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WO1997017354A1 - Complexes organometalliques a ligands oxobenzoyle - Google Patents

Complexes organometalliques a ligands oxobenzoyle Download PDF

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Publication number
WO1997017354A1
WO1997017354A1 PCT/FI1996/000592 FI9600592W WO9717354A1 WO 1997017354 A1 WO1997017354 A1 WO 1997017354A1 FI 9600592 W FI9600592 W FI 9600592W WO 9717354 A1 WO9717354 A1 WO 9717354A1
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WO
WIPO (PCT)
Prior art keywords
group
didentate
metal complex
alkoxo
metal
Prior art date
Application number
PCT/FI1996/000592
Other languages
English (en)
Inventor
Leena Matilainen
Markku Leskelä
Hilkka Knuuttila
Original Assignee
Borealis A/S
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 Borealis A/S filed Critical Borealis A/S
Priority to AU73009/96A priority Critical patent/AU7300996A/en
Publication of WO1997017354A1 publication Critical patent/WO1997017354A1/fr

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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 didentate alkoxo 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.
  • the Lewis acidity of early transition metals having high oxidation states and the coordinative unsaturation of transition metal complexes, as well as structural rigidity of the complex, are important characteristics of many catalytically active complexes.
  • an objective of the present invention is to synthesize coordinatively unsaturated organometallic complexes of Group IV metals with few or no d orbital electrons, since this characteristic is necessary to facilitate metal-centered reactivity in olefin polymerization, and where the halide ligands of a metal halide are replaced with di- or higher dentate alkoxo ligands so that the remaining halide ligands of the complex are in a cis-position to one another.
  • 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 oxobenzoyl ligands .
  • Another objective of the present invention is to provide a method of using the novel complexes as a catalyst in the polymerization of olefins.
  • Y represents a didentate alkoxo ligand
  • M represent ⁇ a Group IV metal
  • X represents a halogen, an alkoxy group or an alkyl group
  • n represents an -integer of 1- 2 can be used as a catalyst in the polymerization of olefins.
  • the didentate alkoxo ligand Y is any oxobenzoyl ligand, and is preferably a ligand derived from a salicylaldehyde precursor or a derivative thereof, wherein the phenyl and carbonyl moieties of the salicylaldehyde precursor may be substituted with one or more straight, branched or cyclic hydrocarbon or aromatic having 1 to 20 carbon atoms, which may be the same or different, and the subtituents on the phenyl group may be at the ortho and para positions relative to the hydroxy moiety of the salicylaldehyde precursor.
  • the Group IV metal of the complex is any Group IV metal, such as titanium, zirconium or hafnium.
  • the Group IV metal is titanium or zirconium.
  • X is any halogen group, such as fluorine, chlorine, bromine or iodine, an alkoxy group having 1 to 4 carbon atoms, or a straight or branched alkyl having 1 to 7 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 when M represents titanium, and one or two didentate alkoxo ligands Y therein when represents zirconium.
  • a solvent molecule such as tetrahydrofuran, may be weakly coordinated thereto since deprotonation of the ligand occurs in the solvent .
  • the solvent molecule does not affect the molar ratios of other ligands or the polymerization property of the complex.
  • the halide ligands of the complexes are in the cis-position, and one oxygen atom of the didentate alkoxo ligand is coordinated anionically to the Group IV metal and another oxygen atom through a lone electron pair. 54 PC17FI96/00592
  • 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 n-butyl lithium or metallic sodium, to obtain a alkali metallated didentate alkoxo ligand precursor.
  • a solvent such as diethylether or tetrahydrofuran
  • an alkali metal source such as n-butyl lithium or metallic sodium
  • the solvent is the evaporated and the alkali metallated didentate alkoxo ligand precursor obtained therefrom.
  • the didentate alkoxo ligand precursor may be added in solid form to a mixture of metallic sodium and a solvent, such as tetrahydrofuran, which is refluxed for 2-6 hours until there is no metallic sodium in the mixture. Thereafter, the solvent is evaporated and the alkali metallated didentate alkoxo ligand precursor obtained therefrom.
  • alkali metallated didentate alkoxo ligand precursor is then dissolved in a solvent, such as toluene or dichloromethane, and cooled to about -78°C.
  • a solvent such as toluene or dichloromethane
  • a solid Group IV metal halide compound such as titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, zirconium tetrachloride, zirconium tetrabromide or zirconium tetrafluoride may be added to the solution of alkali metallated didentate alkoxo ligand precursor, or the Group IV metal halide compound may be dissolved in a solvent, such as toluene or dichloromethane, cooled to -78°C and added dropwise to the solution of alkali metallated didentate alkoxo ligand precursor, to obtain a reaction mixture that is then warmed to about room temperature to 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.
  • a solvent such
  • the alkali metal halide is removed from the reaction mixture and the solvent is evaporated.
  • the resultant solid is dissolved in a solvent, such as toluene, and the Group IV metal complex of the present invention is crystallized from the solution by the diffusion method at about -20°C or by adding 16 to 100 cm 3 pentane to the solution of product.
  • 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 halide compound is about 1-2:1.
