thienyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t
-Butyl) -thienyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-
Trimethylsilyl) -thienyl) -indenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-phenyl) -furyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -furyl)-
4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -4,5-benzoindenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -thienyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-phenyl) -thienyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -thienyl)
-4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -thienyl) -4,5-benzoindenyl)
Zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-phenyl) -furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -furyl) -4
-Phenyl-indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -4-phenyl-indenyl) zirconium dichloride;

Dimethylsilylenebis (2- (2- (5-
Methyl) -thienyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-phenyl) -thienyl) -4-phenyl-
Indenyl) zirconium dichloride, dimethylsilylene bis (2- (2- (5-t-butyl) -thienyl)
-4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -thienyl) -4-phenyl-indenyl)
Zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride,
Dimethylsilylene bis (2- (2- (5-t-butyl)
-Furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-trimethylsilyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -thienyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -thienyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis ( 2- (2- (5-t-butyl) -thienyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -thienyl)-
4-phenyl-dihydroazulenyl) zirconium dichloride and the like.

Of these, a more preferred metallocene compound is dimethylsilylenebis (2- (2- (5-methyl)
-Furyl) -indenyl) zirconium dichloride,
Dimethylsilylene bis (2- (2- (5-t-butyl)
-Furyl) -indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -furyl) -indenyl) zirconium dichloride, dimethylsilylenebis ( 2- (2- (5-methyl)
-Thienyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -thienyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -thienyl) ) -Indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5
-Phenyl) -thienyl) -indenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-t-butyl) -furyl) -4-phenyl-
Indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -furyl)- 4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2
-(5-methyl) -thienyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -thienyl) -4-
Phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -thienyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2
-(5-phenyl) -thienyl) -4-phenyl-indenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-phenyl) -furyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -furyl)-
4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-methyl) -thienyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -thienyl)-
4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -thienyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2
-(5-trimethylsilyl) -thienyl) -4,5-benzoindenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylene Bis (2- (2- (5-trimethylsilyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -furyl) -4-phenyl-dihydro Azulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-methyl)
-Thienyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-t-butyl) -thienyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -thienyl) -4-phenyl-dihydroazulenyl ) Zirconium dichloride or dimethylsilylenebis (2- (2- (5-phenyl) -thienyl)
-4-phenyl-dihydroazulenyl) zirconium dichloride.

Among them, most preferred are dimethylsilylenebis (2- (2- (5-methyl) -furyl) -indenyl) zirconium dichloride and dimethylsilylenebis (2- (2- (5-t-butyl)) -Furyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -furyl)- Indenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-t-butyl) -furyl) -4-phenyl-
Indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -furyl)- 4-phenyl-indenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-phenyl) -furyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -furyl)-
4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -4,5-benzoindenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylene Bis (2- (2- (5-trimethylsilyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride or dimethylsilylenebis (2- (2- (5-phenyl) -furyl)
-4-phenyl-dihydroazulenyl) zirconium dichloride.

The metallocene compound of the present invention is also characterized in that it can be obtained at a high synthesis yield. The olefin polymerization catalyst of the present invention can be broadly classified into the following (1) to (3).

(1) The above-mentioned metallocene compounds (hereinafter sometimes referred to as “component (A)”) and activating compounds (hereinafter sometimes referred to as “component (B)”),
And an organoaluminum compound (hereinafter sometimes referred to as “component (D)”) used as required (hereinafter referred to as “component (D)”) (hereinafter referred to as “metallocene homogeneous catalyst”).
I may say. ).

(2) Component (A), component (B), a particulate carrier (hereinafter sometimes referred to as “component (C)”), and component (D) optionally used. An olefin comprising a metallocene-supported catalyst (hereinafter sometimes referred to as “metallocene-supported catalyst I”) and an organoaluminum compound (hereinafter sometimes referred to as a component (D ′)). Catalyst for polymerization.

(3) The component (A), a specific ion-exchange layered compound or an inorganic silicate (hereinafter sometimes referred to as the component (E)), and the component (D) optionally used. A metallocene-supported catalyst (hereinafter sometimes referred to as “metallocene-supported catalyst II”), and an olefin polymerization catalyst comprising the component (D ′).

As the component (B), an organic aluminum oxy compound or a compound which reacts with the component (A) to form an ion pair is used.

As the organoaluminum oxy compound, an aluminoxane represented by the following general formula (2) or (3) is used.

[0084]

[0085]

In the formula, R ³ is a hydrocarbon group having 1 to 6 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, isobutyl group, pentyl group and hexyl group, allyl group, 2-methylallyl group, propenyl group, isopropenyl group and 2-methyl-1 -An alkenyl group such as a propenyl group and a butenyl group; a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group; and an aryl group. Among them, a hydrocarbon group having 1 to 4 carbon atoms is preferable, and particularly preferable is a case where the hydrocarbon group is an alkyl group. Each R ³ may be the same or different. q is an integer of 4 to 30, preferably 6 to 30,
Particularly preferably, it is an integer of 8 to 30.

The above aluminoxane can be prepared under various known conditions. Specifically, the following method can be exemplified. That is, a method in which a trialkylaluminum is directly reacted with water in an organic solvent such as toluene and ether, and a reaction between a trialkylaluminum and salts having water of crystallization such as copper sulfate hydrate and aluminum sulfate hydrate. A method of reacting a trialkylaluminum with water impregnated in silica gel or the like; a method of directly reacting a mixture of trimethylaluminum and triisobutylaluminum with water in an organic solvent such as toluene or ether; A method of reacting a mixture of aluminum and triisobutylaluminum with salts having water of crystallization such as copper sulfate hydrate and aluminum sulfate hydrate, after reacting water impregnated with silica gel or the like with triisobutylaluminum , A method of further reacting trimethylaluminum, It can be exemplified.

Examples of the compound which forms an ion pair by reacting with the component (A) include JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, and JP-A-3-17905. 179006, JP-A-3-20
7704, Lewis acids, ionic compounds and borane compounds described in US Pat.
Carborane compounds can be mentioned.

As the Lewis acid, a Lewis acid containing a boron atom is preferable, and specific examples thereof include, but are not limited to, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, and tris (3,5). -Fluorophenyl) boron, tris (4-fluoromethylphenyl)
Examples include boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, and tris (pentafluorophenyl) boron. Of these, tris (pentafluorophenyl) boron is particularly preferred.

The ionic compound is a salt composed of a cationic compound and an anionic compound. The anionic compound serves to stabilize the transition metal cation species by reacting with the metallocene compound to cationize the metallocene compound and form an ion pair. Examples of such an anionic compound include an organic boron compound anion, an organic arsenic compound anion, and an organic aluminum compound anion. A compound which is relatively bulky and stabilizes a transition metal cation is preferable. Examples of the cationic compound include a metal cation, an organic metal cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation. Specific examples include a triphenylcarbenium cation, a tributylammonium cation, an N, N-dimethylammonium cation, and a ferrocenium cation.

As the ionic compound, a salt containing a boron compound as an anionic compound can be suitably used. Specifically, triethylammonium tetra (phenyl) boron, tripropylammoniumtetra (phenyl) boron, tri (n-butyl) ammoniumtetra (phenyl) boron, and trimethylammonium (p-tolyl) as trialkyl-substituted ammonium salts Boron, trimethylammonium (o-tolyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium Tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (4-fluorophenyl) Nil) such as boron, and the like.

The N, N-dialkylanilinium salts include N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N, N-2, 4,6-pentamethylanilinium (phenyl) boron and the like. Examples of the dialkylammonium salt include di (n-propyl) ammoniumtetra (pentafluorophenyl) boron and dicyclohexylammoniumtetra (pentafluorophenyl) boron. And
Examples of the trialkylphosphonium salt and triarylphosphonium salt include, for example, trimethylphosphonium tetra (phenyl) boron, tri (methylphenyl)
Examples thereof include phosphonium tetra (phenyl) boron and tri (dimethylphenyl) phosphonium tetra (phenyl) boron.

In the present invention, triphenylcarbenium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) are used as the ionic compound containing a boron atom.
Borates and ferrocenium tetra (pentafluorophenyl) borate can also be mentioned.

Among the above activating compounds, aluminoxane is particularly preferably used.

The component (D) optionally used in the above-mentioned homogeneous metallocene catalyst I has the general formula AlR ⁴ _s R
It is a compound represented by ⁵ _t X _{3- (s + t)} .

In the formula, R ⁴ and R ⁵ are each independently a hydrocarbon group such as an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group, an alkoxy group, a fluorine atom, a methyl group, a trifluorophenyl Represents a phenyl group which may have a substituent such as a group, X represents a halogen atom, and s and t represent any integer satisfying 0 <s + t ≦ 3.

As the component (D) represented by the above general formula,
For example, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum; dimethylaluminum chloride, dimethylaluminum bromide, Dialkylaluminum halides such as diethylaluminum chloride and diisopropylaluminum chloride; methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquibromide,
Examples thereof include alkylaluminum sesquihalides such as isopropylaluminum sesquichloride and the like, and mixtures of two or more thereof. Preferred is trialkylaluminum.

The component (C) used for producing the metallocene-supported catalyst I of the present invention is an inorganic carrier or an organic carrier, and has a particle diameter of 1 to 500 μm, preferably 5 to 300 μm, more preferably , 10-150
Granular or spherical fine particles having a particle size of μm are used as solid inorganic or organic fine particle carriers.

These inorganic fine particle carriers have a specific surface area of 5
0 to 1,000 m ² / g, preferably 100 to 700 m ²
/ G, and the pore volume is preferably in the range of 0.3 to 2.5 m ³ / g.

As the inorganic fine particle carrier, metal oxides,
For example, SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , Zn
O, a mixture thereof or a composite oxide thereof is preferable, and a carrier containing SiO ₂ or Al ₂ O ₃ as a main component is particularly preferable. As more specific inorganic compounds,
_{SiO 2, Al 2 O 3,} MgO, SiO 2 -Al 2 O 3, Si
_{O 2 -MgO, SiO 2 -TiO 2} , SiO 2 -Al 2 O 3 -
MgO and the like are mentioned, and SiO ₂ is particularly preferable.

Prior to use, the inorganic fine particle carrier is
Usually, 100 to 1,000 ° C, preferably 300 to 90
The material fired at 0 ° C, particularly preferably 400 to 900 ° C, is used. The amount of water adsorbed on the surface of the inorganic fine particle carrier after calcination is 0.1% by weight or less, preferably 0.01% by weight or less, and the surface hydroxyl group content is 1.0% by weight or more, preferably 1.5 to 4.0%. % By weight, more preferably 2.0 to 3.5
% By weight. Further, these inorganic fine particle carriers may be subjected to a contact treatment with an organic aluminum compound and / or a halogen-containing silicon compound before use.

