CA2243661A1 - Synthesis of titanocenes - Google Patents
Synthesis of titanocenes Download PDFInfo
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- CA2243661A1 CA2243661A1 CA002243661A CA2243661A CA2243661A1 CA 2243661 A1 CA2243661 A1 CA 2243661A1 CA 002243661 A CA002243661 A CA 002243661A CA 2243661 A CA2243661 A CA 2243661A CA 2243661 A1 CA2243661 A1 CA 2243661A1
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- titanocene
- reaction mixture
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- titanium trichloride
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
Abstract
A method for the preparation of titanium-containing metallocene compounds, including constrained geometry titanium complexes, useful as olefin polymerization catalysts is disclosed. Pursuant to the invention, titanium tetrachloride is converted to titanium trichloride by reaction with a metal compound in a non-interfering solvent to produce a mixture useful directly for reaction with a deprotonated metallocene ligand. The titanocene compounds produced pursuant to the invention are free of trace amounts of aluminum which can adversely affect the polymerization reaction.
Description
W O 98n2476 rCT~US96/1&~
~YNTHE8I8 OF TITANOCENE8 FT~Tn OF TRE TNV~pTlON
This invention relates to the synthesis of titanocenes including constrained geometry titanocene catalysts utilizing a unique titanium trichloride reagent.
BA~-~kGuND OF T~ TNV~NTION
The evolution of metallocene-h~~1 catalysts for the polymerization of ethylene and higher ~-olefins is reviewed in H.H. Brintzinger, et al., Anq~ew.
~hem.Int.~.Enal. 34:1143-1170 (1995) and in P.C.
Mohring, et al., J. Orqanomet~l.Chem. 479:1-29 (1994).
The applications of chiral metallocenes in organic synthesis are reviewed in R.L. Halterman, Chem.Rev.
~:965-994 (1992). These reviews highlight the applications of state-of-the art metallocenes. Most often, these applications center on the use of titanium containing and other Group IV metallocenes.
The early preparation$ of Group IV metallocenes involved reactions of the metal tetrahalides, typically the tetrachlorides, with deprotonated ligands, such as sodium cyclopentadienide, to give the metallocene~ in good yields. The metallorQn~c of current interest possess more complicated ligand structures, and their preparations are not as straightforward. For the preparation of these metallocenes, the use of titanium tetrachloride often results in low yields of the desired metallocenes. Titanium trlchloride (TiC13) is often specified for use in place of titanium tetrachloride (TiCl~); subsequent oxidation gives the desired metallocenes in greatly improved yields.
For some recent examples which specify the use of titanium trichloride, see L.A. Paquette, et al., Orqanome~llics ~:4865-4878 (1995): F. Zaegel, et al., Or~anometallics 14:4576-4584 (1995); and M. E.
Huttenloch, et al., Orqanonetallics 11:3600-3607 (lg92).
Halterman, supra, cites references which show the use of titanium trichloride in several metallocene preparations.
. . .. .. ... . .. ... . ... .
W098/22476 PCT~S96118666 The titanium trichloride so used is produced from commercial titanium tetrachloride. Titanium trichloride produced ~y hydrogen reduction of the tetrachloride is most often used in lab-scale preparations. ~or 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.
Commercially-available 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 pres~nc~ of these impurities can have significant adverse effects during subseguent 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.
D~ ~lNl~ lON8 For the purposes of this invention, the following terms have the meaning stated:
Tit~noq~ns Compound - A compound comprised of titanium bonded to one or more cyclopentadienyl rings.
Tit~nocene Ligand - A chemical precursor which contains cyclopentadienyl or substituted cyclopentadienyl W O 98n2476 PCT~US96/18666 moieties (including indenyl, fluorenyl, etc.) used to prepare a titanocene compound.
Constrained ~eometry Catalyst (CGC) - A catalyst in which the metal center is contained in a ring structure and covalently bonded to a cyclic group via a delocalized ~-system and covalently bonded via a sigma-bond to another atom such as carbon, nitrogen, oxygen, etc. A
small ring size induces constraint about the metal atom center. For titanium-containing CGC's, the incorporated titanium atom can be in a formal ~4, +3, or +2 oxidation state. See EP application 90309496.9, WO 95/00526 and U.S. Patent 5,470,996.
CpSA Ligand - (t-butylamino)(tetramethylcyclo-pentadienyl)dimethylsilane.
(Cp8A) 2- _ doubly-deprotonated CpSA ligand.
