USRE39532E1 - Metallocenes containing ligands of 2-substituted indenyl derivatives, process for their preparation, and their use as catalysts - Google Patents

Metallocenes containing ligands of 2-substituted indenyl derivatives, process for their preparation, and their use as catalysts Download PDF

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USRE39532E1
USRE39532E1 US08/895,909 US89590997A USRE39532E US RE39532 E1 USRE39532 E1 US RE39532E1 US 89590997 A US89590997 A US 89590997A US RE39532 E USRE39532 E US RE39532E
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Andreas Winter
Martin Antberg
Walter Spaleck
Jürgen Rohrmann
Volker Dolle
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Basell Polyolefine GmbH
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00Metallocenes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/0803Compounds with Si-C or Si-Si linkages
    • C07F7/0805Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04Monomers containing three or four carbon atoms
    • C08F110/06Propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/639Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/63912Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/639Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/6392Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/63922Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/63927Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • the present invention relates to novel metallocenes which contain ligands of 2-substituted indenyl derivatives and can very advantageously be used as catalysts in the preparation of polyolefins of high melting point (high isotacticity).
  • Polyolefins of relatively high melting point and thus relatively high crystallinity and relatively high hardness are particularly important as engineering materials (for example large hollow articles, tubes and moldings).
  • Chiral metallocenes are, in combination with aluminoxanes, active, sterospecific catalysts for the preparation of polyolefins (U.S. Pat. No. 4,769,510). These metallocenes also include substituted indene compounds.
  • the use of the ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride/aluminoxane catalyst system is known for the preparation of isotactic polypropylene; cf. EP-A 185 918).
  • metallocenes which contain, as ligands, certain 2-substituted indenyl derivatives are suitable catalysts for the preparation of polyolefins of high isotacticity (melting point) and narrow molecular weight distribution.
  • M 1 is a metal from group IVb, Vb or VIb of the Periodic Table, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably zirconium, hafnium or titanium.
  • the radicals R 10 are identical or different and are as defined for R 11 , R 12 and R 13 .
  • the radicals R 10 are preferably hydrogen atoms or C 1 -C 10 -, preferably C 1 -C 4 -alkyl groups.
  • the particularly preferred metallocenes are thus those in which, in the formula I, M 1 is Zr or Hf, R 1 and R 2 are identical or different and are methyl or chlorine, R 3 and R 4 are hydrogen, R 5 and R 6 are identical or different and are methyl, ethyl or trifluoromethyl, R 7 is a radical, n plus m is zero or 1, and R 10 is hydrogen; in particular the compounds I listed in the working examples.
  • rac-dimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1-indenyl) 2 zirconium dichloride rac-ethylene(2-methyl-4,5,6,7-tetrahydro-1-indenyl) 2 zirconium dichloride, racdimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1-indenyl) 2 dimethylzirconium and rac-ethylene(2-methyl-4,5,6,7-tetrahydro-1-indenyl) 2 dimethylzirconium are particularly important.
  • the chiral metallocenes are employed as racemates for the preparation of highly isotactic poly-1-olefins. However, it is also possible to use the pure R- or S-form. These pure stereoisomeric forms allow the preparation of an optically active polymer. However, the meso form of the metallocenes should be separated off since the polymerization-active center (the metal atom) in these compounds is no longer chiral due to mirror symmetry at the central metal, and it is therefore not possible to produce a highly isotactic polymer.
  • the present invention furthermore provides a process for the preparation of the metallocenes I, which comprises a) reacting a compound of the formula II in which R 3 -R 10 , m and n are defined in the formula I and M 3 is an alkali metal, preferably lithium, with a compound of the formula III M 1 X 4 (III) in which M 1 is a defined in the formula I, and X is a halogen atom, preferably chlorine, and catalytically hydrogenating the reaction product, or
  • the synthesis is carried out under a protective gas and in anhydrous solvents.
  • the dried salt of the formula II/IIa is added to a suspension of the compound of the formula III in a solvent such as toluene, n-hexane, dichloromethane, ether, THF, n-pentane or benzene, preferably dichloromethane or toluene.
  • the reaction temperature is from ⁇ 78° C. to 30° C., preferably from ⁇ 40° C. to 10° C.
  • the reaction duration is from 0.25 to 24 hours, preferably from 1 to 4 hours.
  • a further embodiment of the process according to the invention comprises replacing the compound III, M 1 X 4 , by a compound of the formula IIIa, M 1 X 4 L 2 .
