Catalyst composition and process for oligomerization of ethylene

Patent metadata

Field	Value
Publication number	US-2016167033-A1
Application number	US-201414908026-A
Country	US
Kind code	A1
Filing date	Jul 28, 2014
Priority date	Jul 29, 2013
Publication date	Jun 16, 2016
Grant date	—

Abstract

A catalyst composition including: (a) a chromium compound; (b) a ligand of the general structure
(A) R 1 R 2 P—N(R 3 )—P(R 4 )—NR 5 R 6 or (B) R 1 R 2 P—N(R 3 )—P(XR 7 )R 8 or R 1 R 2 P—N(R 3 )—P(XR 7 ) 2 , with X=O or S,

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently C 1 -C 10 -alkyl, C 6 -C 20 -aryl, C 3 -C 10 -cycloalkyl, aralkyl, alkylaryl, or trialkylsilyl, or any cyclic derivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNP-unit is a member of the ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitution; and (c) an activator or co-catalyst; and a process for tri- and/or tetramerization.

First claim

What is claimed is:

1 . A catalyst composition comprising:
(a) a chromium compound; (b) a ligand of the general structure
(A) R 1 R 2 P—N(R 3 )—P(R 4 )—NR 5 R 6 or
(B) R 1 R 2 P—N(R 3 )—P(XR 7 )R 8 or R 1 R 2 P—N(R 3 )—P(XR 7 ) 2 , with X=O or S,

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently C 1 -C 10 -alkyl, C 6 -C 20 -aryl, C 3 -C 10 -cycloalkyl, aralkyl, alkylaryl, or trialkylsilyl, or any cyclic derivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNP-unit is a member of the ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitution; and
(c) an activator or co-catalyst.

2 . The catalyst composition according to claim 1 , wherein the chromium compound is an organic salt, an inorganic salt, a coordination complex, an organometallic complexes of Cr(II), or Cr(III), or a combination comprising at least one of the foregoing.

3 . The catalyst composition according to claim 2 , wherein the chromium compound is CrCl 3 (THF) 3 , Cr(III)acetylacetonate, Cr(III)octanoate, chromium hexacarbonyl, Cr(III)-2-ethylhexanoate, (benzene)tricarbonyl-chromium, or a combination comprising at least one of the foregoing.

4 . The catalyst composition according to claim 1 , wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, benzyl, tolyl, or xylyl.

5 . The catalyst composition according to claim 1 , wherein the activator or co-catalyst is trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, ethylaluminumsesquichloride, diethylaluminum chloride, ethylaluminumdichloride, methylaluminoxane (MAO), modified methylaminoxane (MMAO), or a combination comprising at least one of the foregoing.

6 . The catalyst composition according to claim 1 , wherein the ligand is Ph 2 P—N(i-Pr)—P(Ph)-N(i-Pr)Ph, Ph 2 P—N(i-Pr)—P(Ph)-N(Me)C 6 H 6 , Ph 2 P—N(i-Pr)—P(Ph)S(i-Pr), Ph 2 P—N(i-Pr)—P(Ph)OC 2 H 5 , Ph 2 P—N(i-Pr)P(Ph)OCH 3 , or a combination comprising at least one of the foregoing.

7 . The catalyst composition according to claim 1 , additionally comprising a solvent, wherein the solvent is one of aromatic hydrocarbons, straight-chain aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, straight-chain olefins, ethers, toluene, benzene, ethylbenzene, cumene, xylenes, mesitylene, hexane, octane, cyclohexane, methylcyclohexane, hexene, heptene, octene, diethylether, tetrahydrofuran, chlorobenzene, or a combination comprising at least one of the foregoing.

8 . The catalyst composition according to claim 7 , wherein the concentration of the chromium compound is from 0.01 to 100 mmol/l.

9 . The catalyst composition according to claim 1 , wherein the ligand/Cr molar ratio is from 0.5 to 50.

10 . The catalyst composition according to claim 5 , wherein the Al/Cr molar ratio is from 1:1 to 1000:1.

11 . A catalyst composition, obtainable by combining at least:
(a) a chromium compound; (b) a ligand of the general structure
(A) R 1 R 2 P—N(R 3 )—P(R 4 )—NR 5 R 6 or
(B) R 1 R 2 P—N(R 3 )—P(XR 7 )R 8 or R 1 R 2 P—N(R 3 )—P(XR 7 ) 2 ,

wherein
X=O or S, and
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently C 1 -C 10 -alkyl, C 6 -C 20 -aryl, C 3 -C 10 -cycloalkyl, aralkyl, alkylaryl, or trialkylsilyl, or any cyclic derivatives of (A) and (B), wherein at least one of the P or N atoms of the PNPN-unit or PNP-unit is a member of the ring system, the ring system being formed from one or more constituent compounds of structures (A) or (B) by substitution; and
(c) an activator or co-catalyst.

12 . A process for tri- and/or tetramerization of ethylene, comprising subjecting the catalyst composition according to claim 1 to a gas phase of ethylene in a reactor and conducting an oligomerization.

13 . The process according to claim 12 , wherein the oligomerization is carried out at a pressure of 1 to 200 bar.

14 . The process according to claim 13 , wherein the oligomerization is carried out at a temperature of from 10 to 200° C.

15 . The process according to claim 14 , wherein the mean residence time is from 10 minutes to 20 hours.

16 . The process according to claim 13 , wherein the pressure is 10 to 50 bar.

17 . The process according to claim 14 , wherein the temperature is from 20 to 100° C.

18 . The process according to claim 15 , wherein the mean residence time is from 1 to 4 hours.

Assignees

• Saudi Basic Ind Corp
• Linde Agk
• Linde Ag

Inventors

• Woehl Anina
• Meiswinkle Andreas
• Boelt Heinz
• Mueller Bernd H
• Mueller Wolfgang
• Peulecke Normen
• Rosenthal Uwe
• Harff Marco
• Al-Hazmi Mohammed H
• Al-Qahtani Abdullah

Classifications

• B01J2231/20

  Olefin oligomerisation or telomerisation · CPC title

• B01J31/1885 Primary

  Ligands comprising two different formal oxidation states of phosphorus in one at least bidentate ligand, e.g. phosphite/phosphinite · CPC title

• C07C2531/22

  Organic complexes · CPC title

• C07C2/32

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

• B01J2531/62

  Chromium · CPC title