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

Patent metadata

Field	Value
Publication number	US-9309167-B2
Application number	US-201313852403-A
Country	US
Kind code	B2
Filing date	Mar 28, 2013
Priority date	May 18, 2010
Publication date	Apr 12, 2016
Grant date	Apr 12, 2016

Abstract

The invention describes a process for oligomerization of olefins into compounds or into a mixture of compounds of general formula C p H 2p with 4≦p≦80 that employs a catalytic composition that comprises at least one organometallic complex of an element of group IV that is selected from titanium, zirconium, and hafnium, wherein the organometallic complex contains at least one alkoxy-type ligand that is functionalized by a heteroatom selected from nitrogen, oxygen, phosphorus and sulfur, or by an aromatic group.

First claim

The invention claimed is:

1. A process for oligomerization of olefins into compounds or into a mixture of compounds of the formula C p H 2p with 4≦p≦80, said process comprising:
oligomerizing an olefin feedstock in the presence of a catalytic composition comprising at least one organometallic complex of an element of group IV selected from titanium, zirconium, and hafnium, wherein said organometallic complex contains at least one alkoxy ligand functionalized by a heteroatom that is selected from nitrogen, oxygen, phosphorus, and sulfur or by an aromatic group, and said organometallic complex is of the following formula:
[M(OR) m Y (4-m) ]

in which:
M is an element from group IV selected from titanium, zirconium, and hafnium,
Y is an atom of chlorine or bromine, a hydrocarbyl radical having 1 to 30 carbon atoms, or a radical selected from alkoxy R′O—, amido R′ 2 N—, and carboxylate R′COO—, where R′is a hydrocarbyl radical having 1 to 30 carbon atoms,
m is an integer of 1 to 4, and
the ligand —OR is an organic compound selected from alkoxy ligands of the formula:
O—(CR 10 R 11 ) n —X-L

in which:
(CR 10 R 11 ) n is —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —(CH 2 ) 4 —, —(CH 2 ) 5 —, —C(CH 3 ) 2 —, —C(CH 3 ) 2 —CH 2 —, —C(CH 3 ) 2 —CH 2 —CH 2 —, —C(CF 3 ) 2 —, —C(CF 3 ) 2 —CH 2 — or —C(CF 3 ) 2 —CH 2 —CH 2 —,
R 10 and R 11 each represent a hydrogen atom, —CH 3 , or —CF 3
L is —PR 4 R 5 ,
X is a hydrocarbon group CR 7 R 8 , an oxygen atom, or a group that comprises —NR 9 ,
R 4 and R 5 are each an alkyl or aryl group that is substituted or unsubstituted,
R 7 , R 8 , and R 9 each represent a hydrogen atom or a hydrocarbon chain, that may or may not be cyclic, having 1 to 30 carbon atoms, and
n is an integer in the range of 1 to 5.

2. The process according to claim 1 , wherein said catalytic composition further comprises a hydrocarbyl aluminum activating agent selected from the group consisting of tris(hydrocarbyl)aluminum compounds, chlorinated or brominated hydrocarbyl aluminum compounds, and aluminoxanes.

3. The process according to claim 1 , wherein M is titanium or zirconium.

4. The process according to claim 1 , wherein Y is an alkoxy R′O—.

5. The process according to claim 1 , wherein p is between 4 and 14.

6. The process according to claim 1 , wherein the olefin feedstock is ethylene.

7. The process according to claim 3 , wherein M is zirconium.

8. The process composition according to claim 3 , wherein M is titanium.

9. The process according to claim 1 , in which said organometallic complex is [(L14) 2 Ti(OiPr) 2 ], [(L16) 2 Ti(OiPr) 2 ], or [(L16) 2 Ti(OnBu) 2 ], wherein L14 and L16 refer to ligands of formulas L14 and L16, respectively, wherein the ligands are represented in their protonated form

iPr stands for isopropyl, and
nBu stands for n-butyl.

10. The process according to claim 1 , wherein m is 2.

11. A process for dimerization of ethylene, said process comprising:
dimerizing ethylene in the presence of a catalytic composition comprising at least one organometallic complex of titanium or zirconium, wherein said organometallic complex contains at least one alkoxy ligand functionalized by a heteroatom that is selected from nitrogen, oxygen, phosphorus, and sulfur or by an aromatic group, and said organometallic complex is of the following formula:
[M(OR) m Y (4-m) ]

in which:
M is titanium or zirconium,
Y is an atom of chlorine or bromine, a hydrocarbyl radical having 1 to 30 carbon atoms, or a radical selected from alkoxy R′O—, amido R′ 2 N—, and carboxylate R′COO—, where R′ is a hydrocarbyl radical having 1 to 30 carbon atoms' is a hydrocarbyl radical having 1 to 30 carbon atoms,
m is an integer of 1 to 4, and
the ligand —OR is an organic compound selected from alkoxy ligands of the formula:
O—(CR 10 R 11 ) n —X-L

 in which:
(CR 10 R 11 ) n is —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —(CH 2 ) 4 —, —(CH 2 ) 5 —, —C(CH 3 ) 2 —, —C(CH 3 ) 2 —CH 2 —, —C(CH 3 ) 2 —CH 2 —CH 2 —, —C(CF 3 ) 2 —, —C(CF 3 ) 2 —CH 2 , or —C(CH 3 ) 2 —CH 2 —CH 2 —,
L is —PR 4 R 5 ,
X is a hydrocarbon group CR 7 R 8 , an oxygen atom, or a group that comprises —N R 9 ,
R 4 and R 5 are each an alkyl or aryl group that is substituted or unsubstituted,
R 7 , R 8 , and R 9 each represent a hydrogen atom or a hydrocarbon chain, that may or may not be cyclic, having 1 to 30 carbon atoms, and
n is an integer in the range of 1 to 5.

12. The process according to claim 11 , wherein said process is selective for dimerization of ethylene into 1-butene, wherein M is titanium.

13. The process of claim 11 , wherein M is titanium, said catalytic composition further comprises triethyl aluminum, and the molar ratio of triethyl aluminum to said organometallic complex is between 1 and 5.

14. The process of claim 11 , wherein M is zirconium, said catalytic composition further comprises ethyl aluminum sesquichloride, and the molar ratio of ethyl aluminum sesquichloride to said organometallic complex is between 6 and 30.

15. The process of claim 13 , in which O—(CR 10 R 11 ) n —X-L is a ligand of formula L14 or formula L16, wherein the ligands are represented in their protonated form:

Assignees

• IFP Energies Nouvelles

Inventors

• Grasset Fabien
• Harry Stephane
• Proriol David
• Magna Lionel

Classifications

• B01J2531/49

  Hafnium · CPC title

• C07C2531/24

  Phosphines · CPC title

• C07C2/36

  as phosphines, arsines, stilbines or bismuthines · CPC title

• B01J2531/46

  Titanium · CPC title

• B01J31/0212 Primary

  Alkoxylates · CPC title