  • L is a donor ligand.
  • suitable donor ligands are tetrahydrofuran, diethyl ether, dimethyl ether, inter alia, preferably tetrahydrofuran (THF).
  • a solution of the salt of the formula II/IIa in one of the abovementioned solvents is added to a solution or suspension of a compound of the formula IIIa in a solvent such as toluene, xylene, ether or THF, preferably THF.
  • a solvent such as toluene, xylene, ether or THF, preferably THF.
  • an alternative procedure is to simultaneously add both components dropwise to a solvent. This is the preferred procedure.
  • the reaction temperature is from ⁇ 40° C. to 100° C., preferably from 0° C. to 50° C., in particular from 10° C. to 35° C.
  • the reaction duration is from 0.25 hour to 48 hours, preferably from 1 hour to 24 hours, in particular from 2 hours to 9 hours.
  • the hydrogenation is carried out in a dry, anhydrous solvent such as H 2 CCl 2 or glyme.
  • the reaction temperature is 20° to 70° C., preferably from ambient temperature to 50° C.
  • the pressure is from 5 to 200 bar, preferably from 20 to 120 bar, in particular from 35 to 100 bar
  • the reaction duration is from 0.25 to 24 hours, preferably from 0.5 to 18 hours, in particular from 1 to 12 hours.
  • Hydrogenation reactors which can be used are steel autoclaves.
  • the hydrogenation catalyst used is platinum, platinum oxide, palladium or another conventional transition-metal catalyst.
  • halogen derivatives obtained in this way can be converted into the alkyl, aryl or alkenyl complexes by known standard methods.
  • the compounds of the formulae II and IIa are synthesized by deprotonation. This reaction is known; cf. J. Am. Chem. Soc., 112 (1990) 2030-2031, ibid. 110 (1988) 6255-6256, ibid. 109 (1987), 6544-6545, J. Organomet. Chem., 322 (1987) 65-70, New. J. Chem. 14 (1990) 499-503 and the working examples.
  • the metallocenes I can thus in principle be prepared in accordance with the reaction scheme below:
  • the cocatalyst used according to the invention in the polymerization of olefins is an aluminoxane of the formula (IV) for the linear type and/or of the formula (V) for the cyclic type, where, in the formulae (IV) and (V), the radicals R may be identical or different and are a C 1 -C 6 -alkyl group, a C 6 -C 18 -aryl group or hydrogen, and p is an integer from 2 to 50, preferably from 10 to 35.
  • the radicals R are preferably identical and are methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
  • radicals R are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, preferably from 0.01 to 40% (of the number of radicals R) being hydrogen or isobutyl.
  • the aluminoxane can be prepared in different ways by known processes.
  • One of the methods is, for example, the reaction of an aluminium-hydrocarbon compound and/or a hydridoaluminum-hydrocarbon compound with water (gaseous, solid, liquid or bound—for example as water of crystallization) in an inert solvent (such as, for example, toluene).
  • an inert solvent such as, for example, toluene.
  • two different trialkylaluminum compounds AlR 3 +AlR′ 3
  • water cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A 302 424).
  • the preactivation of the transition-metal compound is carried out in solution.
  • the metallocene is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon.
  • Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons. Toluene is preferred.
  • the concentration of the aluminoxane in the solution is in the range from about 1% by weight up to the saturation limit, preferably from 5 to 30% by weight, in each case based on the entire solution.
  • the metallocene can be employed in the same concentration, but is preferably employed in an amount of from 10 ⁇ 4 -1 mol per mole of aluminoxane.
  • the preactivation time is from 5 minutes to 60 hours, preferably from 5 to 60 minutes.
  • the preactivation temperature is from ⁇ 78° C. to 100° C., preferably from 0 to 70° C.
  • the metallocene can also be prepolymerized or applied to a support.
  • the prepolymerization is preferably carried out using the olefin (or one of the olefins) employed in the polymerization.
  • suitable supports are silica gels, aluminum oxides, solid aluminoxane or other inorganic support materials.
  • Another suitable support material is a polyolefin powder in finely divided form.
  • a further possible variation of the process comprises using a salt-like compound of the formula R x NH 4-x BR′ 4 or of the formula R 3 PHBR′ 4 as cocatalyst instead of or in addition to an aluminoxane.
  • x here is 1, 2 or 3, the R radicals are identical or different and are alkyl or aryl, and R′ aryl, which may also be fluorinated or partially fluorinated.
  • the catalyst comprises the product of the reaction of a metallocene with one of said compounds (cf. EP-A 277 004).
  • the polymerization or copolymerization is carried out in a known manner in solution, in suspension or in the gas phase, continuously or batchwise, in one or more steps, at a temperature of from 0° to 150° C., preferably from 30° to 80° C.
  • Olefins of the formula R a —CH ⁇ CH—R b are polymerized or copolymerized.
  • R a and R b are identical or different and are a hydrogen atom or an alkyl radical having 1 to 14 carbon atoms.
  • R a and R b together with the carbon atoms connecting them, may also form a ring.
  • olefins are ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, norbornene or norbornadiene.
  • propylene and ethylene are polymerized.
  • the molecular weight regulator added is hydrogen.
  • the overall pressure in the polymerization system is from 0.5 to 100 bar.
  • the polymerization is preferably carried out in the industrially particularly interesting pressure range of from 5 to 64 bar.
  • the metallocene is used in a concentration, based on the transition metal, of from 10 ⁇ 3 to 10 ⁇ 8 , preferably from 10 ⁇ 4 to 10 ⁇ 7 mol of transition metal per dm 3 of solvent or per dm 3 of reactor volume.
  • the aluminoxane is used in a concentration of from 10 ⁇ 5 to 10 ⁇ 1 mol, preferably from 10 ⁇ 4 to 10 ⁇ 2 mol, per dm 3 of solvent or per dm 3 of reactor volume. In principle, however, higher concentrations are also possible.
  • the polymerization is carried out as a suspension or solution polymerization, an inert solvent which is customary for the Ziegler low-pressure process is used.
  • the polymerization is carried out in an aliphatic or cycloaliphatic hydrocarbon; examples of these which may be mentioned are butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane.
  • the polymerization is preferably carried out in the liquid monomer.
  • the monomers are metered in in gaseous or liquid form.
  • the polymerization can have any desired duration since the catalyst system to be used according to the invention exhibits only a low time-dependent drop in polymerization activity.
  • the process is distinguished by the fact that the metallocenes according to the invention give, in the industrially interesting temperature range of between 30° and 80° C, polymers of high molecular weight, high stereospecificity, narrow molecular weight dispersity and, in particular, high melting point, which is to say high crystallinity and high hardness.
  • VN viscosity number is cm 3 /g determined
  • M w weight average molecular weight by gel perme- M w /M
  • the melting points and heats of melting ⁇ H melt were determined using DSC (heating and cooling rate 20° C./min).
  • the 1 H-NMR spectrum exhibits the signals expected for an isomer mixture with respect to shift and integration ratio.
  • the 1 H-NMR spectrum corresponds to expectations for an isomer mixture in signal shift and integration.
  • the dilithio salt obtained in this way was added at ⁇ 78° C. to a suspension of 1.24 g (5.32 mmol) of ZrCl in 50 cm 3 of CH 2 Cl 2 , and the mixture was stirred at this temperature for 3 hours. The mixture was then warmed to room temperature overnight and evaporated.
  • the 1 H-NMR spectrum showed, in addition to the presence of some ZrCl 4 (thf) 2 , a rac/meso mixture. After stirring with n-pentane and drying, the solid, yellow residue was suspended in THF, filtered off and examined by NMR spectroscopy. These three working steps were repeated a number of times; finally, 0.35 g (0.73 mmol/14%) of product was obtained in which the rac form, according to 1 H-NMR, was enriched to more than 17:1.
  • 0.90 (s, 6H, Me-Si); 1.43-1.93 (m, 8H, indenyl-H); 2.10 (s, 6H, 2-Me); 2.44-3.37 (m, 8H, indenyl-H); 6.05 (s, 2H, 3-H-Ind).
  • Ind indenyl
  • THF tetrahydrofuran
  • PP polypropylene
  • PE polyethylene
  • Metallocenes I as catalysts for the polymerization of olefins
  • the activity of the metallocene was 50.3 kg of PP/g of metallocene ⁇ h.
  • Example 1 was repeated, but 19.5 mg (0.04 mmol) of the metallocene were employed, and the polymerization temperature was 50° C.
  • the activity of the metallocene was 18.8 kg of PP/g of metallocene ⁇ h.
  • Example 1 was repeated, but 58.0 mg (0.12 mmol) of the metallocene were used and the polymerization temperature was 30° C.
  • the activity of the metallocene was 9.7 kg of PP/g of metallocene ⁇ h.
  • Examples 1 to 3 were repeated, but the metallocenes dimethylsilyl(2-Me-1-indenyl) 2 zirconium dichloride (metallocene 1), dimethylsilyl(4,5,6,7-tetrahydro-1-indenyl) 2 zirconium dichloride (metallocene 2) and dimethylsilyl(1-indenyl) 2 zirconium dichloride (metallocene 3) were used.
  • Comparative Examples F/G with D/E confirms the positive effect of the 4,5,6,7-tetrahydroindenyl ligand compared with indenyl
  • Comparative Examples F/G/H compared with A/B/C show the positive effect of the substitution in the 2-position of the indenyl ligand.
  • Example 1 was repeated, but 6.8 mg (0.015 mmol) of ethylene(2-Me-4,5,6,7-tetrahydro-1-indenyl) 2 zirconium dichloride were employed.
  • the metallocene activity was 72.5 kg of PP/g of metallocene ⁇ h.
  • Example 4 was repeated, but 28.1 mg (0.062 mmol) of the metallocene were used and the polymerization temperature was 50° C.
  • the metallocene activity was 28.5 kg of PP/g of metallocene ⁇ h.
  • Example 4 was repeated, but 50 mg (0.110 mmol) of the metallocene were used and the polymerization temperature was 30° C.
  • the metallocene activity was 10.9 kg of PP/g of metallocene ⁇ h.
  • Examples 4 to 6 were repeated, but the metallocenes ethylene(1-indenyl) 2 zirconium dichloride (metallocene 4) and ethylene(2-Me-1-indenyl) 2 zirconium dichloride (metallocene 5) were used.

