WO1998022476A1 - Synthese de titanocenes - Google Patents

Synthese de titanocenes Download PDF

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Publication number
WO1998022476A1
WO1998022476A1 PCT/US1996/018666 US9618666W WO9822476A1 WO 1998022476 A1 WO1998022476 A1 WO 1998022476A1 US 9618666 W US9618666 W US 9618666W WO 9822476 A1 WO9822476 A1 WO 9822476A1
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WO
WIPO (PCT)
Prior art keywords
titanocene
reaction mixture
ligand
titanium trichloride
solvent
Prior art date
Application number
PCT/US1996/018666
Other languages
English (en)
Inventor
Craig Blankenship
Original Assignee
Boulder Scientific Company
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
Priority to CA002243661A priority Critical patent/CA2243661A1/fr
Application filed by Boulder Scientific Company filed Critical Boulder Scientific Company
Priority to US09/117,090 priority patent/US6218557B1/en
Priority to PCT/US1996/018666 priority patent/WO1998022476A1/fr
Priority to EP96942783A priority patent/EP0885231A4/fr
Priority to JP10523601A priority patent/JP2000506545A/ja
Priority to AU11612/97A priority patent/AU719067B2/en
Priority to DE69719490T priority patent/DE69719490T2/de
Priority to PCT/US1997/021231 priority patent/WO1998022477A1/fr
Priority to CA002246417A priority patent/CA2246417C/fr
Priority to DK97948419T priority patent/DK0883623T3/da
Priority to EP97948419A priority patent/EP0883623B1/fr
Publication of WO1998022476A1 publication Critical patent/WO1998022476A1/fr
Priority to US10/053,997 priority patent/USRE38683E1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • C07F17/00—Metallocenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/122—Metal aryl or alkyl compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium

