Catalyst composition and process for di-, tri- and/or tetramerization of ethylene

Patent metadata

Field	Value
Publication number	US-9555404-B2
Application number	US-201314135674-A
Country	US
Kind code	B2
Filing date	Dec 20, 2013
Priority date	Jul 11, 2007
Publication date	Jan 31, 2017
Grant date	Jan 31, 2017

Abstract

A catalyst composition and a process for di-, tri- and/or tetramerization of ethylene, wherein the catalyst composition comprises a chromium compound, a ligand of the general structure R 1 R 2 P—N(R 3 )—P(R 4 )—N(R 5 )—PR 6 R 7 , or any cyclic derivatives thereof, wherein at least one of the P or N atoms of the PNPNP-unit is member of a ring system, the ring system being formed from one or more constituent compounds of the ligand by substitution, and a co-catalyst or activator.

First claim

The invention claimed is:

1. A catalyst composition comprising:
(a) a chromium compound;
(b) a ligand of the general structure R 1 R 2 P—N(R 3 )—P(R 4 )—N(R 5 )—PR 6 R 7
wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from halogen, amino, trimethylsilyl, C 1 -C 10 -alkyl, phenyl, benzyl, tolyl and xylyl; and
(c) an activator or co-catalyst;
wherein the concentration of the chromium compound is from 0.1 to 10 mmol/l;
wherein the chromium compound is CrCl 3 (THF) 3 , Cr(III)acetylacetonate, Cr(III)octanoate, chromium hexacarbonyl, Cr(III)-2-ethylhexanoate or (benzene)tricarbonyl-chromium.

2. The catalyst composition according to claim 1 , wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are selected from chloro, amino, methyl, ethyl, isopropyl, and tert-butyl.

3. The catalyst composition according to claim 1 , wherein the activator or co-catalyst is selected from trimethylaluminum, triethylaluminum, tri-isopropylaluminum, tri-isobutylaluminum, ethylaluminumsesquichloride, diethylaluminum chloride, ethylaluminumdichloride, methylaluminoxane (MAO) or mixtures thereof.

4. The catalyst composition according to claim 1 , further comprising a solvent, wherein the solvent is an aromatic hydrocarbon, a straight-chain aliphatic hydrocarbon, a cyclic aliphatic hydrocarbon, a straight-chain olefin, an ether, or mixtures thereof.

5. The catalyst composition according to claim 4 , wherein the solvent is selected from toluene, benzene, ethylbenzene, cumene, xylene, mesitylene, hexane, octane, cyclohexane, methylcyclohexane, hexene, heptene, octene, diethylether, tetrahydrofuran or mixtures thereof.

6. The catalyst composition according to claim 1 , wherein the ligand/Cr ratio is 0.8 to 2.0.

7. The catalyst composition according to claim 3 , wherein the Al/Cr ratio is from 10:1 to 200:1.

8. A catalyst composition; obtained by combining at least;
(a) a chromium compound;
(b) a ligand of the general structure
R 1 R 2 P—N(R 3 )—P(R 4 )—N(R 5 )—PR 6 R 7 ,

wherein R 1 , R 2 , R 3 , R 4 , R5, R 6 and R 7 are independently selected from halogen, amino, trimethylsilyl, C 1 -C 10 -alkyl, phenyl, benzyl, tolyl and xylyl; and
(c) an activator or co-catalyst;
wherein the concentration of the chromium compound is from 0.1 to 10 mmol/l;
wherein the chromium compound is CrCl 3 (THF) 3 , Cr(III)acetylacetonate, Cr(III)octanoate, chromium hexacarbonyl, Cr(III)-2-ethylhexanoate or (benzene)tricarbonyl-chromium.

9. A process for di-, tri- or tetramerization of ethylene, comprising contacting ethylene with the catalyst composition of claim 1 under ethylene oligomerization conditions.

10. The process according to claim 9 , wherein said contacting is carried out at a pressure of 10 to 50 bar.

11. The process according to claim 9 , wherein said contacting is carried out at a temperature of from 20° C. to 100° C.

12. The process according to claim 9 , wherein the process is carried out continuously with a mean residence time of from 1 to 4 hours.

13. The process according to claim 9 comprising subjecting the catalyst to a gas phase of ethylene.

14. The process according to claim 9 , wherein said contacting is carried out in a reactor.

Assignees

• Saudi Basic Ind Corp
• Linde Ag

Inventors

• Fritz Peter M
• Bölt Heinz
• Wöhl Anina
• Müller Wolfgang
• Winkler Florian
• Wellenhofer Anton
• Rosenthal Uwe
• Müller Bernd H
• Hapke Marko
• Peulecke Normen
• Al-Hazmi Mohammed Hassan
• Aliyev Vugar O
• Mosa Fuad Mohammed

Classifications

• C07C2/32

  as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)} · CPC title

• B01J2531/62

  Chromium · CPC title

• C07F9/224

  Phosphorus triamides · CPC title

• C07F9/65848

  Cyclic amide derivatives of acids of phosphorus, in which two nitrogen atoms belong to the ring · CPC title

• C07F9/4883

  Amides or esteramides thereof, e.g. RP(NR'2)2 or RP(XR')(NR''2) (X = O, S) · CPC title