# US 5,349,032 A · Metallocene and process for producing polyolefin using the same

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- Number: US 5,349,032 A
- Document ID: US5349032A
- Status: Granted
- Kind: A
- Application number: 08/212,931
- Filed: 1994-03-15
- Granted: 1994-09-20
- Earliest claimed: 1991-11-28
- Assignees: Showa Denko K.K.
- Inventors: Shigenobu Miyake; Nobuyuki Kibino; Takashi Monoi; Hiroyuki Ohira; Shintaro Inazawa
- Web page: https://patentgrep.com/patent/US5349032A

## CPC

- C07F 17/00: Metallocenes
- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- Y10S 526/943: Polymerization with metallocene catalysts
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

A metallocene having an asymmetric ligand which is represented by the formula below and its enantiomer: ##STR1## and a process for producing a polyolefin using the same as a catalyst component. The metallocene and its enantiomer are particularly effective in the production of highly stereospecific polyolefins.

## Claims

### Claim 1

A process for producing a polyolefin comprising using, as a catalyst component, a metallocene represented by formula (I) or its enantiomer: ##STR8## wherein M represents a transition metal selected from Ti, Zr, and Hf, X.sup.1 and X.sup.2, which may be the same or different, each represents a hydrogen atom, a hydrocarbon group containing from 1 to 10 carbon atoms, an alkylsilyl group, an arylsilyl group, or a halogen atom; R.sup.1, R.sup.2, R.sup.3, R.sup.6, and R.sup.7 each represents a hydrogen atom, a hydrocarbon group containing from 1 to 10 carbon atoms, an alkylsilyl group, or an arylsilyl group, provided that either one of R.sup.1 and R.sup.2 is not a hydrogen atom; R.sup.4 and R.sup.5 each represents a hydrocarbon group containing from 1 to 10 carbon atoms, an alkylsilyl group, or an arylsilyl group, or they are connected together to form a ring; Y represents a carbon atom, a silicon atom, or a germanium atom; and n represents an integer of from 1 to 3.

### Claim 2 (depends on 1)

The process as claimed in claim 1, wherein said metallocene or its enantiomer is used in combination with an organoaluminumoxy compound.

### Claim 3 (depends on 2)

The process as claimed in claim 2, wherein said organoaluminumoxy compound is methylaluminoxane.

### Claim 4 (depends on 1)

The process as claimed in claim 1, wherein Y in formula (I) is a carbon atom.

### Claim 5 (depends on 1)

The process as claimed in claim 1, wherein said metallocene or its enantiomer is a compound represented by formula (II) or its enantiomer: ##STR9## wherein M, X.sup.1, X.sup.2, R.sup.1, R.sup.2, R.sup.3, R.sup.6, R.sup.7 and n are as defined in formula (I); and Y' represents a carbon atom.

### Claim 6 (depends on 5)

The process as claimed in claim 5, wherein M is hafnium.

### Claim 7 (depends on 1)

The process as claimed in claim 1, wherein said metallocene or its enantiomer is a zirconocene represented by formula (III) or its enantiomer: ##STR10## wherein X.sup.1, X.sup.2, R.sup.1, R.sup.2, R.sup.3, R.sup.6, and R.sup.7 are as defined in formula (I), and Y' represents a carbon atom.

### Claim 8 (depends on 1)

The process as claimed in claim 1, wherein R.sup.1 represents a hydrogen atom.

### Claim 9

A process for producing a copolymer of ethylene and an .alpha.-olefin comprising using a solid catalyst obtained by supporting (a) a metallocene represented by formula (I) or its enantiomer: ##STR11## wherein M represents a transition metal selected from ti, Zr, and Hf; X.sup.1 and X.sup.2, which may be the same or different, each represents a hydrogen atom, a hydrocarbon group containing from 1 to 10 carbon atoms, an alkylsilyl group, an arylsilyl group, or a halogen atom; R.sup.1, R.sup.2, R.sup.3, R.sup.6, and R.sup.7 each represents a hydrogen atom, a hydrocarbon group containing from 1 to 10 carbon atoms, an alkylsilyl group, or an arylsilyl group, provided that either one of R.sup.1 and R.sup.2 is not a hydrogen atom; R.sup.4 and R.sup.5 each represents a hydrocarbon group containing from 1 to 10 carbon atoms, an alkylsilyl group, or an arylsilyl group, or they are connected together to form a ring; Y represents a carbon atom, a silicon atom, or a germanium atom; and n represents an integer of from 1 to 3, and (b) an organoaluminumoxy compound on (c) an inorganic oxide carrier in combination with, as a co-catalyst, an organoaluminum compound.

### Claim 10 (depends on 9)

The process as claimed in claim 9, wherein said metallocene or its enantiomer (a) is a metallocene represented by formula (II) or its enantiomer: ##STR12## wherein M, X.sup.1, X.sup.2, R.sup.1, R.sup.2, R.sup.3, R.sup.6, R.sup.7, and n are as defined in formula (I); and Y' represents a carbon atom, said organoaluminumoxy compound (b) is methylaluminoxane, and said inorganic oxide carrier (c) is silica or alumina.

### Claim 11 (depends on 9)

The process as defined in claim 9, wherein said inorganic oxide carrier (c) is silica or alumina having been treated with an organoaluminum compound.