Abstract

The novel metallocenes of the formula I
Figure USRE039532-20070327-C00001

in which, preferably, M1 is Zr or Hf, R1 and R2 are alkyl or halogen, R3 and R4 are hydrogen, R5 and R6 are alkyl or haloalkyl, —(CR8R9)m—R7—(CR8R9)n— is a single- or multi-membered chain in which R7 may also be a (substituted) hetero atom, m+n is zero or 1, and R10 is hydrogen, form, together with aluminoxanes as cocatalysts, a very effective catalyst system for the preparation of polyolefins of high stereospecificity and high melting point.

Description

RELATED APPLICATIONS
This application is a voluntary division under 37 C.F.R. 1.177 of copending reissue application Ser. No. 08/324,260, filed Oct. 17, 1994, now Re 37,208 E, and copending reissue application Ser. No. 08/895,950 both of which are reissues of U.S. Pat. No. 5,276,208 (application Ser. No. 07/789,361, filed Nov. 8, 1991).
The present invention relates to novel metallocenes which contain ligands of 2-substituted indenyl derivatives and can very advantageously be used as catalysts in the preparation of polyolefins of high melting point (high isotacticity).
Polyolefins of relatively high melting point and thus relatively high crystallinity and relatively high hardness are particularly important as engineering materials (for example large hollow articles, tubes and moldings).
Chiral metallocenes are, in combination with aluminoxanes, active, sterospecific catalysts for the preparation of polyolefins (U.S. Pat. No. 4,769,510). These metallocenes also include substituted indene compounds. Thus, for example, the use of the ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride/aluminoxane catalyst system is known for the preparation of isotactic polypropylene; cf. EP-A 185 918). Both this and numerous other polymerization processes coming under the prior art have, in particular, the disadvantage that, at industrially interesting polymerization temperatures, only polymers of relatively low melting points are obtained. Their crystallinity and thus their hardness are too low for use as engineering materials.
Surprisingly, it has now been found that metallocenes which contain, as ligands, certain 2-substituted indenyl derivatives are suitable catalysts for the preparation of polyolefins of high isotacticity (melting point) and narrow molecular weight distribution.
The present invention therefore provides the compounds of the formula I below
Figure USRE039532-20070327-C00002

