Catalysts for olefin polymerization

Patent metadata

Field	Value
Publication number	US-11649256-B2
Application number	US-202017067256-A
Country	US
Kind code	B2
Filing date	Oct 9, 2020
Priority date	Oct 11, 2019
Publication date	May 16, 2023
Grant date	May 16, 2023

Abstract

The present disclosure provides catalyst compounds represented by Formula (I):

where Q is OR 13 , SR 13 , NR 13 R 14 , PR 13 R 14 , or a heterocyclic ring; each R 1-14 is independently hydrogen, C 1 -C 40 hydrocarbyl, substituted C 1 -C 40 hydrocarbyl, a heteroatom, or a heteroatom-containing group, or multiple R 1-14 are joined together to form a C 4 -C 62 cyclic, heterocyclic, or polycyclic ring structure, or combination(s) thereof; each X 1 and X 2 is independently C 1 -C 20 hydrocarbyl, substituted C 1 -C 20 hydrocarbyl, a heteroatom, or a heteroatom-containing group, or X 1 and X 2 join together to form a C 4 -C 62 cyclic, heterocyclic, or polycyclic ring structure; and Y is a hydrocarbyl. The present disclosure also provides catalyst systems including an activator, a support, and a catalyst of the present disclosure. The present disclosure also provides polymerization processes including introducing olefin monomers to a catalyst system. Additionally, the present disclosure provides a polyolefin formed by a catalyst system or method of the present disclosure.

First claim

What is claimed is:

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

wherein:
Q is OR 13 , SR 13 , NR 13 R 14 , PR 13 R 14 , or a heterocyclic ring;
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 , and R 14 is independently hydrogen, C 1 -C 40 hydrocarbyl, substituted C 1 -C 40 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, heterocyclic, or polycyclic ring structure, or a combination thereof,
each of X 1 and X 2 is independently C 1 -C 20 hydrocarbyl, substituted C 1 -C 20 hydrocarbyl, a heteroatom, or a heteroatom-containing group, or X 1 and X 2 join together to form a C 4 -C 62 cyclic, heterocyclic, or polycyclic ring structure, wherein if R 1 and R 12 are an aryltriazole, then X 1 and X 2 are not isopropoxyl; and
Y is a C 1 -C 10 hydrocarbylene.

2. The catalyst compound of claim 1 , wherein:
Q is NR 13 R 14 or PR 13 R 14 , and
R 13 and R 14 are independently selected from hydrogen, C 1 -C 40 hydrocarbyl, or substituted C 1 -C 40 hydrocarbyl.

3. The catalyst compound of claim 1 , wherein R 3 and R 10 are independently a C 1 -C 4 hydrocarbyl.

4. The catalyst compound of claim 2 , wherein R 2 , R 4 , R 9 , and R 11 are hydrogen.

5. The catalyst compound of claim 1 , wherein Y is a C 2 hydrocarbylene.

6. The catalyst compound of claim 2 , wherein R 13 and R 14 are methyl, ethyl, or isopropyl.

7. The catalyst compound of claim 1 , wherein R 1 and R 12 are each represented by the structure:

wherein each instance of R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , and R 22 is independently selected from hydrogen, C 1 -C 40 hydrocarbyl, substituted C 1 -C 40 hydrocarbyl, a heteroatom, or a heteroatom-containing group, or two or more of R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , and R 22 are joined together to form a C 4 -C 62 cyclic, heterocyclic, or polycyclic ring structure, or a combination thereof, and
J is N, P, or CR′, wherein R′ is selected from hydrogen, C 1 -C 40 hydrocarbyl, substituted C 1 -C 40 hydrocarbyl, a heteroatom, or a heteroatom-containing group.

8. The catalyst compound of claim 7 , wherein each instance of R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , and R 22 is independently selected from hydrogen or C 1 -C 4 hydrocarbyl.

9. The catalyst compound of claim 8 , wherein each instance of R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , and R 22 is hydrogen.

10. The catalyst compound of claim 8 , wherein each instance of J is N.

11. The catalyst compound of claim 8 , each instance of J is CR′ and R′ is a C 1 -C 4 hydrocarbyl.

12. The catalyst compound of claim 1 , wherein each of R 5 , R 6 , R 7 , and R 8 is hydrogen.

13. The catalyst compound of claim 1 , wherein each of X 1 and X 2 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. The catalyst compound of claim 15 , wherein the catalyst compound is one or more of:

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

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

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

20. A process for 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 at least one polymerization reactor 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.

21. The process of claim 20 , wherein the ethylene alpha-olefin copolymer has an Mw value of 1,000,000 g/mol or greater.

22. The process of claim 21 , wherein the ethylene alpha-olefin copolymer has an Mw value of from 3,000,000 g/mol to 8,000,000 g/mol.

23. The process of claim 21 , wherein the ethylene alpha-olefin copolymer has an Mw/Mn value of 4 or less.

24. The process of claim 23 , wherein the ethylene alpha-olefin copolymer has an Mw/Mn value of from 1 to 2.

25. The process of claim 23 , wherein the ethylene alpha-olefin copolymer has a comonomer content of from 1 wt % to 8 wt %.

26. A process for 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 in at least one polymerization reactor 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, wherein the catalyst system comprises:
an activator;
an optional support; and
a catalyst compound represented by Formula (I):

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Culcu Gursu
• Faler Catherine A
• Atienza Crisita Carmen H
• Cano David A
• Hagadorn John R

Classifications

• C08F10/02

  Ethene · CPC title

• C08F4/64158

  ONO · CPC title

• C08F2500/34

  Melting point [Tm] · CPC title

• C07F7/28 Primary

  Titanium compounds · CPC title

• C08F2500/38

  Branching index [gvis], i.e. ratio of the intrinsic viscosity of the branched polymer to the intrinsic viscosity of a linear polymer of equal molecular weight and same composition · CPC title