# US 10,766,975 B2 · Catalyst compositions and use thereof

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- Number: US 10,766,975 B2
- Document ID: US10766975B2
- Status: Granted
- Kind: B2
- Application number: 16/308,747
- Filed: 2017-06-28
- Published: 2020-01-02
- Granted: 2020-09-08
- Earliest claimed: 2016-07-28
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Donna J. Crowther; Hua Zhou; Jacqueline A. Lovell
- Web page: https://patentgrep.com/patent/US10766975B2

## CPC

- C08F 10/02: Ethene
- C08F 110/02: Ethene
- C07F 7/003: {without C-Metal linkages}
- C07F 7/28: Titanium compounds
- C08F 2410/01: Additive used together with the catalyst, excluding compounds containing Al or B
- C08F 2410/04: Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
- 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

This invention relates to novel transition metal catalyst compounds comprising four oxygen atoms bonded to a transition metal where two of the oxygen groups are bond to the metal by dative bonds, catalyst systems comprising such and polymerization processes using such.

## Claims

### Claim 1

A catalyst compound represented by the formula:
wherein: a dotted line indicates a dative bond;
M is a group 4 metal;
z is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, provided that when z is 0, then there is a direct bond between the phenyl rings in place of the (CH2)z group;
each of R1, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 and R16 is, independently, hydrogen, a substituted C1 to C40 hydrocarbyl group, a C1 to C40 unsubstituted hydrocarbyl group, or a heteroatom, provided that any of adjacent R groups may form a fused ring or multicenter fused ring system where the rings may be aromatic, partially saturated or saturated, and provided that R9 and R10 may not form a bridge;
each of R2 and R3, is, independently, hydrogen, a substituted C1 to C40 hydrocarbyl group, a C1 to C40 unsubstituted hydrocarbyl group, or a heteroatom, provided that R2 and R3 may not form a bridge; and
each X is, independently, a substituted C1 to C40 hydrocarbyl group, a C1 to C40 unsubstituted hydrocarbyl group, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halide, an amine, a phosphines, an ethers, a combination thereof, where two X's optionally form a part of a fused ring or a ring system.

### Claim 2 (depends on 1)

The compound of claim 1, wherein each of R2 and R3, is, independently, hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, t-butyl, isopropyl, phenyl, naphthyl or an isomer thereof.

### Claim 3 (depends on 1)

The compound of claim 1, wherein each X is independently selected from Cl, Br, F, I, methyl, ethyl, propyl, butyl, pentyl, benzyl or an isomer thereof, and dimethylamido.

### Claim 4 (depends on 1)

The compound of claim 1, wherein M is Ti and each of R1, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 and R16 is, independently, hydrogen or t-butyl.

### Claim 5 (depends on 1)

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

### Claim 6 (depends on 5)

The catalyst system of claim 5, further comprising chain transfer agent represented by the formula AlR3, ZnR2 where each R is, independently, a C1-C8 aliphatic radical.

### Claim 7 (depends on 5)

The catalyst system of claim 5, wherein the activator comprises alumoxane.

### Claim 8 (depends on 5)

The catalyst system of claim 5, wherein the activator comprises a non coordinating anion.

### Claim 9 (depends on 5)

The catalyst system of claim 5, wherein the catalyst system comprises a support.

### Claim 10 (depends on 5)

A process to polymerize olefins comprising contacting one or more olefins with the catalyst system of claim 5.

### Claim 11 (depends on 10)

The process of claim 10, wherein each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, where two X's optionally form a part of a fused ring or a ring system.

### Claim 12 (depends on 10)

The process of claim 10, wherein M is Hf, Ti and/or Zr.

### Claim 13 (depends on 10)

The process of claim 10, wherein z is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

### Claim 14 (depends on 10)

The process of claim 10, wherein z is 0.

### Claim 15 (depends on 10)

The process of claim 10, wherein z is 1.

### Claim 16 (depends on 10)

The process of claim 10, wherein the catalyst compound comprises one or more catalyst compounds represented by the formula:
wherein Me is methyl, Et is ethyl, Bz is benzyl, Ph is phenyl, tBu is t-butyl, and a dotted line indicates a dative bond.

### Claim 17 (depends on 10)

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

### Claim 18 (depends on 17)

The process of claim 17, wherein alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal of 100:1 or more.

