# US 10,479,846 B2 · Hafnocene catalyst compounds and process for use thereof

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- Number: US 10,479,846 B2
- Document ID: US10479846B2
- Status: Granted
- Kind: B2
- Application number: 15/852,553
- Filed: 2017-12-22
- Published: 2018-08-23
- Granted: 2019-11-19
- Earliest claimed: 2017-02-20
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Laughlin G. McCullough
- Web page: https://patentgrep.com/patent/US10479846B2

## CPC

- C08F 10/02: Ethene
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 2420/01: Cp or analog bridged to a non-Cp X neutral donor
- C08F 2420/07: Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

This invention relates to hafnium metallocene compounds having a group substituted (preferably at the 3 position) on at least one cyclopentadienyl ring represented by the formula —R20—SiR′3 or —R20—CR′3 where R20 is a C1 to C4 hydrocarbyl (preferably methyl) and R′ is a C1 to C20 substituted or unsubstituted hydrocarbyl.

## Claims

### Claim 1

A catalyst compound represented by the formula (B):
where:
each R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 is, independently, hydrogen, alkoxide, a C1 to C40 substituted or unsubstituted hydrocarbyl group or is —R20—SiR′3 or —R20—CR′3 where R20 is a C1 to C4 hydrocarbyl, and each R′ is independently a C1 to C20 substituted or unsubstituted hydrocarbyl, provided that at least one R′ is not H, and provided that at least one of R1, R2, R4, R5, R6, R7, R8, R9 and R10 is —R20—SiR′3 or —R20—CR′3; and
each X is, independently, a univalent anionic ligand, or two X are joined and bound to the metal atom to form a metallocycle ring, or two X are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand, provided that X is not fluorine.

### Claim 2 (depends on 1)

The catalyst compound of claim 1, wherein each R1, R2, R4 and R5 is independently hydrogen, alkoxide or a C1 to C40 substituted or unsubstituted hydrocarbyl group;
R3 is independently hydrogen, alkoxide or a C1 to C40 substituted or unsubstituted hydrocarbyl group or is —R20—SiR′3 or —R20—CR′3 where R20 is CH2, and each R′ is independently a C1 to C20 substituted or unsubstituted hydrocarbyl, provided that at least one R′ is not H;
each R6, R7, R8, and R10 is independently hydrogen, alkoxide or a C1 to C40 substituted or unsubstituted hydrocarbyl group;
R9 is —R20—SiR′3 or —R20—CR′3 where R20 is CH2, and each R′ is independently a C1 to C20 substituted or unsubstituted hydrocarbyl, provided that at least one R′ is not H.

### Claim 3 (depends on 1)

The catalyst compound of claim 1, wherein R9 and R3 are, independently, —R20—SiR′3 or —R20—CR′3 where R20 is a C1 to C4 hydrocarbyl, and each R′ is independently a C1 to C20 substituted or unsubstituted hydrocarbyl, provided that at least one R′ is not H.

### Claim 4 (depends on 1)

The catalyst compound of claim 1, wherein each X is independently selected from non-fluorine halides, aryls and C1 to C5 alkyl groups.

### Claim 5 (depends on 1)

The catalyst compound of claim 1, wherein each R1, R2, R4, R5, R6, R7, R8, R9 and R10 is independently hydrogen, or a substituted C1 to C12 hydrocarbyl group or an unsubstituted C1 to C12 hydrocarbyl group, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof or is —R20—SiR′3 or —R20—CR′3 where R20 is independently a methyl, ethyl, propyl, or butyl group, and provided that at least one of R1, R2, R4, R5, R6, R7, R8, R9 and R10 is —R20—SiR′3 or —R20—CR′3.

### Claim 6 (depends on 1)

The catalyst compound of claim 1, wherein at least one of R6 to R10 and optionally at least one of R1 to R5 are, independently, —R20—CMe3, or —R20—SiMe3 where R20 is independently a methyl, ethyl, propyl, or butyl group.

