Catalysts for olefin polymerization

Patent metadata

Field	Value
Publication number	US-10683377-B2
Application number	US-201916457078-A
Country	US
Kind code	B2
Filing date	Jun 28, 2019
Priority date	Jul 16, 2018
Publication date	Jun 16, 2020
Grant date	Jun 16, 2020

Abstract

The present disclosure provides catalyst compounds having a tridentate ethylene bridged amine bis(phenolate) ligand. Catalysts of the present disclosure preferably provide catalyst activity values of 250 gP/mmolCat/hr or greater and polyolefins, such as polyethylene copolymers, having comonomer content of 8.5 wt % or greater, an Mn of 190,000 g/mol or greater, an Mw of 350,000 g/mol or greater, and a narrow Mw/Mn (such as about 2). Catalysts, catalyst systems, and processes of the present disclosure can provide polymers having a high comonomer content (e.g., 8.5 wt % or greater).

First claim

What is claimed is:

1. A catalyst compound represented by Formula (I):

wherein:
M is a group 4 metal;
each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 is independently hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or two or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , or R 17 are joined together to form a C 4 -C 62 cyclic or polycyclic ring structure, or a combination thereof;
each X is independently C 1 -C 20 hydrocarbyl, C 1 -C 20 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or two or more Xs join together to form a C 4 -C 62 cyclic or polycyclic ring structure; and
n is 2 or 3.

2. The catalyst compound of claim 1 , wherein R 17 is hydrogen or C 1 -C 40 hydrocarbyl.

3. The catalyst compound of claim 2 , wherein R 17 C 1 -C 40 hydrocarbyl.

4. The catalyst compound of claim 2 , wherein R 17 is hydrogen.

5. The catalyst compound of claim 1 , wherein n is 2.

6. The catalyst compound of claim 1 , wherein R 1 is represented by the structure:

wherein each of R 18 , R 19 , R 20 , R 21 , and R 22 is independently selected from hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, two or more of R 18 , R 19 , R 20 , R 21 , and R 22 are joined together to form a C 4 -C 62 cyclic or polycyclic ring structure, or a combination thereof.

7. The catalyst compound of claim 6 , wherein each of R 18 , R 19 , R 20 , R 21 , and R 22 is independently selected from hydrogen and C 1 -C 40 hydrocarbyl.

8. The catalyst compound of claim 7 , wherein each of R 18 , R 19 , R 20 , R 21 , and R 22 is hydrogen.

9. The catalyst compound of claim 1 , wherein each of R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 is independently selected from hydrogen and C 1 -C 10 hydrocarbyl.

10. The catalyst compound of claim 9 , wherein two or more of R 5 , R 6 , R 7 , and R 8 are hydrogen and two or more of R 9 , R 10 , R 11 , and R 12 are hydrogen.

11. The catalyst compound of claim 10 , wherein each of R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 is hydrogen.

12. The catalyst compound of claim 1 , wherein M is Zr or Hf.

13. The catalyst compound of claim 1 , wherein each X is methyl, benzyl, or chloro.

14. The catalyst compound of claim 1 , wherein the catalyst compound is one or more of:

15. The catalyst compound of claim 14 , wherein the catalyst compound is one or more of:

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

17. The catalyst system of claim 16 , further comprising a support material.

18. The catalyst system of claim 17 , wherein the support material is selected from Al 2 O 3 , ZrO 2 , SiO 2 , SiO 2 /Al 2 O 3 , SiO 2 /TiO 2 , silica clay, silicon oxide/clay, and mixtures thereof.

19. The catalyst system of claim 16 , wherein the activator comprises an alkylalumoxane.

20. A process for the production of an ethylene alpha-olefin copolymer comprising: polymerizing ethylene and at least one C 3 -C 20 alpha-olefin by contacting the ethylene and the at least one C 3 -C 20 alpha-olefin with a catalyst system of claim 16 in a solution phase at a reactor pressure of from 2 MPa to 200 MPa and a reactor temperature of from 10° C. to 250° C. to form the ethylene alpha-olefin copolymer.

21. The process of claim 20 , wherein the ethylene alpha-olefin copolymer has an Mw value of 300,000 g/mol or greater.

22. The process of claim 21 , wherein the ethylene alpha-olefin copolymer has an Mw value of from 350,000 g/mol to 450,000 g/mol.

23. The process of claim 20 , wherein the ethylene alpha-olefin copolymer has an Mw/Mn value of 5 or less.

24. The process of claim 23 , wherein the ethylene alpha-olefin copolymer has an Mw/Mn value of from 1 to 2.5.

25. The process of claim 20 , wherein the ethylene alpha-olefin copolymer has a comonomer content of from 7 wt % to 12 wt %.

26. The process of claim 25 , wherein the comonomer content of the ethylene alpha-olefin copolymer is from 8 wt % to 10 wt %.

27. A catalyst system comprising an activator, the catalyst compound of claim 14 , and optional support material.

28. A catalyst system comprising an activator, the catalyst compound of claim 1 , and optional support material, wherein
R 17 is hydrogen or C 1 -C 40 hydrocarbyl;
n is 2;
R 1 is represented by the structure:

wherein each of R 18 , R 19 , R 20 , R 21 , and R 22 is independently selected from hydrogen, C 1 -C 40 hydrocarbyl, C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or two or more of R 18 , R 19 , R 20 , R 21 , and R 22 are joined together to form a C 4 -C 62 cyclic or polycyclic ring structure, or a combination thereof;
each of R 18 , R 19 , R 20 , R 21 , and R 22 is independently selected from hydrogen and C 1 -C 40 hydrocarbyl; and
M is Zr or Hf.

29. The catalyst system of claim 28 , wherein each of R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 is independently selected from hydrogen and C 1 -C 10 hydrocarbyl.

30. The catalyst system of claim 29 , wherein two or more of R 5 , R 6 , R 7 , and R 8 are hydrogen and two or more of R 9 , R 10 , R 11 , and R 12 are hydrogen.

31. The catalyst system of claim 28 , wherein each of R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 is hydrogen.

32. The catalyst system of claim 28 , wherein each X is methyl, benzyl, or chloro.

33. A process for the production of an ethylene alpha-olefin copolymer comprising: polymerizing ethylene and at least one C 3 -C 20 alpha-olefin by contacting the ethylene and the at least one C 3 -C 20 alpha-olefin with a catalyst system of claim 27 in a solution phase at a reactor pressure of from 2 MPa to 200 MPa and a reactor temperature of from 10° C. to 250° C. to form the ethylene alpha-olefin copolymer.

34. A process for the production of an ethylene alpha-olefin copolymer comprising: polymerizing ethylene and at least one C 3 -C 20 alpha-olefin by contacting the ethylene and the at least one C 3 -C 20 alpha-olefin with a catalyst system of claim 28 in a solution phase at a reactor pressure of from 2 MPa

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Faler Catherine A
• Whalley Margaret T
• Atienza Crisita Carmen H
• Cano David A

Classifications

• C07F7/003 Primary

  without C-Metal linkages · CPC title

• C08F2800/20

  as weight or mass percentages · CPC title

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title