IP Library Granted Patent US 12,049,532
Granted Patent B2
US 12,049,532 · App. 17/982,767 · Granted Jul 30, 2024

Nickel catalysts with single alkali ions for homopolymerization and copolymerization

Inventors: Loi H. Do (Manvel, TX); Thi V. Tran (Houston, TX)
Assignee: UNIVERSITY OF HOUSTON SYSTEM
C08F4/7098C08F2/06C08F210/02
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Quick Facts
Patent No.
US 12,049,532
App. No.
17/982,767
Granted
Jul 30, 2024
Kind
B2
Abstract

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

Claims (39)

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.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 6, 2023
From: DO, LOI H.; TRAN, THI V.
To: UNIVERSITY OF HOUSTON SYSTEM
Reel/Frame 062890/0409 →
Continuity (3)
Provisional Application 63392560 · Jul 27, 2022
Provisional Application 63402749 · Aug 31, 2022
Related Publication 20240101726A1 · Mar 28, 2024
Cited By (2)
US 12,503,526 US 12,662,556