Nickel-based complex and use thereof in a method for the oligomerisation of olefins

Patent metadata

Field	Value
Publication number	US-9586982-B2
Application number	US-201414901394-A
Country	US
Kind code	B2
Filing date	Jun 26, 2014
Priority date	Jun 28, 2013
Publication date	Mar 7, 2017
Grant date	Mar 7, 2017

Abstract

The invention describes a novel dissymmetric nickel-based complex and the method of preparation thereof from at least one diphosphinamine ligand B1 of formula (R 1 )(R′ 1 )P—N(R 3 )—P(R 2 )(R′ 2 ), or an iminobisphosphine ligand B2 of formula (R 3 )N═P(R 1 )(R′ 1 )—P(R 2 )(R′ 2 ). The invention also concerns the use of said complex in a method for oligomerisation of olefins.

First claim

The invention claimed is:

1. A dissymmetric nickel complex of formula (I):

in which
the groups R 1 and R′ 1 , which may be identical or different, and may or may not be linked, are each selected from non-aromatic groups that do not contain silicon,
the groups R 2 and R′ 2 , which may be identical or different, and may or may not be linked, are each selected from aromatic groups,
R 3 is selected from hydrogen,
halogens,
aliphatic hydrocarbon groups which are cyclical or acyclical and which optionally contain heteroelements, and
aromatic groups which optionally contain heteroelements, and which are unsubstituted or substituted,

X is an anion or an electron donor selected from hydrogen,
halogens,
aliphatic hydrocarbon groups which are cyclical or acyclical, which optionally contain heteroelements, and are unsubstituted or substituted,
aromatic groups which optionally contain heteroelements, which are unsubstituted or substituted,
olefins which optionally contain heteroelements and which are unsubstituted or substituted,
borates, phosphates, sulphates, phosphorous ligands which optionally contain heteroelements, and which are unsubstituted or substituted, and
—OR 4 or —N(R 5 )(R 6 ) where R 4 , R 5 and R 6 are each selected from cyclical aliphatic hydrocarbons groups which optionally contain heteroelements, and aromatic groups which optionally contain heteroelements, and which are unsubstituted or substituted,
wherein if a plurality of X groups are present these X groups may or may not be linked,

a is a whole number between 1 and 4,
b is a whole number between 0 and 6, and
c is a whole number between 1 and 4.

2. A complex according to claim 1 , wherein R 1 and R′ 1 are each selected from methyl, ethyl, isopropyl, n-butyl, iso-butyl, tert-butyl, pentyl, and cyclohexyl groups that are substituted or unsubstituted.

3. A complex according to claim 1 , wherein R 2 and R′ 2 are each selected from phenyl, o-tolyl, m-tolyl, p-tolyl, 3,5-dimethylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 3,5-bis(trifluoromethyl)phenyl, benzyl, naphthyl and pyridyl, which in each case are unsubstituted or substituted and optionally contain heteroelements.

4. A method of preparing a complex according claim 1 , comprising:
bringing into contact a nickel precursor A and at least one diphosphinamine ligand B1 of formula (R 1 )(R′ 1 )P—N(R 3 )—P(R 2 )(R′ 2 ) or at least one iminobisphosphine ligand B2 of formula (R 3 )N═P(R 2 )(R′ 2 ), optionally in the presence of a solvent,
wherein R 1 , R′ 1 , R 2 , R′ 2 and R 3 are as defined in claim 1 .

5. The method according to claim 4 , wherein the contacting is implemented at a temperature of between −80° C. and +110° C., for a time period of between 1 minute and 24 hours.

6. The method according to claim 4 in which the nickel precursor A is selected from nickel (II) chloride, nickel(II)(dimethoxyethane) chloride, nickel(II) bromide, nickel(II)(dimethoxyethane) bromide, nickel(II) fluoride, nickel(II) iodide, nickel(II) sulphate, nickel(II) carbonate, nickel(II) dimethylglyoxime, nickel(II) hydroxide, nickel(II) hydroxyacetate, nickel(II) oxalate, nickel(II) carboxylates, nickel(II) phenates, nickel(II) acetate, nickel(II) trifluoroacetate, nickel(II) triflate, nickel(II) acetylacetonate, nickel(II) hexafluoroacetylacetonate, nickel(0) bis(cycloocta-1,5-diene), nickel(0) bis(cycloocta-1,3-diene), nickel(0) bis(cyclooctatetraene), nickel(0) bis(cycloocta-1,3,7-triene), bis(o-tolylphosphito) nickel(0)(ethylene), nickel(0) tetrakis(triphenylphosphite), nickel(0) tetrakis(triphenylphosphine), nickel (0) bis(ethylene), π-allylnickel(II) chloride, π-allylnickel(II) bromide, methallylnickel(II) chloride dimer, η 3 -allylnickel(II) hexafluorophosphate, η 3 -methallylnickel(II) hexafluorophosphate, and nickel(II) (1,5-cyclooctadiene) in their hydrated or non-hydrated form, used alone or as a mixture, and wherein said nickel precursors are optionally complexed with Lewis bases.

7. A method for oligomerization of olefins comprising bringing said olefins into contact with a complex according to claim 1 , and optionally in the presence of a solvent.

8. The method according to claim 7 , wherein said complex is used in a mixture with a compound C selected from tris(hydrocarbyl)aluminium compounds, chlorine-containing or bromine-containing hydrocarbylaluminium compounds, aluminoxanes, organo-boron compounds, and organic compounds which are susceptible of donating or accepting a proton, used alone or as a mixture.

9. The method according to claim 7 , wherein said olefins are selected from ethylene, propylene, n-butenes, and n-pentenes, used alone or in a mixture, pure or diluted.

10. The method according to claim 7 , wherein nickel is present in a concentration of between 1×10 −8 and 1 mol/l.

11. The method according to claim 7 , wherein oligomerization is performed at a total pressure in the range between atmospheric pressure and 20 MPa, and at a temperature in the range −40° C. to +250° C.

12. The method according to claim 7 , wherein said oligomerization is a dimerization reaction.

13. The method according to claim 12 , wherein the reaction is an ethylene or propylene dimerization reaction.

14. A complex according to claim 1 , wherein R 3 is selected from hydrogen, and alkoxy, aryloxy, sulphur, sulfonamine, sulfonamide, nitro, carbonyl, amino and amido groups which optionally contain heteroelements and which are unsubstituted or substituted.

15. A complex according to claim 1 , wherein
R 1 and R′ 1 are each selected from methyl, ethyl, isopropyl, n-butyl, iso-butyl, tert-butyl, pentyl, and cyclohexyl groups,
R 2 and R′ 2 are each selected from phenyl, o-tolyl, m-tolyl, p-tolyl, 3,5-dimethylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 3,5-bis(trifluoromethyl)phenyl, benzyl, naphthyl and pyridyl,
R 3 is hydrogen, alkoxy, aryloxy, sulphur, sulfonamine, sulfonamide, nitro, carbonyl, amino or amido, and
X in each case is a halogen.

16. A complex according to claim 1 , wherein said complex is of the following formula:

17. A complex according to claim 1 , wherein said complex is of the following formula:

18. The method according to claim 7 , wherein said olefins have 2-20 carbon atoms.

19. The method according to claim 8 , wherein compound C is selected from ethylaluminium sesquichloride, methylaluminium dichloride, ethylaluminium dichloride, isobutylaluminium dichloride, diethylaluminium chloride, trimethylaluminium, tributylaluminium, tri-n-octylaluminium, triethylaluminium, methylaluminoxane, and ethylaluminoxane.

20. The method according to claim 8 , wherein compound C is dichloroethylaluminium or methylaluminoxane (MAO).

21. A complex according to claim 2 , wherein R 2 and R′ 2 are each selected from phenyl, o-tolyl, m-tolyl, p-tolyl, 3,5-dimethylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-ditert-butyl-4-methoxyphenyl, 3,5-bis(trifluoromethyl)phenyl, benzyl, naphthyl and pyridyl, which in each case are unsubstituted or substituted a

Assignees

• Ifp Energies Now
• Univ Amsterdam

Inventors

• Breuil Pierre-Alain
• Boulens Pierre
• Reek Joost
• Olivier-Bourbigou Helene

Classifications

• C07C2531/14

  of aluminium or boron · CPC title

• C07F15/045 Primary

  without a metal-carbon linkage · CPC title

• C07C2531/24

  Phosphines · CPC title

• B01J31/00

  Catalysts comprising hydrides, coordination complexes or organic compounds (catalyst compositions used only in polymerisation reactions C08 {; catalytic antibodies C12N9/0002}) · CPC title

• B01J31/188

  Amide derivatives thereof · CPC title