  • the molar ratio is about 1:1 when M represents titanium, and about 1:1 when zirconium is used as the Group IV metal to obtain a complex having one didentate alkoxo ligand or 2:1 when zirconium is used as the Group IV metal to obtain a complex having two didentate alkoxo ligands.
  • the same titanium complex is obtained when the molar ratio of the alkali metallated didentate alkoxo ligand precursor to titanium is 2:1 and 1:1.
  • the amount of solvent used to dissolve the metallated didentate alkoxo ligand precursor may be about 100 cm 3 -
  • the amount of solvent used should dissolve the alkali metallated didentate alkoxo ligand precursor.
  • the novel Group IV metal complex of didentate alkoxo ligands of the present invention may be used to polymerize or copolymerize olefin monomers, such as ethylene, propene and hexene in the presence of an aluminum cocatalyst, such as methylaluminumoxane .
  • 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 in the cocatalyst to Group IV metal in the complex is from about 25 to 5,000, and is preferably about 1,000, for example, when " the Group IV metal is zirconium.
  • 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 8 to 800 kg polyolefin per gram Group IV metal 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.
  • Examples of the Group IV metal complex of the present invention are cis-dichloro-bis (3-oxo-4- t butyl-6- methylbenzoyl) titanium(IV) , cis-dichloro-bis (3-oxo-4- • ⁇ butyl-e-methylbenzoyl) zirconium(IV) and -ner-trichloro- (3-oxo-4- t butyl-6-methylbenzoyl) (tetrahydrofuran) zirconium(IV) , which are represented by Figures 1-3 attached hereto and described below.
  • the dichloromethane was then evaporated and the deep red crude product was dissolved in toluene.
  • the product was filtered again. A part of the product was crystallized by the diffusion method and the rest of the product was crystallized by adding pentane to the toluene solution of the product (1:6) .
  • the resultant deep red solid was recrystallized twice from pentane-toluene solution.
  • the yield of crystalline cis-dichloro-bis(3-oxo-4- t butyl-6- methylbenzoyl) titanium(IV) was 3.5g (68%) .
  • the deep red crystalline cis-dichloro-bis (3-oxo-4- 'butyl-e-methylbenzoyl) 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 complex decomposed immediately in moist solvents, and is readily soluble in ethers and chlorinated solvents and soluble in aromatics. The resultant complex is insoluble in alkanes.
  • the complex is a deep red crystalline solid at room temperature.
  • the pale yellow crystalline cis-dichloro-bis (3-oxo- 4-''butyl- ⁇ -methylbenzoyl) zirconium(IV) complex is relatively sensitive in air. However, observable decomposition did not occur for several- hours after exposure to air.
  • the pale yellow crystalline complex decomposed immediately in moist solvents, and is readily soluble in ethers and chlorinated solvents and soluble in aromatics. The resultant complex is insoluble in alkanes.
  • the complex is a pale yellow crystalline solid at room temperature.
  • the yellow crystalline complex hydrolyzed immediately in moist solvents, and is readily soluble in ethers and chlorinated solvents and soluble in aromatics.
  • the resultant complex is insoluble in alkanes.
  • the complex is a yellow crystalline solid at room temperature.
  • the polymerizations was performed in a 2 dm3 autoclave reaction (Buchi) .
  • Pentane was charged under a nitrogen atmosphere into the evacuated autoclave at room temperature.
  • a toluene solution of the Group IV metal complex of the present invention and methylaluminumoxane was mixed in a catalyst cylinder and introduced to the reactor.
  • the temperature was raised to 80°C and ethylene (and comonomer) was fed to the reactor.
  • the process was stopped by cooling and degassing the reaction.
  • Polymerization conditions partial pressure of ethylene: 10 bar; temperature: 80°C; solvent medium: pentane.
  • Runtime 1 h Yield: 8.0 g Activities: 727 kg polyethylene/mol Zr h; 1.6 kg polyethylene/g complex h; 8.1 kg polyethylene/g Zr h.
  • the reactivity of the cis-dichloro-bis (3-oxo-4- fc butyl-6-methylbenzoyl) titanium(IV) was also evaluated in ethylene-1-hexene copolymerization and was found to have an activity of about 80 kg polyethylene/g Ti h.
  • the comonomer content of the copolymer was about 3 mol% .
  • the titanium and zirconium complexes of the present invention are highly active in the polymerization of ethylene and copolymerization of ethylene and hexene, when methylaluminumoxane is used as a cocatalyst.
  • the titanium complex cis-dichloro-bis (3-oxo-4- ""butyl-6-methylbenzoyl) titanium(IV) is more active than the zirconium complexes in ethylene polymerization, and the rate of copolymerization of ethylene and hexene is slightly slower than the rate of ethylene polymerization using the titanium complex.
  • the polymerization activity of the Group IV complex can be explained by the cis-configuration of the halide and didentate alkoxo ligands.
  • the halide ligand is easily displaced by the alkoxo ligand to provide a suitable reaction site for the ethylene molecule, where the stronger 7r-donating ability of the alkoxo oxygen compared to the halide, together with the chelation of the alkoxo ligand, makes the displacement of the halide markedly favored over the loss of the alkoxo ligand.
  • the chelation of the alkoxo ligand also provide structural rigidity for the complex.
  • Broad polydispersity values i.e., broad molecular weight distributions, indicate that the complexes of the present invention have more than one active site, which is surprising since the Group IV metal ion is quite heavily sterically crowded.
  • One possible explanation for the broad polydispersity is that the polymerization temperature causes rearrangement of the didentate alkoxo ligands that creates several active sites for the complex.