Definitions

  • This invention relates to the synthesis of titanocenes including constrained geometry titanocene catalysts utilizing a unique titanium trichloride reagent.
  • the early preparations of Group IV metallocenes involved reactions of the metal tetrahalides, typically the tetrachlorides, with deprotonated ligands, such as sodium cyclopentadienide, to give the metallocenes in good yields.
  • the metallocenes of current interest possess more complicated ligand structures, and their preparations are not as straightforward.
  • the use of titanium tetrachloride often results in low yields of the desired metallocenes. Titanium trichloride (TiCl 3 ) is often specified for use in place of titanium tetrachloride (TiCl 4 ) ; subsequent oxidation gives the desired metallocenes in greatly improved yields.
  • titanium trichloride so used is produced from commercial titanium tetrachloride. Titanium trichloride produced by hydrogen reduction of the tetrachloride is most often used in lab-scale preparations. For commercial-scale preparations, this is impractical due to cost and the presence of acidic impurities. These impurities require purification of the titanium trichloride, typically by preparation and isolation of an ether complex, usually the tetrahydrofuran complex.
  • titanium trichloride is produced by the reduction of the tetrachloride with alkyl aluminum compounds.
  • the titanium trichloride so produced contains aluminum chloride, which is not removed.
  • Typical analyses specify 76-79 weight percent of titanium trichloride with the remaining weight percent comprised mostly of aluminum chloride.
  • the use of aluminum-reduced titanium trichloride in metallocene preparations often gives products which contain varying amounts of aluminum- containing impurities. Separation of these impurities from the product titanocenes is not straightforward in most cases, especially on a commercial scale. The presence of these impurities can have significant adverse effects during subsequent uses of the titanocenes, particularly in olefin polymerizations. Accordingly, a need exists for a titanium trichloride reagent useful to produce titanocenes free of aluminum containing impurities.
  • Titanocene Compound - A compound comprised of titanium bonded to one or more cyclopentadienyl rings.
  • Titanocene Ligand - A chemical precursor which contains cyclopentadienyl or substituted cyclopentadienyl moieties (including indenyl, fluorenyl, etc.) used to prepare a titanocene compound.
  • CGC Constrained Geometry Catalyst
  • CpSA Ligand (t-butylamino) (tetramethylcyclo- pentadienyl) dimethylsilane. (CpSA) 2" - doubly-deprotonated CpSA ligand.
  • This invention includes a general method for producing titanium trichloride containing mixtures suitable for the preparation of titanium-containing metallocenes including constrained geometry Ti(IV), Ti(III) and Ti(II) complexes free of aluminum containing impurities.
  • the titanium trichloride containing mixtures are produced by the preferably stoichiometric (1:1) reaction of an organometallic compound, such as n-butyl lithium or n-butyl magnesium chloride, with titanium tetrachloride in a non-interfering solvent medium. These mixtures are used directly without isolation of the titanium trichloride in reactions with appropriate ligands to produce the desired titanocenes, including constrained geometry titanium complexes, in good yields. The resulting titanocene products are specifically free of aluminum-containing impurities.
  • organometallic compound such as n-butyl lithium or n-butyl magnesium chloride
  • the invention is a method for producing a titanium- containing metallocene compound which comprises separately providing a first reaction mixture containing titanium trichloride and a second reaction mixture containing a magnesium or alkali metal or alkaline earth metal salt of a metallocene compound ligand.
  • the first and second mixtures are combined for reaction to produce an intermediate from which an aluminum-free titanocene useful as an olefin polymerization catalyst may be synthesized.
  • the first reaction mixture is produced by reacting TiCl with an alkali metal compound having the formula R ⁇ -M or a Grignard reagent having the formula RMgX.
  • R is a straight or branched chain aliphatic hydrocarbon group, preferably an alkyl group, having 2 to 10 carbon atoms. R may also be an alkaline earth metal such as calcium, barium or strontium.
  • X is the value of M.
  • M is an alkali metal such as sodium, potassium or lithium.
  • X is a halogen, preferably chlorine.
  • n-butyl lithium or n-butyl magnesium chloride are preferred.
  • the reactants are combined in substantially stoichiometric amounts in a non-interfering, preferably hydrocarbon, medium.
  • Useful hydrocarbon media include aliphatic or aromatic hydrocarbons, such as hexane, heptane, cyclohexane, benzene, toluene and xylene. Toluene is preferred for the specific examples shown here.
  • Useful ether and polyether solvents include tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether, and dioxane. Mixtures of any hydrocarbon and ether solvents are useful for the reaction.
  • the reaction is preferably accomplished under dry, oxygen-free conditions.
  • the temperature at which the reaction is conveniently conducted is -20°C or 120 °C, with the optimum temperature range being 30-40 °C.
  • the second reaction mixture is separately provided by deprotonating the desired metallocene ligand with the appropriate base by known methods. See, generally, Paquette, et al., supra; Zaegel, et al., supra ; and Halterman, supra.
  • the first reaction mixture which includes the medium or solvent, titanium trichloride and a metal halide such a LiCl or MC1 2 , is added directly without isolation of the titanium trichloride to the second deprotonated ligand reaction mixture to produce a first titanocene.
  • FIGURE Figure 1 is a generalized depiction of steps (1) , (2), and (3) as comprised by one embodiment of the invention for preparation of a Ti(IV) complex constrained geometry catalyst.
