Solution process to make ethylene copolymers

Patent metadata

Field	Value
Publication number	US-11028192-B2
Application number	US-201816492736-A
Country	US
Kind code	B2
Filing date	Feb 12, 2018
Priority date	Mar 27, 2017
Publication date	Jun 8, 2021
Grant date	Jun 8, 2021

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:and2) obtaining ethylene polymer having an Mw greater than 100,000 g/mol, preferably greater tha 400,000 g/mol.

First claim

The invention claimed is:

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 R 3 is independently an anionic group;
each R 2 is independently H or a C 1 to C 20 hydrocarbyl or C 1 to C 20 substituted hydrocarbyl;
R 4 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 R 5 is independently H or a C 1 to C 20 hydrocarbyl or C 1 to C 20 substituted hydrocarbyl;
each R 6 is independently H or a C 1 to C 20 hydrocarbyl or C 1 to C 20 substituted hydrocarbyl;
each R 7 is independently H or a C 1 to C 20 hydrocarbyl or C 1 to C 20 substituted hydrocarbyl;
each R 8 is independently H or a C 1 to C 20 hydrocarbyl or C 1 to C 20 substituted hydrocarbyl;
where at least one of each adjacent pair of R 7 and R 8 is not H; and
2) obtaining ethylene copolymer comprising ethylene, from 0.5 to 25 mol % C 3 to C 20 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.

2. The process of claim 1 , wherein R 4 is a C 1 to C 20 hydrocarbyl or C 1 to C 20 substituted hydrocarbyl.

3. The process of claim 1 , wherein R 4 is a C 1 to C 20 alkyl.

4. The process of claim 1 , wherein R 4 and R* are independently a phenyl or a substituted phenyl.

5. The process of claim 1 , wherein R* is alkoxy substituted phenyl, where an alkyl in the alkoxy is a C 1 to C 20 alkyl.

6. The process of claim 1 , wherein each R 6 R 7 and R 8 is independently H or a C 1 to C 20 hydrocarbyl.

7. The process of claim 1 , wherein each R 5 , R 6 , R 7 and R 8 is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, or an isomer thereof.

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

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

10. The process of claim 1 , wherein the activator is represented by the formula:

where:
each R 1 is, independently, a halide;
each R 2 is, independently, a halide, a C 6 to C 20 substituted aromatic hydrocarbyl group or a siloxy group of the formula — 0 —Si—R a , where R a is a C 1 to C 20 hydrocarbyl or hydrocarbylsilyl group;
each R 3 is a halide, C 6 to C 20 substituted aromatic hydrocarbyl group or a siloxy group of the formula — 0 —Si—R a , where R a is a C 1 to C 20 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 (Ar 3 C) 30 d 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.

11. The process of claim 10 , wherein (L-H) d 30 is (Ar 3 C) d 30 , where Ar is substituted or unsubstituted aryl group.

12. 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-PhNMe 2 H][(C 6 F 3 (C 6 F 5 ) 2 ) 4 B], 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.

13. 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.

14. 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.

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

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

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

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

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

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 C 3 to C 20 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 R 3 is independently an anionic group;
each R 2 is independently H or a C 1 to C 20 hydrocarbyl or C 1 to C 20 substituted hydrocarbyl;
R 4 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 R 5 is independently H or a C 1 to C 20 hydrocarbyl or C 1 to C 20 substituted hydrocarbyl;
each R 6 is independently H or a C 1 to C 20 hydrocarbyl or C 1 to C 20 substituted hydrocarbyl;
each R 7 is independently H or a C 1 to C 20 hydrocarbyl or C 1 to C 20 substituted hydrocarbyl;
each R 8 is independently H or a C 1 to C 20 hydrocarbyl or C 1 to C 20 substituted hydrocarbyl;
where at least one of each adjacent pair of R 7 and R 8 is not H; and
2) obtaining an ethylene copolymer comprising from 0.5 to 20 mol % diene, optionally from 0.5 to 25 mol % C 3 to C 20 olefin comonomer, and said ethylene copolymer having a Mw greater than 400,000 g/mol, where a % olefin comonomer

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Crowther Donna J
• Zhou Hua
• Lovell Jacqueline A

Classifications

• C08F2420/10

  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 · CPC title

• C08F232/04

  having one carbon-to-carbon double bond · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F10/00 Primary

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F210/06

  Propene · CPC title