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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)

Abstract

Cette invention concerne un complexe d'un métal du groupe IV composé de ligands alcoxo bidentés et représenté par la formule (I) X4-nMYn, dans laquelle Y représente un ligand alcoxo bidenté, M représente un métal du groupe IV, X représente un halogène, un groupe alcoxy ou un groupe alkyle et n est un entier égal à 1 ou 2. L'invention concerne en outre un procédé de préparation dudit complexe et un procédé de polymérisation ou de copolymérisation de monomères d'oléfine.
PCT/FI1996/000592 1995-11-06 1996-11-05 Complexes organometalliques a ligands oxobenzoyle WO1997017354A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU73009/96A AU7300996A (en) 1995-11-06 1996-11-05 Organometallic complexes having oxobenzoyl ligands

Applications Claiming Priority (2)

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US732195P 1995-11-06 1995-11-06
US60/007,321 1995-11-06

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9837679B2 (en) 2014-11-26 2017-12-05 Lockheed Martin Advanced Energy Storage, Llc Metal complexes of substituted catecholates and redox flow batteries containing the same
US9938308B2 (en) 2016-04-07 2018-04-10 Lockheed Martin Energy, Llc Coordination compounds having redox non-innocent ligands and flow batteries containing the same
US9991544B2 (en) 2012-07-27 2018-06-05 Lockheed Martin Advanced Energy Storage, Llc Aqueous redox flow batteries comprising metal ligand coordination compounds
US9991543B2 (en) 2012-07-27 2018-06-05 Lockheed Martin Advanced Energy Storage, Llc Aqueous redox flow batteries featuring improved cell design characteristics
WO2018111312A1 (fr) * 2016-12-14 2018-06-21 Lockheed Martin Advanced Energy Storage, Llc Complexes de catécholate de titane à insaturation coordinative et procédés associés à ceux-ci
US10065977B2 (en) 2016-10-19 2018-09-04 Lockheed Martin Advanced Energy Storage, Llc Concerted processes for forming 1,2,4-trihydroxybenzene from hydroquinone
US10164284B2 (en) 2012-07-27 2018-12-25 Lockheed Martin Energy, Llc Aqueous redox flow batteries featuring improved cell design characteristics
US10253051B2 (en) 2015-03-16 2019-04-09 Lockheed Martin Energy, Llc Preparation of titanium catecholate complexes in aqueous solution using titanium tetrachloride or titanium oxychloride
US10316047B2 (en) 2016-03-03 2019-06-11 Lockheed Martin Energy, Llc Processes for forming coordination complexes containing monosulfonated catecholate ligands
US10320023B2 (en) 2017-02-16 2019-06-11 Lockheed Martin Energy, Llc Neat methods for forming titanium catecholate complexes and associated compositions
US10343964B2 (en) 2016-07-26 2019-07-09 Lockheed Martin Energy, Llc Processes for forming titanium catechol complexes
US10377687B2 (en) 2016-07-26 2019-08-13 Lockheed Martin Energy, Llc Processes for forming titanium catechol complexes
US10644342B2 (en) 2016-03-03 2020-05-05 Lockheed Martin Energy, Llc Coordination complexes containing monosulfonated catecholate ligands and methods for producing the same
US10741864B2 (en) 2016-12-30 2020-08-11 Lockheed Martin Energy, Llc Aqueous methods for forming titanium catecholate complexes and associated compositions
US10930937B2 (en) 2016-11-23 2021-02-23 Lockheed Martin Energy, Llc Flow batteries incorporating active materials containing doubly bridged aromatic groups

