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WO1997017355A1 - ORGANOMETALLIC COMPLEXES HAVING β-DIKETONATE LIGANDS - Google Patents

ORGANOMETALLIC COMPLEXES HAVING β-DIKETONATE LIGANDS Download PDF

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Publication number
WO1997017355A1
WO1997017355A1 PCT/FI1996/000593 FI9600593W WO9717355A1 WO 1997017355 A1 WO1997017355 A1 WO 1997017355A1 FI 9600593 W FI9600593 W FI 9600593W WO 9717355 A1 WO9717355 A1 WO 9717355A1
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group
didentate
organometallic complex
alkoxo
complex according
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French (fr)
Inventor
Leena Matilainen
Markku Leskelä
Hilkka Knuuttila
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Borealis AS
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Borealis AS
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Priority to AU73010/96A priority Critical patent/AU7301096A/en
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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages

Definitions

  • the present invention relates to an organometallic complex having 3-diketonate ligands that is useful as a catalyst in the polymerization of olefins.
  • the present invention is also directed to a method for preparing the organometallic complex and the use thereof as a catalyst in the polymerization of olefins.
  • Group IV metal complexes of -diketonate ligands have been a subject of considerable interest since the 1960's.
  • the mechanism for rearrangement of the stereochemically non-rigid octahedral bis-chelate complexes, ( ⁇ -diketonate) 2 M(IV)X 2 where M represents a Group IV metal and X represents a halide or an alkoxide group has been studied by many researchers.
  • the mechanism for rearrangement is proposed to be a torsional twist that produces a 6 coordinate trigonal prismatic transition stage.
  • the j ⁇ -diketonate ligands of the ( / S- diketonate) 2 M(IV)X 2 complexes coordinate by free electron pairs from oxygen atoms and anionically via oxygen atoms. Most of the ( ⁇ -diketonate) 2 M(IV) X 2 complexes adopt the cis-configuration, even though steric factors favor the trans-configuration. The existence of a T ⁇ - electron interaction between the metal and chelate ligand is believed to be a cis-stabilizing electronic factor.
  • An object of the present invention is to provide a novel Group IV metal complex of didentate alkoxo ligands.
  • a further object of the present invention is to provide a novel Group IV metal complex of ⁇ -diketonate ligands.
  • An object of the present invention is to further provide a novel Group IV metal bis-/S-diketonate complex.
  • Y represents a didentate alkoxo ligand
  • M represents a Group IV metal
  • X represents a halogen or an alkoxide group
  • n represents an integer of 1 to 2
  • the didentate alkoxo ligand Y is any 0-diketonate ligand, and is preferably a ligand derived from 1,3- diphenyl-1, 3-propanedione or a derivative thereof, where the phenyl moiety may be substituted with one or more straight or branched chain hydrocarbon having 1 to 4 carbon atoms, which may be the same or different.
  • the Group IV metal of the complex is any Group IV metal, such as titanium, zirconium or hafnium.
  • the Group IV metal is titanium.
  • X is any halogen group, such as fluorine, chlorine, bromine or iodine, or an alkoxide group having 1 to 4 carbon atoms .
  • X represents a chlorine atom.
  • the Group IV metal complex may have one or two didentate alkoxo ligands Y in the complex.
  • the Group IV metal complex has two didentate alkoxo ligands Y therein.
  • the remaining halide ligands may be replaced by an alkyl group having 1 to 7 carbon atoms.
  • the Group IV metal complex of the present invention is prepared by first reacting a didentate alkoxo ligand precursor that is dissolved in a solvent, such as diethylether or tetrahydrofuran, with an alkali metal source, such as methyl lithium or sodium, to obtain a alkali metallated didentate alkoxo ligand precursor.
  • a solvent such as diethylether or tetrahydrofuran
  • an alkali metal source such as methyl lithium or sodium
  • the alkali metallated didentate alkoxo ligand precursor is then dissolved or suspended in a solvent, such as toluene or dichloromethane, and cooled to about -78°C.
  • a Group IV metal halide compound such as titanium tetrachloride, titanium tetrabromide or titanium tetrafluoride is added dropwise to the alkali metallated didentate alkoxo ligand precursor dissolved or suspended in a solvent, to obtain a reaction mixture that is then warmed to about room temperature, to about 25°C, and allowed to react for two to three hours, whereby the halide from the metal tetrahalide compound is displaced by the didentate alkoxo ligand from the alkali metallated didentate alkoxo ligand precursor.
  • Pentane is then added to the mixture to precipitate the Group IV metal complex, which is then filtered and dissolved in hot dichloromethane.
  • the Group IV metal complex of the present invention crystallizes from the solution as red crystals as the dichloromethane/co plex solution cools.
  • the molar ratio of the didentate alkoxo ligand precursor to alkali metal used to obtain the alkali metallated didentate alkoxo ligand precursor is about 1:1-1.5, and is preferably about 1:1.
  • the molar ratio of the alkali metallated didentate alkoxo ligand precursor to the Group IV metal tetrahalide compound is about 2-3:1, and is preferably about 2.5:1, and more preferably about 2:1.
  • the amount of solvent used to dissolve the alkali metallated didentate alkoxo ligand precursor is about 75-125 cm 3 , and is preferably about 100 cm 3 .
  • the novel Group IV metal complex of didentate alkoxo ligands of the present invention may be used to polymerize olefin monomers, such as propene and ethylene, in the presence of a cocatalyst, such as methylaluminumoxane.
  • a titanium J is- ⁇ -diketonate complex is preferred as the catalyst in the polymerization of ethylene.
  • the amount of Group IV metal in the complex required for olefin polymerization is from 1 to 100 ⁇ mol; while the molar ratio of aluminum to Group IV metal is from about 25 to 5,000, and is preferably about 1,000, for example, when the Group IV metal is titanium.
  • the partial pressure of olefin monomer is from about 1 to 50 bar, and the polymerization temperature ranges from about 0 to 150°C. Pentane, isobutane, propane, heptane and toluene may be used as the polymerization solvent.
  • the activity of the Group IV complex ranges from about 100 to 1,000 kg polyolefin per gram complex per hour, depending upon the polymerization conditions.
  • the weight average molecular weight and molecular weight distribution of the polyolefin can be controlled by varying the process conditions, and ranges from about 600,000 to 1,500,000 and preferably from about 1,000,000 to 1,200,000 and about 10-20 and preferably from about 14-17, respectively.
  • a preferred embodiment of the present invention is a cis-dichloro-bis (1, 3-diphenyl-l,3-propanedionato) - titanium(IV) complex represented by the figure attached hereto.
  • the cis-dichloro-bis (1, 3-diphenyl-1, 3- propanedionato) -titanium(IV) complex is highly active in the polymerization of ethylene, when methylaluminumoxane is used as a cocatalyst.
  • the polymerization activity of the Group IV complex can be explained by the cis- configuration of the halide and didentate alkoxo ligands. Specifically, the halide ligand is easily removed to provide a suitable reaction site for the ethylene molecule.
  • the Group IV metal complex product was recrystallized twice from toluene- dichloromethane (1:6) .
  • the yield of the deep red crystalline cis-dichloro-bis (1,3-diphenyl-1 , 3- propanedionato) -titanium(IV) complex was 3.3 g (86%) .
  • the deep red crystalline cis-dichloro-bis (1,3- diphenyl-1,3-propanedionato) -titanium(IV) complex is relatively sensitive in air. However, observable decomposition did not occur for several hours after exposure to air.
  • the deep red crystalline cis-dichloro- bis (1 , 3-diphenyl-1 , 3 -propanedionato) -titanium (IV) complex hydrolyzed immediately in moist solvents, and is readily soluble in ethers, chlorinated solvents and aromatics. The resultant complex is insoluble or slightly insoluble in alkanes.
  • the complex is a deep red crystalline solid at room temperature.
  • Partial pressure of ethylene 10 bar, Total pressure; 14.6 bar.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

An organometallic complex having the formula (I): X4-nMYn, wherein Y represents a didentate alkoxo ligand; M represents a Group IV metal; X represents a halogen or an alkoxide group; and n represents an integer of 1 to 2; a method of preparing thereof; and a method of polymerizing olefin monomers.

Description

ORGANOMETALLIC COMPLEXES HAVING J-DIKETONATE LIGANDS
This application claims priority on Provisional Application Serial No. 60/007,322 filed on November β , 1995.
Field of the Invention
The present invention relates to an organometallic complex having 3-diketonate ligands that is useful as a catalyst in the polymerization of olefins. The present invention is also directed to a method for preparing the organometallic complex and the use thereof as a catalyst in the polymerization of olefins.
Background of the Invention
Group IV metal complexes of -diketonate ligands have been a subject of considerable interest since the 1960's. Specifically, the mechanism for rearrangement of the stereochemically non-rigid octahedral bis-chelate complexes, (β-diketonate)2M(IV)X2 where M represents a Group IV metal and X represents a halide or an alkoxide group, has been studied by many researchers. The mechanism for rearrangement is proposed to be a torsional twist that produces a 6 coordinate trigonal prismatic transition stage.
The jβ-diketonate ligands of the (/S- diketonate) 2M(IV)X2 complexes coordinate by free electron pairs from oxygen atoms and anionically via oxygen atoms. Most of the (β-diketonate)2M(IV) X2 complexes adopt the cis-configuration, even though steric factors favor the trans-configuration. The existence of a TΓ- electron interaction between the metal and chelate ligand is believed to be a cis-stabilizing electronic factor. In the study of Group IV metal complexes of β- diketonate ligands, it is desirable to obtain a Group IV metal complex of 0-diketonate ligands that may be used as a soluble catalyst in the polymerization of olefins . Hence, the present invention is directed to such a novel S-diketonate complex that adopts the cis- configuration.
Summary of the Invention
An object of the present invention is to provide a novel Group IV metal complex of didentate alkoxo ligands.
A further object of the present invention is to provide a novel Group IV metal complex of β-diketonate ligands.
An object of the present invention is to further provide a novel Group IV metal bis-/S-diketonate complex.
Another object of the present invention is to provide a method for preparing the novel Group IV metal complex of didentate alkoxo or (S-diketonate ligands or the novel Group IV metal bis-/S-diketonate complex. Another objective of the present invention is to provide a method of using the novel complexes as a catalyst in the polymerization of olefins.
Detailed Description
The inventors have found that a Group IV metal complex of didentate alkoxo ligands having the formula (I)
4-nMYn (I) wherein Y represents a didentate alkoxo ligand; M represents a Group IV metal; X represents a halogen or an alkoxide group; and n represents an integer of 1 to 2,
can be used as a catalyst in the polymerization of olefins.
The didentate alkoxo ligand Y is any 0-diketonate ligand, and is preferably a ligand derived from 1,3- diphenyl-1, 3-propanedione or a derivative thereof, where the phenyl moiety may be substituted with one or more straight or branched chain hydrocarbon having 1 to 4 carbon atoms, which may be the same or different. The Group IV metal of the complex is any Group IV metal, such as titanium, zirconium or hafnium. Preferably the Group IV metal is titanium. X is any halogen group, such as fluorine, chlorine, bromine or iodine, or an alkoxide group having 1 to 4 carbon atoms . Preferably X represents a chlorine atom.
The Group IV metal complex may have one or two didentate alkoxo ligands Y in the complex. Preferably the Group IV metal complex has two didentate alkoxo ligands Y therein. When there are only two didentate ligands Y in the complex, the remaining halide ligands may be replaced by an alkyl group having 1 to 7 carbon atoms.
The Group IV metal complex of the present invention is prepared by first reacting a didentate alkoxo ligand precursor that is dissolved in a solvent, such as diethylether or tetrahydrofuran, with an alkali metal source, such as methyl lithium or sodium, to obtain a alkali metallated didentate alkoxo ligand precursor. The alkali metallated didentate alkoxo ligand precursor is then dissolved or suspended in a solvent, such as toluene or dichloromethane, and cooled to about -78°C. A Group IV metal halide compound, such as titanium tetrachloride, titanium tetrabromide or titanium tetrafluoride is added dropwise to the alkali metallated didentate alkoxo ligand precursor dissolved or suspended in a solvent, to obtain a reaction mixture that is then warmed to about room temperature, to about 25°C, and allowed to react for two to three hours, whereby the halide from the metal tetrahalide compound is displaced by the didentate alkoxo ligand from the alkali metallated didentate alkoxo ligand precursor. Pentane is then added to the mixture to precipitate the Group IV metal complex, which is then filtered and dissolved in hot dichloromethane. The Group IV metal complex of the present invention crystallizes from the solution as red crystals as the dichloromethane/co plex solution cools.
The molar ratio of the didentate alkoxo ligand precursor to alkali metal used to obtain the alkali metallated didentate alkoxo ligand precursor is about 1:1-1.5, and is preferably about 1:1.
The molar ratio of the alkali metallated didentate alkoxo ligand precursor to the Group IV metal tetrahalide compound is about 2-3:1, and is preferably about 2.5:1, and more preferably about 2:1.
The amount of solvent used to dissolve the alkali metallated didentate alkoxo ligand precursor is about 75-125 cm3, and is preferably about 100 cm3. The novel Group IV metal complex of didentate alkoxo ligands of the present invention may be used to polymerize olefin monomers, such as propene and ethylene, in the presence of a cocatalyst, such as methylaluminumoxane. A titanium J is-β-diketonate complex is preferred as the catalyst in the polymerization of ethylene. The amount of Group IV metal in the complex required for olefin polymerization is from 1 to 100 μmol; while the molar ratio of aluminum to Group IV metal is from about 25 to 5,000, and is preferably about 1,000, for example, when the Group IV metal is titanium. The partial pressure of olefin monomer is from about 1 to 50 bar, and the polymerization temperature ranges from about 0 to 150°C. Pentane, isobutane, propane, heptane and toluene may be used as the polymerization solvent. The activity of the Group IV complex ranges from about 100 to 1,000 kg polyolefin per gram complex per hour, depending upon the polymerization conditions. The weight average molecular weight and molecular weight distribution of the polyolefin can be controlled by varying the process conditions, and ranges from about 600,000 to 1,500,000 and preferably from about 1,000,000 to 1,200,000 and about 10-20 and preferably from about 14-17, respectively.
A preferred embodiment of the present invention is a cis-dichloro-bis (1, 3-diphenyl-l,3-propanedionato) - titanium(IV) complex represented by the figure attached hereto. The cis-dichloro-bis (1, 3-diphenyl-1, 3- propanedionato) -titanium(IV) complex is highly active in the polymerization of ethylene, when methylaluminumoxane is used as a cocatalyst. The polymerization activity of the Group IV complex can be explained by the cis- configuration of the halide and didentate alkoxo ligands. Specifically, the halide ligand is easily removed to provide a suitable reaction site for the ethylene molecule.
Synthesis of cis-dichloro-bis (1.3-diphenyl-1, 3- propanedionato) titanium (IV)
3.0 g (0.0134 mol) of 1, 3-diphenyl-1, 3- propanedione was dissolved in diethylether. The solution was cooled to -78°C. 8.5 cm3 (0.0136 mol) of methyl lithium was added dropwise. The reaction mixture was allowed to warm to room temperature and was stirred for about 2 hours . The diethylether was then evaporated under reduced pressure. The resultant white solid was redissolved in dichloromethane and cooled to -78°C. 0.74 cm3 (0.0067 mol) of TiCl4 was added dropwise. The reaction mixture was allowed to warm to room temperature and was stirred for about 2 hours. The resultant deep red mixture was filtered through Celite and the dichloromethane was evaporated. The Group IV metal complex product was recrystallized twice from toluene- dichloromethane (1:6) . The yield of the deep red crystalline cis-dichloro-bis (1,3-diphenyl-1 , 3- propanedionato) -titanium(IV) complex was 3.3 g (86%) .
The deep red crystalline cis-dichloro-bis (1,3- diphenyl-1,3-propanedionato) -titanium(IV) complex is relatively sensitive in air. However, observable decomposition did not occur for several hours after exposure to air. The deep red crystalline cis-dichloro- bis (1 , 3-diphenyl-1 , 3 -propanedionato) -titanium (IV) complex hydrolyzed immediately in moist solvents, and is readily soluble in ethers, chlorinated solvents and aromatics. The resultant complex is insoluble or slightly insoluble in alkanes. The complex is a deep red crystalline solid at room temperature.
Polymerization of Ethylene
5 mg cis-dichloro-bis (1 , 3 -diphenyl-1 , 3 - propanedionato) -titanium(IV) complex described above in 5 ml toluene
5.4 ml 10% methylaluminumoxane toluene solution, Al/Ti = 1000
Reaction medium : pentane
Partial pressure of ethylene : 10 bar, Total pressure; 14.6 bar.
Temperature: 80°C Yield: 48 g of polyethlyene
Activity of catalyst complex: 113.2 kg PE/g Ti h; 5393.2 kg PE/mol Ti h; 9.6 kg PE/g cat h.