(Cp~A)2-TiClz - [(t-butylamido)(tetramethylcyclo-pentadienyl)dimethylsilane]titanium dichloride.
8ubstantially 8toichiometric A~ount - An amount not less than 90% nor more that 110% of stoichiometric.
~UNMARY OF T~ INV~TION
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 W 0 9X~2476 PCT~US96/18666 - resulting titanocene products are specifically free of aluminum-containing impurities.
D~TA~LED DBSCRI~TION OF THE INVENTION
The invention is a method for producing a titanium-con~ining metallocene compound which comprisesseparately 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 TiCl4 with an alkali metal compound having the formula ~-M or a Grignard reagent having the formula RMgX. In each formula, 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. In the formula ~-M, M is an alkali metal such as sodium, potassium or lithium. In the formula KMgX, 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, cycloheY~e, 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.
W098~2476 PCT~S96/18~6 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 i~ separately provided by deprotonating the desired metallocene ligand with the appropriate base by known methods. See, generally, Paquette, et al., ~u~ra; Zaegel, et al., su~ra; and Halterman, supra.
The first reaction mixture, which includes the medium or solvent, titanium trichloride and a metal halide such a LiCl or MCl2, is added directly without isolation of the titanium trichloride to the second deprotonated ligand reaction mixture to produce a first titanocene.
DE~CRIPTION OF THE FIGU~
Figure l is a generalized depiction of steps (l), (2), and (3) as comprised by one embodiment of the invention for preparation of a Ti(IV) complex constrained geometry catalyst.
Ste~ Al~mi~um-Free TiCl3 Step (l~ of Figure l illustrates the reaction of TiCl4 in substantially stoichiometric amount with n-butyl lithium or n-butyl magnesium chloride to produce TiCl3 and lithium or magnesium chloride in a hydrocarbon or ether medium, or mixed hydrocarbon and ether medium.
Step (2) - Deprotonation Of a Metallocene Co~pound Liqand Step (2) of Figure l illustrates the double deprotonation of the metallocene compound ligand (~-butylamino)(tetramethylcyclopentadienyl)dimethylsilane (CpSA ligand) with an organometallic deprotonating agent, preferably an organolithium or an organomagnesium W 0 98/22476 PCT~USg6/18666 ~u.~oulld (Grignard reagent), in a hydrocarbon medium, preferably toluene.
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.
Any 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. For CpSA, 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.
The 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) - Reaction of TiCl3 With De~rotonated Liqands- Production of (CDSA)2-TiCl2 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- ~iC12.
In this embodiment of the invention, the agitated Step (1) reaction mixture is transferred directly into the reactor containing a~itated Step (2) reaction mixture. Preferably, 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.
wo9~n~76 PCT~S96/1~6 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 i9 added, and the mixture is filtered. Solvent~ are distilled to concentrate the product.
The solid titanocene can be isolated from this mixture by methods dependent upon the actual compound being produced. For the (CpSA)2-TiCl2 example shown in Figure l, the solid product was collected in 75-80% yield a~ described in Example 6. Additional material of lower purity can be isolated upon further manipulation of the mother liquors. Alternatively, the product solution obtained after removal of the magnesium salts can be used directly to produce other metallocenes described in Example 6.
EXEMPLIFICATION OF THE INV~NTION
Preparative Procedures For Titanium Trichloride 25Reactant Mixtures and Resultinq Metallocenes The general procedure for the preparation of titanium trichloride-containing mixtures by the reaction of titanium tetrachloride and an organometallic compound under an inert atmosphere is first described, followed by three specific examples. 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 WOg8~76 PCT~S96/18666 assem~ly. The solvent was added via the other side-neck of the reaction flask, which was then capped with a rubber septum. TiC14 (ca. 25 mL, 42-44 g. 0.22-0.23 mol) was transferred from a weighed bottle to the reaction flask using a syringe. The rubber septum was replaced with a dried, nitrogen-purged addition funnel. The THF
and/or the organometallic compound was transferred to the addition funnel and then added to the TiCl4/solvent reaction mixture at the de6ired temperature.
~MPLE 1 A solution of n-butyllithium (BuLi) in he~nes (156 mL of a 1.60 M solution, 0.250 mol of BuLi) was added to TiCl4 (43.0 g, 0.227 mol) in 300 mL of toluene over 30 min. The initial temperature of the reaction mixture was 10~C, the temperature increased to 40~C during the addition, and was then maintained at 35-40DC using external cooling. After the addition of the BuLi, the reaction mixture was stirred at 35-40-C for 1 hour.
