WO1999050273A1 - Preparation of transition metal imine complexes - Google Patents

Preparation of transition metal imine complexes Download PDF

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Publication number
WO1999050273A1
WO1999050273A1 PCT/US1999/006818 US9906818W WO9950273A1 WO 1999050273 A1 WO1999050273 A1 WO 1999050273A1 US 9906818 W US9906818 W US 9906818W WO 9950273 A1 WO9950273 A1 WO 9950273A1
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recited
transition metal
compound
primary amine
imine
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PCT/US1999/006818
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French (fr)
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Steven Dale Ittel
Samuel David Arthur
Joel David Citron
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E.I. Du Pont De Nemours And Company
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Priority to IL13801699A priority Critical patent/IL138016A0/en
Priority to CA002324311A priority patent/CA2324311A1/en
Priority to BR9908408-2A priority patent/BR9908408A/en
Priority to AT99916184T priority patent/ATE225358T1/en
Priority to JP2000541176A priority patent/JP2002509935A/en
Priority to EP99916184A priority patent/EP1080097B1/en
Priority to DE69903285T priority patent/DE69903285T2/en
Priority to AU34552/99A priority patent/AU758417B2/en
Publication of WO1999050273A1 publication Critical patent/WO1999050273A1/en

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/06Cobalt compounds
    • C07F15/065Cobalt compounds without a metal-carbon linkage
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/006Palladium compounds
    • C07F15/0066Palladium compounds without a metal-carbon linkage
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/02Iron compounds
    • C07F15/025Iron compounds without a metal-carbon linkage
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/04Nickel compounds
    • C07F15/045Nickel compounds without a metal-carbon linkage
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02Ethene