in which
  • M1 is a metal from group IVb, Vb or VIb of the Periodic Table,
  • R1 and R2 are identical or different and are a hydrogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group, a C8-C40-arylalkenyl group or a halogen atom,
  • R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, which may be halogenated, a C6-C10-aryl group, an —NR2 15, —SR15, —OSiR3 15, —SiR3 15 or —PR2 15 radical in which R15 is a halogen atom, a C1-C10-alkyl group or a C6-C10-aryl group,
  • R5 and R6 are identical or different and are as defined for R3 and R4, with the proviso that R5 and R6 are not hydrogen,
  • R7 is
    Figure USRE039532-20070327-C00003

    where
  • R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C6-C10-aryl group, a C6-C10-fluoroaryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R11 and R12 or R11 and R13, in each case with the atoms connecting them, form a ring,
  • M2 is silicon, germanium or tin,
  • R8 and R9 are identical or different and are as defined for R11,
  • m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2, and,
  • the radicals R10 are identical or different and are as defined for R11, R12 and R13.
  • Alkyl is straight-chain or branched alkyl. Halogen (halogenated) is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
In the formula I, M1 is a metal from group IVb, Vb or VIb of the Periodic Table, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably zirconium, hafnium or titanium.
  • R1 and R2 are identical or different and are a hydrogen atom, a C1-C10-, preferably C1-C3-alkyl group, a C1-C10-, preferably C1-C3-alkoxy group, a C6-C10-, preferably C6-C8-aryl group, a C6-C10-, preferably C6-C8-aryloxy group, a C2-C10-, preferably C2-C4-alkenyl group, a C7-C40-, preferably C7-C10-arylalkyl group, a C7-C40-, preferably C7-C12-alkylaryl group, a C8-C40-, preferably C8-C12-arylalkenyl group or a halogen atom, preferably chlorine.
  • R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C1-C10-, preferably C1-C4-alkyl group, which may be halogenated, a C6-C10-, preferably C6-C8-aryl group, an —NR2 15, —SR15, —O-SiR3 15, —SiR3 15 or —PR2 15 radical in which R15 is a halogen atom, preferably a chlorine atom, or a C1-C10-, preferably C1-C3-alkyl group or a C6-C10-, preferably C6-C8-aryl group. R3 and R4 are particularly preferably hydrogen.
  • R5 and R6 are identical or different, preferably identical, and are as defined for R3 and R4, with the proviso that R5 and R6 cannot be hydrogen. R5 and R6 are preferably (C1-C4)-alkyl, which may be halogenated, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or trifluoromethyl, in particular methyl.
  • R7 is
    Figure USRE039532-20070327-C00004
  • ═BR11, ═AlR11, —Ge—, —Sn—, —O—, —S—, ═SO, ═SO2, ═NR11, ═CO, ═PR11 or ═P(O)R11, where R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-, preferably C1-C4-alkyl group, in particular a methyl group, a C1-C10-fluoroalkyl group, preferably a CF3 group, a C6-C10-, preferably C6-C8-aryl group, a C6-C10-fluoroaryl group, preferably a pentafluorophenyl group, a C1-C10-, preferably C1-C4-alkoxy group, in particular a methoxy group, a C2-C10-, preferably C2-C4-alkenyl group, a C7-C40-, preferably C7-C10-arylalkyl group, a C8-C40-, preferably C8-C12-arylalkenyl group or a C7-C40-, preferably C7-C12-alkylaryl group, or R11 and R12 or R11 and R13, in each case together with the atoms connecting them, form a ring.
  • M2 is silicon, germanium or tin, preferably silicon or germanium.
  • R7 is preferably ═CR11R12, ═SiR11R12, ═GeR11R12, —O—, —S—, ═SO, ═PR11 or ═P(O)R11.
  • R8 and R9 are identical or different and are as define as for R11.
  • m and n are identical or different and are zero, 1 or 2, preferably zero or 1, where m plus n is zero, 1 or 2, preferably zero or 1.
The radicals R10 are identical or different and are as defined for R11, R12 and R13. The radicals R10 are preferably hydrogen atoms or C1-C10-, preferably C1-C4-alkyl groups.
The particularly preferred metallocenes are thus those in which, in the formula I, M1 is Zr or Hf, R1 and R2 are identical or different and are methyl or chlorine, R3 and R4 are hydrogen, R5 and R6 are identical or different and are methyl, ethyl or trifluoromethyl, R7 is a
Figure USRE039532-20070327-C00005

