US20010016634A1 - Preparation of transition metal imine complexes - Google Patents

Preparation of transition metal imine complexes Download PDF

Info

Publication number
US20010016634A1
US20010016634A1 US09/778,427 US77842701A US2001016634A1 US 20010016634 A1 US20010016634 A1 US 20010016634A1 US 77842701 A US77842701 A US 77842701A US 2001016634 A1 US2001016634 A1 US 2001016634A1
Authority
US
United States
Prior art keywords
recited
transition metal
compound
primary amine
imine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US09/778,427
Other versions
US6310153B2 (en
Inventor
Steven Ittel
Samuel Arthur
Joel Citron
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DuPont Polymers Inc
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to US09/778,427 priority Critical patent/US6310153B2/en
Publication of US20010016634A1 publication Critical patent/US20010016634A1/en
Application granted granted Critical
Publication of US6310153B2 publication Critical patent/US6310153B2/en
Anticipated expiration legal-status Critical
Assigned to DUPONT POLYMERS, INC. reassignment DUPONT POLYMERS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: E. I. DU PONT DE NEMOURS AND COMPANY
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene

Definitions

  • 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.
  • 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. Pat. No. 5,714,556, World Patent Applications 96/23010, 97/48737, 97/48735, 97/38024, and U.S. patent application Ser. No. 08/991,372, 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.
  • 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:
  • (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 and metals in Groups 8-10 are especially preferred. Specific preferred transition metals are nickel, cobalt, iron and palladium, and nickel is especially preferred.
  • 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 1 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. Pat. No. 5,714,556, World Patent Applications 96/23010, 97/48737, 97/48735, 97/38024, and U.S. patent application Ser. No. 08/991,372, filed Dec. 16, 1997, and other references.
  • 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.
  • 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.
  • 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

    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. [0001]
    • 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. Pat. No. 5,714,556, World Patent Applications 96/23010, 97/48737, 97/48735, 97/38024, and U.S. patent application Ser. No. 08/991,372, 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. [0002]
  • 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. [0003]
  • 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. [0004]
  • 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. tom 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. tom 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. tom Dieck et al., Chem. Ber., vol. 109, p. 1657 et seq. (1976). [0005]
  • R. van Asselt, et al., Recl. 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. [0006]
    • 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. [0007]
    • 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: [0008]
    Figure US20010016634A1-20010823-C00001
  • 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. [0009]
  • 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. [0010]
  • 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. [0011]
  • 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 and metals in Groups 8-10 are especially preferred. Specific preferred transition metals are nickel, cobalt, iron and palladium, and nickel is especially preferred. [0012]
  • 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. [0013]
  • 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. [0014]
  • Preferred primary amines in the process are aryl amines, i.e., R[0015] 1 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. [0016]
  • 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. [0017]
  • 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. Pat. No. 5,714,556, World Patent Applications 96/23010, 97/48737, 97/48735, 97/38024, and U.S. patent application Ser. No. 08/991,372, filed Dec. 16, 1997, and other references. [0018]
  • In the Examples, all pressures are gauge pressures. [0019]
    • EXAMPLE 1
  • [0020]
    Figure US20010016634A1-20010823-C00002
  • 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 3.95 g (I) as a brown, methylene chloride-soluble powder. [0021]
    • 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. [0022]
    • EXAMPLE 3
  • [0023]
    Figure US20010016634A1-20010823-C00003
  • A mixture of 1.84 g (10.1 mmol) acenaphthenequinone, 3.00 g (20.0 mmol) 2,6-diethylaniline, 2.25 g (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. [0024]
    • 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. [0025]

Claims (17)

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.
US09/778,427 1998-03-31 2001-02-07 Preparation of transition metal imine complexes Expired - Lifetime US6310153B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US09/778,427 US6310153B2 (en) 1998-03-31 2001-02-07 Preparation of transition metal imine complexes

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US8005198P 1998-03-31 1998-03-31
US09/277,910 US6232259B1 (en) 1998-03-31 1999-03-29 Preparation of transition metal imine complexes
US09/778,427 US6310153B2 (en) 1998-03-31 2001-02-07 Preparation of transition metal imine complexes

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US09/277,910 Division US6232259B1 (en) 1998-03-31 1999-03-29 Preparation of transition metal imine complexes

Publications (2)