Definitions

  • Imine complexes of certain transition metals such as iron, palladium, cobalt, nickel and others are important parts of catalyst systems for the polymerization of olefins, see for instance U.S. Patent 5,714,556, World Patent Applications 96/23010, 97/48737, 97/48735, 97/38024, and U.S. Patent Application 08/991372, filed Dec. 16, 1997 all of which are hereby included by reference.
  • These and other references generally describe the synthesis of these types of imine complexes as the reaction of the imine containing ligand with various types of transition metal compounds to form the transition metal imine complex.
  • These methods usually involve the use of substantially anhydrous conditions to avoid hydrolysis of the starting transition metal compound and/or any intermediates or the desired final complex.
  • the imines themselves are not commercially available, usually being made from the corresponding carbonyl compound, such as a ketone or aldehyde, and an amine, often an aromatic amine.
  • water is a byproduct. Since this imine forming reaction is usually considered to be an equilibrium, to drive the reaction to completion the water is often removed during the synthesis of the imine, for example by distillation, preferably azeotropic distillation, or by formation of a hydrate, preferably an inorganic hydrate.
  • imine complexes of transition metals are often made in two step processes, imine synthesis, and then synthesis of the metal complex. A simpler, especially one step, synthesis would be preferable if they used the same starting materials since they would usually be cheaper than a two step synthesis.
  • This invention concerns a process for the production of a transition metal complex of an imine, comprising, contacting under imine forming conditions in an aprotic solvent, a transition metal compound, a first organic compound containing at least one aldehyde or ketone group, and a second organic compound which is a primary amine to form said transition metal complex of said imine, and provided that said transition metal is nickel, palladium, iron and cobalt.
  • imines can be made by the reaction of a carbonyl group such as a ketone or aldehyde with a primary amine, the reaction being: -NH, NR 1 + H 2 0 (1)
  • (1) Since (1) is generally thought of as being an equilibrium reaction, it is usually driven to completion (formation of the imine) by removing the byproduct water that is formed. This can be done in a variety of ways, for instance removing the water by azeotropic distillation or as a hydrate of an inorganic salt.
  • removing the water by azeotropic distillation or as a hydrate of an inorganic salt In order to efficientlky utilize carbonyl compound and amine used in (1), they should preferably be present in the reaction in approximately the same ratio as they are in the product.
  • imine complexes [the imine (s) in the complex may contain one or more imine groups] of certain transition metals can be made in an aprotic solvent by addition of salts of those metals to a process in which reaction (1) is being carried out, even though water is generated as a byproduct.
  • reaction (1) is carried out in the presence of a suitable salt of the desired transition metal.
  • the ratio of transition metal salt to the other ingredients is not critical, but in order to efficiently utilize all of the ingredients the ratio of moles transition metal compound to moles of the other reactants is such that they are approximately the same as they are in final desired imine complex.
  • the transition metal compound is preferably present at the beginning of the process, but may be added at any time during the formation of the imine.
  • Useful transition metal compounds include metal halides, especially chlorides and bromides, and carboxylates. Zerovalent metal compounds that are not too sensitive to water may be used in conjunction with a suitable oxidizing agent (which are known in the art) . Preferred transition metal compounds are halides, especially chlorides and bromides.
  • Transition metals are those metals in Groups 3-12 (IUPAC notation) , and metals in Groups 3-11 are preferred ana metals in Groups 8-10 are especially preferred. Specific preferred transition metals are nickel, cobalt, iron and palladium, and nickel is especially preferred.
  • Preferred primary amines in the process are aryl amines, i.e., R is an aryl or substituted aryl group.
  • Aryl herein includes groups that have one or more aromatic rings which may be fused, as in naphthyl, or connected by a- covalent bond, as in 2-phenylphenyl (o-biphenylyl) . It is preferred that the aromatic rings of the aryl group are carbocyclic rings, and it is more preferred that R 1 is phenyl or substituted phenyl.
  • Useful substitutents on a substituted phenyl group are alkyl, especially alkyl containing 1 to 4 carbon atoms, halo, especially chloro, phenyl, and halo substituted alkyl, especially fluoro substituted alkyl. It is also preferred that the phenyl group be substituted in the 2, or 2 and 6, positions.
  • aprotic the solvent has no protons whose pKa is about 20 or more, more preferably about 25 or more.
  • Useful solvents include aromatic hydrocarbons such as benzene and toluene, xylene, chlorobenzene and o-dichlorobenzene . Since the transition metal complex may often be used in conjunction with other types of compounds (such as alkyl aluminum compounds) as a catalyst system for the polymerization of olefin, the absence of protic solvents is an advantage, since the solvent need not be removed before adding an alkyl aluminum compound.
  • the carbonyl compound may contain more than one carbonyl group which may form an imine.
  • Useful carbonyl compounds include ⁇ , ⁇ -diones, 2 , 6-pyridinedicarboxyaldehydes , 2 , 6-diacylpyridines , cyclic ⁇ , ⁇ -diones, 1,3-diones and ketoaldehydes .
  • Specific useful carbonyl compounds include glyoxal, 2, 3-butanedione, acenapthenequinone, 2, 6-diacetylpyridine, 2, 6-pyridinedicarboxaldehyde, 1, 2-cyclohexanedione, and pyruvaldehyde .
  • the transition metal imine complex after it is made, may be isolated, as by removing the solvent under vacuum or by crystallization, or the solution may be used directly (i.e., without isolation of the complex, but the solution may be filtered to remove any insoluble impurities) in a polymerization of one or more olefins.
  • Olefins which may be polymerized with various transition metal complexes of imines, and the conditions for polymerizations will be found in U.S. Patent 5,714,556, World Patent Applications 96/23010, 97/48737, 97/48735, 97/38024, and U.S. Patent
  • Nickel dibromide was purified of insoluble material by dissolving 2.22 g anhydrous nickel dibromide in 100 mL ethanol containing 1 mL water, filtering through diatomaceous earth and rotary evaporating dry. A mixture of 1.84 g (10.1 mmol) acenapthenequinone, 3.00 g (20.0 mmol) 2, 6-diethylaniline, 2.1 g (9.6 mmol) nickel dibromide and 50 mL toluene was refluxed under nitrogen with water removal for 24 h to give a deep red-black reaction mixture.
  • Example 2 A suspension of 2.0 mg (0.0030 mmol) (I) of Example 1 in 5 mL dry, deaerated toluene was mixed with 1.0 mL 1.7M modified methylaluminoxane in toluene
  • Example 4 A mixture of 20 mL dry, deaerated toluene and
  • the ethylene was vented and the solution was stirred with 25 mL 6N HCl and 20 mL additional toluene, and the toluene layer was separated, water-washed and rotary-evaporated to yield, after washing with methylene chloride and acetone and vacuum-oven drying (70°C) , 0.96 g of soft, tacky polyethylene .