After cooling to room temperature, the addition funnel, ¢ondenser, and Claisen adapter were removed while maintaining an inert atmosphere of nitrogen over the TiCl3 product mixture. The resulting TiC13 containing mixture was used directly in reactions with deprotonated metallocene ligands.
EX~MP1F 2 THF (100 mL) was added to a solution of TiCl4 (43.4 g, 0.229 mol) in 200 mL of toluene over 30 minutes at 0-15~C. Then BuLi in hexanes (156 mL of a 1.60 M
solution, 0.250 mol) was added over 40 min at 5-lO-C.
The resulting mixture was heated to 35-40~C and stirred for 1 hour. After cooling, the resulting TiC13 slurry was used direct~y in reactions with deprotonated ligands.
EXAMP~ 3 THF (75 mL) was added to a solution of TiCl4 (42.0 g, 0.221 mol) in 150 mL of toluene over 20 min at 0-15~C.
W O 9&~2476 rCTAUS96/186G6 _g_ Then a solution of butylmagnesium chloride ~BuMgCl) in THF (115 mL of a 2.10M solution, 0.242 mol of BuMgCl) was added over 30 min. The initial temperature of the reaction mixture was O~C; the temperature increased to 40~C during the addition and was then maintained at 35-40~C using external cooling. After the BuMgCl addition, the reaction mixture was stirred for 1 hour at 35-40-C. The resulting TiCl3 product slurry was used directly in reactions with deprotonated ligands.
EXAMP~
The D-protonation of Cp8A ~ig~nd ~ith i-Propylmagn-s;um Chloride The reaction apparatus consisted of a 2000-mL 3-neck flask e~uipped with a mechAnical stirrer; on one side-neck was placed a Claisen adapter with a Vigereaux columnand 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 45-50CC. A solution of i-propylmagnesium chloride (i-PrMgCl) in ether (205 mL of a 2.30 M solution, 0.472 mol of i-PrMgCl) was added over l hour using an addition funnel. After the i-PrMgCl addition, the reaction mixture was gradually heated to 85-90~C over 2 hours and stirred at this temperature for an additional 2 hours. The (CpSA)Z~(MgCl)2 formed a gummy solid at thi~ stage. The heating is removed and the temperature of the reaction mixture cooled to 60-65~C. At this temperature, THF (150 mL) was added dropwise over 15 min, which dissolved the solid (CpSA)2-(MgCl)2. The reaction mixture is then cooled to room temperature. The distillation head, Vigereaux column, and addition funnel are then removed from the reaction W 0 9~22476 PCTrUS96/18666 apparatus while maintaining an inert atmosphere of nitrogen over the product mixture. This (CpSA) 2- (MgCl) 2 solution was then used directly in a reaction with a TiCl3 slurry prepared previously.
EXAMP~ 5 The Deprotonation of Cp8A
Liaand wi~ n-Butyl~ithium 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 condenserand 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 he~Anes (305 mL of a 0.170 ~ solution, 0.518 mol of BuLi) was added over 1.5 hours; the temperature was maintained at -20 to -15-C during this addition. The reaction mixture was then warmed to 0-5-C over 1.5 hours and stirred at this temperature for 3 hours. The resulting (CpSA)2-Liz slurry, which consisted of a white solid with a pale yellow supernatant, was used directly in a reaction with a TiC13 slurry prepared as described in Examples 1 to 3.
EX~MP~E 6 The Preparation of (C~A)2-TiCl2 The TiCl3 containing mixture from Example 1 above was transferred under nitrogen pressure via a wide-bore cannula to the (CpSA)Z~(MgCl) 2 solution from Example 4 above over 2-3 min. Toluene (100 mL) was added to the TiCl3 flask which contained some residual TiC13, and this wash was quickly transferred to the reaction flask. The initial temperature of the reaction mixture was 22-C: the temperature increased to 3~~C during the TiCl3 addition.
