Ligands for production of 1-octene in chromium assisted ethylene oligomerization process

Patent metadata

Field	Value
Publication number	US-11925927-B2
Application number	US-202217980253-A
Country	US
Kind code	B2
Filing date	Nov 3, 2022
Priority date	Nov 12, 2018
Publication date	Mar 12, 2024
Grant date	Mar 12, 2024

Abstract

Catalyst compositions and processes for the oligomerization of ethylene to 1-octene are described. The catalyst composition includes a triamino bisphospino (NPNPN) ligand system with specific phosphorous and nitrogen ligands. The terminal nitrogen atoms include linear alkyl hydrocarbons that differ in the number of carbon atoms by 3.

First claim

The invention claimed is:

1. A catalyst composition for the oligomerization of ethylene to 1-octene, the catalyst composition comprising:
a chromium (III) species; and
a ligand having the formula of:

wherein Ar 1 and Ar 2 are independently a substituted or unsubstituted C 6 -C 11 aryl, n is 0 or 1, and m=n+3.

2. The catalyst composition of claim 1 , wherein one or both of Ar 1 and Ar 2 is selected from the group consisting of a phenyl group, a substituted phenyl group, a fused aromatic ring, and a substituted fused aromatic ring.

3. The catalyst composition of claim 2 , wherein one or both of Ar 1 and Ar 2 is a substituted phenyl group comprising one or more substituents selected from the group consisting of linear or branched alkyl groups, halogen, hydroxyl, alkoxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, nitro, amide, nitrile, acyl, alkyl silane, thiol, and thioether substituents.

4. The catalyst composition of claim 1 , wherein one or both of Ar 1 and Ar is an alkyl-substituted phenyl group comprising one or more alkyl group substituents.

5. The catalyst composition of claim 4 , wherein the alkyl group substituents are linear or branched C 1 to C 4 alkyl.

6. The catalyst composition of claim 1 , wherein one or both of Ar 1 and Ar 2 is a fused —C 10 H 7 ring.

7. The catalyst composition of claim 2 , wherein the ligand has the structure of:

wherein R 1 and R 2 represent alkyl groups.

8. The catalyst composition of claim 7 , wherein R 1 and R 2 are independently-selected linear or branched C 1 to C 5 alkyl groups.

9. The catalyst composition of claim 1 , wherein the ligand has the structure of:

wherein R 1 and R 2 represent alkyl groups.

10. The catalyst composition of claim 6 , wherein R 1 and R 2 are independently-selected linear or branched C 1 to C 5 alkyl groups.

11. The catalyst composition of claim 1 , wherein the composition further comprises an activator or co-catalyst.

12. The catalyst composition of claim 11 , wherein the activator or co-catalyst is a methylaluminoxane compound.

13. The catalyst composition of claim 1 , wherein the chromium (III) species is chromium (III) acetylacetonate, Cr(2,2,6,6,-tetramethyl-3,5-heptadionate) 3 , chromium(III)2-ethylhexanoate, chromium trichloride tris-tetrahydrofuran, chromium (III) octanoate, or chromium (III) naphthenate.

14. The catalyst composition of claim 1 , wherein the chromium (III) species is chromium (III) acetylacetonate, and the composition further comprises an activator or co-catalyst, wherein the activator or co-catalyst is MMAO-3A.

15. A process to produce 1-octene from ethylene, the process comprising contacting a reactant comprising an olefin source with a solution comprising the catalyst composition of claim 1 to produce an oligomer composition comprising 1-octene.

16. The process of claim 15 , wherein the solution comprises a solvent, wherein the solvent is a saturated hydrocarbon or an aromatic hydrocarbon.

17. The process of claim 16 , wherein the solvent is n-hexane, n-heptane, methylcyclohexane, toluene, or a mixture thereof.

18. The process of claim 15 , wherein the product further comprises 1-hexene, and a selectivity for 1-octene is greater than 60 wt. % and a weight ratio of 1-hexene to 1-octene is less than 0.3.

19. The process of claim 15 , wherein solvent insoluble material is produced at less than 2 wt. %.

20. The process of claim 15 , wherein the catalyst composition comprises:

wherein R 1 and R 2 represent alkyl groups.

21. The process of claim 15 , wherein the chromium (III) species is chromium (III) acetylacetonate, and the catalyst composition further comprises an activator or co-catalyst, wherein the activator or co-catalyst is MMAO-3A.

22. The process of claim 15 , wherein the contacting occurs at a temperature of 15° C. to 100° C. and/or a pressure of 2 MPa to 20 MPa.
wherein R 1 and R 2 represent alkyl groups.

Assignees

• Sabic Global Technologies Bv

Inventors

• Al-Nezari Abdulaziz
• Korobkov Ilia
• Albahily Khalid

Classifications

• B01J31/189 Primary

  containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand · CPC title

• B01J31/143 Primary

  of aluminium · CPC title

• B01J2231/20

  Olefin oligomerisation or telomerisation · CPC title

• B01J2531/62

  Chromium · CPC title

• B01J31/187

  Amide derivatives thereof · CPC title