Abstract

Transition metal imine complexes can be prepared by reacting the imine precursors, a carbonyl compound and a primary amine, in the presence of a selected transition metal compound. The complexes may be used as catalysts for olefin polymerization.

Description

TITLE PREPARATION OF TRANSITION METAL IMINE COMPLEXES FIELD OF THE INVENTION Preparation of imine complexes of certain transition metals from selected metal compounds and organic compounds which are precursors of imines in essentially a single step are described. The imine complexes are useful in the polymerization of olefins, and may be used directly without isolation. TECHNICAL BACKGROUND
Imine complexes of certain transition metals such as iron, palladium, cobalt, nickel and others are important parts of catalyst systems for the polymerization of olefins, see for instance U.S. Patent 5,714,556, World Patent Applications 96/23010, 97/48737, 97/48735, 97/38024, and U.S. Patent Application 08/991372, filed Dec. 16, 1997 all of which are hereby included by reference. These and other references generally describe the synthesis of these types of imine complexes as the reaction of the imine containing ligand with various types of transition metal compounds to form the transition metal imine complex. These methods usually involve the use of substantially anhydrous conditions to avoid hydrolysis of the starting transition metal compound and/or any intermediates or the desired final complex.
For the most part, the imines themselves are not commercially available, usually being made from the corresponding carbonyl compound, such as a ketone or aldehyde, and an amine, often an aromatic amine. When made by this method, water is a byproduct. Since this imine forming reaction is usually considered to be an equilibrium, to drive the reaction to completion the water is often removed during the synthesis of the imine, for example by distillation, preferably azeotropic distillation, or by formation of a hydrate, preferably an inorganic hydrate. Thus imine complexes of transition metals are often made in two step processes, imine synthesis, and then synthesis of the metal complex. A simpler, especially one step, synthesis would be preferable if they used the same starting materials since they would usually be cheaper than a two step synthesis.
Many complexes of imines and transition metals have been synthesized and reported in the literature. In addition to the above references, see for instance: H. torn Dieck et al . , Inorg. Chim. Acta, vol. 177, p. 191-197 (1990); R. van Asselt, et al . , J. Am. Chem. Soc, vol. 116, p. 977-985 (1994); H. torn Dieck, et al., Z. Naturforsch. B, vol. 33, p. 1381 et seq. (1978); H. G. von Schnering, et al., Chem. Ber., vol. 109, p. 1665 et seq. (1976); and H. torn Dieck et al . , Chem. Ber., vol. 109, p. 1657 et seq. (1976). R. van Asselt, et al . , Reel. Trav. Chim. Pays-Bas., vol. 113, p. 88-98 (1994) describes the synthesis of certain zinc and nickel α-diimine complexes from the diketone and aromatic amine. In many of the syntheses, (glacial) acetic acid is present .
SUMMARY OF THE INVENTION This invention concerns a process for the production of a transition metal complex of an imine, comprising, contacting under imine forming conditions in an aprotic solvent, a transition metal compound, a first organic compound containing at least one aldehyde or ketone group, and a second organic compound which is a primary amine to form said transition metal complex of said imine, and provided that said transition metal is nickel, palladium, iron and cobalt.
DETAILS OF THE INVENTION It is well known that imines can be made by the reaction of a carbonyl group such as a ketone or aldehyde with a primary amine, the reaction being: -NH, NR1 + H20 (1)
Figure imgf000005_0001
Since (1) is generally thought of as being an equilibrium reaction, it is usually driven to completion (formation of the imine) by removing the byproduct water that is formed. This can be done in a variety of ways, for instance removing the water by azeotropic distillation or as a hydrate of an inorganic salt. In order to efficientlky utilize carbonyl compound and amine used in (1), they should preferably be present in the reaction in approximately the same ratio as they are in the product.
