# US 11,028,191 B2 · Polymerization catalysts with improved ethylene enchainment

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- Number: US 11,028,191 B2
- Document ID: US11028191B2
- Status: Granted
- Kind: B2
- Application number: 16/337,725
- Filed: 2017-09-26
- Published: 2020-01-30
- Granted: 2021-06-08
- Earliest claimed: 2016-09-30
- Assignees: Univation Technologies, LLC
- Applicants: Univation Technologies, LLC
- Inventors: Roger L. Kuhlman; Mahsa McDougal; Timothy M. Boller; C. Jeff Harlan; Timothy R. Lynn; Cliff R. Mure; John F. Szul; Daniel P. Zilker, Jr.
- Web page: https://patentgrep.com/patent/US11028191B2

## CPC

- C08F 4/65925: {two cyclopentadienyl rings being mutually non-bridged}
- B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls}
- C08F 210/14: Monomers containing five or more carbon atoms
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- B01J 2231/122: Cationic (co)polymerisation, e.g. single-site or Ziegler-Natta type
- B01J 2531/46: Titanium
- B01J 2531/48: Zirconium
- B01J 2531/49: Hafnium
- C08F 4/6428: {with an aluminoxane, i.e. a compound containing an Al-O-Al- group}
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

Embodiments of the present disclosure directed towards polymerization catalysts having improved ethylene enchainment. As an example, the present disclosure provides a polymerization catalyst having improved ethylene enchainment, the polymerization catalyst comprising a zirconocene catalyst of Formula (I) where R1 is a C1 to C20 alkyl, aryl or aralkyl group, wherein R2 is an C1 to C20 alkyl, aryl or aralkyl group, and where R3 is a C1 to C20 alkyl or a hydrogen, and where each X is independently a halide, C1 to C20 alkyl, aralkyl group or hydrogen.

## Claims

### Claim 1

A polymerization catalyst having improved selectivity for ethylene enchainment, the polymerization catalyst comprising a zirconocene catalyst of Formula I:
wherein R1 is a C1 to C20 alkyl, aryl or aralkyl group, wherein R2 is an C1 to C20 alkyl, aryl or aralkyl group, and wherein R3 is a C1 to C20 alkyl or a hydrogen, wherein each X is independently a halide, C1 to C20 alkyl, aralkyl group or hydrogen, and wherein R3 is a C1 alkyl or a linear C3 alkyl.

### Claim 2 (depends on 1)

The polymerization catalyst of claim 1, wherein R2 is a C1 alkyl.

### Claim 3 (depends on 2)

The polymerization catalyst of claim 2, wherein R1 is a C1 alkyl.

### Claim 4 (depends on 1)

The polymerization catalyst of claim 1, wherein R1 is a C3 alkyl.

### Claim 5 (depends on 1)

The polymerization catalyst of claim 1, wherein the polymerization catalyst of Formula I is included in a bimodal polymerization catalyst system further including a non-metallocene olefin polymerization catalyst.

### Claim 6

A bimodal polyethylene composition having improved ethylene enchainment comprising a high molecular weight polyethylene component and a low molecular weight polyethylene component formed together in a single reactor via a bimodal polymerization catalyst system comprising:
a non-metallocene olefin polymerization catalyst; and
a zirconocene catalyst of the Formula I:
wherein R1 is a C1 to C20 alkyl, aryl or aralkyl group, wherein R2 is an C1 to C20 alkyl, aryl or aralkyl group, and wherein R3 is a C1 to C20 alkyl or a hydrogen, wherein each X is independently a halide, C1 to C20 alkyl, aralkyl group or hydrogen, and wherein R3 is a C1 alkyl or a linear C3 alkyl.

### Claim 7 (depends on 6)

The bimodal polyethylene composition of claim 6, wherein the low molecular weight polyethylene has a butyl branching frequency of from 0.43 to 0.72.

### Claim 8

A method of producing a bimodal polyethylene having improved ethylene enchainment, the method comprising:
polymerizing ethylene in a reactor in presence of a bimodal polymerization catalyst system to form the bimodal polyethylene, wherein the bimodal polymerization catalyst comprises:
a non-metallocene catalyst; and
a zirconocene catalyst of Formula I:
wherein R1 is a C1 to C20 alkyl, aryl or aralkyl group, wherein R2 is an C1 to C20 alkyl, aryl or aralkyl group, and wherein R3 is a C1 to C20 alkyl or a hydrogen, wherein each X is independently a halide, C1 to C20 alkyl, aralkyl or hydrogen, and wherein R3 is a C1 alkyl or a linear C3 alkyl.