Nickel catalysts with single alkali ions for homopolymerization and copolymerization

Patent metadata

Field	Value
Publication number	US-12049532-B2
Application number	US-202217982767-A
Country	US
Kind code	B2
Filing date	Nov 8, 2022
Priority date	Jul 27, 2022
Publication date	Jul 30, 2024
Grant date	Jul 30, 2024

Abstract

This invention relates to nickel catalysts with alkali ions for homopolymerization and copolymerization.

First claim

What is claimed is:

1. A bimetallic catalyst complex having a structure selected from Formula (5) and Formula (6):

wherein in Formula (5) and Formula (6):
Ar is 2,6-dimethoxyphenyl;
L is an optionally substituted phenyl group;
M is Li, Na, K, or Cs;
A − is a weakly coordinating anion;
X is selected from hydrogen, an electron donating group, and an electron withdrawing group;
Y, and Z are each independently selected from hydrogen, an electron donating group, and an electron withdrawing group, provided that Y and Z are not both hydrogen; and
R 1 , R 2 , and R 3 are each independently selected from optionally substituted aryl, optionally substituted alkyl, and optionally substituted cycloalkyl.

2. The bimetallic catalyst complex of claim 1 , wherein the electron donating group is selected from the group consisting of: alkoxy, phenoxy, amino, alkylamino, dialkylamino, hydroxy, alkyl, and cycloalkyl; and the h electron withdrawing group is selected from the group consisting of: NO 2 , —CN, —C(O)-alkyl, C(O)Oalkyl, C(O)Nalkyl, —SO 3 H, —SO 2 alkyl, —PO 3 H, —PO 3 alkyl, —CF 3 , and halo.

3. The bimetallic catalyst complex of claim 1 , wherein
Ar is 2,6-dimethoxyphenyl;
L is a phenyl group;
M is Li, Na, K, or Cs;
A − is [(3,5-(CF 3 ) 2 C 6 H 3 ) 4 B] − ;
X is methyl;
Y, and Z are each independently selected from hydrogen, an electron donating group, and an electron withdrawing group, provided that Y and Z are not both hydrogen; and
R 1 , R 2 , and R 3 are each methyl.

4. A method for catalyzing homopolymerization of an optionally substituted olefin, comprising:
contacting an optionally substituted olefin with the bimetallic catalyst complex of claim 1 , whereby the optionally substituted olefin undergoes homopolymerization.

5. The method of claim 4 , wherein the step of contacting the optionally substituted olefin with the bimetallic catalyst complex is performed in the presence of at least one solvent.

6. The method of claim 5 , wherein the at least one solvent is a non-polar solvent, a polar solvent, or combination thereof.

7. The method of claim 4 , further comprising contacting at least one activator with the bimetallic catalyst complex and the optionally substituted olefin.

8. The method of claim 7 , wherein the at least one activator is selected from the group consisting of Ni(COD) 2 , triarylborane, methylaluminoxane, and trialkylaluminum.

9. The method of claim 4 , wherein the optionally substituted olefin is an optionally substituted terminal olefin or an optionally substituted internal olefin.

10. The method of claim 4 , wherein the optionally substituted olefin is ethylene.

11. A method for catalyzing copolymerization of a first optionally substituted olefin and at least one other optionally substituted olefin, comprising:
contacting a first optionally substituted olefin and at least one other optionally substituted olefin with the bimetallic catalyst complex of claim 1 , whereby the first optionally substituted olefin and the at least one other optionally substituted olefin undergoes copolymerization, and wherein the first optionally substituted olefin and the at least one other optionally substituted olefin are different from one another.

12. The method of claim 11 , wherein the step of contacting the first optionally substituted olefin and the at least one other optionally substituted olefin with the bimetallic catalyst complex is performed in the presence of at least one solvent.

13. The method of claim 12 , wherein the at least one solvent is a non-polar solvent, a polar solvent, or combination thereof.

14. The method of claim 11 , further comprising contacting at least one activator with the bimetallic catalyst complex, the first optionally substituted olefin, and the at least one other optionally substituted olefin.

15. The method of claim 14 , wherein the at least one activator is selected from the group consisting of Ni(COD) 2 , triarylborane, methylaluminoxane, and trialkylaluminum.

16. The method of claim 11 , wherein the first optionally substituted olefin and the at least one other optionally substituted olefin are each independently an optionally substituted terminal olefin or an optionally substituted internal olefin.

17. A method for catalyzing homopolymerization of an optionally substituted olefin, comprising:
contacting an optionally substituted olefin with the bimetallic catalyst complex of claim 3 , whereby the optionally substituted olefin undergoes homopolymerization.

18. The method of claim 17 , further comprising contacting at least one activator with the bimetallic catalyst complex and the optionally substituted olefin.

19. A method for catalyzing copolymerization of a first optionally substituted olefin and at least one other optionally substituted olefin, comprising:
contacting a first optionally substituted olefin and at least one other optionally substituted olefin with the bimetallic catalyst complex of claim 3 , whereby the first optionally substituted olefin and the at least one other optionally substituted olefin undergoes copolymerization, and wherein the first optionally substituted olefin and the at least one other optionally substituted olefin are different from one another.

20. The method of claim 19 , further comprising contacting at least one activator with the bimetallic catalyst complex, the first optionally substituted olefin, and the at least one other optionally substituted olefin.

Assignees

• Univ Houston System

Inventors

• Do Loi H
• Tran Thi V

Classifications

• C08F10/02

  Ethene · CPC title

• C08F210/02

  Ethene · CPC title

• C08F2/06

  Organic solvent · CPC title

• B01J2531/0291

  Ligands adapted to form modular catalysts, e.g. self-associating building blocks as exemplified in the patent document EP-A-1 479 439 · CPC title

• B01J2531/15

  Caesium · CPC title