Amine bridged anilide phenolate catalyst compounds

Patent metadata

Field	Value
Publication number	US-11066494-B2
Application number	US-201916575780-A
Country	US
Kind code	B2
Filing date	Sep 19, 2019
Priority date	Sep 20, 2018
Publication date	Jul 20, 2021
Grant date	Jul 20, 2021

Abstract

The present disclosure provides catalyst compounds having an amine bridged anilide phenolate ligand. In at least one embodiment, catalysts of the present disclosure provide catalyst activity values of about 90 gP/mmolCat·h −1 or greater and polyolefins, such as polyethylene copolymers, having comonomer content of from about 4 wt % to about 12 wt %, an Mn of about 90,000 g/mol or more, an Mw of 155,000 g/mol or more, and an Mw/Mn of from 1 to 2.5.

First claim

What is claimed is:

1. A catalyst compound represented by Formula 4):

wherein:
M is a group 4 metal;
R 1 is an aromatic group or substituted aromatic group;
each of R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 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 , and R 14 are joined together to form a C 4 -C 62 cyclic or polycyclic ring structure;
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.

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

3. The catalyst compound of claim 2 , wherein R 2 C 1 -C 10 hydrocarbyl.

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

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

wherein each of R 15 , R 16 , R 17 , R 18 , and R 19 is independently selected from hydrogen, C 1 -C 40 hydrocarbyl or C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or two or more of R 15 , R 16 , R 17 , and R 19 are joined together to form a C 4 -C 62 cyclic or polycyclic ring structure.

6. The catalyst compound of claim 5 , wherein each of R 15 , R 16 , R 17 , R 18 , and R 19 is independently selected from hydrogen and C 1 -C 40 hydrocarbyl.

7. The catalyst compound of claim 6 , wherein each of R 15 , R 16 , R 17 , R 18 , and R 19 is hydrogen.

8. The catalyst compound of claim 5 , wherein R 15 is isopropyl.

9. The catalyst compound of claim 8 , wherein R 19 is isopropyl.

10. The catalyst compound of claim 1 , wherein R 3 is selected from phenyl, substituted phenyl, carbazole, substituted carbazole, naphthyl, substituted naphthyl, anthracenyl, substituted anthracenyl, fluorenyl, substituted fluorenyl, a heteroatom or a heteroatom-containing group.

11. The catalyst compound of claim 10 , wherein R 3 is phenyl, anthracenyl, naphthyl, fluorenyl, or carbazole.

12. The catalyst compound of claim 1 , wherein each of R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 is independently selected from hydrogen and C 1 -C 10 hydrocarbyl.

13. The catalyst compound of claim 12 , wherein each of R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 is hydrogen.

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

15. The catalyst compound of claim 14 , wherein each X is methyl, benzyl, or chloro.

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

17. The catalyst compound of claim 16 , wherein the catalyst compound is one or more of:

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

19. The catalyst system of claim 18 , further comprising a support material.

20. The catalyst system of claim 19 , 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, or mixtures thereof.

21. The catalyst system of claim 18 , wherein the activator comprises an alkylalumoxane.

22. 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 18 in the 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 an ethylene alpha-olefin copolymer.

23. The process of claim 22 , wherein the ethylene alpha-olefin copolymer has an Mw value of 100,000 g/mol or greater.

24. The process of claim 23 , wherein the ethylene alpha-olefin copolymer has an Mw value of from 500,000 g/mol to 650,000 g/mol.

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

26. The process of claim 22 , wherein the ethylene alpha-olefin copolymer has a comonomer content of from 4.5 wt % to 7.5 wt %.

27. The process of claim 22 , wherein the ethylene alpha-olefin copolymer has a melt temperature of from 122° C. to 127° C.

28. The process of claim 22 , wherein the catalyst system has a catalyst activity value of 90 gP/mmolCat·h −1 or greater, and the ethylene alpha-olefin copolymer has a comonomer content of from about 4 wt % to 10 wt %, a Mn of 90,000 g/mol or greater, a Mw of from 155,000 g/mol to 625,000 g/mol, and a Mw/Mn of from 1 to 2.

29. The process of claim 22 , wherein the catalyst system has a catalyst activity value of 90 gP/mmolCat·h −1 or greater, and the ethylene alpha-olefin copolymer has a comonomer content of from about 4.5 wt % to about 7.5 wt %, a Mn of about 90,000 g/mol to about 420,000 g/mol, a Mw of from about 155,000 g/mol to about 625,000 g/mol, and a Mw/Mn of from 1 to 2.5.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

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

Classifications

• C08F210/16

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

• C08F4/76

  selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum · CPC title

• C08F4/65908

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

• C07F5/00

  Compounds containing elements of Groups 3 or 13 of the Periodic Table · CPC title

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title