Examples of the fine particle organic carrier include fine particle organic polymers, for example, fine particle polymers of polyolefins such as polyethylene, polypropylene, poly-1-butene and poly-4-methyl-1-pentene, and fine particle polymers such as polystyrene. Can be exemplified.

Examples of the component (E) used for producing the metallocene-supported catalyst II include an ion-exchange layered compound or an inorganic silicate. The term “ion-exchangeable layered compound” used in the present application does not include silicate.

As the above-mentioned ion-exchangeable layered compound,
Hexagonal close packing type, antimony type, CdCl_TwoType,
CdI_TwoIon crystallinity with layered crystal structure such as mold
And specific examples thereof include α-Zr (H
AsO_Four)_Two・ H_TwoO, α-Zr (HPO_Four)_Two, Α-Zr
(KPO_Four)_Two・ 3H_TwoO, α-Ti (HPO_Four)_Two, Α-
Ti (HAsO_Four)_Two・ H_TwoO, α-Sn (HPO_Four)_Two・
H_TwoO, γ-Zr (HPO _Four)_Two, Γ-Ti (HP
O_Four)_Two, Γ-Ti (NH_FourPO_Four)_Two・ H_TwoPolyvalent metals such as O
And crystalline acid salts thereof.

The above-mentioned ion-exchange layered compound may be used after being subjected to salt treatment and / or acid treatment, if necessary. An ion-exchangeable layered compound that has not been subjected to salt treatment or acid treatment is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak binding force to each other. Is possible.

Examples of the above inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. They are,
Synthetic products may be used, or naturally occurring minerals may be used. Specific examples of clays and clay minerals include the allophane group such as allophane, the kaolin group such as dickite, nacrite, kaolinite, and anoxite; the halloysite group such as metahaloysite and halloysite; Stone tribe, montmorillonite, sauconite, beidellite,
Non-tronite, saponite, smectites such as hectorite, vermiculite minerals such as vermiculite,
Examples include mica minerals such as illite, sericite and chlorite, attapulgite, sepiolite, palygorskite, bentonite, Kibushi clay, gairome clay, hissingelite, pyrophyllite, and ryokudeite group. These may form a mixed layer. Examples of the artificially synthesized product include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

Among the above inorganic silicates, kaolin family,
Halosite family, serpentine family, smectite, vermiculite mineral, mica mineral, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite are preferred, and smectite, vermiculite mineral, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite are further preferred. preferable. These may be used as they are without any particular treatment, or may be used after having been subjected to treatments such as ball milling and sieving. Further, they may be used alone or as a mixture of two or more.

The acid strength of the above-mentioned inorganic silicate can be changed by a salt treatment and / or an acid treatment, if necessary. In the salt treatment, the surface area and the interlayer distance can be changed by forming an ion complex, a molecular complex, an organic derivative, and the like. That is, by using the ion exchange property and replacing the exchangeable ions between the layers with another large bulky ion, a layered material in which the layers are expanded can be obtained.

The component (E) may be used without any treatment, but it is preferable that the exchangeable metal cation contained is ion-exchanged with a cation dissociated from the following salts and / or acids. .

The salts used for ion exchange are compounds containing a cation containing at least one atom selected from the group consisting of atoms of groups 1 to 14, and preferably 1 to 14.
A cation containing at least one atom selected from the group consisting of Group 14 atoms, and an anion derived from at least one atom or group of atoms selected from the group consisting of halogen atoms, inorganic acids and organic acids. And more preferably a cation containing at least one atom selected from the group consisting of atoms of groups 2 to 14;
l, Br, I, F, PO 4, SO 4, NO 3, CO 3, C 2
O ₄ , ClO ₃ , ClO ₄ , OOCCH ₃ , CH ₃ COCH
COCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ ,
O (SO ₄ ), OH, O ₂ Cl ₂ , OCl ₃ , OOCH, O
It is a compound comprising at least one anion selected from the group consisting of OCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₆ H ₅ O ₇ . Further, two or more of these salts may be used simultaneously.

The acid used for the above-mentioned 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 simultaneously. As a method of combining the salt treatment and the acid treatment, a method of performing an 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, the acid treatment has an effect of removing ions on the surface and ion exchange, and has a crystal structure of Al, Fe, M
It has the effect of eluting some cations such as g and Li.

The conditions for treatment with salts and acids are not particularly limited. However, usually the salt and acid concentrations are at 0.
It is preferable that the treatment is carried out under the conditions of 1 to 30% by weight, the treatment temperature in the temperature range from room temperature to the boiling point of the solvent used, the treatment time in the range of 5 minutes to 24 hours, and the elution of at least a part of the compound to be treated. In addition, salts and acids are generally used in an aqueous solution.

In the case of performing the salt treatment and / or the acid treatment, the shape may be controlled by pulverization or granulation before, during, or after the treatment. Further, other chemical treatments such as an alkali treatment, an organic compound treatment, and an organic metal treatment may be used together. The component (E) thus obtained has a pore volume of at least 20 mm in radius measured by a mercury porosimetry of 0.1 c.
It is preferably c / g or more, particularly preferably 0.3 to 5 cc / g. Such a component (E), when treated in an aqueous solution, contains adsorbed water and interlayer water. Here, the adsorbed water is
The water adsorbed on the surface of the ion-exchange layered compound or the inorganic silicate or the crystal fracture surface, and the interlayer water is water existing between the layers of the crystal.

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

Next, a method for producing the metallocene-supported catalysts I and II will be described.

The metallocene-supported catalyst I is obtained by reacting the component (A) with the component (B) and, if desired, the component (D) in the presence of the component (C). The order in which the components (A) and (B) are added to the component (C) can be arbitrarily changed. For example, component (A) dissolved in a suitable hydrocarbon solvent can be added first to component (C), and then component (B). Also,
The component (B) and the component (A) previously reacted can be simultaneously added to the component (C). The component (B) can be added first to the component (C), and then the component (A) can be added. The temperature during the reaction is usually -20 to 200 ° C, preferably 0 to 120 ° C, and the time required for the reaction is usually 0.1 min or more, preferably 1 min to 200 min. Further, the metallocene-supported catalyst I obtained as described above can be used after being prepolymerized with a small amount of olefin if necessary.

As the olefin used for the prepolymerization, ethylene, propylene, 1-butene, 1-hexene, 3-olefin
Examples thereof include methyl-1-butene and 4-methyl-1-pentene, and a mixture of two or more olefins may be used.

The metallocene-supported catalyst I suitably used for producing the olefin polymer of the present invention is a metallocene-supported catalyst prepared by sequentially carrying out the following steps (a) to (c) or Pre-activated metallocene-supported catalysts obtained by sequentially carrying out steps a) to (d) can be mentioned. (A) reacting the metallocene compound (A) with an aluminoxane in an inert solvent to obtain a metallocene catalyst;
(B) contacting the metallocene catalyst obtained in the above step (a) with the inorganic fine particle carrier at a temperature of 85 to 150 ° C. in the presence of an inert solvent so that the metallocene catalyst is supported on the inorganic fine particle carrier; Obtaining a catalyst of the type (c) above
(b) a step of washing the slurry containing the crude metallocene-supported catalyst obtained in the step at least twice with an aliphatic hydrocarbon at a temperature of -50 to 50 ° C to obtain a purified metallocene-supported catalyst; The metallocene-supported catalyst obtained in the above step (c) is brought into contact with the olefin to prepolymerize the olefin, and 0.01 to 1 per kg of the metallocene-supported catalyst.
A step of further supporting 00 kg of the olefin prepolymer on the metallocene supported catalyst to obtain a preactivated metallocene supported catalyst.

In the above step (a), 1 mole of the metallocene compound (A) is converted to aluminum atom with respect to 1 mole of the metallocene compound (A).
0 to 1,000 moles, preferably 20 to 500 moles, of aluminoxane in an inert solvent for -50 to 100
° C, preferably 0 to 50 ° C for 1 minute to 10 minutes.
The metallocene compound (A) is reacted with the aluminoxane for a period of time, preferably 3 minutes to 5 hours, to produce a metallocene catalyst.

The use of an inert solvent is preferred in that the reaction proceeds uniformly and efficiently. The amount of the inert solvent used is not particularly limited, but is usually 10 to 10,000 liters, preferably 1 to 1 mol per 1 mol of the metallocene compound (A).
It is about 0 to 1,000 liters.

Examples of usable inert solvents include, for example, aromatic hydrocarbons such as benzene, toluene, xylene and cumene, butane, tetramethylbutane, pentane, ethylpentane, trimethylpentane, hexane, methylhexane, ethylhexane and dimethyl. Hexane, heptane, methylheptane, octane, nonane, decane, hexadecane, aliphatic hydrocarbons such as octadecane, cyclopentane, methylcyclopentane, cyclohexane, cycloaliphatic hydrocarbons such as cyclooctane, the above aromatic hydrocarbons,
Examples thereof include aliphatic hydrocarbons, halogenated hydrocarbons obtained by replacing alicyclic hydrocarbons with halogens, and mixed solvents thereof. Further, ethers such as ethyl ether and tetrahydrofuran can also be used as the inert solvent.

Preferred inert solvents are aromatic hydrocarbons. In addition, a solvent of a commercially available aluminoxane solution can be used as it is, or it can be used for the reaction by further adding other aromatic hydrocarbons and the like.

In the step (b) following the step (a),
By contacting the metallocene catalyst obtained in the step (a) with the inorganic fine particle carrier at a temperature of 85 to 150 ° C. in the presence of the inert solvent used as the reaction solvent in the step (a), the metallocene catalyst is A crude metallocene-supported catalyst as a solid product supported on an inorganic fine particle carrier is obtained. In this contact reaction, an inert solvent can be additionally used as necessary.

The ratio of the metallocene catalyst to the inorganic fine particle carrier in the crude metallocene-supported catalyst depends on the transition derived from the metallocene compound (A) contained in the reaction product of the metallocene compound (A) as the metallocene catalyst and the aluminoxane. The inorganic fine particle carrier is 1 to 1 mole of the metal atom.
The proportion is 1,000 kg, preferably 5 to 500 kg.
The amount of the inert solvent used in the step (b) is based on 1 mol of the transition metal atom derived from the metallocene compound (A) contained in the reaction product of the metallocene compound (A) as the metallocene catalyst and the aluminoxane. 10 to 10,000
Liters, preferably 10 to 1,000 liters.