The reaction mixture was stirred for 15 min at 35~C, at CA 0224366l l998-07-20 W O 98/22476 PCT~USg6/18666 - which time dichloromethane (13.5 g) was added over 1 min;
the temperature increased to 38-C. The resulting red-brown mixture was stirred for 2 hours with gradual cooling to 25~C. Solvents were removed by simple distillation under reduced pressure (60-80 mm Hg) to a final volume of ca. 600 mL; the temperature ranged from 30 to 60-C during this distillation. After cooling to 20-C and pressurizing with nitrogen, toluene (400 mL) was added to the product mixture. Magnesium salts were removed from this mixture by pressure filtration under nitrogen using Celite~ filter-aid. The reaction flask and filter cake were washed with two 200-m~ portions of fresh toluene. The red-brown filtrate was concentrated by simple distillation under reduced pressure as before to a volume of 400 mL. 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 mL) were added over 30 min with stirring at 20-25-C. A first crop of orange, crystalline (CpSA)2-TiCl2 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.
Alternatively, the product solution in toluene obtained after removal of the magnesium salts was used directly to prepare other metallocenes. For example, the toluene solution of (CpSA)2-TiCl2 was treated with 2 equivalents of methylmagnesium chloride ~THF solution) to give (CpSA)2-Ti(CH3) 2 in 70-7596 overall yield.
~YNTHE8I8 OF TITANOCENE8 FT~Tn OF TRE TNV~pTlON
This invention relates to the synthesis of titanocenes including constrained geometry titanocene catalysts utilizing a unique titanium trichloride reagent.
BA~-~kGuND OF T~ TNV~NTION
The evolution of metallocene-h~~1 catalysts for the polymerization of ethylene and higher ~-olefins is reviewed in H.H. Brintzinger, et al., Anq~ew.
~hem.Int.~.Enal. 34:1143-1170 (1995) and in P.C.
Mohring, et al., J. Orqanomet~l.Chem. 479:1-29 (1994).
The applications of chiral metallocenes in organic synthesis are reviewed in R.L. Halterman, Chem.Rev.
~:965-994 (1992). These reviews highlight the applications of state-of-the art metallocenes. Most often, these applications center on the use of titanium containing and other Group IV metallocenes.
The early preparation$ of Group IV metallocenes involved reactions of the metal tetrahalides, typically the tetrachlorides, with deprotonated ligands, such as sodium cyclopentadienide, to give the metallocene~ in good yields. The metallorQn~c of current interest possess more complicated ligand structures, and their preparations are not as straightforward. For the preparation of these metallocenes, the use of titanium tetrachloride often results in low yields of the desired metallocenes. Titanium trlchloride (TiC13) is often specified for use in place of titanium tetrachloride (TiCl~); subsequent oxidation gives the desired metallocenes in greatly improved yields.
For some recent examples which specify the use of titanium trichloride, see L.A. Paquette, et al., Orqanome~llics ~:4865-4878 (1995): F. Zaegel, et al., Or~anometallics 14:4576-4584 (1995); and M. E.
Huttenloch, et al., Orqanonetallics 11:3600-3607 (lg92).
Halterman, supra, cites references which show the use of titanium trichloride in several metallocene preparations.
. . .. .. ... . .. ... . ... .
W098/22476 PCT~S96118666 The titanium trichloride so used is produced from commercial titanium tetrachloride. Titanium trichloride produced ~y hydrogen reduction of the tetrachloride is most often used in lab-scale preparations. ~or 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.
Commercially-available 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 pres~nc~ of these impurities can have significant adverse effects during subseguent 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.
D~ ~lNl~ lON8 For the purposes of this invention, the following terms have the meaning stated:
Tit~noq~ns Compound - A compound comprised of titanium bonded to one or more cyclopentadienyl rings.
Tit~nocene Ligand - A chemical precursor which contains cyclopentadienyl or substituted cyclopentadienyl W O 98n2476 PCT~US96/18666 moieties (including indenyl, fluorenyl, etc.) used to prepare a titanocene compound.
Constrained ~eometry Catalyst (CGC) - A catalyst in which the metal center is contained in a ring structure and covalently bonded to a cyclic group via a delocalized ~-system and covalently bonded via a sigma-bond to another atom such as carbon, nitrogen, oxygen, etc. A
small ring size induces constraint about the metal atom center. For titanium-containing CGC's, the incorporated titanium atom can be in a formal ~4, +3, or +2 oxidation state. See EP application 90309496.9, WO 95/00526 and U.S. Patent 5,470,996.
CpSA Ligand - (t-butylamino)(tetramethylcyclo-pentadienyl)dimethylsilane.
(Cp8A) 2- _ doubly-deprotonated CpSA ligand.
(Cp~A)2-TiClz - [(t-butylamido)(tetramethylcyclo-pentadienyl)dimethylsilane]titanium dichloride.