It has suprisingly been found that imine complexes [the imine (s) in the complex may contain one or more imine groups] of certain transition metals can be made in an aprotic solvent by addition of salts of those metals to a process in which reaction (1) is being carried out, even though water is generated as a byproduct. Thus reaction (1) is carried out in the presence of a suitable salt of the desired transition metal. The ratio of transition metal salt to the other ingredients is not critical, but in order to efficiently utilize all of the ingredients the ratio of moles transition metal compound to moles of the other reactants is such that they are approximately the same as they are in final desired imine complex. The transition metal compound is preferably present at the beginning of the process, but may be added at any time during the formation of the imine.
Useful transition metal compounds include metal halides, especially chlorides and bromides, and carboxylates. Zerovalent metal compounds that are not too sensitive to water may be used in conjunction with a suitable oxidizing agent (which are known in the art) . Preferred transition metal compounds are halides, especially chlorides and bromides.
Any transition metal may be used. Transition metals are those metals in Groups 3-12 (IUPAC notation) , and metals in Groups 3-11 are preferred ana metals in Groups 8-10 are especially preferred. Specific preferred transition metals are nickel, cobalt, iron and palladium, and nickel is especially preferred.
Process conditions for forming imines are well known and will be found in the various references cited in the Technical Background section, and also in R. L. Reeves in S. Patai, Ed., The Chemistry of the Carbonyl Group, Interscience Publishers, London, 1966, p. 608-619, and J. K. Whitesell in B. M. Trost, et al . , Ed., Comprehensive Organic Synthesis, Vol. 6, Pergamon Press, Oxford, 1991, p. 719, which are both hereby included by reference. The present process is preferably performed at a temperature of about 0°C to about 250°C, more preferably about 20°C to about 130°C. While pressure is not critical, and the process will probably be most often be carried out at ambient pressure, higher or lower pressures (than atmospheric pressure) may be used, for example to control the process temperature while distilling off byproduct water.
Preferred primary amines in the process are aryl amines, i.e., R is an aryl or substituted aryl group. Aryl herein includes groups that have one or more aromatic rings which may be fused, as in naphthyl, or connected by a- covalent bond, as in 2-phenylphenyl (o-biphenylyl) . It is preferred that the aromatic rings of the aryl group are carbocyclic rings, and it is more preferred that R1 is phenyl or substituted phenyl. Useful substitutents on a substituted phenyl group are alkyl, especially alkyl containing 1 to 4 carbon atoms, halo, especially chloro, phenyl, and halo substituted alkyl, especially fluoro substituted alkyl. It is also preferred that the phenyl group be substituted in the 2, or 2 and 6, positions.
The reaction is conducted in an aprotic solvent. By aprotic is meant the solvent has no protons whose pKa is about 20 or more, more preferably about 25 or more. Useful solvents include aromatic hydrocarbons such as benzene and toluene, xylene, chlorobenzene and o-dichlorobenzene . Since the transition metal complex may often be used in conjunction with other types of compounds (such as alkyl aluminum compounds) as a catalyst system for the polymerization of olefin, the absence of protic solvents is an advantage, since the solvent need not be removed before adding an alkyl aluminum compound.
The carbonyl compound may contain more than one carbonyl group which may form an imine. Useful carbonyl compounds include α,β-diones, 2 , 6-pyridinedicarboxyaldehydes , 2 , 6-diacylpyridines , cyclic α,β-diones, 1,3-diones and ketoaldehydes .