The contact between the metallocene catalyst and the inorganic fine particle carrier is 85 to 150 ° C., preferably 90 to 130 ° C.
Particularly preferably, the reaction is carried out at a temperature of 95 to 120 ° C. for 5 minutes to 100 hours, preferably for 10 minutes to 50 hours. In particular, the temperature condition is an important factor, and by contacting within the above temperature range, the obtained metallocene-supported catalyst has a high polymerization activity, and when this catalyst is used for olefin polymerization, the obtained olefin polymer is high. It becomes a polymer having a bulk specific gravity and good particle properties.

In the following step (c), the crude metallocene-supported catalyst containing the inert solvent obtained in step (b) is
Washing at least twice with an aliphatic hydrocarbon at a temperature of 50 to 50 ° C. gives a purified metallocene-supported catalyst.

Examples of the aliphatic hydrocarbon used for washing include the aliphatic hydrocarbons exemplified as the inert solvent and a mixture thereof. Preferably, n-hexane,
Isopentane or a mixture thereof.

As a cleaning method in the step (c), for example,
(b) After completion of the step, after the inert solvent is separated from the slurry comprising the inert solvent and the crude metallocene-supported catalyst by filtration, centrifugation, decantation, or the like, the crude metallocene is separated using an aliphatic hydrocarbon. A method of washing the supported catalyst can be adopted. Further, after completion of the step (b), an aliphatic hydrocarbon is added without separating the inert solvent from the slurry comprising the inert solvent and the crude metallocene catalyst, and a mixed solvent of the inert solvent and the aliphatic hydrocarbon is added. After separation by the same means as described above, a method of washing the crude metallocene-supported catalyst using an aliphatic hydrocarbon may be employed. As the cleaning method performed in the step (c), the latter method is more preferable.

In the washing, 1 to 500 liters, preferably 10 to 100 liters, of an aliphatic hydrocarbon is used for 1 kg of the inorganic fine particle carrier used in the step (b), and -50 to 50 ° C, preferably -30 to 40
C., particularly preferably at a temperature of -30 to 30.degree. C., until the metallocene catalyst is not eluted into the washed aliphatic hydrocarbon. It is sufficient to wash at least two times, usually four times or more, but it is not limited to this.

The washing temperature condition is an important factor. The metallocene-supported catalyst obtained by washing within the above temperature range has a high polymerization activity, and is obtained when olefin polymerization is carried out using this catalyst. Olefin polymers have particularly high bulk specific gravity and good particle properties.

The preactivated metallocene-supported catalyst used in the present invention is obtained by bringing the metallocene-supported catalyst obtained in the step (c) into contact with an olefin in step (d) to prepolymerize the olefin, It is obtained by supporting 0.01 to 100 kg of the olefin prepolymer per 1 kg of the type catalyst on the metallocene supported type catalyst.

Examples of the olefin prepolymer supported on the preactivated metallocene supported catalyst include olefins having 2 to 20 carbon atoms, for example, ethylene, propylene, 1-butene, 1-pentene and 4-methyl-1-pentene. , 2-
Methyl-1-pentene, 1-hexene, 1-octene,
Homopolymers such as 1-decene and 1-dodecene and copolymers composed of a combination of two or more thereof,
In particular, ethylene homopolymer, propylene homopolymer, ethylene / olefin copolymer of ethylene mainly containing ethylene and olefins other than ethylene, or propylene / olefin copolymer of propylene mainly containing propylene and olefins other than propylene Coalescing is preferred.
These olefin prepolymers have an intrinsic viscosity [η] of 0.1 to 10 dl / measured in decalin at 135 ° C.
g, preferably in the range of 0.2 to 7 dl / g.

A preferred olefin prepolymerization method is
(c) A method in which an olefin to be prepolymerized is introduced into a slurry in which the metallocene-supported catalyst obtained in the step is dispersed in an aliphatic hydrocarbon, and the olefin is prepolymerized by contacting the olefin with the metallocene-supported catalyst. . As a slurry in which the metallocene-supported catalyst is dispersed in an aliphatic hydrocarbon, the catalyst obtained in the final stage of the step (c), washing,
It may be used without being separated from the aliphatic hydrocarbon, or after separation, it may be used again after being redispersed in the same aliphatic hydrocarbon.

The prepolymerization of the olefin can be carried out in a liquid phase using the olefin to be polymerized itself as a solvent or in a gas phase without using a solvent. In order to advance the prepolymerization uniformly, it is preferable to carry out the reaction in the presence of an aliphatic hydrocarbon.

[0135] Preliminary polymerization of olefins carried out in aliphatic hydrocarbons, to the supported metallocene catalyst 1 kg, aliphatic hydrocarbons 0.005～5M ^3, preferably 0.01～1M ³
Olefin in a slurry consisting of 0.01 to 1,000.
0 kg, preferably 0.1-500 kg, and -5
Under a temperature condition of 0 to 100 ° C, preferably 0 to 50 ° C,
It is carried out by contacting the olefin for 1 minute to 50 hours, preferably for 3 minutes to 20 hours.

In the above-mentioned olefin prepolymerization, the reaction product of the metallocene compound (A) and, preferably, the aluminoxane as the activating compound (B) is supported on the metallocene-supported catalyst. It is not particularly necessary to add a cocatalyst represented by an organoaluminum compound such as an alkylaluminum or an aluminoxane, but it can be added if desired. The amount of these cocatalysts to be added is limited to not more than 1,000 moles, preferably not more than 500 moles as aluminum atoms per mole of the transition metal atom derived from the metallocene compound (A) in the metallocene-supported catalyst. preferable.

In the present invention, the above-mentioned olefin prepolymerization is carried out in the presence of hydrogen, and the weight average molecular weight (Mw) of the resulting olefin prepolymer is from 100,000 to 50%.
It is desirable to control so as to be in the range of 000 g / mol.

The metallocene-supported catalyst II that can be used in the present invention is prepared by contacting the components (A), (E) and (D). The contact method is not particularly limited, but the following method can be exemplified. (1) The components (A) and (E) are brought into contact. (2) The component (D) is added after the components (A) and (E) are brought into contact. (3) The component (E) is added after the components (A) and (D) are brought into contact. (4) The component (A) is added after the components (E) and (D) are brought into contact. (5) The components (A), (E) and (D) are brought into contact simultaneously.

This contact may be performed not only at the time of catalyst preparation but also at the time of olefin prepolymerization or olefin polymerization. Further, at the time of or after the contact of the above components, polyethylene, a polymer such as polypropylene, silica, a solid of an inorganic oxide such as alumina, coexist with each component, or by contacting each component Is also good.
The above components may be contacted in an inert gas such as nitrogen or an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene. Contact is -20 ° C
Is performed in a temperature range having a lower limit and a boiling point of a solvent as an upper limit,
In particular, it is preferable to perform the reaction in a temperature range in which the lower limit is room temperature and the boiling point of the solvent is the upper limit.

The amounts of the components used are as follows.
That is, the amount of the component (A) is usually 10 ^{−4 to} 10 mmol, preferably 10 ^{−3 to 5} mmol per 1 g of the component (E).
l, and the component (D) is usually 0.01 to 10 ⁴ mmol
1, preferably 0.1 to 100 mmol. Also,
The atomic ratio of the transition metal in the component (A) to the aluminum in the component (D) 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.

Further, the component (D) may be additionally used as necessary. That is, when the catalyst is prepared using the component (A) and / or the component (E) and the component (D),
Apart from this catalyst preparation, the component (D) may be additionally added to the reaction system. At this time, the amount of the component (D) used is usually 1: 0 to 10 as an atomic ratio of the aluminum atom in the component (D) to the transition metal atom derived from the metallocene compound (a) in the component (A). ⁴ , preferably 1: 1 to 1
It is selected to 10 ³ become like.

The metallocene-supported catalyst II obtained as described above is also prepolymerized with an olefin and further loaded with an olefin prepolymer on the supported catalyst, similarly to the metallocene-supported catalyst I, and then this catalyst is used. It can also be used for producing the olefin polymer of the present invention.

The metallocene-supported catalyst I or II obtained above is further used as an olefin polymerization catalyst obtained by combining with an organoaluminum compound (component (D ')), which is suitable for the production of the olefin polymer of the present invention. Can be used for

In the production of the olefin polymer, the component (D ′) used in combination with the metallocene-supported catalyst I or II is the metallocene-supported catalyst I or II.
The organoaluminum compound used for the production of II is selected from those described above, but may be the same as the organoaluminum compound used for producing the metallocene-supported catalyst I or II, or may be another organoaluminum compound. There may be.

The amount of the component (D ′) used in the production of the olefin polymer is based on 1 mol of the transition metal atom derived from the metallocene compound (a) in the metallocene-supported catalyst or the preactivated metallocene-supported catalyst. , (D ') component as 1 to 5,000 mol, preferably 5
The proportion is preferably from 3,000 mol to 3,000 mol, particularly preferably from 10 mol to 1,000 mol.

The amount of the metallocene-supported catalyst or the preactivated metallocene-supported catalyst was 1 × 10 ⁻¹⁰ per liter of polymerization volume, in terms of transition metal atoms derived from the metallocene compound (a) in the catalyst. ~ 1 × 10 ^-3 mol,
Preferably it is 1 × 10 ^-9 to 1 × 10 ^-4 mol. By setting the amount of the catalyst in the above range, an efficient and controlled polymerization reaction rate of olefin can be maintained.

The term "polymerization volume" refers to the volume of the liquid phase portion in the polymerization vessel in the case of liquid phase polymerization and the volume of the gas phase portion in the polymerization vessel in the case of gas phase polymerization. means.

In the present invention, the term "olefin" refers to an olefin having 2 to 20 carbon atoms, specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- Octene, 1-decene, 1-
Dodecene, 1-hexadecene, 4-methyl-1-pentene and the like, and also a mixture of two or more of these. In addition, styrene, vinylcyclohexane, diene and the like may be copolymerized with these olefins. When styrene is used as the olefin, it is more preferable to copolymerize ethylene and styrene.

In the present invention, the most preferably used olefin is propylene or a mixture of propylene and at least one olefin other than propylene. Most preferred as the at least one olefin except for propylene is ethylene or a mixture of ethylene and 1-butene.

In the present invention, the “olefin polymer” is a homopolymer of olefin or a copolymer of two or more olefins. The olefin polymer produced using the olefin polymerization catalyst of the present invention preferably contains a propylene unit or 50% by weight or more of propylene units based on the weight of the copolymer.
It is a propylene / olefin copolymer of propylene and an olefin other than propylene. The propylene / olefin copolymer may be any of a random copolymer, a block copolymer, and a random block copolymer.