Publication Number Publication Date
US20010016634A1 true US20010016634A1 (en) 2001-08-23
US6310153B2 US6310153B2 (en) 2001-10-30

Family

ID=22154954

Family Applications (2)

Application Number Title Priority Date Filing Date
US09/277,910 Expired - Lifetime US6232259B1 (en) 1998-03-31 1999-03-29 Preparation of transition metal imine complexes
US09/778,427 Expired - Lifetime US6310153B2 (en) 1998-03-31 2001-02-07 Preparation of transition metal imine complexes

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US09/277,910 Expired - Lifetime US6232259B1 (en) 1998-03-31 1999-03-29 Preparation of transition metal imine complexes

Country Status (12)

Country Link
US (2) US6232259B1 (en)
EP (1) EP1080097B1 (en)
JP (1) JP2002509935A (en)
KR (1) KR100580421B1 (en)
CN (1) CN1247602C (en)
AT (1) ATE225358T1 (en)
AU (1) AU758417B2 (en)
BR (1) BR9908408A (en)
CA (1) CA2324311A1 (en)
DE (1) DE69903285T2 (en)
IL (1) IL138016A0 (en)
WO (1) WO1999050273A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030119921A1 (en) * 2001-08-01 2003-06-26 De Boer Eric Johannes Maria Ligands and catalyst systems thereof for ethylene oligomerisation to linear alpha olefins
US20030144514A1 (en) * 2000-02-09 2003-07-31 De Boer Eric Johannes Maria Non-symmetrical ligands and catalyst systems thereof for ethylene oligomerisation to linear alpha olefins
US20040116758A1 (en) * 2002-09-25 2004-06-17 De Boer Eric Johannes Maria Catalyst systems for ethylene oligomerisation to linear alpha olefins
US20050014983A1 (en) * 2003-07-07 2005-01-20 De Boer Eric Johannes Maria Process for producing linear alpha olefins
US20050059786A1 (en) * 2000-10-03 2005-03-17 De Boer Eric Johannes Maria Process for the co-oligomerisation of ethylene and alpha olefins
US7547783B2 (en) 2004-03-24 2009-06-16 Shell Oil Company Transition metal complexes
US7589245B2 (en) 2004-07-13 2009-09-15 Shell Oil Company Process for preparing linear alpha olefins

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6417305B2 (en) * 1996-12-17 2002-07-09 E. I. Du Pont De Nemours And Company Oligomerization of ethylene
DE19959251A1 (en) * 1999-12-09 2001-06-13 Basf Ag Polymerization-active transition metal complex compounds with a sterically demanding ligand system
CN1361183A (en) * 2000-12-25 2002-07-31 中国科学院长春应用化学研究所 Catalyst for multinuclear alpha-diimine nickel olefine polymerization
EP1463582B1 (en) * 2002-01-09 2009-04-08 E.I. Du Pont De Nemours And Company Catalyst for olefin polymerization
US7053259B2 (en) 2002-09-17 2006-05-30 E. I. Du Pont De Nemours And Company Process of producing α-olefins
CN101010351B (en) * 2004-07-09 2011-06-22 纳幕尔杜邦公司 Catalysts for olefin polymerization or oligomerization
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
EP2707398B1 (en) 2011-05-13 2017-08-09 Univation Technologies, LLC Spray-dried catalyst compositions and polymerization processes employing the same
US8697821B1 (en) * 2013-06-10 2014-04-15 King Fahd University Of Petroleum And Minerals Pressure sensitive adhesive
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

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101182365A (en) 1995-01-24 2008-05-21 纳幕尔杜邦公司 Alpha -olefins and olefin polymers and processes therefor
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
CA2251057A1 (en) 1996-04-09 1997-10-16 Mitsui Chemicals, Incorporated Olefin polymerization catalysts, olefin polymerization methods, and olefin polymer compositions and heat molded products
DE69702978T3 (en) 1996-06-17 2009-08-13 Exxonmobil Chemical Patents Inc., Baytown POLYMERIZATION METHOD UNDER INCREASED PRESSURE WITH TRANSFER METAL CATALYST SYSTEMS
AU718884B2 (en) 1996-06-17 2000-04-20 Exxon Chemical Patents Inc. Mixed transition metal catalyst systems for olefin polymerization
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

