# US 11,078,306 B2 · Biomodal polymerization catalysts

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- Number: US 11,078,306 B2
- Document ID: US11078306B2
- Status: Granted
- Kind: B2
- Application number: 16/338,111
- Filed: 2017-09-26
- Published: 2020-01-23
- Granted: 2021-08-03
- Earliest claimed: 2016-09-30
- Assignees: Univation Technologies, LLC
- Applicants: Univation Technologies, LLC
- Inventors: Cliff R. Mure; Timothy R. Lynn
- Web page: https://patentgrep.com/patent/US11078306B2

## CPC

- C08F 10/02: Ethene
- C08F 4/65904: {in combination with another component of C08F4/64}
- C08F 4/65925: {two cyclopentadienyl rings being mutually non-bridged}
- C08F 4/64148: {NN(R)N}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 2420/03: Cp or analog not bridged to a non-Cp X ancillary neutral donor
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Embodiments of the present disclosure directed towards bimodal polymerization catalysts. As an example, the present disclosure provides a bimodal polymerization catalyst system including a non-metallocene olefin polymerization catalyst and a zirconocene catalyst of Formula I: (Formula I) where each of R1, R2, and R4 are independently a C1 to C20 alkyl, aryl or aralkyl group or a hydrogen, where R3 is a C1 to C20 alkyl, aryl or aralkyl group, and where each X is independently a halide, C1 to C20 alkyl, aralkyl group or hydrogen.

## Claims

### Claim 1

A bimodal polymerization catalyst system comprising:
a non-metallocene olefin polymerization catalyst; and
a zirconocene catalyst of Formula I:
where R4 is independently a C1 alkyl or a hydrogen, where R3 is a C1 to C20 alkyl, aryl or aralkyl group, where each X is independently a halide, C1 to C20 alkyl, aralkyl group or hydrogen; and
where R1 and R2 of Formula I together, with the carbon atoms to which they are bonded, form a cycloalkyl group; or
R1 is a C1 alkyl and R2 is a C3 alkyl.

### Claim 2 (depends on 1)

The bimodal polymerization catalyst system of claim 1, wherein the non-metallocene olefin polymerization catalyst comprises a Group 15 metal-containing catalyst compound.

### Claim 3 (depends on 1)

The bimodal polymerization catalyst system of claim 1, wherein the non-metallocene olefin polymerization catalyst comprises a catalyst of the formula:

### Claim 4 (depends on 1)

The bimodal polymerization catalyst system of claim 1, where R3 of Formula I is a C1 to C20 alkyl.

### Claim 5

A method of producing a bimodal polyethylene, the method comprising:
polymerizing ethylene in a single reactor in presence of a bimodal polymerization catalyst system to form the bimodal polyethylene, wherein the bimodal polymerization catalyst system comprises:
a non-metallocene olefin polymerization catalyst; and
a zirconocene catalyst of Formula I:
where R4 is independently a C1 alkyl or a hydrogen, where R3 is a C1 to C20 alkyl, aryl or aralkyl group, where each X is independently a halide, C1 to C20 alkyl, aralkyl group or hydrogen, and where:
R1 and R2 of Formula I together, with the carbon atoms to which they are bonded, form a cycloalkyl group; or
R1 is a C1 alkyl and R2 is a C3 alkyl.

### Claim 6 (depends on 5)

The method of claim 5, further comprising forming a slurry including the non-metallocene olefin polymerization catalyst.

### Claim 7 (depends on 6)

The method of claim 6, further comprising forming a trim solution including the zirconocene catalyst of Formula I.

### Claim 8 (depends on 7)

The method of claim 7, further comprising mixing the slurry with the trim solution to form the bimodal polymerization catalyst system.

### Claim 9

A bimodal polymerization catalyst system comprising:
a non-metallocene olefin polymerization catalyst; and
a zirconocene catalyst of Formula I:
wherein R1 is a C1 alkyl, R2 is a C3 alkyl, R4 is a C1 alkyl, R3 is a C1 to C20 alkyl, aryl or aralkyl group, and each X is independently a halide, C1 to C20 alkyl, aralkyl group or hydrogen.