# US 5,703,180 A · Catalyst for olefin polymerization, process for olefin polymerization using the same, ethylene/.alpha.-olefin copolymer, graft modified ethylene/.alpha.-olefin copolymer, and ethylene copolymer composition

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- Number: US 5,703,180 A
- Document ID: US5703180A
- Status: Granted
- Kind: A
- Application number: 08/618,109
- Filed: 1996-03-19
- Granted: 1997-12-30
- Earliest claimed: 1992-11-19
- Assignees: Mitsui Petrochemical Industries, Ltd.
- Inventors: Toshiyuki Tsutsui; Ken Yoshitsugu; Mamoru Takahashi; Akira Todo
- Web page: https://patentgrep.com/patent/US5703180A

## CPC

- C08J 5/18: Manufacture of films or sheets
- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 255/00: Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F 255/02: on to polymers of olefins having two or three carbon atoms
- C08L 23/02: not modified by chemical after-treatment
- C08L 23/0815: {with aliphatic 1-olefins containing one carbon-to-carbon double bond}
- C08L 51/06: grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
- C08F 4/65904: {in combination with another component of C08F4/64}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 4/65925: {two cyclopentadienyl rings being mutually non-bridged}
- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- C08J 2323/08: Copolymers of ethene (C08J2323/16 takes precedence)
- Y10S 526/943: Polymerization with metallocene catalysts
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

An ethylene/.alpha.-olefin copolymer obtained by copolymerizing ethylene with an .alpha.-olefin of 3 to 20 carbon atoms in the presence of a catalyst for olefin polymerization comprising an organoaluminum oxy-compound (a) and at least two kinds of transition metal compounds (b). This ethylene/.alpha.-olefin copolymer has high melt tension and high flowability.

## Claims

### Claim 1

A catalyst for olefin polymerization, comprising:
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50.

### Claim 2 (depends on 1)

The catalyst for olefin polymerization of claim 1 wherein the (b-I) formula I transition metal compound is bis(1,3-n-butylmethylcyclopentadienyl)zirconium dichloride and the (b-II) formula (II) transition metal compound is bis(1,3-dimethylcyclopentadienyl)zirconium dichloride, and the molar ratio of (b-I)/(b-II) is in the range of 90/10 to 80/20.

### Claim 3

A process for olefin polymerization, comprising polymerizing an olefin in the presence of a catalyst for olefin polymerization comprising:
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50.

### Claim 4 (depends on 3)

The process for olefin polymerization of claim 3, wherein the (b-I) formula I transition metal compound is bis(1,3-n-butylmethylcyclopentadienyl)zirconium dichloride and the (b-II) formula (II) transition metal compound is bis(1,3-dimethylcyclopentadienyl)zirconium dichloride, and the molar ratio of (b-I)/(b-II) is in the range of 90/10 to 80/20.

### Claim 5

A catalyst for olefin polymerization, comprising:
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50, and
(c) an organoaluminum compound.

### Claim 6 (depends on 5)

The catalyst for olefin polymerization of claim 5, wherein the (b-I) formula I transition metal compound is bis(1,3-n-butylmethylcyclopentadienyl)zirconium dichloride and the (b-II) formula (II) transition metal compound is bis(1,3-dimethylcyclopentadienyl)zirconium dichloride, and the molar ratio of (b-I/(b-II) is in the range of 90/10 to 80/20 and the organoaluminum compound (c) is triisobutylaluminum.

### Claim 7

A process for olefin polymerization, comprising polymerizing an olefin in the presence of a catalyst for olefin polymerization comprising:
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50, and
(c) an organoaluminum compound.

### Claim 8 (depends on 7)

The process for olefin polymerization of claim 7, wherein the (b-I) formula I transition metal compound is bis(1,3-n-butylmethylcyclopentadienyl)zirconium dichloride and the (b-II) formula (II) transition metal compound is bis(1,3-dimethylcyclopentadienyl)zirconium dichloride, and the molar ratio of (b-I)/(b-II) is in the range of 90/10 to 80/20 and the organoaluminum compound (c) is triisobutylaluminum.

### Claim 9

A catalyst for olefin polymerization, comprising:
a carrier,
an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50,
said aluminoxane compound (a), said transition metal compound (b-I) and said transition metal compound (b-II) being supported on the carrier.

### Claim 10

A process for olefin polymerization, comprising polymerizing an olefin in the presence of a catalyst for olefin polymerization comprising:
a carrier,
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group; a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50,
said aluminoxane compound (a), said transition metal compound (b-I) and said transition metal compound (b-II) being supported on the carrier.

### Claim 11

A catalyst for olefin polymerization, comprising:
a solid catalyst component comprising:
a carrier,
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50,
said aluminoxane compound (a), said transition metal compound (b-I) and said transition metal compound (b-II) being supported on the carrier; and
(d) an organoaluminum compound.

### Claim 12 (depends on 11)

The catalyst for olefin polymerization of claim 11, wherein the (b-I) formula I transition metal compound is bis(1,3-n-butylmethylcyclopentadienyl)zirconium dichloride and the (b-II) formula (II) transition metal compound is bis(1,3-dimethylcyclopentadienyl)zirconium dichloride, and the molar ratio of (B-I)/(b-II) is in the range of 90/10 to 80/20 and the organoaluminum compound (d) is trisobutylaluminum.

### Claim 13

A process for olefin polymerization, comprising polymerizing an olefin in the presence of:
a solid catalyst component comprising:
a carrier,
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50,
said aluminoxane compound (a), said transition metal compound (b-I) and said transition metal compound (b-II) being supported on the carrier; and
(d) an organoaluminum compound.