Specific useful carbonyl compounds include glyoxal, 2, 3-butanedione, acenapthenequinone, 2, 6-diacetylpyridine, 2, 6-pyridinedicarboxaldehyde, 1, 2-cyclohexanedione, and pyruvaldehyde . The transition metal imine complex, after it is made, may be isolated, as by removing the solvent under vacuum or by crystallization, or the solution may be used directly (i.e., without isolation of the complex, but the solution may be filtered to remove any insoluble impurities) in a polymerization of one or more olefins. Olefins which may be polymerized with various transition metal complexes of imines, and the conditions for polymerizations will be found in U.S. Patent 5,714,556, World Patent Applications 96/23010, 97/48737, 97/48735, 97/38024, and U.S. Patent
Application 08/991372, filed Dec. 16, 1997, and other references .
In the Examples, all pressures are gauge pressures . Example 1
+ 2
Figure imgf000008_0001
Figure imgf000008_0002
(i) Nickel dibromide was purified of insoluble material by dissolving 2.22 g anhydrous nickel dibromide in 100 mL ethanol containing 1 mL water, filtering through diatomaceous earth and rotary evaporating dry. A mixture of 1.84 g (10.1 mmol) acenapthenequinone, 3.00 g (20.0 mmol) 2, 6-diethylaniline, 2.1 g (9.6 mmol) nickel dibromide and 50 mL toluene was refluxed under nitrogen with water removal for 24 h to give a deep red-black reaction mixture. The mixture was rotary evaporated to remove toluene and the concentrate was stirred with 50 mL methylene chloride and filtered through diatomaceous earth to remove unreacted nickel bromide. The filtrate was rotary evaporated and then held under high vacuum to yield 4.84 g dark red, waxy solids. The product was crushed and slurried in 40 mL hexane and suction-filtered. Drying under nitrogen yielded 3.95g (I) as a brown, methylene chloride-soluble powder.
Example 2 A suspension of 2.0 mg (0.0030 mmol) (I) of Example 1 in 5 mL dry, deaerated toluene was mixed with 1.0 mL 1.7M modified methylaluminoxane in toluene
(contains about 30% isobutyl groups) in a septum vial under nitrogen, swirling occasionally over 5 min, resulting in a dark maroon solution. A 600-mL stirred autoclave was loaded with 200 mL dry toluene. The solvent was stirred and saturated with ethylene at 50°C and 0.7 MPa for 10 min. The autoclave was vented and the toluene solution of catalyst was taken up into a 10-mL syringe and was injected into the autoclave through a head port. The autoclave was immediately pressured to 1.0 MPa with ethylene and was stirred for 30 min in a 50°C water bath as ethylene was fed to maintain pressure. After 30 min the ethylene was vented and resulting clear polymer gel was extracted with acetone and vacuum-oven dried (70°C/nitrogen purge) to yield 6.7 g polyethylene.
Example 3
NiCI2.6 H2O
+ 2
Figure imgf000009_0001
Figure imgf000009_0002
-H2O
Figure imgf000009_0003
: ιi )
A mixture of 1.84 g (10.1 mmol) acenaphthenequinone, 3.00 g (20.0 mmol)
2, 6-diethylaniline, 2.25g (9.5 mmol) nickel dichloride hexahydrate, 30 mg p-toluenesulfonic acid and 50 mL toluene was refluxed for 48 h under nitrogen with water removal . The deep red-brown reaction mixture was suction-filtered on a glass fritted funnel to remove unreacted nickel dichloride. The black filtrate solution was sparged with nitrogen before using as a catalyst .
Example 4 A mixture of 20 mL dry, deaerated toluene and
1.0 mL 1.7M modified methylalumoxane was magnetically stirred at room temperature under 41 kPa ethylene in a 50-mL Schlenk flask for a few minutes to saturate the solvent with ethylene. Then 1.5 mL of the solution of (II) made in Example 10 was added; a black solution immediately resulted. This solution was stirred under 41 kPa ethylene for 16 h; it remained black but became more viscous with time. The ethylene was vented and the solution was stirred with 25 mL 6N HCl and 20 mL additional toluene, and the toluene layer was separated, water-washed and rotary-evaporated to yield, after washing with methylene chloride and acetone and vacuum-oven drying (70°C) , 0.96 g of soft, tacky polyethylene .

