# US 5,708,101 A · Stereospecific olefin polymerization catalysts

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- Number: US 5,708,101 A
- Document ID: US5708101A
- Status: Granted
- Kind: A
- Application number: 08/696,004
- Filed: 1996-08-12
- Granted: 1998-01-13
- Earliest claimed: 1996-08-12
- Assignees: California Institute of Technology
- Inventors: John E. Bercaw; Timothy A. Herzog
- Web page: https://patentgrep.com/patent/US5708101A

## CPC

- C07F 17/00: Metallocenes
- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F 4/61912: {in combination with an organoaluminium compound}
- C08F 4/61927: {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 catalyst system for the polymerization of .alpha.-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula ##STR1## wherein: R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R.sup.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; R.sup.4 and R.sup.6 are substituents both having van der Waals radii larger than the van der Waals radii of groups R.sup.1 and R.sup.3 ; R.sup.5 is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E.sup.1, E.sup.2 are independently selected from the group consisting of Si(R.sup.9).sub.2, Si(R.sup.9).sub.2 --Si(R.sup.9).sub.2, Ge(R.sup.9).sub.2, Sn(R.sup.9).sub.2, C(R.sup.9).sub.2, C(R.sup.9).sub.2 --C(R.sup.9).sub.2, where R.sup.9 is C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; and the ligand may have C.sub.S or C.sub.1 -symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from .alpha.-olefin monomers.

## Claims

### Claim 1

A metallocene of the formula ##STR20## wherein: the metallocene has C.sub.S - or C.sub.1 -symmetry;
M is an element selected from the group consisting of group III, group IV, group V, and lanthanide group elements;
n is the valence of M minus 2;
X is selected from the group consisting of fluorine, chlorine, bromine, iodine, hydrogen, C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl, and --OR.sup.7 where R.sup.7 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl, alkylaryl, arylalkyl, fluoroalkyl, and fluoroaryl with 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical;
R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl wherein each pair of adjacent radicals, R.sup.1 and R.sup.2 or R.sup.2 and R.sup.3, together may also form a substituted or unsubstituted cyclic group having 4 to 15 carbon atoms, and Si(R.sup.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl and C.sub.3 to C.sub.10 cycloalkyl;
R.sup.4 and R.sup.6 are substituents both having van der Waals radii that are larger than the van der Waals radii of groups R.sup.1 and R.sup.3 ;
R.sup.5 is a substituent having a van der Waals radius that is less than the van der Waals radius of a methyl group; and
E.sup.1 and E.sup.2 are independently selected from the group consisting of Si(R.sup.9).sub.2, Si(R.sup.9).sub.2 --Si(R.sup.9).sub.2, Ge(R.sup.9).sub.2, Sn(R.sup.9).sub.2, C(R.sup.9).sub.2, and C(R.sup.9).sub.2 --C(R.sup.9).sub.2, where R.sup.9 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl, and C.sub.3 to C.sub.10 cycloalkyl.

### Claim 2 (depends on 1)

The metallocene of claim 1, wherein M is selected from the group consisting of titanium, zirconium, hafnium, scandium, yttrium, and the lanthanides.

### Claim 3 (depends on 1)

The metallocene of claim 1, wherein X is selected from the group consisting of chlorine, bromine, iodine, hydrogen, methyl, neopentyl and benzyl.

### Claim 4 (depends on 1)

The metallocene of claim 1, wherein R.sup.4 and R.sup.6 are independently selected from the group consisting of C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl which in turn may have a C.sub.1 to C.sub.10 alkyl as a substituent, C.sub.6 to C.sub.15 aryl or alkylaryl, and Si(R.sup.8).sub.3.

### Claim 5 (depends on 1)

The metallocene of claim 1, wherein R.sup.5 is hydrogen.

### Claim 6 (depends on 1)

The metallocene of claim 1, wherein R.sup.2 is selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, and trimethylsilyl.

### Claim 7 (depends on 1)

The metallocene of claim 1, wherein E.sup.1 and E.sup.2 are both Si(Me).sub.2.

### Claim 8 (depends on 1)

The metallocene of claim 1, wherein
M is selected from the group consisting of titanium, zirconium, hafnium, scandium, yttrium, and the lanthanides;
X is selected from the group consisting of chlorine, bromine, iodine, hydrogen, methyl, neopentyl, and benzyl;
R.sup.1 and R.sup.3 are the same and are selected from the group consisting of hydrogen and methyl;
R.sup.2 is selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, tert-butyl, trimethylsilyl, and phenyl;
R.sup.4 and R.sup.6 are the same and are selected from the group consisting of methyl, ethyl, isopropyl, tert-butyl, phenyl, --CH(Me)(Et), --CH(Me)(.sup.t Bu), neopentyl, and trimethylsilyl.