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030144514A1 (en) * 2000-02-09 2003-07-31 De Boer Eric Johannes Maria Non-symmetrical ligands and catalyst systems thereof for ethylene oligomerisation to linear alpha olefins
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
US20050059786A1 (en) * 2000-10-03 2005-03-17 De Boer Eric Johannes Maria Process for the co-oligomerisation of ethylene and alpha olefins
US7238764B2 (en) 2000-10-03 2007-07-03 Shell Oil Company Process for the co-oligomerisation of ethylene and alpha olefins
US20030119921A1 (en) * 2001-08-01 2003-06-26 De Boer Eric Johannes Maria Ligands and catalyst systems thereof for ethylene oligomerisation to linear alpha olefins
US20050159601A1 (en) * 2001-08-01 2005-07-21 De Boer Eric J.M. Ligands and catalyst systems thereof for ethylene oligomerisation to linear alpha olefins
US7304159B2 (en) 2001-08-01 2007-12-04 Shell Oil Company Ligands and catalyst systems thereof for ethylene oligomerisation to linear alpha olefins
US20040116758A1 (en) * 2002-09-25 2004-06-17 De Boer Eric Johannes Maria Catalyst systems for ethylene oligomerisation to linear alpha olefins
US7053020B2 (en) 2002-09-25 2006-05-30 Shell Oil Company Catalyst systems for ethylene oligomerisation to linear alpha olefins
US20050014983A1 (en) * 2003-07-07 2005-01-20 De Boer Eric Johannes Maria Process for producing linear alpha olefins
US7547783B2 (en) 2004-03-24 2009-06-16 Shell Oil Company Transition metal complexes
US7589245B2 (en) 2004-07-13 2009-09-15 Shell Oil Company Process for preparing linear alpha olefins

Also Published As

Publication number Publication date
JP2002509935A (en) 2002-04-02
DE69903285T2 (en) 2003-06-18
AU3455299A (en) 1999-10-18
US6310153B2 (en) 2001-10-30
ATE225358T1 (en) 2002-10-15
CA2324311A1 (en) 1999-10-07
CN1296490A (en) 2001-05-23
EP1080097A1 (en) 2001-03-07
EP1080097B1 (en) 2002-10-02
KR20010042295A (en) 2001-05-25
WO1999050273A1 (en) 1999-10-07
IL138016A0 (en) 2001-10-31
BR9908408A (en) 2000-10-17
DE69903285D1 (en) 2002-11-07
KR100580421B1 (en) 2006-05-16
CN1247602C (en) 2006-03-29
AU758417B2 (en) 2003-03-20
US6232259B1 (en) 2001-05-15

Similar Documents

Publication Publication Date Title
US6232259B1 (en) Preparation of transition metal imine complexes
JP3296496B2 (en) Polymerization of ethylene with specific iron or cobalt complexes, novel pyridine bis (imines), and novel complexes of pyridine bis (imines) with iron and kodort
JP3400988B2 (en) Polymerization catalyst
US6060569A (en) Polymerization of ethylene
EP1183279B1 (en) Polymerization of ethylene
EP1379562A2 (en) Supported olefin polymerization catalysts
JP2003527475A (en) Improved polymerization method
US5492983A (en) Catalysts and process for the preparation of catalysts which may be used for the polymerization of ethylene
US6677423B2 (en) Polymerization of ethylene
US20070155621A1 (en) Ionic liquids as solvents
CA2726532C (en) Sterically encumbered bidentate and tridentate naphthoxy-imine metallic complexes
US7214748B2 (en) Process for the production of an azo-catalyst for the polymerization of olefins
US20070213485A1 (en) Ionic Liquids As Supports
JP2003268028A (en) Method for producing ethylene-based polymer
US20030191017A1 (en) Olefin polymerization catalyst
WO2002083751A1 (en) Olefin polymerization catalyst
AU2002309590A1 (en) Olefin polymerization catalyst
AU2002254480A1 (en) Supported olefin polymerization catalysts
JP2003192715A (en) Olefin polymerization catalyst and method for polymerizing olefin

Legal Events

Date Code Title Description
STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12

AS Assignment

Owner name: DUPONT POLYMERS, INC., DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:E. I. DU PONT DE NEMOURS AND COMPANY;REEL/FRAME:049587/0098

Effective date: 20190617