Claims

CLAIMS What is claimed is :
1. A process for the production of a transition metal complex of an imine, comprising, contacting under imine forming conditions in an aprotic solvent, a transition metal compound, a first organic compound containing at least one aldehyde or ketone group, and a second organic compound which is a primary amine to form said transition metal complex of said imine, and provided that said transition metal is nickel, palladium, iron, or cobalt.
2. The process as recited in claim 1 wherein byproduct water is removed by distillation or formation of a hydrate.
3. The process as recited in claim 1 wherein water is removed by azeotropic distillation.
4. The process as recited in claim 1 or 3 wherein said second compound is a primary aryl amine or a substituted aryl primary amine.
5. The process as recited in claim 1 or 3 wherein said transition metal is nickel.
6. The process as recited in claim 1 or 3 wherein said transition metal compound is a chloride, bromide, or carboxylate.
7. The process as recited in claim 1 wherein a temperature is about 0┬░C to about 250┬░C.
8. The process as recited in claim 1 wherein said aprotic solvent is a hydrocarbon.
9. The process as recited in claim 1 or 3 additionally comprising contacting said complex with one or more polymerizable olefins and optionally cocatalysts to polymerize said polymerizable olefins.
10. The process as recited in claim 9 wherein said complex is not isolated before said contacting with one or more polymerizable olefins.
11. The process as recited in claim 5 wherein said second compound is a primary amine or a substituted aryl primary amine.
12. The process as recited in claim 6 wherein said second compound is a primary amine or a substituted aryl primary amine .
13. The process as recited in claim 9 wherein said second compound is a primary amine or a substituted aryl primary amine .
14. The process as recited in claim 6 wherein transition metal is nickel.
15. The process as recited in claim 9 wherein transition metal is nickel.
16. The process as recited in claim 9 wherein transition metal compound is a chloride, bromide or carbonate .
17. The process as recited in claim 15 wherein transition metal compound is a chloride, bromide or carbonate .
10
PCT/US1999/006818 1998-03-31 1999-03-30 Preparation of transition metal imine complexes WO1999050273A1 (en)

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IL13801699A IL138016A0 (en) 1998-03-31 1999-03-30 Preparation of transition metal imine complexes
CA002324311A CA2324311A1 (en) 1998-03-31 1999-03-30 Preparation of transition metal imine complexes
BR9908408-2A BR9908408A (en) 1998-03-31 1999-03-30 Process for producing imine transition metal complex.
AT99916184T ATE225358T1 (en) 1998-03-31 1999-03-30 PRODUCTION OF TRANSITION METAL IMINO COMPLEXES
JP2000541176A JP2002509935A (en) 1998-03-31 1999-03-30 Production of transition metal imine complexes
EP99916184A EP1080097B1 (en) 1998-03-31 1999-03-30 Preparation of transition metal imine complexes
DE69903285T DE69903285T2 (en) 1998-03-31 1999-03-30 MANUFACTURE OF TRANSITION METAL IMINO COMPLEXES
AU34552/99A AU758417B2 (en) 1998-03-31 1999-03-30 Preparation of transition metal imine complexes