### Claim 9 (depends on 8)

The metallocene of claim 8, wherein R.sup.4 and R.sub.6 are isopropyl; E.sup.1 and E.sup.2 are Si(Me).sub.2 ; M is selected from the group consisting of Zr and Hf; n equals 2; X is chlorine; R.sup.1 and R.sup.3 are hydrogen; and R.sup.2 is selected from the group consisting of isopropyl and trimethylsilyl.

### Claim 10 (depends on 1)

The metallocene of claim 1, wherein R.sup.1 and R.sup.3 are hydrogen, and R.sup.2 is chiral.

### Claim 11 (depends on 1)

The metallocene of claim 1, wherein
R.sup.1 and R.sup.2 are the same and are selected from the group consisting of C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl wherein R.sup.1 and R.sup.2 together may also form a substituted or unsubstituted cyclic group having 4 to 15 carbon atoms, and Si(R.sup.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl, and C.sub.3 to C.sub.10 cycloalkyl; and
R.sup.3 is hydrogen.

### Claim 12 (depends on 11)

The metallocene of claim 11, wherein
R.sup.1 and R.sup.2 are the same and are selected from the group consisting of methyl, trimethylsilyl, and tert-butyl, or R.sup.1 and R.sup.2 together form the 6 membered ring of an indenyl, or tetrahydroindenyl.

### Claim 13 (depends on 12)

The metallocene of claim 12, wherein R.sup.1 and R.sup.2 together form the 6 membered ring of a tetrahydroindenyl, and R.sup.4 and R.sup.6 are both isopropyl.

### Claim 14 (depends on 1)

The metallocene of claim 1, wherein R.sup.1 and R.sup.3 are hydrogen, and R.sup.4 and R.sup.6 are different from one another.

### Claim 15 (depends on 14)

The metallocene of claim 14, wherein
R .sup.4 is isopropyl or tert-butyl;
R .sup.6 is methyl; and
R .sup.2 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, and 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent.

### Claim 16

A metallocene of the formula ##STR21## wherein: the metallocene has C.sub.S - or C.sub.1 -symmetry;
M is an element selected from the group consisting of group III, group IV, group V, and lanthanide group elements;
n is the valence of M minus 2;
X is selected from the group consisting of trimethylsilymethyl and bis(trimethylsilyl)methyl;
R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl wherein each pair of adjacent radicals, R.sup.1 and R.sup.2 or R.sup.2 and R.sup.3, together may also form a substituted or unsubstituted cyclic group having 4 to 15 carbon atoms, and Si(R.sub.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl and C.sub.3 to C.sub.10 cycloalkyl;
R.sup.4 and R.sup.6 are substituents both having van der Waals radii that are larger than the van der Waals radii of groups R.sup.1 and R.sub.3 ;
R.sup.5 is a substituent having a van der Waals radius that is less than the van der Waals radius of a methyl group; and
E.sup.1 and E.sup.2 are independently selected from the group consisting of Si(R.sup.9).sub.2, Si(R.sup.9).sub.2 --Si(R.sup.9).sub.2, Ge(R.sup.9).sub.2, Sn(R.sup.9).sub.2, C(R.sup.9).sub.2, and C(R.sup.9).sub.2 --C(R.sup.9).sub.2, where R.sup.9 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl, and C.sub.3 to C.sub.10 cycloalkyl.

### Claim 17

A catalyst comprising a metal and a ligand of the formula ##STR22## wherein: R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl wherein each pair of adjacent radicals, R.sup.1 and R.sup.2 or R.sup.2 and R.sup.3, together may also form a substituted or unsubstituted cyclic group having 4 to 15 carbon atoms, and Si(R.sup.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl;
R.sup.4 and R.sup.6 are substituents both having van der Waals radii larger than the van der Waals radii of groups R.sup.1 and R.sup.3 ;
R.sup.5 is a substituent having a van der Waals radius that is less than the van der Waals radius of a methyl group;
E.sup.1 and E.sup.2 are independently selected from the group consisting of Si(R.sup.9).sub.2, Si(R.sup.9).sub.2 --Si(R.sup.9).sub.2, Ge(R.sup.9).sub.2, Sn(R.sup.9).sub.2, C(R.sup.9).sub.2, and C(R.sup.9).sub.2 --C(R.sup.9).sub.2, where R.sup.9 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl, and C.sub.3 to C.sub.10 cycloalkyl.

### Claim 18 (depends on 17)

The catalyst of claim 17, wherein the metal is selected from the group consisting of group III, group IV, group V and lanthanide group elements.

### Claim 19 (depends on 18)

The catalyst of claim 18, wherein the metal is selected from the group consisting of titanium, zirconium, hafnium, scandium, yttrium, and the lanthanides.