The olefin polymer produced by using the catalyst for olefin polymerization of the present invention is one in which stereoregularity is particularly controlled. That is, with respect to the total number of moles of propylene units constituting the olefin polymer, the number of moles of propylene units caused by the 2,1-insertion reaction of the propylene monomer and the number of moles of propylene caused by the 1,3-insertion reaction of the propylene monomer. The ratio of the number of moles of the unit is independently 2 mol% or less, preferably 1 m
ol% or less, particularly preferably 0.5 mol% or less. In particular, the most important feature of the present invention is that the olefin polymer produced by the optimal selection of the conditions for producing the catalyst and / or the olefin polymer of the present invention can be obtained by the total number of moles of propylene units constituting the olefin polymer. The ratio of the number of moles of propylene units caused by the 2,1-insertion reaction of the propylene monomer and the number of moles of propylene units caused by the 1,3-insertion reaction of the propylene monomer is less than 0.05 mol%. , More preferably less than 0.04 mol%, particularly preferably 0.1 mol%.
It can be controlled to less than 02 mol%.

The isotactic pentad fraction (I ₅ ) of the olefin polymer produced is not particularly limited, but is preferably 0.400 to 0.990, more preferably 0.800 to 0.990. 0.960, more preferably 0.820 to 0.960, particularly preferably 0.840.
0.930.

Further, the olefin polymer, particularly the propylene polymer, produced in the present invention can be obtained by a differential scanning calorimeter (DS).
And C) measured melting point with (Tm), between the isotactic pentad ratio and (I _5), it is also characterized by satisfying the following relational expression (4).

Tm <142.1 × I ₅ +22.0 (4)

[0155] Further, the olefin polymers prepared using the olefin polymerization catalyst of the present invention, in particular propylene polymers, head - propylene unit chain consisting of tail bonds, ¹³
Isotactic triad fraction (I ₃ ) measured by C-NMR is 0.50 to 0.99, more preferably,
0.60 to 0.98, more preferably 0.80 to 0.90
0.98, particularly preferably 0.85 to 0.94.

With respect to the total number of moles of propylene units constituting the olefin polymer, the number of moles of propylene units resulting from the 2,1-insertion reaction of the propylene monomer and the 1,3-insertion reaction of the propylene monomer were determined. Of the propylene units, the isotactic pentad fraction (I ₅ ), and the isotactic triad fraction (I ₃ ) caused by the ¹³ C nucleus were measured according to the following methods. It is determined based on the measurement result of the magnetic resonance spectrum.

That is, a test sample (olefin polymer) is dissolved in a mixed solution of o-dichlorobenzene / brominated benzene = 8/2 by weight so that the concentration in the mixed solution becomes 20% by weight. . The ¹³ C nuclear magnetic resonance spectrum of this test solution is measured at a measurement wavelength of 67.20 MHz and a measurement temperature of 130 ° C. As the measuring device, for example, “JEOL-GX270NMR (trade name)” manufactured by JEOL Ltd. can be used.

"Isotactic pentad fraction (I ₅ )" and "isotactic triad fraction (I ₃ )" are those of propylene homopolymer in the case of A. Zambelli and the like. "Macromolecules 6,92
5 (1973) ", which is an index that indicates the stereoregularity of the polymer, which is measured and determined by the ¹³ C nuclear magnetic resonance spectrum proposed. The method for determining the assignment of peaks in the measurement of the ¹³ C nuclear magnetic resonance spectrum is described in A. Zamb
elli) and other "Macromolecules (Macrom)
olecules) 8,687 (1975). The isotactic triad fraction (I ₃ ) of the copolymer was calculated based on the method proposed in JP-A-7-149833 and JP-A-8-283343.

[0159] isotactic pentad ratio (I ₅₎
Means the ratio of propylene units having five consecutive meso bonds to the total number of propylene units constituting the olefin polymer, and the isotactic triad fraction (I ₃ ) It represents the ratio of propylene units having three consecutive meso bonds to the total number of propylene units in the olefin polymer molecular chain. Therefore isotactic pentad fraction (I _5), indicating that high isotacticity higher isotactic triad fraction (I _3). Among them, the isotactic pentad fraction (I ₅ ) is used as an index for isotacticity of the homopolymer, and the isotactic triad fraction (I ₃ ) is used for the homopolymer and the copolymer. It is used as an index for isotacticity of the polymer.

With respect to the total number of moles of propylene units constituting the olefin polymer, the number of moles of propylene units due to the 2,1-insertion reaction of the propylene monomer and the 1,3-insertion reaction of the propylene monomer were determined. The proportion occupied by the resulting mole number of propylene units is defined as the ¹³ C nuclear magnetic resonance spectrum based on the method published by T. Tsutsui et al. In “Polymer, 30, 1350 (1989)”. Is an index indicating the stereoregularity of an olefin polymer containing a propylene unit, which is measured and determined by the following formula.

The melting point (Tm) is measured using a “DSC7 differential scanning calorimeter” manufactured by Perkin-Elmer. First, the temperature of the polymer as a test sample was raised from room temperature to 230 ° C. at a rate of 30 ° C./min, and maintained at the same temperature for 10 minutes, and then lowered to −20 ° C. at a rate of −20 ° C./min. Hold at the same temperature for 10 minutes. After that, again at 20 ° C /
When the temperature was increased at a rate of minutes, the temperature at which the peak of melting was reached was taken as the melting point.

The olefin polymer obtained by using the metallocene compound of the present invention has a weight average molecular weight (Mw).
It preferably has a value of 5 × 10 ^{4 to} 5 × 10 ⁵ g / mol, more preferably 1 × 10 ^{5 to} 5 × 10 ⁵ g / mol. Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight is preferably 1.5 to 3.8,
More preferably, 1.5 to 3.5, more preferably 1.8.
-3.0, most preferably 1.8-2.5.

The olefin polymer obtained by using the metallocene compound of the present invention can be prepared by using a melt flow rate (J
(Measured under condition 14 in Table 1 according to IS K7210)
However, it is preferably in the range of 0.5 to 300 g / 10 min, more preferably 0.5 to 100 g / 10 min. Melt flow rate is less than 0.5 g / 10 min or 3
If it is more than 00 g / 10 minutes, molding with a conventionally known molding machine becomes difficult, which is not preferable.

In the present invention, as a process for producing an olefin polymer, a known olefin polymerization process can be used, and aliphatic hydrocarbons such as butane, pentane, hexane, heptane, isooctane, cyclopentane, cyclohexane, methylcyclohexane and the like can be used. It is possible to adopt a slurry polymerization method in which olefins are polymerized in an inert solvent such as an alicyclic hydrocarbon such as an alicyclic hydrocarbon, toluene, xylene, and ethylbenzene, and a gasoline fraction or a hydrogenated diesel oil fraction. it can. Further, a bulk polymerization method using the olefin itself as a solvent or a gas phase polymerization method in which the polymerization of the olefin is carried out in a gas phase can also be adopted. A polymerization process combining two or more of these processes can also be employed. As a combination of the polymerization processes, a combination in which the first stage is performed by a bulk polymerization method and the subsequent second stage is performed by a gas phase polymerization method is most preferable. Further, it is also possible to use a solution polymerization method.

The production of the olefin polymer of the present invention is carried out at a polymerization temperature of -50 to 150 ° C, preferably 20 to 120 ° C.
More preferably, the polymerization pressure is 40 to 100 ° C., and the polymerization pressure is atmospheric pressure to
9.9 MPa (gage pressure), preferably 0.4 to 5.0 M
It is performed under the condition of Pa (gage pressure). If necessary, the molecular weight of the olefin polymer obtained by introducing a chain transfer agent such as hydrogen may be adjusted.

After completion of the polymerization reaction, unreacted monomers and hydrogen are separated from the polymerization system, and a catalyst deactivation treatment or the like is performed to obtain an olefin polymer.

The olefin polymer obtained by the production method of the present invention may contain an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent, a lubricant, a flame retardant, an antiblocking agent, a coloring agent, an inorganic or After blending various additives such as organic fillers and various synthetic resins, the mixture is usually heated and melted and kneaded at a temperature of 190 to 350 ° C. for about 20 seconds to 30 minutes using a melt kneading machine, if necessary. After extruding into a strand shape, the product is further cut into granules, that is, pellets, and used for the production of various molded products. For example, films, sheets, fibers, injection molded products, blow molded products, containers,
It can be suitably used as a drawn yarn, a nonwoven fabric, a foam, and the like, and can also be suitably used as a sealant.

[0168]

EXAMPLES The present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Definitions of terms used in Examples and Comparative Examples and measurement methods are as follows. (1) Melt flow rate (MFR) (unit: g / 10)
Min): Condition 14 in Table 1 based on JIS K7210
(Under a load of 21.18 N and a temperature of 230 ° C.). (2) Isotactic pentad fraction (I ₅ ): As a measuring device, “JEOL-GX27” manufactured by JEOL Ltd.
"0" (trade name) was measured by the method described above. (3) Isotactic triad fraction (I ₃ ): As a measuring device, “JEOL-GX27” manufactured by JEOL Ltd.
"0" (trade name) was measured by the method described above. (4) With respect to the total number of moles of propylene units constituting the olefin polymer, the number of moles of propylene units caused by the 2,1-insertion reaction of the propylene monomer and the number of moles of 1,3-insertion of the propylene monomer. Proportion of moles of propylene unit (unit: mol%): "JEOL-GX270" manufactured by JEOL Ltd. as a measuring device
(Trade name) was measured by the method described above. The lower detection limit is 0.02 mol%.

(5) Weight average molecular weight (Mw) (unit: g)
/ Mol): Gel permeation chromatography (GPC) method, as a column, "P" manufactured by Tosoh Corporation
Using "SKgel GMH6-HT" (trade name) as a measuring device, "GPC-150C" manufactured by Waters Corporation
Using (trade name), test specimen (olefin polymer)
It was dissolved in o-dichlorobenzene so as to have a concentration of 0.05% by weight, and the obtained solution was measured and measured at a temperature of 135 ° C. (6) Number average molecular weight (Mn) of weight average molecular weight (Mw)
(Mw / Mn): Gel Permeation Chromatography (GPC) method, using “PSKgel GMH6-HT” (trade name) manufactured by Tosoh Corporation as a column, and using Waters Corporation as a measuring device. G
Using "PC-150C" (trade name), a test sample (olefin polymer) was dissolved in o-dichlorobenzene so that the concentration became 0.05 wt%, and the obtained solution was heated at 135 ° C. Measured and determined. (7) Melting point (° C.): “DSC7” manufactured by Perkin-Elmer
Using a "type differential scanning calorimeter". (8) Intrinsic viscosity (η) (unit: dl / g): 135 using an automatic viscosity measuring device (“AVS2” (trade name) manufactured by Mitsui Toatsu Co., Ltd.) and using tetralin as a solvent.
Measured at a temperature of ° C. (9) When the olefin polymer is a propylene / olefin copolymer of propylene and an olefin other than propylene, the content of olefin units (unit:% by weight): ¹³
It was determined by C NMR measurement.

