Process for oligomerization of olefins that uses a catalytic composition that comprises an organometallic complex that contains a phenoxy ligand that is functionalized by a heteroatom

Patent metadata

Field	Value
Publication number	US-9260358-B2
Application number	US-59988208-A
Country	US
Kind code	B2
Filing date	Apr 14, 2008
Priority date	May 14, 2007
Publication date	Feb 16, 2016
Grant date	Feb 16, 2016

Abstract

The invention describes a process for oligomerization of the olefins into compounds or into a mixture of compounds of general formula CpH2p with 4≦p≦80 that implements a catalytic composition that comprises at least one organometallic complex of an element of group IV that is selected from among titanium, zirconium, or hafnium, whereby said organometallic complex contains at least one aryloxy-type (or phenyloxy-type) ligand that is functionalized by a heteroatom that is selected from among nitrogen, oxygen, phosphorus or sulfur or by an aromatic group.

First claim

The invention claimed is:

1. A process comprising catalytically oligomerizing olefins into compounds or into a mixture of compounds of formula C p H 2p with 4≦p≦80, the catalyst being a catalytic composition comprising at least one organometallic complex of an element of group IV, which is titanium, zirconium or hafnium, wherein said organometallic complex contains at least one aryloxy ligand functionalized by a heteroatom, which is nitrogen, oxygen, phosphorus or sulfur or by an aromatic group, said organometallic complex having the following formula:
[M(OAr) n Y (4-n) ]
wherein:
M is an element from group IV, which is titanium, zirconium, or hafnium,
Y is an atom of chlorine, or bromine, or a hydrocarbyl radical that comprises 1 to 30 carbon atoms, or a radical, which is alkoxy R′O—, amido R′ 2 N—, or carboxylate R′COO—, where R′ is a hydrocarbyl radical comprising 1 to 30 carbon atoms,
n is an integer of 1 to 4,
the ligand —OAr is an aryloxy ligand of the formula:

in which:
R 2 , R 3 , R 4 and R 5 , identical or different, represent a hydrogen atom, a halogen, or a hydrocarbyl radical that comprises 1 to 30 carbon atoms,
B is methoxy (—OMe), dimethylamino (—NMe 2 ), or pyrrolidino, and A is —CH 2 —, —C(CH 3 ) 2 — or —(CH 2 ) 2 —.

2. The process for oligomerization of olefins according to claim 1 , in which said catalytic composition further comprises a hydrocarbylaluminum activating agent, which is a tris(hydrocarbyl)aluminum compound or a chlorinated or brominated hydrocarbylaluminum compound or an aluminoxane.

3. The process for oligomerization of olefins according to claim 1 , in which said catalytic composition does not comprise external additives.

4. The process for oligomerization of olefins according to claim 1 , in which said spacer group A is —C(CH 3 ) 2 — or —(CH 2 ) 2 —.

5. The process for oligomerization of olefins according to claim 4 , in which B is or pyrrolidino.

6. The process for oligomerization of olefins according to claim 4 , in which B is methoxy (—OMe).

7. The process for oligomerization of olefins according to claim 1 , in which M is titanium.

8. The process for oligomerization of olefins according to claim 1 , in which M is zirconium.

9. The process for oligomerization of olefins according to claim 2 , wherein the olefins comprise at least one of ethylene, propylene, or butene.

10. The process for oligomerization of olefins according to claim 9 , in which the olefins comprise ethylene.

11. The process for oligomerization of olefins according to claim 10 , in which the process is dimerization of ethylene.

12. The process for oligomerization of olefins according to claim 11 , which is selective dimerization of ethylene into 1-butene.

13. The process for oligomerization of olefins according to claim 1 , which is carried out under a total pressure of 0.5 to 15 MPa, and at a temperature of 20 to 180° C.

14. The process for oligomerization of olefins according to claim 1 , which is implemented intermittently.

15. The process for oligomerization of olefins according to claim 1 , which is implemented continuously.

16. The process for oligomerization of olefins according to claim 2 , wherein said catalyst composition has a molar ratio between the activating agent and said organometallic complex of the element of group IV that is titanium, zirconium, or hafnium of between 1/1 and 1800/1.

17. The process for oligomerization of olefins according to claim 11 , in which M is titanium, the activating agent is triethylaluminum, with a molar ratio of activating agent to organometallic complex of between 1/1 and 5/1.

18. The process for oligomerization of olefins according to claim 2 , in which M is zirconium, ethyl aluminum sesquichloride is the activating agent, with a molar ratio of activating agent to organometallic complex of between 6/1 and 30/1.

19. The process for oligomerization of olefins according to claim 1 , in which p is between 4 and 50.

20. The process for oligomerization of olefins according to claim 19 , in which p is between 4 and 26.

21. The process for oligomerization of olefins according to claim 19 , in which p is between 4 and 14.

22. A process comprising catalytically oligomerizing olefins into compounds or into a mixture of compounds of formula C p H 2p with 4≦p≦80, the catalyst being a catalytic composition comprising at least one organometallic complex of an element of group IV, which is titanium, zirconium or hafnium, wherein said organometallic complex contains at least one aryloxy ligand functionalized by a heteroatom, which is nitrogen, oxygen, phosphorus or sulfur or by an aromatic group, said organometallic complex having the following formula:
[M(OAr) n Y (4-n) ]
wherein:
M is an element from group IV, which is titanium, zirconium, or hafnium,
Y is an atom of chlorine, or bromine, or a hydrocarbyl radical that comprises 1 to 30 carbon atoms, or a radical, which is alkoxy R′O—, amido R′ 2 N—, or carboxylate R′COO—, where R′ is a hydrocarbyl radical comprising 1 to 30 carbon atoms,
n is an integer of 1 to 4,
the ligand —OAr is an aryloxy ligand of one of the following groups

23. A process comprising catalytically oligomerizing olefins into compounds or into a mixture of compounds of formula C p H 2p with 4≦p≦80, the catalyst being a catalytic composition comprising at least one organometallic complex of an element of group IV, which is titanium, zirconium or hafnium, wherein said organometallic complex contains at least one aryloxy ligand functionalized by a heteroatom, which is nitrogen, oxygen, phosphorus or sulfur or by an aromatic group, said organometallic complex being one of the following compounds:

24. The process for oligomerization of olefins according to claim 4 , in which B is dimethylamino (—NMe 2 ).

Assignees

• Cazaux Jean-Benoit
• Magna Lionel
• Saussine Lucien
• IFP Energies Nouvelles

Inventors

• Cazaux Jean-Benoit
• Magna Lionel
• Saussine Lucien

Classifications

• B01J2231/20

  Olefin oligomerisation or telomerisation · CPC title

• B01J2531/0238

  Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P · CPC title

• B01J2523/47

  Titanium · CPC title

• B01J2523/48

  Zirconium · CPC title

• C07C2531/14

  of aluminium or boron · CPC title