### Claim 14

A catalyst for olefin polymerization, comprising:
a carrier,
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50, and
(c) an organoaluminum compound,
said aluminoxane compound (a), said transition metal compound (b-I), said transition metal compound (b-II) and said organoaluminum compound (c) being supported on the carrier.

### Claim 15

A process for olefin polymerization, comprising polymerizing an olefin in the presence of a catalyst for olefin polymerization comprising:
a carrier,
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50, and
(c) an organoaluminum compound,
said aluminoxane compound (a), said transition metal compound (b-I), said transition metal compound (b-II) and said organoaluminum compound (c) being supported on the carrier.

### Claim 16

A catalyst for olefin polymerization, comprising:
a solid catalyst component comprising:
a carrier
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50, and
(c) an organoaluminum compound,
said aluminoxane compound (a), said transition metal compound (b-I), said transition metal compound (b-II) and said organoaluminum compound (c) being supported on the carrier; and
(d) an organoaluminum compound.

### Claim 17

A process for olefin polymerization, comprising polymerizing an olefin in the presence of:
a solid catalyst component comprising:
a carrier
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein At least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50, and
(c) an organoaluminum compound,
said aluminoxane compound (a), said transition metal compound (b-I), said transition metal compound (b-II) and said organoaluminum compound (c) being supported on the carrier; and
(d) an organoaluminum compound.

### Claim 18

A catalyst for olefin polymerization obtained by prepolymerizing an olefin on a solid catalyst component, said solid catalyst component comprising:
a carrier,
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50, and
said aluminoxane compound (a), said transition metal compound (b-I) and said transition metal compound (b-II) being supported on the carrier.

### Claim 19

A process for olefin polymerization, comprising polymerizing an olefin in the presence of a catalyst for olefin polymerization obtained by prepolymerizing an olefin on a solid catalyst component, said solid catalyst component comprising:
a carrier,
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50,
said aluminoxane compound (a), said transition metal compound (b-I) and said transition metal compound (b-II) being supported on the carrier.

### Claim 20

A catalyst for olefin polymerization, comprising:
a prepolymerized catalyst component obtained by prepolymerizing an olefin on a solid catalyst component, said solid catalyst component comprising:
a carrier,
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50,
said aluminoxane compound (a), said transition metal compound (b-I) and said transition metal compound (b-II) being supported on the carrier; and
(d) an organoaluminum compound.

### Claim 21

A process for olefin polymerization, comprising polymerizing an olefin in the presence of:
a prepolymerized catalyst component obtained by prepolymerizing an olefin on a solid catalyst component, said solid catalyst component comprising:
a carrier,
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50,
said aluminoxane compound (a), said transition metal compound (b-I) and said transition metal compound (b-II) being supported on the carrier; and
(d) an organoaluminum compound.

### Claim 22

A catalyst for olefin polymerization obtained by prepolymerizing an olefin on a solid catalyst component, said solid catalyst component comprising:
a carrier,
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50, and
(c) an organoaluminum compound,
said aluminoxane compound (a), said transition metal compound (b-I), said transition metal compound (b-II) and said organoaluminum compound (c) being supported on the carrier.

### Claim 23

A process for olefin polymerization, comprising polymerizing an olefin in the presence of a catalyst for olefin polymerization obtained by prepolymerizing an olefin on a solid catalyst component, said solid catalyst component comprising:
a carrier,
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50, and
(c) an organoaluminum compound,
said aluminoxane compound (a), said transition metal compound (b-I), said transition metal compound (b-II) and said organoaluminum compound (c) being supported on the carrier.

### Claim 24

A catalyst for olefin polymerization, comprising:
a prepolymerized catalyst component obtained by prepolymerizing an olefin on a solid catalyst component, said solid catalyst component comprising:
a carrier,
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50, and
(c) an organoaluminum compound,
said aluminoxane compound (a), said transitional metal compound (b-I), said transition metal compound (b-II) and said organoaluminum compound (c) being supported on the carrier; and
(d) an organoaluminum compound.

### Claim 25

A process for olefin polymerization, comprising polymerizing an olefin in the presence of:
a prepolymerized catalyst component obtained by prepolymerizing an olefin on a solid catalyst component, said solid catalyst component comprising:
a carrier,
(a) an aluminoxane compound,
(b-I) at least one transition metal compound represented by the following formula (I):
ML.sup.1.sub.x (I)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.1 is a ligand coordinating to the transition metal atom M, at least two of L.sup.1 are groups selected from the group consisting of a substituted cyclopentadienyl group having two or more substituents, wherein at least one substituent is selected from a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents are selected from the group consisting of methyl and ethyl, L.sup.1 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, and
(b-II) at least one transition metal compound represented by the following formula (II):
ML.sup.2.sub.x (II)
wherein M is a transition metal atom selected from Group IVB of the periodic table, L.sup.2 is a ligand coordinating to the transition metal atom, at least two of L.sup.2 are substituted cyclopentadienyl groups having 2 or 3 substituent groups, said substituent groups being selected from the group consisting of a methyl group and an ethyl group, L.sup.2 other than the cyclopentadienyl group is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, and X is the valence of the transition metal atom M, wherein the molar ratio (b-I)/(b-II) is in the range of 99/1 to 50/50, and
(c) an organoaluminum compound,
said aluminoxane compound (a), said transitional metal compound (b-I), said transition metal compound (b-II) and said organoaluminum compound (c) being supported on the carrier; and
(d) an organoaluminum compound.