Example 1 Synthesis of rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -indenyl) zirconium dichloride (1) 2- (2- (5-methyl)- Synthesis of furyl) -indene 2-Methylfuran 2 was placed in a 500 ml glass reaction vessel.
0 g (0.24 mol) and 250 ml of THF were added, and the mixture was cooled to -50 ° C in a dry ice-methanol bath. 160 ml (0.24 mol) of a 1.50 mol / L n-butyllithium-hexane solution was added dropwise thereto. After dropping, the mixture was returned to room temperature and stirred for 3 hours. It was cooled again to −30 ° C. in a dry ice-methanol bath, and
100 ml of a THF solution containing g (0.24 mol) was added dropwise. After the dropwise addition, the mixture was returned to room temperature and stirred for 16 hours. The reaction solution was cooled to −20 ° C. in a dry ice-methanol bath,
100 ml of 2N hydrochloric acid was added dropwise. The reaction solution was transferred to a separating funnel and washed with a saline solution until neutral, anhydrous sodium sulfate was added, and the mixture was allowed to stand overnight to dry. The anhydrous sodium sulfate was filtered, and the solvent was distilled off under reduced pressure. Thereto, 600 ml of toluene and 0.5 g of p-toluenesulfonic acid (2.6 g) were added.
mmol) and heated under reflux for 1 hour. The reaction solution was transferred to a separating funnel and washed with a saline solution until neutral,
Anhydrous sodium sulfate was added and left overnight to dry. The anhydrous sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 22 g of 2- (2- (5-methyl) -furyl) -indene as pale yellow crystals (46% yield). . The structure was confirmed by NMR.

(2) Synthesis of dimethyl bis (2- (2- (5-methyl) -furyl) -indenyl) silane In a 200 ml glass reaction vessel, 2- (2- (5-methyl) -furyl)- 30 g of inden (0.15 mo
l), copper isocyanate 0.9 g (7.4 mmol), T
HF (300 ml) was added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. Here, 1.50 mol / L of n
-Butyl lithium-hexane solution 102 ml (0.15
mol) was added dropwise. After the dropwise addition, the mixture was stirred for 16 hours while gradually returning to room temperature. The solution was cooled again to -50 ° C in a dry ice-methanol bath, and dimethyldichlorosilane 9.9 was added.
70 ml of a THF solution containing g (0.077 mol) was added dropwise. After the dropwise addition, the mixture was stirred for 16 hours while gradually returning to room temperature. Distilled water was added to the reaction solution, transferred to a separating funnel, and washed with saline until neutral. Anhydrous sodium sulfate was added thereto, and the mixture was allowed to stand overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, the residue was purified on a silica gel column, and recrystallized from hexane to give dimethylbis (2-
27 g (78% yield) of colorless crystals of (2- (5-methyl) -furyl) -indenyl) silane were obtained.

(3) Dimethylsilylenebis (2- (2-
Synthesis of (5-methyl) -furyl) -indenyl) zirconium dichloride In a 100 ml glass reaction vessel, dimethylbis (2-
(2- (5-methyl) -furyl) -indenyl) silane 5.0 g (0.011 mol), diethyl ether 10
Add 0 ml and dry ice-methanol bath at -70 ° C
Cooled down. Here, 15 ml (0.023 mol) of a 1.50 mol / L n-butyllithium-hexane solution
Was added dropwise. After the dropwise addition, the mixture was returned to room temperature and stirred for 16 hours. The solvent of the reaction solution was concentrated under reduced pressure to about 20 ml, and toluene 1
70 ml in a dry ice-methanol bath.
Cooled to ° C. There, 2.6 g of zirconium tetrachloride
(0.012 mol) was added. Thereafter, the mixture was stirred for 2 days while gradually returning to room temperature. As a result of NMR measurement of a part of the reaction solution, no peak considered to be a meso form was confirmed. The solvent was distilled off under reduced pressure, and recrystallization was performed with toluene / hexane. As a metallocene compound, rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -indenyl) zirconium dichloride (purity 99% or more) was used. 2.8 g (42% yield) were obtained. The ¹ H-NMR value (CDCl ₃ ) measured for the metallocene compound was as follows. ¹ H-NMR value (CDCl ₃ ): δ 1.12 (s, 6
H), δ 2.42 (s, 6H), δ 6.07 (d, 2
H), δ 6.27 (d, 2H), δ 6.71 (t, 2
H), δ 6.92 (s, 2H), δ 6.92 (d, 2
H), δ 7.31 (t, 2H), δ 7.54 (d, 2
H).

[Rac-dimethylsilylenebis (2-
(Production of propylene homopolymer using (2- (5-methyl) -furyl) -indenyl) zirconium dichloride as a catalyst] In a SUS autoclave, 1 L of toluene, a methylaluminoxane-toluene solution (MMAO3A manufactured by Tosoh Akzo) (Al / Zr = 10,000), dimethylsilylenebis (2- (2- (5-methyl) -furyl)
- indenyl) zirconium dichloride - toluene solution 3ml (0.34 × 10 ^-6 mol) was added sequentially, 30
Heated to ° C. Here, propylene was introduced at a pressure of 0.3 MPa, and polymerization was performed for 1 hour. After the polymerization, the polymer was filtered, and the catalyst component was decomposed with 1 liter of hydrochloric methanol. Thereafter, filtration, washing and drying were sequentially performed to obtain 8.7 g of a propylene homopolymer. The polymerization activity was 26 kg-polymer / mmol (Zr) · hr. As a result of analyzing the obtained propylene homopolymer, the MFR was 0.004.
g / 10 minutes, isotactic pentad fraction (I ₅ )
Is 0.928, the isotactic triad fraction (I ₃ ) is 0.946, and the 2,1-insertion reaction of the propylene monomer with respect to the total number of moles of the propylene units constituting the propylene homopolymer. Is less than the lower detection limit, that is, 0.02 mol%.
Is less than 1.61 × 10 ⁶ g / mol, Mw
/ Mn was 3.0 and the melting point was 146.2 ° C.

Comparative Example 1 Synthesis of rac-dimethylsilylenebis (2-methyl-indenyl) zirconium dichloride
Rac-Dimethylsilylenebis (2-methyl-indenyl) zirconium dichloride was synthesized by the method described in 00887.

[Production of propylene homopolymer using rac-dimethylsilylenebis (2-methyl-indenyl) zirconium dichloride as a catalyst] In an autoclave made of SUS, 1 L of toluene and a solution of methylaluminoxane-toluene (“MMAO3A (Tosoh Akzo)” (Trade name))) (Al / Zr = 10,000), 3 ml of rac-dimethylsilylenebis (2-methyl-indenyl) zirconium dichloride-toluene solution (0.42 × 1
0 ^-6 mol) in that order and heated to 30 ° C. Here, propylene was introduced at a pressure of 0.3 MPa, and polymerization was performed for 1 hour. After the polymerization, the polymer was filtered, and the catalyst component was decomposed with 1 liter of hydrochloric methanol. Thereafter, filtration, washing, and drying were sequentially performed to obtain 19.5 g of a propylene homopolymer. The polymerization activity was 46 kg-polymer / mmol (Z
r) · hr. As a result of analyzing the obtained propylene homopolymer, the MFR was 0.53 g / 10 min, the isotactic pentad fraction (I ₅ ) was 0.945, and the isotactic triad fraction (I ₃ ) was 0. .961, and the ratio of the number of moles of propylene units resulting from the 2,1-insertion reaction of the propylene monomer to the total number of moles of propylene units constituting the obtained propylene homopolymer is 0.29 mol. %, 1, of the propylene monomer
3- The proportion of the number of moles of propylene units due to the insertion reaction is less than the lower detection limit, that is, less than 0.02 mol%, and Mw is 3.48 × 10 ⁵ g / mol, Mw /
Mn was 1.9 and melting point was 153.1 ° C.

<Example 2> [Production of propylene / ethylene copolymer using rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -indenyl) zirconium dichloride] 900 ml of hexane and 1 mmol of triisobutylaluminum were added to an autoclave having an inner volume of 1.5 L, and the temperature was raised to 70 ° C. with stirring. Then, ethylene was fed and pressurized to 0.19 MPa.
Propylene was fed to adjust the total pressure to 0.58 MPa. Thereafter, the metallocene compound was prepared in advance as in Example 1.
Rac-dimethylsilylenebis (2- (2
0.001 mmol of-(5-methyl) -furyl) -indenyl) zirconium dichloride per Zr atom
And methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd .: p
-MAO) to 0.3 mmol in terms of Al atomic weight and 10
The metallocene catalyst mixed for 1 minute was injected with propylene, and propylene was continuously fed to reduce the total pressure to 0.78.
The polymerization was carried out at a constant pressure of 70 ° C. for 10 minutes while maintaining the pressure at MPa. After 10 minutes, the polymer was degassed, the polymer was recovered in a large amount of methanol, and dried with a reduced pressure drier to a constant weight to obtain 3.4 g of a polymer. The polymerization activity is 20.
When the obtained propylene / ethylene copolymer was analyzed at 2 kg-polymer / (mmol-Zr · h), the content of ethylene units was 20.9% by weight (28.4 mol%).
%) And an isotactic triad fraction (I ₃ ) of 0.
Both the ratio of the number of moles of propylene units due to the 899,2,1-insertion reaction and the ratio of the number of moles of propylene units due to the 1,3-insertion reaction are less than the detection limit, that is, 0 0.02 mol%, intrinsic viscosity [η] is 1.52 dl / g, weight average molecular weight (Mw) is 156,000, and ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) is 2.24. Met.

<Example 3> [Production of preactivated metallocene-supported catalyst using rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -indenyl) zirconium dichloride] (1) Metallocene Production of supported catalyst In a glass reactor equipped with a stirrer having an inner volume of 500 ml and purged with nitrogen gas, 89 ml of a toluene solution of methylaluminoxane (concentration: 3 mol / l, trade name: PMAO, manufactured by Tosoh Akzo Co., Ltd.) was added. 267mmo in atom conversion
l) and chiral dimethylsilylenebis (2- (2- (5-methyl) -furyl) -indenyl) zirconium dichloride as a bridged metallocene compound 0.9
29 mmol was added, and the mixture was reacted by stirring and holding at a temperature of 25 ° C. for 15 minutes to obtain a reaction product of a metallocene compound and an aluminoxane, that is, a metallocene catalyst. Subsequently, silica having an average particle size of 51 μm (SYLOPOL® 948, Grace.
(Davison) 6.7 g, and the temperature of the reactor was 11
The temperature was raised to 0 ° C., and the reaction product obtained above was kept in contact with silica for 60 minutes while being stirred to carry out a contact reaction, thereby obtaining a slurry containing the crude metallocene-supported catalyst supporting the metallocene catalyst. . After cooling the temperature of the reactor to −10 ° C., while maintaining the temperature of the reactor at −10 ° C., n-hexane 2
After adding 50 ml and stirring for 10 minutes, the stirrer was stopped, and the solvent was separated by decantation. Subsequently, while maintaining the temperature of the reactor at −10 ° C., 250 ml of n-hexane was charged into the reactor and stirred and washed for 5 minutes. Then, the agitator was stopped and the washing solvent was separated by decantation. Was repeated four times to obtain a purified metallocene-supported catalyst. Furthermore, n-hexane 250m
was charged into a reactor, and the metallocene-supported catalyst was dispersed to form a slurry.