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US60/080,051 1998-03-31

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US20050014983A1 (en) * 2003-07-07 2005-01-20 De Boer Eric Johannes Maria Process for producing linear alpha olefins
CN101010351B (en) * 2004-07-09 2011-06-22 纳幕尔杜邦公司 Catalysts for olefin polymerization or oligomerization
AR049714A1 (en) * 2004-07-13 2006-08-30 Shell Int Research ALFA OLEFINAS LINEAR PREPARATION PROCESS
TW200951150A (en) * 2008-02-29 2009-12-16 Sumitomo Chemical Co Diene polymer and production process thereof
CN101580488B (en) * 2008-05-16 2011-09-14 中国石油化工股份有限公司 Preparation method and application of tridentate pyridine imine ligand
BR112013029135B1 (en) 2011-05-13 2020-12-15 Univation Technologies, Llc COMPOSITION AND POLYMERIZATION PROCESS
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JP7180861B2 (en) * 2018-08-01 2022-11-30 国立大学法人北陸先端科学技術大学院大学 Electrolyte, lithium ion secondary battery, compound
JP2020189809A (en) * 2019-05-23 2020-11-26 旭化成株式会社 Method for manufacturing imine

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996023010A2 (en) * 1995-01-24 1996-08-01 E.I. Du Pont De Nemours And Company α-OLEFINS AND OLEFIN POLYMERS AND PROCESSES THEREFOR

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5714556A (en) 1995-06-30 1998-02-03 E. I. Dupont De Nemours And Company Olefin polymerization process
US5942461A (en) * 1995-11-06 1999-08-24 Minnesota Mining And Manufacturing Company Polymerizable compositions comprising alpha-olefin hydrocarbon monomers and methods of use therefor
KR100311595B1 (en) 1996-04-09 2001-12-17 나까니시 히로유끼 Olefin Polymerization Catalyst, Olefin Polymerization Method, and Olefin Polymer Composition
HU223533B1 (en) 1996-06-17 2004-08-30 Exxonmobil Chemical Patents Inc. Mixed transition metal catalyst systems for olefin polymerization
HUP0003447A3 (en) 1996-06-17 2004-03-01 Exxonmobil Chem Patents Inc Elevated pressure polymerization processes with transition metal catalyst systems
IL129929A0 (en) * 1996-12-17 2000-02-29 Du Pont Polymerization of ethylene with specific iron or cobalt complexes novel pyridinebis (imines) and novel complexes of pyridinebis(imines) with iron and cobalt

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996023010A2 (en) * 1995-01-24 1996-08-01 E.I. Du Pont De Nemours And Company α-OLEFINS AND OLEFIN POLYMERS AND PROCESSES THEREFOR

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ASSELT VAN R ET AL: "SYNTHESIS AND CHARACTERIZATION OF RIGID BIDENTATE NITROGEN LIGANDS AND SOME EXAMPLES OF COORDINATION TO DIVALENT PALLADIUM. X-RAY CRYSTAL STRUCTURES OF BIS(P-TOLYLIMINO)ACENAPHTHENE AND METHYLCHLORO BIS(0,0'-DIISOPROPYLPHENYL-IMINO) ACENAPHTHENE PALLADIUM(II)", RECUEIL DES TRAVAUX CHIMIQUES DES PAYS-BAS, vol. 113, 1 January 1994 (1994-01-01), pages 88 - 98, XP002047441, ISSN: 0165-0513 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7179871B2 (en) 2000-02-09 2007-02-20 Shell Oil Company Non-symmetrical ligands and catalyst systems thereof for ethylene oligomerization to linear alpha olefins
WO2004026795A2 (en) 2002-09-17 2004-04-01 E.I. Du Pont De Nemours And Company PROCESS FOR PRODUCING α-OLEFINS
US7053020B2 (en) 2002-09-25 2006-05-30 Shell Oil Company Catalyst systems for ethylene oligomerisation to linear alpha olefins
US7547783B2 (en) 2004-03-24 2009-06-16 Shell Oil Company Transition metal complexes

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