### 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 the activator is represented by the formula:
Zd+(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 the activator is represented by the formula:
Zd+(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,
tropillium tetrakis(perfluoronaphthyl)borate,
triphenylcarbenium tetrakis(perfluoronaphthyl)borate,
triphenylphosphonium tetrakis(perfluoronaphthyl)borate,
triethylsilylium tetrakis(perfluoronaphthyl)borate,
benzene(diazonium) tetrakis(perfluoronaphthyl)borate,
trimethylammonium tetrakis(perfluorobiphenyl)borate,
triethylammonium tetrakis(perfluorobiphenyl)borate,
tripropylammonium tetrakis(perfluorobiphenyl)borate,
tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate,
tri(t-butyl)ammonium tetrakis(perfluorobiphenyl)borate,
N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,
N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(perfluorobiphenyl)borate,
tropillium tetrakis(perfluorobiphenyl)borate,
triphenylcarbenium tetrakis(perfluorobiphenyl)borate,
triphenylphosphonium tetrakis(perfluorobiphenyl)borate,
triethylsilylium tetrakis(perfluorobiphenyl)borate,
benzene(diazonium) tetrakis(perfluorobiphenyl)borate,
[4-t-butyl-PhNMe2H][(C6F3(C6F5)2)4B],
trimethylammonium tetraphenylborate,
triethylammonium tetraphenylborate,
tripropylammonium tetraphenylborate,
tri(n-butyl)ammonium tetraphenylborate,
tri(t-butyl)ammonium tetraphenylborate,
N,N-dimethylanilinium tetraphenylborate,
N,N-diethylanilinium tetraphenylborate,
N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate,
tropillium tetraphenylborate,
triphenylcarbenium tetraphenylborate,
triphenylphosphonium tetraphenylborate,
triethylsilylium tetraphenylborate,
benzene(diazonium)tetraphenylborate,
trimethylammonium tetrakis(pentafluorophenyl)borate,
triethylammonium tetrakis(pentafluorophenyl)borate,
tripropylammonium tetrakis(pentafluorophenyl)borate,
tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,
tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,
N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate,
tropillium tetrakis(pentafluorophenyl)borate,
triphenylcarbenium tetrakis(pentafluorophenyl)borate,
triphenylphosphonium tetrakis(pentafluorophenyl)borate,
triethylsilylium tetrakis(pentafluorophenyl)borate,
benzene(diazonium) tetrakis(pentafluorophenyl)borate,
trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate,
triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,
dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
benzene(diazonium) tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
tri(t-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
benzene(diazonium) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,
dicyclohexylammonium tetrakis(pentafluorophenyl)borate,
tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,
tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,
triphenylcarbenium tetrakis(perfluorophenyl)borate,
1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,
tetrakis(pentafluorophenyl)borate,
4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, and
triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

### Claim 23 (depends on 10)

The process of 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.

### Claim 24 (depends on 10)

The process of claim 10, further comprising recovering polymer.

### Claim 25 (depends on 10)

The process of claim 10, wherein the olefins comprise ethylene and/or propylene.

### Claim 26 (depends on 22)

The process of claim 22, wherein the catalyst compound comprises one or more catalyst compounds represented by the formula:
wherein Me is methyl, t is ethyl, Bz is benzyl, Ph is phenyl, tBu is t-butyl, and a dotted line indicates a dative bond.

### Claim 27 (depends on 16)

The process of claim 16, wherein the activator is an alumoxane.

### Claim 28 (depends on 26)

The process of claim 26, wherein the catalyst system further comprising chain transfer agent represented by the formula AlR3, ZnR2—where each R is, independently, a C1-C8 aliphatic radical.

### Claim 29 (depends on 27)

The process of claim 27, wherein the catalyst system further comprising chain transfer agent represented by the formula AlR3, ZnR2—where each R is, independently, a C1-C8 aliphatic radical.

### Claim 30 (depends on 6)

The catalyst system of claim 6, wherein each R is methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, an isomer thereof or a combination thereof.

### Claim 31 (depends on 28)

The catalyst system of claim 28, wherein each R is methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, an isomer thereof or a combination thereof.

### Claim 32 (depends on 29)

The catalyst system of claim 29, wherein each R is methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, an isomer thereof or a combination thereof.