# US 11,028,192 B2 · Solution process to make ethylene copolymers

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- Number: US 11,028,192 B2
- Document ID: US11028192B2
- Status: Granted
- Kind: B2
- Application number: 16/492,736
- Filed: 2018-02-12
- Published: 2020-07-09
- Granted: 2021-06-08
- Earliest claimed: 2017-03-27
- 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/US11028192B2

## CPC

- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F 210/06: Propene
- C08F 210/14: Monomers containing five or more carbon atoms
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 232/08: having condensed rings (coumarone-indene polymers C08F244/00)
- C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 232/04: having one carbon-to-carbon double bond
- C08F 236/00: Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds (C08F232/00 takes precedence)
- C08F 2420/10: Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

This invention relates to a process to polymerize olefins comprising contacting, in solution phase at a temperature of 60° C. to 200° C., ethylene, and at least one olefin comonomer with a catalyst system comprising a non-coordinating anion activator and a metallocene catalyst compound, preferably represented by the formula: and 2) obtaining ethylene polymer having an Mw greater than 100,000 g/mol, preferably greater tha 400,000 g/mol.

## Claims

### Claim 1

A process to polymerize olefins comprising contacting, in solution phase at a temperature of 85° C. to 200° C., ethylene, at least one olefin comonomer, and optional diene, with a catalyst system comprising a non-coordinating anion activator and a metallocene catalyst compound represented by the formula:
wherein:
M is Hf;
each R3 is independently an anionic group;
each R2 is independently H or a C1 to C20 hydrocarbyl or C1 to C20 substituted hydrocarbyl;
R4 is a hydrocarbyl radical having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof;
R* is phenyl or a substituted phenyl;
each R5 is independently H or a C1 to C20 hydrocarbyl or C1 to C20 substituted hydrocarbyl;
each R6 is independently H or a C1 to C20 hydrocarbyl or C1 to C20 substituted hydrocarbyl;
each R7 is independently H or a C1 to C20 hydrocarbyl or C1 to C20 substituted hydrocarbyl;
each R8 is independently H or a C1 to C20 hydrocarbyl or C1 to C20 substituted hydrocarbyl;
where at least one of each adjacent pair of R7 and R8 is not H; and
2) obtaining ethylene copolymer comprising ethylene, from 0.5 to 25 mol % C3 to C20 olefin comonomer, and optionally from 0.5 to 20 mol % diene, said ethylene copolymer having a Mw greater than 100,000 g/mol where the % olefin comonomer incorporated is X % or more, where X=(Z−858,441)/(−26,760), where Z is the Mn in g/mol of the ethylene copolymer.

### Claim 2 (depends on 1)

The process of claim 1, wherein R4 is a C1 to C20 hydrocarbyl or C1 to C20 substituted hydrocarbyl.

### Claim 3 (depends on 1)

The process of claim 1, wherein R4 is a C1 to C20 alkyl.

### Claim 4 (depends on 1)

The process of claim 1, wherein R4 and R* are independently a phenyl or a substituted phenyl.

### Claim 5 (depends on 1)

The process of claim 1, wherein R* is alkoxy substituted phenyl, where an alkyl in the alkoxy is a C1 to C20 alkyl.

### Claim 6 (depends on 1)

The process of claim 1, wherein each R6 R7 and R8 is independently H or a C1 to C20 hydrocarbyl.

### Claim 7 (depends on 1)

The process of claim 1, wherein each R5, R6, R7 and R8 is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, or an isomer thereof.

### Claim 8 (depends on 1)

The process of claim 1 claim 1, wherein the catalyst compound comprises:

### Claim 9 (depends on 1)

The process of claim 1, wherein the activator comprises 0 mol % alumoxane.

### Claim 10 (depends on 1)

The process of claim 1, wherein the activator is represented by the formula:
where:
each R1 is, independently, a halide;
each R2 is, independently, a halide, a C6 to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula —0—Si—Ra, where Ra is a C1 to C20 hydrocarbyl or hydrocarbylsilyl group;
each R3 is a halide, C6 to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula —0—Si—Ra, where Ra is a C1 to C20 hydrocarbyl or hydrocarbylsilyl group;
L is an neutral Lewis base; (L-H)+is a Bronsted acid; d is 1, 2, or 3, or (L-H)30 d is (Ar3C)30d where Ar is substituted or unsubstituted aryl group;
wherein the anion has a molecular weight of greater than 1020 g/mol; and
wherein at least three of the substituents on the B atom each have a molecular volume of greater than 250 cubic A.

### Claim 11 (depends on 10)

The process of claim 10, wherein (L-H)d30 is (Ar3C)d30 , where Ar is substituted or unsubstituted aryl group.

### Claim 12 (depends on 1)

The process of claim 1, wherein the activator is one or more of:
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)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, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis (perfluorobiphenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylphosphonium tetrakis(perfluorobiphenyl)borate, triethylsilylium tetrakis(perfluorobiphenyl)borate, [4-t-butyl-PhNMe2H][(C6F3(C6F5)2)4B], triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)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, and triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

### Claim 13 (depends on 1)

The process of claim 1, wherein the process occurs at a temperature of from about 60° C. to about 160° 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 14 (depends on 1)

The process of claim 1, wherein the comonomer comprises one or more of propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene and isomers thereof.

### Claim 15 (depends on 1)

The process of claim 1, wherein the comonomer comprises propylene.

### Claim 16 (depends on 1)

The process of claim 1, wherein the comonomer comprises propylene and norbornene.

### Claim 17 (depends on 1)

The process of claim 1, wherein the comonomer comprises octene.

### Claim 18 (depends on 1)

The process of claim 1, wherein the comonomer comprises propylene and diene.

### Claim 19 (depends on 18)

The process of claim 18, where the diene is ethylidene norbornene and/or vinyl norbomene.

### Claim 20

A process to polymerize olefins comprising contacting, in solution phase at a temperature of 85° C. to 200° C., ethylene, diene, and optionally a C3 to C20 olefin comonomer, with a catalyst system comprising a non-coordinating anion activator and a metallocene catalyst compound represented by the formula:
wherein
M is Hf or Zr;
each R3 is independently an anionic group;
each R2 is independently H or a C1 to C20 hydrocarbyl or C1 to C20 substituted hydrocarbyl;
R4 is a hydrocarbyl radical having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof;
R* is phenyl or a substituted phenyl;
each R5 is independently H or a C1 to C20 hydrocarbyl or C1 to C20 substituted hydrocarbyl;
each R6 is independently H or a C1 to C20 hydrocarbyl or C1 to C20 substituted hydrocarbyl;
each R7 is independently H or a C1 to C20 hydrocarbyl or C1 to C20 substituted hydrocarbyl;
each R8 is independently H or a C1 to C20 hydrocarbyl or C1 to C20 substituted hydrocarbyl;
where at least one of each adjacent pair of R7 and R8 is not H; and
2) obtaining an ethylene copolymer comprising from 0.5 to 20 mol % diene, optionally from 0.5 to 25 mol % C3 to C20 olefin comonomer, and said ethylene copolymer having a Mw greater than 400,000 g/mol, where a % olefin comonomer incorporated is X % or more, where X=(Z−858,441)/(−26,760), where Z is Mn in g/mol of the ethylene copolymer.