8ubstantially 8toichiometric A~ount - An amount not less than 90% nor more that 110% of stoichiometric.
~UNMARY OF T~ INV~TION
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 W 0 9X~2476 PCT~US96/18666 - resulting titanocene products are specifically free of aluminum-containing impurities.
D~TA~LED DBSCRI~TION OF THE INVENTION
The invention is a method for producing a titanium-con~ining metallocene compound which comprisesseparately 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 TiCl4 with an alkali metal compound having the formula ~-M or a Grignard reagent having the formula RMgX. In each formula, 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. In the formula ~-M, M is an alkali metal such as sodium, potassium or lithium. In the formula KMgX, 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, cycloheY~e, 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.
W098~2476 PCT~S96/18~6 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 i~ separately provided by deprotonating the desired metallocene ligand with the appropriate base by known methods. See, generally, Paquette, et al., ~u~ra; Zaegel, et al., su~ra; and Halterman, supra.
The first reaction mixture, which includes the medium or solvent, titanium trichloride and a metal halide such a LiCl or MCl2, is added directly without isolation of the titanium trichloride to the second deprotonated ligand reaction mixture to produce a first titanocene.
DE~CRIPTION OF THE FIGU~
Figure l is a generalized depiction of steps (l), (2), and (3) as comprised by one embodiment of the invention for preparation of a Ti(IV) complex constrained geometry catalyst.
Ste~ Al~mi~um-Free TiCl3 Step (l~ of Figure l illustrates the reaction of TiCl4 in substantially stoichiometric amount with n-butyl lithium or n-butyl magnesium chloride to produce TiCl3 and lithium or magnesium chloride in a hydrocarbon or ether medium, or mixed hydrocarbon and ether medium.
Step (2) - Deprotonation Of a Metallocene Co~pound Liqand Step (2) of Figure l illustrates the double deprotonation of the metallocene compound ligand (~-butylamino)(tetramethylcyclopentadienyl)dimethylsilane (CpSA ligand) with an organometallic deprotonating agent, preferably an organolithium or an organomagnesium W 0 98/22476 PCT~USg6/18666 ~u.~oulld (Grignard reagent), in a hydrocarbon medium, preferably toluene.
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.
Any 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. For CpSA, 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.
The 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) - Reaction of TiCl3 With De~rotonated Liqands- Production of (CDSA)2-TiCl2 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- ~iC12.
In this embodiment of the invention, the agitated Step (1) reaction mixture is transferred directly into the reactor containing a~itated Step (2) reaction mixture. Preferably, 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.
wo9~n~76 PCT~S96/1~6 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 i9 added, and the mixture is filtered. Solvent~ are distilled to concentrate the product.
The solid titanocene can be isolated from this mixture by methods dependent upon the actual compound being produced. For the (CpSA)2-TiCl2 example shown in Figure l, the solid product was collected in 75-80% yield a~ described in Example 6. Additional material of lower purity can be isolated upon further manipulation of the mother liquors. Alternatively, the product solution obtained after removal of the magnesium salts can be used directly to produce other metallocenes described in Example 6.
EXEMPLIFICATION OF THE INV~NTION
Preparative Procedures For Titanium Trichloride 25Reactant Mixtures and Resultinq Metallocenes The general procedure for the preparation of titanium trichloride-containing mixtures by the reaction of titanium tetrachloride and an organometallic compound under an inert atmosphere is first described, followed by three specific examples. 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 WOg8~76 PCT~S96/18666 assem~ly. The solvent was added via the other side-neck of the reaction flask, which was then capped with a rubber septum. TiC14 (ca. 25 mL, 42-44 g. 0.22-0.23 mol) was transferred from a weighed bottle to the reaction flask using a syringe. The rubber septum was replaced with a dried, nitrogen-purged addition funnel. The THF
and/or the organometallic compound was transferred to the addition funnel and then added to the TiCl4/solvent reaction mixture at the de6ired temperature.
~MPLE 1 A solution of n-butyllithium (BuLi) in he~nes (156 mL of a 1.60 M solution, 0.250 mol of BuLi) was added to TiCl4 (43.0 g, 0.227 mol) in 300 mL of toluene over 30 min. The initial temperature of the reaction mixture was 10~C, the temperature increased to 40~C during the addition, and was then maintained at 35-40DC using external cooling. After the addition of the BuLi, the reaction mixture was stirred at 35-40-C for 1 hour.