(2) Production of Preactivated Metallocene-Supported Catalyst A 500 ml-volume glass reactor equipped with a stirrer replaced with nitrogen gas was charged with the metallocene-supported catalyst obtained in (1) above and n
-Transfer the slurry with hexane and bring the reactor temperature to 0 ° C
Was adjusted to Then, while maintaining the temperature of the reaction vessel at 0 ° C. while stirring, a propylene / hydrogen mixed gas having a molar ratio of 10: 1 was supplied at a supply rate of 300 ml / min for 40 minutes to perform prepolymerization, and the produced propylene homopolymer was obtained. The catalyst was supported on the metallocene supported catalyst. After the used n-hexane solvent was separated from the reaction mixture by decantation, 250 ml of n-hexane was added and stirred for 5 minutes to wash the preactivated metallocene-supported catalyst, and the washing solvent was separated by decantation. The washing operation was repeated 5 times. Next, 250 ml of n-hexane was charged into the reactor,
The obtained preactivated metallocene supported catalyst was dispersed in n-hexane to form a slurry. The solvent of the slurry of the obtained preactivated metallocene-supported catalyst and n-hexane was separated by filtration, and then dried under reduced pressure at a temperature of 25 ° C. to obtain a preactivated metallocene-supported catalyst composed of solid particles. The obtained preactivated metallocene-supported catalyst was analyzed to determine how many g of the propylene polymer was supported per 1 g of the metallocene-supported catalyst. Supported catalyst 1 before pre-activation
1 g of the propylene polymer was supported per g.

[Rac-dimethylsilylenebis (2-
Production of Propylene Homopolymer by Preactivated Metallocene-Supported Catalyst Using (2- (5-Methyl) -furyl) -indenyl) zirconium Dichloride] A 3 L Internal Volume Gas Phase Reactor Fully Nitrogen-Substituted 70 in
At 150 ° C., 150 g of coarse polypropylene particles and 0.5 mmol of triethylaluminum were added, and 85 rpm
m. Next, 87 mg of the pre-activated metallocene supported catalyst prepared above was added per supported catalyst before pre-activation, and the mixture was further stirred for 5 minutes. Then
A propylene monomer is supplied into the reactor, the reaction pressure is increased to 2.3 MPa (gauge pressure), and the polymerization is carried out under a constant polymerization condition of 70 ° C. and 2.3 MPa (gauge pressure). When the amount reached 300 g, the monomer supply was stopped, and the pressure was reduced to atmospheric pressure.
Under a nitrogen stream, 300 g of a powdery polymer was withdrawn from the reactor. Then, in the same manner as described above, except that 150 g of the powdery polymer remaining in the reactor after the withdrawal operation was used instead of the 150 g of the coarse polypropylene particles, the same polymerization was continued twice, and the third polymerization was performed. Using the polymerization result of
The polymerization activity was calculated and the obtained propylene homopolymer was analyzed. The polymerization time was about 1.5 hours each. From the above results, the polymerization activity was 1,720 g · polymer / g · catalyst per 1 g of the supported catalyst before preactivation. When the obtained propylene homopolymer was analyzed, the weight average molecular weight (Mw) was 2.05 × 10
⁵ g / mol, ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) is 2.4, MFR is 6 g / 10 min, melting point is 137 ° C., isotactic pentad fraction ( I ₅ ) is 0.869, the isotactic triad fraction (I ₃ ) is 0.906, and the propylene monomer is 2,1,1 based on the total number of moles of propylene units constituting the propylene homopolymer. The proportion of the moles of propylene units due to the insertion reaction is 0.36 m
ol%, and the ratio of the number of moles of propylene units due to the 1,3-insertion reaction of the propylene monomer to the total number of moles of propylene units constituting the propylene homopolymer was 0.18 mol%. Was.

Example 4 Propylene / Ethylene Copolymer with Preactivated Metallocene-Supported Catalyst Using [rac-Dimethylsilylenebis (2- (2- (5-methyl) -furyl) -indenyl) zirconium Dichloride Production of Monomer] The monomer fed into the reactor is a propylene / ethylene mixed monomer, and the ethylene monomer concentration in the reactor is 2.8 m
A propylene / ethylene copolymer was produced in the same manner as in Example 3 except that the content was changed to ol%. The polymerization activity was 2300 g · polymer / g / g of the supported catalyst before preactivation.
g catalyst. When the obtained propylene / ethylene copolymer was analyzed, the weight average molecular weight (Mw) was 2.
01 × 10 ⁵ g / mol, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2.
5, MFR is 6.6 g / 10 min, ethylene unit content is 2.0% by weight, melting point is 122 ° C., isotactic triad fraction (I ₃ ) is 0.913, and propylene / ethylene The ratio of the number of moles of the propylene unit caused by the 2,1-insertion reaction of the propylene monomer to the total number of moles of the propylene units constituting the polymer is 0.41 mol%, and the propylene / ethylene copolymer With respect to the total number of moles of propylene units constituting
The proportion of the moles of propylene units due to the 1,3-insertion reaction of the propylene monomer is less than the detection limit,
That is, it was less than 0.02 mol%.

Example 5 [Synthesis of rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-indenyl) zirconium dichloride] (1) Dimethylbis (2- (2 Synthesis of-(5-methyl) -furyl) -4-phenyl-indenyl) silane In a 200 ml glass reaction vessel, 12 g of 2- (2- (5-methyl) -furyl) -4-phenyl-indene was added.
(0.045 mol), 0.3 g of copper isocyanate (2.
5 mmol) and 150 ml of THF, and cooled to -70 ° C in a dry ice-methanol bath. Here 1.5
0 mol / L n-butyllithium-hexane solution 30
ml (0.045 mol) was added dropwise. After the dropwise addition, the mixture was stirred for 16 hours while gradually returning to room temperature. It was cooled again to -50 ° C in a dry ice-methanol bath, and THF containing 2.9 g (0.022 mol) of dimethyldichlorosilane was added.
40 ml of the solution were added dropwise. After the dropwise addition, the mixture was stirred for 16 hours while gradually returning to room temperature. Distilled water was added to the reaction solution, transferred to a separating funnel, and washed with saline until neutral. Anhydrous sodium sulfate was added thereto, and the mixture was allowed to stand overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified on a silica gel column.
11 g (82% yield) of a pale yellow liquid of (2- (5-methyl) -furyl) -4-phenyl-indenyl) silane was obtained.

(2) rac-dimethylsilylenebis (2
Synthesis of-(2- (5-methyl) -furyl) -4-phenyl-indenyl) zirconium dichloride In a 100 ml glass reaction vessel, dimethylbis (2-
5.3 g (8.8 mmol) of (2- (5-methyl) -furyl) -4-phenyl-indenyl) silane and 150 ml of diethyl ether were added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. Here 1.50mol / L
N-butyllithium-hexane solution 12 ml (18 m
mol) was added dropwise. After the dropwise addition, the mixture was returned to room temperature and stirred for 16 hours. The solvent of the reaction solution was concentrated under reduced pressure to about 20 ml, 200 ml of toluene was added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. Thereto, 2.0 g (8.6 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred for 3 days while gradually returning to room temperature. NM in part of the reaction solution
As a result of the measurement of R, a peak considered to be a meso form was not confirmed. The solvent was distilled off under reduced pressure and recrystallized from dichloromethane / hexane to give dimethylsilylenebis (2- (2-
Racemic form of (5-methyl) -furyl) -4-phenyl-indenyl) zirconium dichloride (purity 99%
3.0 g (yield 45%) as yellow-orange crystals. ¹ H-NMR value (CDCl ₃ ) Racemic form: δ 1.15
(S, 6H), δ 2.42 (s, 6H), δ 6.06
(D, 2H), δ 6.26 (d, 2H), δ 6.81
(Dd, 2H), δ 6.93 (d, 2H), δ 7.03
(S, 2H), δ 7.31 to δ 7.64 (m, 12
H).

[Rac-dimethylsilylenebis (2-
(Production of propylene homopolymer using (2- (5-methyl) -furyl) -4-phenyl-indenyl) zirconium dichloride as a catalyst] In a SUS autoclave, 1 L of toluene and a methylaluminoxane-toluene solution (MMAO3A manufactured by Tosoh Akzo Co., Ltd.) ) (Al / Zr = 10,0)
00), rac-dimethylsilylenebis (2- (2-
(5-methyl) -furyl))-4-phenyl-indenyl) zirconium dichloride-toluene solution 3 ml
(0.29x10 ^{- 6} mol) was added, sequentially, and heated to 30 ° C.. Here, propylene was introduced at a pressure of 0.3 MPa, and polymerization was performed for 1 hour. After polymerization, the polymer is filtered,
The catalyst component was decomposed with 1 liter of hydrochloric methanol. Thereafter, filtration, washing and drying were sequentially performed to obtain 32 g of a propylene homopolymer. The polymerization activity is 110 kg-polymer /
mmol (Zr) · hr. As a result of analyzing the obtained propylene homopolymer, the MFR was 0.03 g / 10
Min, isotactic pentad fraction (I ₅ ) of 0.9
73, the isotactic triad fraction (I ₃ ) is 0.
985, and the ratio of the number of moles of propylene units due to the 2,1-insertion reaction of the propylene monomer to the total number of moles of propylene units constituting the propylene homopolymer is 0.22 mol%, and The ratio of the number of moles of propylene units resulting from the 1,3-insertion reaction of the propylene monomer to the total number of moles of propylene units constituting the propylene homopolymer is 0.05%.
mol%, Mw is 7.33 × 10 ⁵ g / mol,
Mw / Mn was 2.22 and the melting point was 159.1 ° C.