radical, n plus m is zero or 1, and R10 is hydrogen; in particular the compounds I listed in the working examples.
Of the metallocenes I mentioned in the working examples, rac-dimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1-indenyl)2zirconium dichloride, rac-ethylene(2-methyl-4,5,6,7-tetrahydro-1-indenyl)2zirconium dichloride, racdimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1-indenyl)2dimethylzirconium and rac-ethylene(2-methyl-4,5,6,7-tetrahydro-1-indenyl)2dimethylzirconium are particularly important.
The chiral metallocenes are employed as racemates for the preparation of highly isotactic poly-1-olefins. However, it is also possible to use the pure R- or S-form. These pure stereoisomeric forms allow the preparation of an optically active polymer. However, the meso form of the metallocenes should be separated off since the polymerization-active center (the metal atom) in these compounds is no longer chiral due to mirror symmetry at the central metal, and it is therefore not possible to produce a highly isotactic polymer.
The principle of resolution of the stereoisomers is known.
The present invention furthermore provides a process for the preparation of the metallocenes I, which comprises
a) reacting a compound of the formula II
Figure USRE039532-20070327-C00006

in which R3-R10, m and n are defined in the formula I and M3 is an alkali metal, preferably lithium, with a compound of the formula III
M1X4  (III)
in which M1 is a defined in the formula I, and X is a halogen atom, preferably chlorine, and catalytically hydrogenating the reaction product, or
b) reacting a compound of the formula IIa
Figure USRE039532-20070327-C00007

with a compound of the formula III
M1X4  (III)
in which all the substituents are as defined under a), and, if desired, derivatizing the reaction product obtained under a) or b).
The synthesis is carried out under a protective gas and in anhydrous solvents. The dried salt of the formula II/IIa is added to a suspension of the compound of the formula III in a solvent such as toluene, n-hexane, dichloromethane, ether, THF, n-pentane or benzene, preferably dichloromethane or toluene. The reaction temperature is from −78° C. to 30° C., preferably from −40° C. to 10° C. The reaction duration is from 0.25 to 24 hours, preferably from 1 to 4 hours.
A further embodiment of the process according to the invention comprises replacing the compound III, M1X4, by a compound of the formula IIIa, M1X4L2. In this formula, L is a donor ligand. Examples of suitable donor ligands are tetrahydrofuran, diethyl ether, dimethyl ether, inter alia, preferably tetrahydrofuran (THF).
In this case, a solution of the salt of the formula II/IIa in one of the abovementioned solvents is added to a solution or suspension of a compound of the formula IIIa in a solvent such as toluene, xylene, ether or THF, preferably THF. However, an alternative procedure is to simultaneously add both components dropwise to a solvent. This is the preferred procedure. The reaction temperature is from −40° C. to 100° C., preferably from 0° C. to 50° C., in particular from 10° C. to 35° C. The reaction duration is from 0.25 hour to 48 hours, preferably from 1 hour to 24 hours, in particular from 2 hours to 9 hours.
The hydrogenation is carried out in a dry, anhydrous solvent such as H2CCl2 or glyme. The reaction temperature is 20° to 70° C., preferably from ambient temperature to 50° C., the pressure is from 5 to 200 bar, preferably from 20 to 120 bar, in particular from 35 to 100 bar, and the reaction duration is from 0.25 to 24 hours, preferably from 0.5 to 18 hours, in particular from 1 to 12 hours. Hydrogenation reactors which can be used are steel autoclaves. The hydrogenation catalyst used is platinum, platinum oxide, palladium or another conventional transition-metal catalyst.
The halogen derivatives obtained in this way can be converted into the alkyl, aryl or alkenyl complexes by known standard methods.
The compounds of the formulae II and IIa are synthesized by deprotonation. This reaction is known; cf. J. Am. Chem. Soc., 112 (1990) 2030-2031, ibid. 110 (1988) 6255-6256, ibid. 109 (1987), 6544-6545, J. Organomet. Chem., 322 (1987) 65-70, New. J. Chem. 14 (1990) 499-503 and the working examples.
The synthesis of the protonated forms of the compounds of these formulae has also been described, with the difference that they are not correspondingly substituted in the α- and β-positions (Bull. Soc. Chim., 1967, 2954). The bridging units required for their synthesis are generally commercially available, but the indenyl compounds required, by contrast, are not. Some literature references containing synthesis procedures are indicated; the procedure for indene derivatives which are not mentioned is analogous: J. Org. Chem., 49 (1984) 4226-4237, J. Chem. Soc., Perkin II, 1981, 403-408, J. Am. Chem. Soc., 106 (1984) 6702, J. Am. Chem. Soc., 65 (1943) 567, J. Med. Chem., 30 (1987) 1303-1308, Chem. Ber. 85 (1952) 78-85 and the working examples.
The metallocenes I can thus in principle be prepared in accordance with the reaction scheme below:
Figure USRE039532-20070327-C00008
Figure USRE039532-20070327-C00009
The cocatalyst used according to the invention in the polymerization of olefins is an aluminoxane of the formula (IV)
Figure USRE039532-20070327-C00010