After cooling to room temperature, the addition funnel, ¢ondenser, and Claisen adapter were removed while maintaining an inert atmosphere of nitrogen over the TiCl3 product mixture. The resulting TiC13 containing mixture was used directly in reactions with deprotonated metallocene ligands.
EX~MP1F 2 THF (100 mL) was added to a solution of TiCl4 (43.4 g, 0.229 mol) in 200 mL of toluene over 30 minutes at 0-15~C. Then BuLi in hexanes (156 mL of a 1.60 M
solution, 0.250 mol) was added over 40 min at 5-lO-C.
The resulting mixture was heated to 35-40~C and stirred for 1 hour. After cooling, the resulting TiC13 slurry was used direct~y in reactions with deprotonated ligands.
EXAMP~ 3 THF (75 mL) was added to a solution of TiCl4 (42.0 g, 0.221 mol) in 150 mL of toluene over 20 min at 0-15~C.
W O 9&~2476 rCTAUS96/186G6 _g_ Then a solution of butylmagnesium chloride ~BuMgCl) in THF (115 mL of a 2.10M solution, 0.242 mol of BuMgCl) was added over 30 min. The initial temperature of the reaction mixture was O~C; the temperature increased to 40~C during the addition and was then maintained at 35-40~C using external cooling. After the BuMgCl addition, the reaction mixture was stirred for 1 hour at 35-40-C. The resulting TiCl3 product slurry was used directly in reactions with deprotonated ligands.
EXAMP~
The D-protonation of Cp8A ~ig~nd ~ith i-Propylmagn-s;um Chloride The reaction apparatus consisted of a 2000-mL 3-neck flask e~uipped with a mechAnical stirrer; on one side-neck was placed a Claisen adapter with a Vigereaux columnand 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 45-50CC. A solution of i-propylmagnesium chloride (i-PrMgCl) in ether (205 mL of a 2.30 M solution, 0.472 mol of i-PrMgCl) was added over l hour using an addition funnel. After the i-PrMgCl addition, the reaction mixture was gradually heated to 85-90~C over 2 hours and stirred at this temperature for an additional 2 hours. The (CpSA)Z~(MgCl)2 formed a gummy solid at thi~ stage. The heating is removed and the temperature of the reaction mixture cooled to 60-65~C. At this temperature, THF (150 mL) was added dropwise over 15 min, which dissolved the solid (CpSA)2-(MgCl)2. The reaction mixture is then cooled to room temperature. The distillation head, Vigereaux column, and addition funnel are then removed from the reaction W 0 9~22476 PCTrUS96/18666 apparatus while maintaining an inert atmosphere of nitrogen over the product mixture. This (CpSA) 2- (MgCl) 2 solution was then used directly in a reaction with a TiCl3 slurry prepared previously.
EXAMP~ 5 The Deprotonation of Cp8A
Liaand wi~ n-Butyl~ithium 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 condenserand 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 he~Anes (305 mL of a 0.170 ~ solution, 0.518 mol of BuLi) was added over 1.5 hours; the temperature was maintained at -20 to -15-C during this addition. The reaction mixture was then warmed to 0-5-C over 1.5 hours and stirred at this temperature for 3 hours. The resulting (CpSA)2-Liz slurry, which consisted of a white solid with a pale yellow supernatant, was used directly in a reaction with a TiC13 slurry prepared as described in Examples 1 to 3.
EX~MP~E 6 The Preparation of (C~A)2-TiCl2 The TiCl3 containing mixture from Example 1 above was transferred under nitrogen pressure via a wide-bore cannula to the (CpSA)Z~(MgCl) 2 solution from Example 4 above over 2-3 min. Toluene (100 mL) was added to the TiCl3 flask which contained some residual TiC13, and this wash was quickly transferred to the reaction flask. The initial temperature of the reaction mixture was 22-C: the temperature increased to 3~~C during the TiCl3 addition.
The reaction mixture was stirred for 15 min at 35~C, at CA 0224366l l998-07-20 W O 98/22476 PCT~USg6/18666 - which time dichloromethane (13.5 g) was added over 1 min;
the temperature increased to 38-C. The resulting red-brown mixture was stirred for 2 hours with gradual cooling to 25~C. Solvents were removed by simple distillation under reduced pressure (60-80 mm Hg) to a final volume of ca. 600 mL; the temperature ranged from 30 to 60-C during this distillation. After cooling to 20-C and pressurizing with nitrogen, toluene (400 mL) was added to the product mixture. Magnesium salts were removed from this mixture by pressure filtration under nitrogen using Celite~ filter-aid. The reaction flask and filter cake were washed with two 200-m~ portions of fresh toluene. The red-brown filtrate was concentrated by simple distillation under reduced pressure as before to a volume of 400 mL. 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 mL) were added over 30 min with stirring at 20-25-C. A first crop of orange, crystalline (CpSA)2-TiCl2 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.
Alternatively, the product solution in toluene obtained after removal of the magnesium salts was used directly to prepare other metallocenes. For example, the toluene solution of (CpSA)2-TiCl2 was treated with 2 equivalents of methylmagnesium chloride ~THF solution) to give (CpSA)2-Ti(CH3) 2 in 70-7596 overall yield.
Claims (12)
1. In a process for producing a titanocene wherein a titanium trichloride reagent is reacted with a titanocene ligand, the improvement which comprises:
(i) utilizing as said titanium trichloride reagent a mixture produced by reacting titanium tetrachloride with a compound having the formula R-M, in which R is a straight or branched chain alkyl group having 2 to 8 carbon atoms and M is an alkali metal, or the formula RMgX, in which X is a halogen in substantially stoichiometric amount in a non-interfering solvent wherein a reaction mixture containing titanium trichloride, said solvent and a MCl or MgCl2 is produced;
and (ii) reacting said step (i) reaction mixture directly with said titanocene ligand to produce a titanocene.
(i) utilizing as said titanium trichloride reagent a mixture produced by reacting titanium tetrachloride with a compound having the formula R-M, in which R is a straight or branched chain alkyl group having 2 to 8 carbon atoms and M is an alkali metal, or the formula RMgX, in which X is a halogen in substantially stoichiometric amount in a non-interfering solvent wherein a reaction mixture containing titanium trichloride, said solvent and a MCl or MgCl2 is produced;
and (ii) reacting said step (i) reaction mixture directly with said titanocene ligand to produce a titanocene.
2. The process of claim 1 in which said titanium trichloride and said ligand are reacted at a temperature in the range of -20 to 120°C.
3. The process of claim 1 in which said compound RM
is added to titanium tetrachloride at an initial temperature range of 10-20°C, after which the reaction mixture is heated to 34-40°C for about one hour.
is added to titanium tetrachloride at an initial temperature range of 10-20°C, after which the reaction mixture is heated to 34-40°C for about one hour.
4. The process of claim 1 in which said non-interfering solvent is a hydrocarbon.
5. The process of claim 1 in which said non-interfering solve is a hexane, a heptane, benzene, toluene, a xylene, or a mixture thereof.
6. The process of claim 1 in which the ether solvent is a cyclic or cyclic ethers or a polyether.
7. The process of claim 1 in which an non-interfering solvent is an ether.
8. The process of claim 1 in which the non-interfering solvent is dimethyl ether, diethyl ether or dibutyl ether.
9. In a process for producing a titanocene wherein a titanium trichloride reagent is reacted with a titanocene ligand, the improvement which comprises:
(i) utilizing as said titanium trichloride reactant a mixture produced by reacting titanium tetrachloride with a compound having the formula R-M, in which R is a straight or branched chain alkyl group having 2 to 8 carbon atoms and M is an alkali metal, or the formula RMgX, in which X is a halogen in substantially stoichiometric amount in a non-interfering liquid medium wherein a reaction mixture containing titanium trichloride, said solvent and MCl or MgCl2 is produced;
(ii) reacting said step (i) reaction mixture with a deprotonated titanocene ligand to produce a second reaction mixture including said liquid medium, and a titanocene corresponding to said titanocene ligand; and (iii) optionally isolating said titanocene of step (ii) from said step (ii) second reaction mixture.
(i) utilizing as said titanium trichloride reactant a mixture produced by reacting titanium tetrachloride with a compound having the formula R-M, in which R is a straight or branched chain alkyl group having 2 to 8 carbon atoms and M is an alkali metal, or the formula RMgX, in which X is a halogen in substantially stoichiometric amount in a non-interfering liquid medium wherein a reaction mixture containing titanium trichloride, said solvent and MCl or MgCl2 is produced;
(ii) reacting said step (i) reaction mixture with a deprotonated titanocene ligand to produce a second reaction mixture including said liquid medium, and a titanocene corresponding to said titanocene ligand; and (iii) optionally isolating said titanocene of step (ii) from said step (ii) second reaction mixture.