### Claim 7 (depends on 1)

A catalyst system comprising activator and the catalyst of claim 1.

### Claim 8 (depends on 7)

The catalyst system of claim 7, wherein the activator comprises alumoxane and/or non-coordinating anion.

### Claim 9 (depends on 7)

The catalyst system of claim 7, wherein the catalyst system further comprises a support.

### Claim 10 (depends on 7)

A process to polymerize olefins comprising contacting one or more olefins with the catalyst system of claim 7.

### Claim 11 (depends on 10)

The process of claim 10, wherein the olefins and catalyst system are contacted in the gas phase.

### Claim 12 (depends on 10)

The process of claim 10, wherein the olefins and catalyst system are contacted in the slurry phase.

### Claim 13 (depends on 10)

The process of claim 10, wherein the olefins and catalyst system are contacted in the solution phase.

### Claim 14 (depends on 10)

The process of claim 10, wherein the olefins and catalyst system are contacted in a slurry loop reactor.

### Claim 15 (depends on 10)

The process of claim 10, wherein the polymerization is a continuous process.

### Claim 16 (depends on 10)

The process of claim 10, wherein the catalyst compound comprises one or more of: (Me3SiCH2Cp)2HfCl2; (Me3SiCH2Cp)2HfMe2; (Cp)(Me3SiCH2Cp)HfCl2; (Cp)(Me3SiCH2Cp)HfMe2; (PrCp)(Me3SiCH2Cp)HfCl2; (Me4Cp)(Me3SiCH2Cp)HfCl2; and (Me5Cp)(Me3SiCH2Cp)HfCl2.

### Claim 17 (depends on 10)

The process of claim 10, wherein the activator comprises alumoxane.

### Claim 18 (depends on 10)

The process of claim 10, wherein the olefins comprise ethylene and optionally one more C3 to C20 alpha olefins.

### Claim 19 (depends on 10)

The process of claim 10, wherein the activator comprises a non-coordinating anion activator.

### Claim 20 (depends on 10)

The process of claim 10, wherein activator is represented by the formula:
(Z)d+(Ad−)
wherein Z is (L-H) or a reducible Lewis Acid, L is an neutral Lewis base; H is hydrogen; (L-H)+ is a Bronsted acid; Ad− is a non-coordinating anion having the charge d−; and d is an integer from 1 to 3.

### Claim 21 (depends on 10)

The process of claim 10, wherein activator is represented by the formula:
(Z)d+(Ad−)
wherein Ad− is a non-coordinating anion having the charge d−; d is an integer from 1 to 3, and Z is a reducible Lewis acid represented by the formula: (Ar3C+), where Ar is aryl or aryl substituted with a heteroatom, a C1 to C40 hydrocarbyl, or a substituted C1 to C40 hydrocarbyl.

### Claim 22 (depends on 10)

The process of claim 10, wherein the activator is one or more of:
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammonium tetrakis(perfluoronaphthyl)borate, tripropylammonium tetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(perfluoronaphthyl)borate, and triphenylcarbenium tetrakis(perfluoronaphthyl)borate.

### Claim 23 (depends on 10)

The process claim 10, wherein the process occurs at a temperature of from about 0° C. to about 300° C., at a pressure in the range of from about 0.35 MPa to about 10 MPa, and at a time up to 300 minutes in the absence of fluorine.

### Claim 24 (depends on 7)

The catalyst system of claim 7, wherein each R1, R2, R4 and R5 is independently hydrogen, alkoxide or a C1 to C40 substituted or unsubstituted hydrocarbyl group;
R3 is independently hydrogen, alkoxide or a C1 to C40 substituted or unsubstituted hydrocarbyl group or is —R20—SiR′3 or —R20—CR′3 where R20 is CH2, and each R′ is independently a C1 to C20 substituted or unsubstituted hydrocarbyl, provided that at least one R′ is not H;
each R6, R7, R8, and R10 is independently hydrogen, alkoxide or a C1 to C40 substituted or unsubstituted hydrocarbyl group;
R9 is —R20—SiR′3 or —R20—CR′3 where R20 is CH2, and each R′ is independently a C1 to C20 substituted or unsubstituted hydrocarbyl, provided that at least one R′ is not H.