<Example 6> [Dimethylsilylenebis (2- (2- (5-methyl)-
Synthesis of furyl) -4,5-benzoindenyl) zirconium dichloride] (1) Synthesis of dimethylbis (2- (2- (5-methyl) -furyl) -4,5-benzoindenyl) silane 200 ml glass 23-g 2- (2- (5-methyl) -furyl) -4,5-benzoindene
(0.095 mol), 1-methylimidazole
4 ml (5.0 mmol) and 150 ml of THF were added,
Cooled to -70 ° C in a dry ice-methanol bath.
60 ml (0.095 mol) of a 1.59 mol / L n-butyllithium-hexane solution was added dropwise thereto. After the dropwise addition, the mixture was stirred for 16 hours while gradually returning to room temperature. Cool again to -50 ° C in a dry ice-methanol bath,
6.1 g (0.047 mol) of dimethyldichlorosilane
50 ml of a THF solution containing was added dropwise. After the dropwise addition, the mixture was stirred for 16 hours while gradually returning to room temperature. Distilled water was added to the reaction solution, transferred to a separating funnel, and washed with saline until neutral. Anhydrous sodium sulfate was added thereto, and the mixture was allowed to stand overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified on a silica gel column, and dimethylbis (2- (2- (5-methyl) -furyl) -4,5-benzoindenyl) silane was pale yellow. 15.2 g (yield 59%) of a solid was obtained.

(2) Dimethylsilylenebis (2- (2-
Synthesis of (5-methyl) -furyl) -4,5-benzoindenyl) zirconium dichloride In a 100 ml glass reaction vessel, dimethylbis (2-
5.1 g (9.3 mmol) of (2- (5-methyl) -furyl) -4,5-benzoindenyl) silane and 180 ml of diethyl ether were added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. Here 1.59mol / L
12 ml of n-butyllithium-hexane solution (19 m
mol) was added dropwise. After the dropwise addition, the mixture was returned to room temperature and stirred for 16 hours. The solvent of the reaction solution was concentrated under reduced pressure to about 20 ml, 200 ml of toluene was added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. Thereto, 2.2 g (9.3 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred for 16 hours while gradually returning to room temperature. The solvent was distilled off under reduced pressure and recrystallized from dichloromethane / hexane to give dimethylsilylenebis (2- (2- (5-methyl) -furyl).
Racemic (-4,5-benzoindenyl) zirconium dichloride (purity: 99% or more) was added as a yellow crystal to form 0.1.
5 g (7.8% yield) was obtained. ¹ H-NMR value (CDCl ₃ ) Racemic form: δ 1.14
(S, 6H), δ 2.46 (s, 6H), δ 6.13
(D, 2H), δ 6.34 (d, 2H), δ 6.87
(D, 2H), δ 6.96 (d, 2H), δ 7.40
(S, 2H), δ 7.48 to δ 7.55 (m, 4H),
δ 7.72 (d, 2H), δ 7.99 (d, 2H).

[Dimethylsilylenebis (2- (2- (5
-Propylene polymerization using -methyl) -furyl) -4,5-benzoindenyl) zirconium dichloride] SU
In a S autoclave, toluene 1L, methylaluminoxane-toluene solution (MMAO3A manufactured by Tosoh Akzo)
(Al / Zr = 10,000), dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4,5-benzoindenyl) zirconium dichloride-toluene solution 3 ml (0.28 × 10 ⁻⁶ mol) In order, 3
Heated to 0 ° C. Here, propylene was introduced at a pressure of 0.3 MPa, and polymerization was performed for 1 hour. After the polymerization, the polymer was filtered, and the catalyst component was decomposed with 1 liter of hydrochloric methanol. Thereafter, filtration, washing and drying were sequentially performed to obtain 6.9 g of polypropylene. The polymerization activity was 25 kg-polymer / mmol (Zr) · hr. As a result of analyzing the obtained propylene homopolymer, the MFR was 0.04 g / 1.
0 minutes, the isotactic pentad fraction (I ₅ ) is 0.
930, the isotactic triad fraction (I ₃ ) is 0.9514, and it is caused by the 2,1-insertion reaction of the propylene monomer with respect to the total number of moles of the propylene units constituting the propylene homopolymer. The proportion of the number of moles of the propylene unit is 0.43 mol%, and the total number of moles of the propylene unit constituting the propylene homopolymer is the ratio of the propylene unit due to the 1,3-insertion reaction of the propylene monomer. When the ratio of the number of moles is less than the detection limit, that is, less than 0.02 mol%,
Is 8.97 × 10 ⁵ g / mol and Mw / Mn is 2.8.
8. The melting point was 150.2 ° C.

Example 7 Dimethylsilylenebis (2- (2- (5-phenyl)
Synthesis of -furyl) -indenyl) zirconium dichloride] (1) Synthesis of 2- (2- (5-phenyl) -furyl) -indene In a 1000 ml glass reaction vessel, 2-phenylfuran 33 g (0.23 mol) was added. 300 ml of THF was added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath.
To this, 147 ml (0.23 mol) of a 1.56 mol / L n-butyllithium-hexane solution was dropped. After the addition, the mixture was returned to room temperature and stirred for 4 hours. Dry ice again
Cool to −70 ° C. in a methanol bath and add 2-indanone 3
100 ml of a THF solution containing 0 g (0.23 mol) was added dropwise. After the dropwise addition, the mixture was returned to room temperature and stirred for 16 hours. The reaction solution was cooled to −20 ° C. in a dry ice-methanol bath, and 100 ml of 4N hydrochloric acid was added dropwise. This reaction solution is
The mixture was transferred to a separating funnel, washed with a saline solution until neutral, anhydrous sodium sulfate was added, and the mixture was allowed to stand overnight to dry. The anhydrous sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and 600 ml of toluene and 0.5 g of p-toluenesulfonic acid were added thereto.
(2.6 mmol) was added and the mixture was refluxed for 1 hour. The reaction solution was transferred to a separating funnel and washed with a saline solution until neutral, anhydrous sodium sulfate was added, and the mixture was allowed to stand overnight to dry. The anhydrous sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 19 g of colorless needle crystals of 2- (2- (5-phenyl) -furyl) -indene (yield 31%). Was. The structure was confirmed by NMR.

(2) Synthesis of dimethylbis (2- (2- (5-phenyl) -furyl) -indenyl) silane In a 200 ml glass reaction vessel, (2- (2- (5-
Phenyl) -furyl) -indene 19 g (72 mmol)
l), 300 ml of THF was added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. 1.56mol here
/ L of n-butyllithium-hexane solution 102ml
(0.15 mol) was added dropwise. After the dropwise addition, the mixture was stirred for 16 hours while gradually returning to room temperature. The mixture was cooled again to -70 ° C in a dry ice-methanol bath, 0.3 ml (3.6 mmol) of 1-methylimidazole was added, and T containing 4.6 g (36 mmol) of dimethyldichlorosilane was added.
70 ml of HF solution was added dropwise. After the dropwise addition, the mixture was stirred for 16 hours while gradually returning to room temperature. Distilled water was added to the reaction solution, transferred to a separating funnel, and washed with saline until neutral. Anhydrous sodium sulfate was added thereto, and the mixture was allowed to stand overnight to dry the reaction solution. The anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was recrystallized from dichloromethane / hexane to give 17 g of pale yellow crystals of dimethylbis (2- (2- (5-phenyl) -furyl) -indenyl) silane (yield). 82%).

(3) Dimethylsilylenebis (2- (2-
Synthesis of (5-phenyl) -furyl) -indenyl) zirconium dichloride In a 500 ml glass reaction vessel, dimethylbis (2-
9.0 g (17 mmol) of (2- (5-phenyl) -furyl) -indenyl) silane, 100 ml of toluene,
150 ml of diethyl ether was added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. 1.56m here
ol / L n-butyllithium-hexane solution 20 ml
(32 mmol) was added dropwise. After dropping, return to room temperature.
Stirred for hours. The solvent of the reaction solution was concentrated under reduced pressure to about 20 ml, 300 ml of toluene was added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. Thereto, 3.7 g (16 mmol) of zirconium tetrachloride was added. afterwards,
The mixture was stirred overnight while gradually returning to room temperature. As a result of measurement by 1 H-NMR, the racemic / meso ratio when complexed was 81 /
It was 19. The solvent was distilled off under reduced pressure, and recrystallized from dichloromethane / hexane to give the racemic form (purity of 99% or more)
2.2 g (19% yield) were obtained. ¹ H-NMR value (CDCl ₃ ) Racemic form: δ 1.12
(S, 6H), δ 6.53 (d, 2H), δ 6.73
(T, 2H), δ 6.77 (d, 2H), δ 6.97
(D, 2H), δ 7.03 (s, 2H), δ 7.32.
(T, 2H), 7.35 (t, 2H), δ 7.45
(T, 4H), δ 7.59 (d, 2H), δ 7.74
(D, 4H).

[Dimethylsilylenebis (2- (2- (5
Production of propylene homopolymer using -phenyl) -furyl) -indenyl) zirconium dichloride as a catalyst] In a SUS autoclave, 1 L of toluene, a methylaluminoxane-toluene solution (MMA manufactured by Tosoh Akzo Co., Ltd.)
O3A) (Al / Zr = 10,000), dimethylsilylenebis (2- (2- (5-phenyl) -furyl) -indenyl) zirconium dichloride-toluene solution 3
ml (0.30 × 10 ⁻⁶ mol) in order,
Heated. Here, propylene was introduced at a pressure of 0.3 MPa, and polymerization was performed for 1 hour. After the polymerization, the polymer was filtered, and the catalyst component was decomposed with 1 liter of hydrochloric methanol. Thereafter, filtration, washing and drying were sequentially performed to obtain 2.7 g of polypropylene. The polymerization activity is 9 kg-polymer / m
mol (Zr) · hr. As a result of analyzing the obtained propylene homopolymer, the MFR was 0.01 g / 10
Min, isotactic pentad fraction (I ₅ ) of 0.9
354, the isotactic triad fraction (I ₃ ) is 0.9541, and is caused by the 2,1-insertion reaction of the propylene monomer with respect to the total number of moles of the propylene units constituting the propylene homopolymer. The ratio of the number of moles of propylene units is less than the detection limit, that is, 0.02
mol%. Furthermore, the ratio of the number of moles of propylene units caused by the 1,3-insertion reaction of the propylene monomer to the total number of moles of propylene units constituting the propylene homopolymer is less than the detection limit, that is,
Less than 0.02 mol%, and Mw is 1.06 × 10 ⁶
g / mol, Mw / Mn 2.47, melting point 149.7
° C.