### Claim 20 (depends on 17)

The catalyst of claim 17, wherein R.sup.4 and R.sup.6 are independently selected from the group consisting of C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl which in turn may have a C.sub.1 to C.sub.10 alkyl as a substituent, C.sub.6 to C.sub.15 aryl or alkylaryl, and Si(R.sup.8).sub.3.

### Claim 21 (depends on 17)

The catalyst of claim 17, wherein R.sup.5 is hydrogen.

### Claim 22 (depends on 17)

The catalyst of claim 17, wherein R.sup.2 is selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, and trimethylsilyl.

### Claim 23 (depends on 17)

The catalyst of claim 17, wherein E.sup.1 and E.sup.2 are both Si(Me).sub.2.

### Claim 24 (depends on 17)

The catalyst of claim 17, wherein
R.sup.1 and R.sup.3 are the same and are hydrogen or methyl;
R.sup.2 is selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, tert-butyl, trimethylsilyl, and phenyl;
R.sup.4 and R.sup.6 are the same and are selected from the group consisting of methyl, ethyl, isopropyl, tert-butyl, phenyl, --CH(Me)(Et), --CH(Me)(.sup.t Bu), neopentyl, and trimethylsilyl.

### Claim 25 (depends on 24)

The catalyst of claim 24, wherein R.sup.4 and R.sup.6 are isopropyl; E.sup.1 and E.sup.2 are Si(Me).sub.2 ; R.sup.1 and R.sup.3 are hydrogen; and R.sup.2 is selected from the group consisting of isopropyl and trimethylsilyl.

### Claim 26 (depends on 17)

The catalyst of claim 17, wherein R.sup.1 and R.sup.3 are hydrogen, and R.sup.2 is chiral.

### Claim 27 (depends on 17)

The catalyst of claim 17, wherein
R.sup.1 and R.sup.2 are the same and are selected from the group consisting of C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl wherein R.sup.1 and R.sup.2 together may also form a substituted or unsubstituted cyclic group having 4 to 15 carbon atoms, and Si(R.sup.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl, and C.sub.3 to C.sub.10 cycloalkyl; and
R.sup.3 is hydrogen.

### Claim 28 (depends on 27)

The catalyst of claim 27, wherein
R.sup.1 and R.sup.2 are the same and are selected from the group consisting of methyl, trimethylsilyl, tert-butyl, or R.sup.1 and R.sup.2 together form the 6 membered ring of an indenyl, or tetrahydroindenyl.

### Claim 29 (depends on 28)

The catalyst of claim 28, wherein R.sup.1 and R.sup.2 together form the 6 membered ring of a tetrahydroindenyl, and R.sup.4 and R.sup.6 are both isopropyl.

### Claim 30 (depends on 17)

The catalyst of claim 17, wherein R.sup.1 and R.sup.3 are hydrogen, and R.sup.4 and R.sup.6 are different from one another.

### Claim 31 (depends on 30)

The catalyst of claim 30, wherein
R.sup.4 is isopropyl or tert-butyl;
R.sup.6 is methyl; and
R.sup.2 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, and 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent.

### Claim 32 (depends on 17)

The catalyst of claim 17, further comprising an activator.

### Claim 33 (depends on 32)

The catalyst of claim 32, wherein the activator is methylaluminoxane.

### Claim 34 (depends on 17)

The catalyst of claim 17, further comprising n ligands independently selected from the group consisting of fluorine, chlorine, bromine, iodine, hydrogen, C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl and --OR.sup.7 where R.sup.7 selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl, alkylaryl, arylalkyl, fluoroalkyl, and fluoroaryl with 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical; and
wherein n is the valence of the metal minus 2.

### Claim 35

A method for polymerizing olefins comprising the step of contacting an olefin with a catalyst comprising a metal and a ligand of the formula ##STR23## wherein: R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl wherein each pair of adjacent radicals, R.sup.1 and R.sup.2 or R.sup.2 and R.sup.3, together may also form a substituted or unsubstituted cyclic group having 4 to 15 carbon atoms, and Si(R.sup.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl;
R.sup.4 and R.sup.6 are substituents both having van der Waals radii larger than the van der Waals radii of groups R.sup.1 and R.sup.3 ;
R.sup.5 is a substituent having a van der Waals radius less than the van der Waals radius of a methyl group;
E.sup.1 and E.sup.2 are independently selected from the group consisting of Si(R.sup.9).sub.2, Si(R.sup.9).sub.2 --Si(R.sup.9).sub.2, Ge(R.sup.9).sub.2, Sn(R.sup.9).sub.2, C(R.sup.9).sub.2, and C(R.sup.9).sub.2 --C(R.sup.9).sub.2, where R.sup.9 is C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl.