IP Library Granted Patent US 7,674,867
Granted Patent B2
US 7,674,867 · App. 10/566,839 · Granted Mar 9, 2010

Process for the preparation of an metal-organic compound comprising at least one imine ligand

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Quick Facts
Patent No.
US 7,674,867
App. No.
10/566,839
Granted
Mar 9, 2010
Kind
B2
Abstract

The invention relates to a process for the preparation of a metal-organic compound, comprising at least one phosphinimine ligand, characterized in that the HA adduct of a phosphinimine ligand according to formula (1) is contacted with a metal-organic reagent of formula (2) in the presence of 1, respectively 2 equivalents of a base, wherein HA represents an acid, of which H represents its proton and A its conjugate base, with Y═N—H as formula (1), and M v (L 1 ) k (L 2 ) l (L 3 ) m (L 4 ) n X as formula (2), and wherein Y is a substituted phosphorous atom, and M represents a group 4 or group 5 metal ion, V represents the valency of the metal ion, being 3, 4 or 5 L 1 , L 2 , L 3 , and L 4 represent a ligand or a group 17 halogen atom on M and may be equal or different, k, l, m, n=0, 1, 2, 3, 4 with k+l+m+n+1=V, and X represents a group 17 halogen atom. The invention further relates to a process for the preparation of a polyolefin by making a metal-organic compound according to the process of the invention, wherein the base is an olefin polymerization compatible base, which metal-organic compound is activated anywhere in, or before a polymerization reactor.

Claims (32)

1. A one step process for the preparation of a metal-organic compound, wherein at least one imine ligand compound according to formula 1 or the HA adduct thereof, wherein HA represents an acid, of which H represents its proton and A its conjugate base, is contacted with a metal-organic regent of formula 2 in the presence of 1 or 2 equivalents of a base respectively, with

Y═N—R  as formula 1,

wherein Y is selected from a substituted carbon, nitrogen, or phosphorous atom and R represents a substituent, and with

M v (L 1 ) k (L 2 ) l (L 3 ) m (L 4 ) n X  as formula 2,

wherein: M represents a group 4 or group 5 metal ion

V represents the valency of the metal ion, being 3, 4 or 5

L1, L2, L3, and L4 represent a ligand or a group 17 halogen atom on M and may be equal or different, at least one of the ligands L is chosen from cyclopentadienyl, C1-C20 hydrocarbyl, substituted cyclopentadienyls, indenyl, C1-C20 hydrocarbyl substituted indenyls, and halogen substituted C1-C20 hydrocarbyi substituted indenyls

X represents a group 17-halogen atom,

k, l, m, n=0, 1, 2, 3, 4 with k+l+m+n+1=V.

2. A process according to claim 1 wherein R represents a hydrogen atom and wherein Y is selected from the group consisting of

i) a phosphorus substituent defined by the formula:

wherein each R1 j, with j =1-3 is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, an amido radical, a C1-20 hydrocarbyl radical unsubstituted or substituted by a halogen atom, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, an amido radical, a silyl radical of the formula:

and a germanyl radical of the formula:

wherein R2j is independently selected from the group consisting of hydrogen, a C1-8 alkyl , a alkoxy radical, a C6-10 aryl and aryloxy radicals,

each substituent R1j or R2j may be linked with another R1 or R2 to form a ring system,

ii) a substituent defined by formula 6:

wherein each of Sub1 and Sub2 is independently selected from the group consisting of hydrocarbyl radicals having from 1 to 30 carbon atoms; silyl radicals, amido radicals, substituted amido radicals, phosphido radicals, and substituted phosphido radicals; and

wherein Sub1 and Sub2 may be linked with each other to form a ring system.

3. A process according to claim 1 , wherein the base is a dialkylamine, a trialkylamine, a monoarylamine, diarylamine or a triarylamine.

4. A process according to claim 1 , wherein the base is triethylamine, pyridine, tripropylamine, tributylamine, 1,4-diaza-bicyclo [2.2. 2]octane, pyrrolidine or piperidine.

5. A process according to claim 1 , wherein the base is a carboxylate, a fluoride, a hydroxide, a cyanide, an amide, a carbonate of Li, Na, K, Rb, Cs, or an ammonium salt or a group 2 metal salt of Mg, Ca, or Ba thereof, an alkali metal phosphate, or phosphate ester, or their alkoxides or phenoxides, thallium hydroxide, alkylammonium hydroxides or fluorides, or alkali metals, hydrides or carbonates of Li, Na, K, Rb, Cs or group 2 hydrides.

6. A process according to claim 5 , wherein the alkali metal is chosen from Li, Na, or K.

7. A process according to claim 1 , wherein the base is a group 1, 2, 12, 13 hydrocarbanion.

8. A process according to claim 7 , wherein the base is an organomagnesium- or an organolithium compound.

9. A process according to claim 1 wherein the reaction is carried out in an aprotic solvent.

10. A process according to claim 9 , wherein the solvent is the base.

11. Process for the preparation of a polyolefin by making a metal-organic compound according to the process of claim 1 , wherein the base is an olefin polymerisation compatible base, which metal-organic compound is activated anywhere in, or before a polymerisation reactor.

12. Process according to any of claims 11 , wherein the metal-organic compound is formed used without purification.

13. Process according to claim 11 , wherein the metal-organic compound is formed in the polymerisation equipment.

14. Process according to claim 13 , wherein said process is performed in the presence of between 5 and 10 equivalents of the imine ligand compound according to formula 1.

15. A process according to claim 1 , wherein said C1-C20 hydrocarbyl contains hetero- or group 17 halogen atoms.

16. A process according to claim 5 , wherein said an alkali metal phosphate is selected from the group consisting of Li, Na, K, Rb, and Cs.

Assignments (5)
CHANGE OF NAME Recorded Sep 7, 2016
From: LANXESS ELASTOMERS B.V.
To: ARLANXEO NETHERLANDS B.V.
Reel/Frame 039752/0894 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 31, 2012
From: LANXESS BUNA GMBH
To: LANXESS ELASTOMERS B.V.
Reel/Frame 028882/0001 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 30, 2012
From: DSM IP ASSETS B.V.
To: LANXESS BUNA GMBH
Reel/Frame 028875/0867 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 7, 2007
From: IJPEIJ, EDWIN; ARTS, HENRICUS; VAN DOREMAELE, GERARDUS; BEIJER, FELIX; BURGT VAN DER, FRANCIS; ZUIDEVELD, MARTIN ALEXANDER
To: DSM IP ASSETS B.V.
Reel/Frame 018924/0986 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 3, 2006
From: IJPEIJ, EDWIN GERARD; ARTS, HENRICUS JOHANNES; DOREMAELE, GERARDUS HENRICUS JOSEPHUS; BEIJER, FELIX HUGO
To: DSM IP ASSETS B.V.
Reel/Frame 018093/0502 →