Example 8 Propylene / ethylene copolymer on a preactivated metallocene-supported catalyst using [rac-dimethylsilylenebis (2- (2- (5-methyl) -furyl) -indenyl) zirconium dichloride Production of 0.5 mmol in a 1.5 liter internal volume reactor
1.35 mmol of triethylaluminum and hydrogen
After charging 800 ml of liquefied propylene, the temperature was raised to 50 ° C. and stabilized. At that time, the pressure in the reactor is 2.
It was 03 MPa (gage pressure). Thereafter, ethylene was fed so that the pressure in the reactor was 0.1 MPa higher than the pressure before charging, that is, until the pressure was 2.13 MPa (gauge pressure), and the temperature and pressure in the reactor were further stabilized. . Thereafter, the polymerization reaction was started by supplying 84 mg of the preactivated metallocene-supported catalyst prepared according to the method described in Example 3 into the reactor while being accompanied by 200 ml of liquefied propylene, and the polymerization reaction was started at 50 ° C. For 30 minutes to copolymerize propylene and ethylene. As a result, 135 g of a propylene / ethylene copolymer was obtained, and the polymerization activity was 6,430 g · polymer / g · catalyst per 1 g of the supported catalyst before preactivation. When the obtained propylene / ethylene copolymer was analyzed, it was found that M
FR is 1.4 g / 10 min, and the content of ethylene unit is 3.
The melting point was 5% by weight and the melting point was 124 ° C.

[0192]

By using the metallocene compound of the present invention as a catalyst, it is possible to produce an olefin polymer having a high polymerization activity, a high molecular weight and a strictly controlled stereoregularity. Further, the metallocene compound has an excellent feature that it can be obtained with a low and simple synthesis step and a high synthesis yield using inexpensive raw materials. Furthermore, since it has the feature that the amount of dl-form (racemic form) produced is much larger than that of the meso-form, there is an advantage that the production cost can be significantly reduced especially in the production of the racemic form.

 ──────────────────────────────────────────────────の Continued on the front page F term (reference) 4J028 AA01 AA01A AB00 AB00A AB01 AB01A AC01 AC01A AC06 AC08 AC09 AC10 AC10A AC25 AC26 AC27 AC28A BA00A BA00B BA01A BA01B BA02A BA02B BA03A BA03B BA04A BB00B BB01 BB01 BB01 BB01 BB01 BB00 BC13A BC13B BC14B BC15B BC16B BC19B BC25A BC25B BC33A CA25A CA25C CA27A CA27C CA28A CA28C CA29A CA29C CA30A CA30C CB02C CB94C DA01 DA02 DA03 DA04 DA05 DA08 DA09 DB03A DB03B DB03C DB05A EA01 EB01 GA02 GB01 GB07 4J128 AA01 AB00 AB01 AC01 AC10 AC28 AD00 BA00A BA00B BA01A BA01B BA02A BA02B BA03A BA03B BA04A BB00A BB00B BB01A BB01B BB02A BB02B BB03A BB03B BB04B BC12A BC12B BC13A BC13B BC14B BC15B BC16B BC19B BC25A BC25B BC33A CA25A CA25C CA27A CA27C CA28A CA28C CA29A CA29C CA30A CA30C CB02C CB 94C DA01 DA02 DA03 DA04 DA05 DA08 DA09 DB03A DB03B DB03C DB05A EA01 EB02 EB04 EB05 EB07 EB08 EB09 EB10 EB21 EC01 EC02 FA02 GA01 GA03 GA06 GA07 GA14 GA19 GB01 GB07

Claims (13)

[Claims] 1. A metallocene compound represented by the following general formula (1). _{Q (C 5 H 4-m} R 1 m) (C 5 H 4-n R 2 n) MXY (1) ( _{wherein, (C 5 H 4-m} R 1 m) and (C ₅ H _4-n R ² _n ) represents a cyclopentadienyl group, and C ₅ H _4-m and C ₅ H _4-n
Represents a cyclopentadienyl ring. m represents an integer of 1 to 3, and n represents an integer of 2 or 3 independently of m. R ¹ and R ² are C ₅ H _4-m and C ₅ H, respectively.
A bonding group bonded to _4-n , which independently represents a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group or a heteroaromatic group. Each of R ¹ _m and each of R ² _n may be the same or different from each other. The heteroaromatic group has a heteroaromatic ring and, if necessary, at least one bonding group bonded to the ring, and the bonding group is a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon. Group. A pair of R ² out of R ² _n are bonded to each other to form at least one ring. When m is an integer of 2 or 3, one pair of R ¹ of R ¹ _m is bonded to each other to form at least one ring independently of the ring formed by the pair of R ^2. Is also good. The pair of R ¹
And the ring formed by the pair of R ² may have, independently of each other, at least one bonding group bonded to the ring, and the bonding group has 1 to 20 carbon atoms. It is a hydrocarbon group, a silicon-containing hydrocarbon group or a heteroaromatic group. The heteroaromatic group has a heteroaromatic ring and, if necessary, at least one bonding group bonded to the aromatic ring, wherein the bonding group is a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing group. It is a hydrocarbon group. However, the bonding group represented by R ¹ _m and R ² _n and the pair of R ¹
And at least one of the bonding groups or groups bonded to the ring formed by the pair of R ² and the ring formed by the pair of R ² is a heteroaromatic group, and the heteroaromatic group is a heteroaromatic group. It has a ring and at least one bonding group bonded to the heteroaromatic ring, and the bonding group is a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group. Q represents (C ₅ H _4-m R ¹ _m ) and (C ₅ H
_4-n R ² _n ) is a divalent hydrocarbon group, an unsubstituted silylene group, a hydrocarbon-substituted silylene group,
³ is a boron compound having a ₂ NB structure. Where R ³
Is a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group or a heteroaromatic group. M represents a titanium atom, a zirconium atom or a hafnium atom. X and Y may be the same or different and represent a hydrogen atom, a halogen atom or a hydrocarbon group. ) Wherein n is an integer 3, bonded to at least one of R ² other than R ² of the pair forming a ring together with a heteroaromatic group, said heteroaromatic group, It has a heteroaromatic ring and at least one bonding group bonded to the heteroaromatic ring, wherein the bonding group is a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group. The metallocene compound according to claim 1, wherein Wherein n is an integer 3, bonded to at least one of R ² other than R ² of the pair forming the rings to each other,
Cyclopentadienyl ring C ₅ H _4-n claim 1 or 2 metallocene compound, wherein the bonded to the 2-position of. 4. The metallocene compound has a structure in which a plane of symmetry containing M does not exist due to at least one of a difference in R ¹ and R ^{2 and} a difference in a bonding position thereof to a cyclopentadienyl ring. The metallocene compound according to any one of claims 1 to 3, wherein the metallocene compound is formed. 5. R¹ _mAnd R^Two _nA group of bonding groups represented by
Each time, the pair of R ¹And a pair of R^Two
Of the bonding group or bonding groups bonded to the ring formed by
At least one linking group is a heteroaromatic group;
A heteroaromatic group comprising a heteroaromatic ring and the heteroaromatic ring;
Having at least one linking group attached to the ring;
The bonding group is a hydrocarbon group having 1 to 20 carbon atoms or silicon
The heteroaromatic ring is 2-fluorofuran.
Ring, 2-thienyl ring, 2-benzofuryl ring, or
5. A compound according to claim 1, which is a 2-benzothienyl ring.
The metallocene compound according to the above item. 6. R¹ _mAnd R^Two _nA group of bonding groups represented by
Each time, the pair of R ¹And a pair of R^Two
A bonding group or a group of bonding groups bonded to the ring formed by
That is, at least one bonding group is 2- (5-methyl)-
Furyl group, 2- (5-t-butyl) -furyl group, 2-
(5-trimethylsilyl) -furyl group, 2- (5-fe
Nyl) -furyl group, 2- (5-methyl) -thienyl group,
2- (5-t-butyl) -thienyl group, 2- (5-tri
Methylsilyl) -thienyl group, 2- (5-phenyl)-
Thienyl group, 2- (4,5-dimethyl) -furyl group, 2
-(4,5-dimethyl) -thienyl group, 2-benzofury
And a 2-benzothienyl group.
Metallocene compounds listed. 7. The metallocene compound is dimethylsilylenebis (2- (2- (5-methyl) -furyl) -indenyl) zirconium dichloride or dimethylsilylenebis (2- (2- (5-t-butyl) -furyl). ) -Indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -furyl) -indenyl) Zirconium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -thienyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -thienyl) -indenyl) zirconium dichloride , Dimethylsilylene bis (2- (2- ( 5-trimethylsilyl) -thienyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -thienyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -Ruffle)
-4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2-
(5-trimethylsilyl) -furyl) -4-phenyl-
Indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -furyl) -4
-Phenyl-indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (2- (5-methyl) -thienyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-
t-butyl) -thienyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -thienyl)-
4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -thienyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2
-(5-methyl) -furyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -furyl) -4,5-benzoindenyl) zirconium dichloride, Dimethylsilylenebis (2- (2- (5-t-butyl) -furyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -4 , 5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -thienyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5 -Phenyl) -thienyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilyl Bis (2- (2- (5-t-
Butyl) -thienyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-trimethylsilyl) -thienyl) -4,5
-Benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2-
(5-t-butyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride , Dimethylsilylene bis (2- (2-
(5-phenyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -thienyl) -4
-Phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-
(Butyl) -thienyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -thienyl)
-4-phenyl-dihydroazulenyl) zirconium dichloride or dimethylsilylenebis (2-
(2- (5-phenyl) -thienyl) -4-phenyl-
7. The metallocene compound according to claim 6, which is dihydroazulenyl) zirconium dichloride. 8. An olefin polymerization catalyst comprising the metallocene compound according to claim 1, an activating compound, and optionally an organoaluminum compound. 9. A supported catalyst component produced by using the metallocene compound according to any one of claims 1 to 7, an activating compound, a particulate carrier, and, if desired, an organoaluminum compound, and an organoaluminum. An olefin polymerization catalyst containing a compound. 10. A supported catalyst component produced by using the metallocene compound, the ion-exchange layered compound or the inorganic silicate according to any one of claims 1 to 7, and, if desired, an organic aluminum compound; An olefin polymerization catalyst containing an aluminum compound. 11. A method for producing an olefin polymer using the olefin polymerization catalyst according to claim 8. Description: 12. The olefin polymer is a propylene homopolymer or a propylene / olefin copolymer of propylene containing at least 50% by weight of propylene units based on the weight of the copolymer and olefins other than propylene. The method for producing an olefin polymer according to claim 11, wherein 13. The method according to claim 1, wherein the total number of moles of propylene units constituting the olefin polymer is equal to the number of moles of propylene units caused by the 2,1-insertion reaction of the propylene monomer and the number of moles of the propylene monomer is 1,3-inserted. The ratio occupied by the number of moles of propylene units caused by the polymerization was 0.1%.
The method for producing an olefin polymer according to claim 12, wherein the amount is less than 05 mol%.