Claims

We claim :
1. An organometallic complex having the Formula (I)
Figure imgf000009_0001
wherein Y represents a didentate alkoxo ligand; M represents a Group IV metal; X represents a halogen or an alkoxide group; and n represents an integer of 1 to 2.
2. The organometallic complex according to claim 1, wherein Y is a /3-diketonate ligand.
3. The organometallic complex according to claim 1, wherein Y is a ligand derived from 1, 3-diphenyl-1, 3- propanedione or a derivative thereof, and the phenyl moiety thereof may be substituted with one or more straight or branched chain hydrocarbon having 1 to 4 carbon atoms, which may be the same or different.
4. The organometallic complex according to claim 1, wherein M is selected from the group consisting of titanium, zirconium and hafnium.
5. The organometallic complex according to claim 1, wherein M is titanium.
6. The organometallic complex according to claim 1, wherein X is selected from the group consisting of fluorine, chlorine, bromine, iodine and an alkoxide group having 1 to 4 carbon atoms.
7. The organometallic complex according to claim 1, wherein X is chlorine.
8. The organonmetallic complex according to claim 1, wherein Y is a ligand derived from 1,3-diphenyl-l,3- propanedione; M is titanium; X is chlorine; and n is the integer 2.
9. The organometallic complex according to claim 1 that is cis-dichloro-bis (1, 3-diphenyl-1, 3-propane¬ dionato) titanium (IV) .
10. A method for preparing an organometallic complex having the Formula (I)
X<-nMYn (I)
wherein Y representε a didentate alkoxo ligand; M represents a Group IV metal; X represents a halogen or an alkoxide group; and n represents an integer of 1 to 2; comprising the steps of: reacting a didentate alkoxo ligand precursor with an alkali metal source to obtain an alkali metallated didentate alkoxo ligand precursor; dissolving the alkali metallated didentate alkoxo ligand precursor in a solvent, and cooling the resultant solution to about -78°C; adding a Group IV metal halide compound to the alkali metallated didentate alkoxo ligand precursor to obtain a reaction mixture; warming the reaction mixture to about 25°C; and precipitating the organometallic complex from the reaction solution.
11. The method for preparing the organometallic complex according to claim 10, wherein the molar ratio of the didentate alkoxo ligand precursor to alkali metal used to obtain the alkali metallated didentate alkoxo ligand precursor is about 1:1-1.5.
12. The method for preparing the organometallic complex according to claim 10, wherein the molar ratio of the didentate alkoxo ligand precursor to alkali metal used to obtain the alkali metallated didentate alkoxo ligand precursor is about 1:1.
13. The method for preparing an organometallic complex according to claim 10, wherein the molar ratio of the alkali metallated didentate alkoxo ligand precursor to the Group IV metal halide compound is about 2-3 :1.
14. The method for preparing an organometallic complex according to claim 10, wherein the molar ratio of the alkali metallated didentate alkoxo ligand precursor to the Group IV metal halide compound is about 2.5:1.
15. The method for preparing an organometallic complex according to claim 10, wherein the molar ratio of the alkali metallated didentate alkoxo ligand precursor to the Group IV metal halide compound is about 2:1.
16. A method of polymerizing olefin monomers, comprising the step of reacting the olefin monomers in the presence of an organometallic complex represented by Formula (I)
„MYπ
wherein Y represents a didentate alkoxo ligand; M represents a Group IV metal; X represents a halogen or an alkox-ide group; and n represents an integer of 1 to 2.
17. The method of polymerizing olefin monomers according to claim 16, wherein the olefin monomer is selected from the group consisting of propene and ethylene.
PCT/FI1996/000593 1995-11-06 1996-11-05 ORGANOMETALLIC COMPLEXES HAVING β-DIKETONATE LIGANDS Ceased WO1997017355A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU73010/96A AU7301096A (en) 1995-11-06 1996-11-05 Organometallic complexes having beta-diketonate ligands

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US60/007,322 1995-11-06

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634528A (en) * 1968-08-17 1972-01-11 Toa Gosei Chem Ind Process for preparing 1 5 9-cyclo-dodecatrienes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634528A (en) * 1968-08-17 1972-01-11 Toa Gosei Chem Ind Process for preparing 1 5 9-cyclo-dodecatrienes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Volume 78, No. 22, 4 June 1973, (Columbus, Ohio, USA), page 74, Abstract No. 137643s; & JP,A,47 033 178 (MASAYA et al.), 17 November 1972. *
MACROMOL. RAPID COMMUN., Volume 15, 1994, CHRISTOPH JANIAK et al., "Zirconium Beta-diketonate/methylaluminoxane Systems as Singlesite Catalysts for the Preparation of High-molecular-weight Polyethylene", pages 655-658. *

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