  • Step (1) of Figure 1 illustrates the reaction of TiCl 4 in substantially stoichiometric amount with n-butyl lithium or n-butyl magnesium chloride to produce TiCl 3 and lithium or magnesium chloride in a hydrocarbon or ether medium, or mixed hydrocarbon and ether medium.
  • Step (2) of Figure 1 illustrates the double deprotonation of the metallocene compound ligand (t- butylamino) (tetramethylcyclopentadienyl) dimethylsilane (CpSA ligand) with an organometallic deprotonating agent, preferably an organolithium or an organomagnesium compound (Grignard reagent) , in a hydrocarbon medium, preferably toluene.
  • organometallic deprotonating agent preferably an organolithium or an organomagnesium compound (Grignard reagent)
  • the solvent medium and the organometallic compound may be the same as or different from the solvent medium and the organometallic compound used in Step (1) .
  • the concentration of the CpSA ligand in the solvent is appropriately 0.05 to 1.5 M, preferably 0.45 to 0.6 M.
  • Grignard reagent may be used to deprotonate the metallocene compound ligand, e.g. , CpSA.
  • Useful Grignard reagents have the formula RMgX as defined above.
  • Isopropyl magnesium chloride is preferred.
  • a practical range of Grignard concentration in the solvent is 0.5 to 3.0 M, preferably 1.9 to 2.3 M.
  • the temperature is controlled to be 45-50 °C. at the end of the Grignard feed, and then heated to 85-90 °C for the prescribed time.
  • Step (2) reaction mixture is preferably used directly in Step (3) as the toluene solution present in the reaction vessel in which it is produced.
  • Step (3) of Figure 1 illustrates one method for reacting the titanium trichloride containing reaction mixture of Step (1) with the (CpSA) 2" containing second reaction mixture of Step (2) to produce [(t-butylamido) (tetramethylcyclopentadienyl) dimethylsilane]titanium dichloride, (CpSA) 2" TiCl 2 .
  • the agitated Step (1) reaction mixture is transferred directly into the reactor containing agitated Step (2) reaction mixture.
  • the vessel which contained the Step (1) mixture is rinsed with toluene which is then charged to the Step (3) reactor.
  • the exothermic reaction mixture becomes reddish brown in color. A temperature rise of about 15°C. is usually observed.
  • a chloride-containing oxidizing agent such as dichloromethane or silver chloride, is then charged to the reaction vessel utilized in Step (3) .
  • the resulting reaction mixture is agitated for a time appropriate, usually about two hours, for the Step (3) reaction to occur.
  • Solvents are removed under reduced pressure, i.e., 60-80 mm Hg, to about one-half of the starting volume. Hydrocarbon solvent, e.g., toluene, is added back, Celite ® filter aid is added, and the mixture is filtered. Solvents are distilled to concentrate the product.
  • Hydrocarbon solvent e.g., toluene
  • the solid titanocene can be isolated from this mixture by methods dependent upon the actual compound being produced.
  • the reaction apparatus consisted of a 500-mL 3-neck flask equipped with a mechanical stirrer. On one side-neck was placed a Claisen adapter with a reflux condenser and a thermometer inserted into the reaction mixture. This apparatus was previously dried and then purged with nitrogen after assembly. The solvent was added via the other side-neck of the reaction flask, which was then capped with a rubber septum.
  • TiCl 4 (ca. 25 mL, 42-44 g.
  • the reaction apparatus consisted of a 2000-mL 3-neck flask equipped with a mechanical stirrer; on one side- neck was placed a Claisen adapter with a Vigereaux column and distillation head for solvent distillation. A thermometer was inserted into the reaction flask through the Claisen adapter. The glass apparatus was previously dried and purged with nitrogen after assembly. Toluene (425 mL) and CpSA ligand (55.0 g, 0.219 mol) were added to the reaction flask. The temperature of the reaction mixture was adjusted to 45-50°C.
  • the reaction apparatus consisted of a 2000-mL 3-neck flask equipped with a mechanical stirrer; on one side- neck was placed a Claisen adapter with a reflux condenser and a thermometer inserted into the reaction flask.
  • the glass apparatus was previously dried and purged with nitrogen after assembly.
  • Ether (300 mL) and CpSA ligand (62.9 g, 0.250 mol) were added to the reaction flask.
  • the reaction mixture was cooled to -20°C.
  • a solution of BuLi in hexanes 305 mL of a 0.170 M solution, 0.518 mol of BuLi was added over 1.5 hours; the temperature was maintained at -20 to -15°C during this addition.
  • This toluene solution is again filtered under nitrogen pressure to remove residual magnesium salts.
  • the filtrate is concentrated again to a volume of 200 mL by simple distillation under reduced pressure.
  • Heptanes 400 L were added over 30 min with stirring at 20-25°C.
  • a first crop of orange, crystalline (CpSA) 2" TiCl 2 is collected by filtration under nitrogen, washing with heptanes, to give 61.1 g of product in 76% yield.
  • a second crop was obtained by concentration of the mother liquors to ca. 100 mL and dilution with heptanes.
  • the product solution in toluene obtained after removal of the magnesium salts was used directly to prepare other metallocenes.
  • the toluene solution of (CpSA) 2" TiCl 2 was treated with 2 equivalents of methylmagnesium chloride (THF solution) to give (CpSA) 2" Ti(CH 3 ) 2 in 70-75% overall yield.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne un procédé qui permet de préparer des composés métallocènes contenant du titane, notamment des complexes de titane à géométrie contrainte, utiles comme catalyseurs de polymérisation des oléfines. Selon l'invention, on convertit le tétrachlorure de titane en trichlorure de titane par réaction avec un composé métallique dans un solvant neutre, de façon à produire un mélange qui peut être directement utilisé pour la réaction avec un ligand métallocène déprotoné. Les composés titanocènes produits selon l'invention sont dépourvus de traces d'aluminium risquant de perturber la réaction de polymérisation.
PCT/US1996/018666 1996-11-22 1996-11-22 Synthese de titanocenes WO1998022476A1 (fr)