### Claim 25 (depends on 7)

The catalyst system of claim 7, wherein R9 and R3 are, independently, —R20—SiR′3 or —R20—CR′3 where R20 is a C1 to C4 hydrocarbyl, and each R′ is independently a C1 to C20 substituted or unsubstituted hydrocarbyl, provided that at least one R′ is not H.

### Claim 26 (depends on 7)

The catalyst system of claim 7, wherein each X is independently selected from non-fluorine halides, aryls and C1 to C5 alkyl groups.

### Claim 27 (depends on 7)

The catalyst system of claim 7, wherein each R1, R2, R4, R5, R6, R7, R8, R9 and R10 is independently hydrogen, or a substituted C1 to C12 hydrocarbyl group or an unsubstituted C1 to C12 hydrocarbyl group, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof or is —R20—SiR′3 or —R20—CR′3 where R20 is independently a methyl, ethyl, propyl, or butyl group, and provided that at least one of R1, R2, R4, R5, R6, R7, R8, R9 and R10 is —R20—SiR′3 or —R20—CR′3.

### Claim 28 (depends on 7)

The catalyst system of claim 7, wherein at least one of R6 to R10 and optionally at least one of R1 to R5 are, independently, —R20—CMe3, or —R20—SiMe3 where R20 is independently a methyl, ethyl, propyl, or butyl group.

### Claim 29 (depends on 10)

The process of claim 10, wherein each R1, R2, R4 and R5 is independently hydrogen, alkoxide or a C1 to C40 substituted or unsubstituted hydrocarbyl group;
R3 is independently hydrogen, alkoxide or a C1 to C40 substituted or unsubstituted hydrocarbyl group or is —R20—SiR′3 or —R20—CR′3 where R20 is CH2, and each R′ is independently a C1 to C20 substituted or unsubstituted hydrocarbyl, provided that at least one R′ is not H;
each R6, R7, R8, and R10 is independently hydrogen, alkoxide or a C1 to C40 substituted or unsubstituted hydrocarbyl group;
R9 is —R20—SiR′3 or —R20—CR′3 where R20 is CH2, and each R′ is independently a C1 to C20 substituted or unsubstituted hydrocarbyl, provided that at least one R′ is not H.

### Claim 30 (depends on 10)

The process of claim 10, wherein R9 and R3 are, independently, —R20—SiR′3 or —R20—CR′3 where R20 is a C1 to C4 hydrocarbyl, and each R′ is independently a C1 to C20 substituted or unsubstituted hydrocarbyl, provided that at least one R′ is not H.

### Claim 31 (depends on 10)

The process of claim 10, wherein each X is independently selected from non-fluorine halides, aryls and C1 to C5 alkyl groups.

### Claim 32 (depends on 10)

The process of claim 10, wherein each R1, R2, R4, R5, R6, R7, R8, R9 and R10 is independently hydrogen, or a substituted C1 to C12 hydrocarbyl group or an unsubstituted C1 to C12 hydrocarbyl group, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof or is —R20—SiR′3 or —R20—CR′3 where R20 is independently a methyl, ethyl, propyl, or butyl group, and provided that at least one of R1, R2, R4, R5, R6, R7, R8, R9 and R10 is —R20—SiR′3 or —R20—CR′3.

### Claim 33 (depends on 10)

The process of claim 10, wherein at least one of R6 to R10 and optionally at least one of R1 to R5 are, independently, —R20—CMe3, or —R20—SiMe3 where R20 is independently a methyl, ethyl, propyl, or butyl group.