# US 11,440,979 B2 · Catalysts, catalyst systems, and methods for using the same

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- Number: US 11,440,979 B2
- Document ID: US11440979B2
- Status: Granted
- Kind: B2
- Application number: 16/958,891
- Filed: 2019-02-05
- Published: 2020-10-29
- Granted: 2022-09-13
- Earliest claimed: 2018-02-19
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Alex E. Carpenter; Danielle Gold Singleton
- Web page: https://patentgrep.com/patent/US11440979B2

## CPC

- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C07F 17/00: Metallocenes
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65925: {two cyclopentadienyl rings being mutually non-bridged}
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 2410/03: Multinuclear procatalyst, i.e. containing two or more metals, being different or not
- 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
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

Catalysts, catalysts systems and methods of polymerizing olefins are provided. The catalyst system may contain two catalysts. Polyolefin polymers are also provided.

## Claims

### Claim 1

A catalyst represented by formula (Ia):
wherein:
each M is a group 4 metal;
E is N;
each of X1, X2, X3, and X4 is independently hydrogen, halogen, hydroxyl, —N(C1-C40 hydrocarbyl)2, C1-C40 hydrocarbyl, or substituted C1-C40 hydrocarbyl;
each of R1, R2, and R3 is independently hydrogen, halogen, C1-C40 hydrocarbyl, substituted C1-C40 hydrocarbyl, C6-C10 aryl, substituted C6-C10 aryl, —NR′2, —SR′, —OR′, —OSiR′3, or —PR′2, wherein each R′ is hydrogen, halogen, C1-C10 alkyl, or C6-C10 aryl or one or both of R1 and R2 or R2 and R3 are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring;
each of R4, R5, 105 and 106 is independently hydrogen or Ci-C40 hydrocarbyl; and
each of R6, R7, R8, R9, R10, R11, R12, R13, R14, R17, R18, R19, R20, R21, R22, R23, R24, and R25 is independently hydrogen, halogen, C1-C40 hydrocarbyl, substituted C1-C40 hydrocarbyl, C6-C10 aryl, substituted C6-C10 aryl, —NR′2, —SR′, —OR′, —OSiR′3, or —PR′2, wherein each R′ is hydrogen, halogen, C1-C10 alkyl, or C6-C10 aryl aryl, or one or more of R6 and R7, R7 and R8, R8 and R9, R10 and R11, R11 and R12, R12 and R13, R13 and R14, R17 and R18, R18 and R19, R17 and R20, R21 and R22, R22 and R23, R23 and R24, R24 and R25, and R21 and R25 are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring.

### Claim 2 (depends on 1)

The catalyst of claim 1, wherein M is hafnium or zirconium.

### Claim 3 (depends on 1)

The catalyst of claim 1, wherein one or more of R6 and R7, R7 and R8, R8 and R9, R17 and R18, R18 and R19, R17 and R20 are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring.

### Claim 4 (depends on 1)

The catalyst of claim 1, wherein one of R6 and R7, R7 and R8, and R8 and R9 are joined to form a saturated ring or unsaturated ring substituted with one or more of halogen, C1-C40 hydrocarbyl, substituted C1-C40 hydrocarbyl, —NR′2, —SR′, —OR′, —OSiR′3, or —PR′2, wherein each R′ is hydrogen, halogen, C1-C10 alkyl, or C6-C10 aryl.

### Claim 5 (depends on 4)

The catalyst of claim 4, wherein one of R16 and R17, R17 and R18, and R18 and R19 are joined to form a saturated ring or unsaturated ring substituted with one or more of halogen, C1-C40 hydrocarbyl, substituted C1-C40 hydrocarbyl, —NR′2, —SR′, —OR′, —OSiR′3, or —PR′2, wherein each R′ is hydrogen, halogen, C1-C10 alkyl, or C6-C10 aryl.

### Claim 6 (depends on 1)

The catalyst of claim 1, wherein each of R1, R2, and R3 is independently hydrogen, C1-C40 hydrocarbyl, or substituted C1-C40 hydrocarbyl.

### Claim 7 (depends on 1)

The catalyst of claim 1, wherein each of X1, X2, X3, and X4 is independently halogen or C1-C40 hydrocarbyl.

### Claim 8 (depends on 1)

The catalyst of claim 1, wherein each of R4, R5, R15, and R16 is hydrogen.

### Claim 9 (depends on 1)

The catalyst of claim 1, wherein each of R6, R7, R8, R9, R17, R18, R19, and R20 is hydrogen.

### Claim 10 (depends on 1)

The catalyst of claim 1, wherein each of R10, R11, R12, R13, R14, R21, R22, R23, R24, and R25 is independently hydrogen or C1-C20 hydrocarbyl.

### Claim 11 (depends on 1)

The catalyst of claim 1, wherein each of R10, R11, R12, R13, and R14 is methyl.

### Claim 12 (depends on 1)

The catalyst of claim 1, wherein the catalyst represented by formula (Ia) is one or more of:

### Claim 13 (depends on 1)

The catalyst of claim 1, wherein the catalyst represented by formula (Ia) is one or more of:

### Claim 14 (depends on 1)

A catalyst system comprising the product of the combination of:
(a) the catalyst of claim 1;
(b) optionally, a bridged or unbridged metallocene catalyst other than the catalyst of (a); and
(c) an activator.

### Claim 15 (depends on 14)

The catalyst system of claim 14, further comprising a support material; and a molar ratio of activator to catalyst is from 1.5:1 to 5:1.

### Claim 16 (depends on 14)

A method of polymerizing olefins to produce at least one polyolefin composition, the method comprising:
(a) contacting at least one olefin with the catalyst system of claim 14; and
(b) obtaining a polyolefin.

### Claim 17 (depends on 16)

The method of claim 16, wherein contacting occurs at a temperature of 0° C. to 300° C., at a pressure in the range of from 0.35 MPa to 10 MPa, and at a time up to 300 min; and the olefin comprises ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, or mixtures thereof.