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10164284B2 (en) 2012-07-27 2018-12-25 Lockheed Martin Energy, Llc Aqueous redox flow batteries featuring improved cell design characteristics
US9991544B2 (en) 2012-07-27 2018-06-05 Lockheed Martin Advanced Energy Storage, Llc Aqueous redox flow batteries comprising metal ligand coordination compounds
US9991543B2 (en) 2012-07-27 2018-06-05 Lockheed Martin Advanced Energy Storage, Llc Aqueous redox flow batteries featuring improved cell design characteristics
US10014546B2 (en) 2012-07-27 2018-07-03 Lockheed Martin Advanced Energy Storage, Llc Aqueous redox flow batteries comprising metal ligand coordination compounds
US10056639B2 (en) 2012-07-27 2018-08-21 Lockheed Martin Energy, Llc Aqueous redox flow batteries featuring improved cell design characteristics
US10734666B2 (en) 2014-11-26 2020-08-04 Lockheed Martin Energy, Llc Metal complexes of substituted catecholates and redox flow batteries containing the same
US9837679B2 (en) 2014-11-26 2017-12-05 Lockheed Martin Advanced Energy Storage, Llc Metal complexes of substituted catecholates and redox flow batteries containing the same
US10253051B2 (en) 2015-03-16 2019-04-09 Lockheed Martin Energy, Llc Preparation of titanium catecholate complexes in aqueous solution using titanium tetrachloride or titanium oxychloride
US10316047B2 (en) 2016-03-03 2019-06-11 Lockheed Martin Energy, Llc Processes for forming coordination complexes containing monosulfonated catecholate ligands
US10644342B2 (en) 2016-03-03 2020-05-05 Lockheed Martin Energy, Llc Coordination complexes containing monosulfonated catecholate ligands and methods for producing the same
US9938308B2 (en) 2016-04-07 2018-04-10 Lockheed Martin Energy, Llc Coordination compounds having redox non-innocent ligands and flow batteries containing the same
US10343964B2 (en) 2016-07-26 2019-07-09 Lockheed Martin Energy, Llc Processes for forming titanium catechol complexes
US10377687B2 (en) 2016-07-26 2019-08-13 Lockheed Martin Energy, Llc Processes for forming titanium catechol complexes
US10065977B2 (en) 2016-10-19 2018-09-04 Lockheed Martin Advanced Energy Storage, Llc Concerted processes for forming 1,2,4-trihydroxybenzene from hydroquinone
US10930937B2 (en) 2016-11-23 2021-02-23 Lockheed Martin Energy, Llc Flow batteries incorporating active materials containing doubly bridged aromatic groups
US12062795B2 (en) 2016-11-23 2024-08-13 Lockheed Martin Energy, Llc Flow batteries incorporating active materials containing doubly bridged aromatic groups
WO2018111312A1 (fr) * 2016-12-14 2018-06-21 Lockheed Martin Advanced Energy Storage, Llc Complexes de catécholate de titane à insaturation coordinative et procédés associés à ceux-ci
US10497958B2 (en) 2016-12-14 2019-12-03 Lockheed Martin Energy, Llc Coordinatively unsaturated titanium catecholate complexes and processes associated therewith
US10741864B2 (en) 2016-12-30 2020-08-11 Lockheed Martin Energy, Llc Aqueous methods for forming titanium catecholate complexes and associated compositions
US10320023B2 (en) 2017-02-16 2019-06-11 Lockheed Martin Energy, Llc Neat methods for forming titanium catecholate complexes and associated compositions

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