Priority Applications (12)

Application Number Priority Date Filing Date Title
AU11612/97A AU719067B2 (en) 1996-11-22 1996-11-22 Synthesis of titanocenes
US09/117,090 US6218557B1 (en) 1996-11-22 1996-11-22 Synthesis of titanocenes
PCT/US1996/018666 WO1998022476A1 (fr) 1996-11-22 1996-11-22 Synthese de titanocenes
EP96942783A EP0885231A4 (fr) 1996-11-22 1996-11-22 Synthese de titanocenes
JP10523601A JP2000506545A (ja) 1996-11-22 1996-11-22 チタノセンの合成
CA002243661A CA2243661A1 (fr) 1996-11-22 1996-11-22 Synthese de titanocenes
DE69719490T DE69719490T2 (de) 1996-11-22 1997-11-19 Herstellung von chiralen titanocenen
DK97948419T DK0883623T3 (da) 1996-11-22 1997-11-19 Fremstilling af chirale titanocener
CA002246417A CA2246417C (fr) 1996-11-22 1997-11-19 Preparation de titanocenes chiraux
PCT/US1997/021231 WO1998022477A1 (fr) 1996-11-22 1997-11-19 Preparation de titanocenes chiraux
EP97948419A EP0883623B1 (fr) 1996-11-22 1997-11-19 Preparation de titanocenes chiraux
US10/053,997 USRE38683E1 (en) 1996-11-22 2002-01-19 Preparation of titanocenes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/US1996/018666 WO1998022476A1 (fr) 1996-11-22 1996-11-22 Synthese de titanocenes
CA002243661A CA2243661A1 (fr) 1996-11-22 1996-11-22 Synthese de titanocenes

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US08/885,805 Continuation-In-Part US5847176A (en) 1996-11-22 1997-06-30 Preparation of chiral titanocenes

Publications (1)

Publication Number Publication Date
WO1998022476A1 true WO1998022476A1 (fr) 1998-05-28

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Application Number Title Priority Date Filing Date
PCT/US1996/018666 WO1998022476A1 (fr) 1996-11-22 1996-11-22 Synthese de titanocenes

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EP (1) EP0885231A4 (fr)
CA (1) CA2243661A1 (fr)
WO (1) WO1998022476A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5350723A (en) * 1992-05-15 1994-09-27 The Dow Chemical Company Process for preparation of monocyclopentadienyl metal complex compounds and method of use
US5504224A (en) * 1994-03-14 1996-04-02 The Dow Chemical Company Preparation of monocyclopentadienyl metal complexes by nucleophilic substitution of bis(cyclopentadienyl) metal complexes

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5455333A (en) * 1993-08-16 1995-10-03 Albemarle Corporation Preparation of metallocenes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5350723A (en) * 1992-05-15 1994-09-27 The Dow Chemical Company Process for preparation of monocyclopentadienyl metal complex compounds and method of use
US5504224A (en) * 1994-03-14 1996-04-02 The Dow Chemical Company Preparation of monocyclopentadienyl metal complexes by nucleophilic substitution of bis(cyclopentadienyl) metal complexes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FELD RAOUL et al., "The Organic Chemistry of Titanium", WASHINGTON, D.C.: BUTTERWORTHS, 1965, page 154. *
See also references of EP0885231A4 *

Also Published As

Publication number Publication date
CA2243661A1 (fr) 1998-05-28
EP0885231A1 (fr) 1998-12-23
EP0885231A4 (fr) 2000-02-09

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