10. In a process for producing a titanocene wherein a titanium trichloride reactant is reacted with titanocene ligand, the improvement which comprises:
(i) utilizing as said titanium trichloride reactant a mixture produced by reacting titanium tetrachloride with a compound having the formula R-M, in which R is a straight or branched chain alkyl group having 2 to 10 carbon atoms and M is an alkali metal, or the formula RMgX, in which X is a halogen in substantially stoichiometric amount in a non-interfering solvent wherein a reaction mixture containing titanium trichloride, said solvent and MCl or MgCl2 is produced;
(ii) reacting said step (i) mixture with a deprotonated titanocene ligand to produce a reaction mixture including said solvent, and a titanocene corresponding to said titanocene ligand and MCl or NgCl2;
(iii) separating said MCl or MgCl2 from said step (ii) reaction mixture; and thereafter (iv) utilizing said step (ii) reaction mixture to prepare another titanocene.
(i) utilizing as said titanium trichloride reactant a mixture produced by reacting titanium tetrachloride with a compound having the formula R-M, in which R is a straight or branched chain alkyl group having 2 to 10 carbon atoms and M is an alkali metal, or the formula RMgX, in which X is a halogen in substantially stoichiometric amount in a non-interfering solvent wherein a reaction mixture containing titanium trichloride, said solvent and MCl or MgCl2 is produced;
(ii) reacting said step (i) mixture with a deprotonated titanocene ligand to produce a reaction mixture including said solvent, and a titanocene corresponding to said titanocene ligand and MCl or NgCl2;
(iii) separating said MCl or MgCl2 from said step (ii) reaction mixture; and thereafter (iv) utilizing said step (ii) reaction mixture to prepare another titanocene.
11. A method for producing a constrained geometry titanocene catalyst which comprises:
(i) reacting n-butyl lithium or isobutyl lithium with titanium tetrachloride in substantially stoichiometric amount in a non-interfering hydrocarbon medium to produce a first reaction mixture containing titanium trichloride and lithium chloride; and (ii) combining said first reaction mixture with a titanocene ligand in a non-interfering medium for reaction to produce a titanocene corresponding to said ligand.
(i) reacting n-butyl lithium or isobutyl lithium with titanium tetrachloride in substantially stoichiometric amount in a non-interfering hydrocarbon medium to produce a first reaction mixture containing titanium trichloride and lithium chloride; and (ii) combining said first reaction mixture with a titanocene ligand in a non-interfering medium for reaction to produce a titanocene corresponding to said ligand.
12. The claim 11 method in which said titanocene corresponding to said ligand produced in step (ii) is (CpSA)2-TiCl2 ([(t-butylamido)(tetramethylcyclo-pentadienyl)dimethylsilane]titanium dichloride).
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1996/018666 WO1998022476A1 (en) | 1996-11-22 | 1996-11-22 | Synthesis of titanocenes |
| EP96942783A EP0885231A4 (en) | 1996-11-22 | 1996-11-22 | Synthesis of titanocenes |
| CA002243661A CA2243661A1 (en) | 1996-11-22 | 1996-11-22 | Synthesis of titanocenes |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1996/018666 WO1998022476A1 (en) | 1996-11-22 | 1996-11-22 | Synthesis of titanocenes |
| CA002243661A CA2243661A1 (en) | 1996-11-22 | 1996-11-22 | Synthesis of titanocenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2243661A1 true CA2243661A1 (en) | 1998-05-28 |
Family
ID=25680384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002243661A Abandoned CA2243661A1 (en) | 1996-11-22 | 1996-11-22 | Synthesis of titanocenes |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0885231A4 (en) |
| CA (1) | CA2243661A1 (en) |
| WO (1) | WO1998022476A1 (en) |
Family Cites Families (3)
| 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 |
| US5455333A (en) * | 1993-08-16 | 1995-10-03 | Albemarle Corporation | Preparation of metallocenes |
| 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 |
-
1996
- 1996-11-22 WO PCT/US1996/018666 patent/WO1998022476A1/en not_active Application Discontinuation
- 1996-11-22 CA CA002243661A patent/CA2243661A1/en not_active Abandoned
- 1996-11-22 EP EP96942783A patent/EP0885231A4/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| EP0885231A4 (en) | 2000-02-09 |
| EP0885231A1 (en) | 1998-12-23 |
| WO1998022476A1 (en) | 1998-05-28 |
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