# US 12,595,322 B2 · Gas-phase biphenylphenol polymerization catalysts

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- Number: US 12,595,322 B2
- Document ID: US12595322B2
- Status: Granted
- Kind: B2
- Application number: 17/786,672
- Filed: 2020-12-17
- Published: 2023-03-30
- Granted: 2026-04-07
- Earliest claimed: 2019-12-19
- Assignees: Dow Global Technologies LLC
- Applicants: Dow Global Technologies LLC
- Inventors: Angela I. Padilla-Acevedo; Andrew J. Young; Roger L. Kuhlman; Susan Brown; Matthew E. Belowich; David R. Neithamer; Jerzy Klosin; David M. Pearson; Leslie E. O'Leary; Joseph F. DeWilde
- Web page: https://patentgrep.com/patent/US12595322B2

## CPC

- C08F 110/02: Ethene
- C08F 2/34: Polymerisation in gaseous state
- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 4/659: Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Embodiments are directed towards a use of a supported gas-phase biphenylphenol polymerization catalyst to make a polymer via a gas-phase polymerization process, wherein the supported gas-phase biphenylphenol polymerization catalyst is made from a gas-phase biphenylphenol polymerization precatalyst of Formula I.

## Claims

### Claim 1

A method for making a polymer, the method comprising:
contacting a supported gas-phase biphenylphenol polymerization catalyst with an olefin under polymerization conditions in a gas-phase polymerization reactor to make the polymer via a gas-phase polymerization process, wherein the supported gas-phase biphenylphenol polymerization catalyst is made from a gas-phase biphenylphenol polymerization precatalyst of Formula I:
wherein each of R5, R7, R8, and R10 is independently is a (C1 to C20) alkyl, aryl, aralkyl, halogen, or a hydrogen;
wherein each of R4 and R11 independently is a halogen or a hydrogen;
wherein each of R2 and R13 independently is a (C1 to C20) alkyl, aryl or aralkyl or a hydrogen;
wherein each of R15 and R16 independently is a 2,7-disubstituted carbazol-9-yl or a 3,6-disubstituted carbazol-9-yl;
wherein L is a linear C3 or C4 alkylene that forms a 3-carbon bridge or 4-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded;
wherein each of R1, R3, R12, and R14 independently is a (C1-C5) alkyl, halogen, or a hydrogen;
wherein each of R6 and R9 is a hydrogen or (C1-C8) alkyl;
wherein each X independently is a halogen, a hydrogen, a (C1-C20) alkyl, a (C7-C20) aralkyl, a (C1-C6) alkyl-substituted (C6-C12) aryl, or a (C1-C6) alkyl-substituted benzyl,—CH2Si (RC) 3, where RC is (C1-C12) hydrocarbon;
wherein M is Zr or Hf; and
wherein the polymer formed at B-conditions (H2/C2=0.0017 and C6/C2=0.004 at 100° C. and 230 pounds per square inch (psi) ethylene) has a molecular weight (Mw) in a range of from about 150,000 Daltons to about 1,200,000 Daltons; or wherein the polymer formed at K-conditions (H2/C2=0.0068 and C6/C2=0.004 at 100° C. and 230 psi) has Mw of less than about 500,000 Daltons.

### Claim 2 (depends on 1)

The method of claim 1, wherein each X is a methyl.

### Claim 3 (depends on 1)

The method of claim 1, wherein each of R1, R3, R12, and R14 is a hydrogen.

### Claim 4 (depends on 1)

The method of claim 1, wherein the gas-phase biphenylphenol polymerization precatalyst of Formula I is selected from the group consisting of the structures of (i), (ii), (iii), (iv), (v), (vi), (vii), (viii) and (ix)

### Claim 5 (depends on 1)

The method of claim 1, wherein the gas-phase biphenylphenol polymerization precatalyst is selected from the group consisting of the structures of (iii) and (v)

### Claim 6

A gas-phase polymerization catalyst system to make a polymer via a gas-phase polymerization process, the gas-phase polymerization catalyst system comprising:
a metallocene olefin polymerization catalyst; and
the supported gas-phase biphenylphenol polymerization catalyst made from the gas-phase biphenylphenol polymerization precatalyst of Formula I:
wherein each of R5, R7, R8, and R10 is independently is a (C1 to C20) alkyl, aryl, aralkyl, halogen, or a hydrogen;
wherein each of R4 and R11 independently is a halogen or a hydrogen;
wherein each of R2 and R13 independently is a (C1 to C20) alkyl, aryl or aralkyl or a hydrogen;
wherein L is a linear C3 or C4 alkylene that forms a 3-carbon bridge or 4-carbon bridge, respectively, between the two oxygen atoms to which L is covalently bonded;
wherein each of R1, R3, R12, and R14 independently is a (C1-C8) alkyl, halogen, or a hydrogen;
wherein each of R6 and R9 is a hydrogen or (C1-C8) alkyl;
wherein each X independently is a halogen, a hydrogen, a (C1-C20) alkyl, a (C7-C20) aralkyl, a (C1-C6) alkyl-substituted (C6-C12) aryl, or a (C1-C6) alkyl-substituted benzyl,—CH2Si (RC) 3, where RC is (C1-C12) hydrocarbon;
wherein M is Zr or Hf; and
wherein each of R15 and R16 is a 3,6-di-t-butylcarbazol-9-yl.

### Claim 7 (depends on 6)

A gas-phase polymerization method to make a polymer, the method comprising:
polymerizing an olefin monomer in a gas-phase polymerization reactor in presence of the gas-phase polymerization catalyst system of claim 6 to make the polymer.