for the linear type and/or of the formula (V)
Figure USRE039532-20070327-C00011

for the cyclic type, where, in the formulae (IV) and (V), the radicals R may be identical or different and are a C1-C6-alkyl group, a C6-C18-aryl group or hydrogen, and p is an integer from 2 to 50, preferably from 10 to 35.
The radicals R are preferably identical and are methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
If the radicals R are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, preferably from 0.01 to 40% (of the number of radicals R) being hydrogen or isobutyl.
The aluminoxane can be prepared in different ways by known processes. One of the methods is, for example, the reaction of an aluminium-hydrocarbon compound and/or a hydridoaluminum-hydrocarbon compound with water (gaseous, solid, liquid or bound—for example as water of crystallization) in an inert solvent (such as, for example, toluene). In order to prepare an aluminoxane containing different alkyl groups R, two different trialkylaluminum compounds (AlR3+AlR′3) in accordance with the desired composition are reacted with water (cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A 302 424).
The precise structure of the aluminoxanes IV and V is not known.
Irrespective of the preparation method, a varying content of unreacted aluminum starting compound, in free form or as an adduct, is common to all the aluminoxane solutions.
It is possible to preactivate the metallocene I using an aluminoxane of the formula (IV) and/or (V) before use in the polymerization reaction. This considerably increases the polymerization activity and improves the particle morphology.
The preactivation of the transition-metal compound is carried out in solution. The metallocene is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon. Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons. Toluene is preferred.
The concentration of the aluminoxane in the solution is in the range from about 1% by weight up to the saturation limit, preferably from 5 to 30% by weight, in each case based on the entire solution. The metallocene can be employed in the same concentration, but is preferably employed in an amount of from 10−4-1 mol per mole of aluminoxane. The preactivation time is from 5 minutes to 60 hours, preferably from 5 to 60 minutes. The preactivation temperature is from −78° C. to 100° C., preferably from 0 to 70° C.
The metallocene can also be prepolymerized or applied to a support. The prepolymerization is preferably carried out using the olefin (or one of the olefins) employed in the polymerization.
Examples of suitable supports are silica gels, aluminum oxides, solid aluminoxane or other inorganic support materials. Another suitable support material is a polyolefin powder in finely divided form.
A further possible variation of the process comprises using a salt-like compound of the formula RxNH4-xBR′4 or of the formula R3PHBR′4 as cocatalyst instead of or in addition to an aluminoxane. x here is 1, 2 or 3, the R radicals are identical or different and are alkyl or aryl, and R′ aryl, which may also be fluorinated or partially fluorinated. In this case, the catalyst comprises the product of the reaction of a metallocene with one of said compounds (cf. EP-A 277 004).
The polymerization or copolymerization is carried out in a known manner in solution, in suspension or in the gas phase, continuously or batchwise, in one or more steps, at a temperature of from 0° to 150° C., preferably from 30° to 80° C. Olefins of the formula Ra—CH═CH—Rb are polymerized or copolymerized. In this formula, Ra and Rb are identical or different and are a hydrogen atom or an alkyl radical having 1 to 14 carbon atoms.
However, Ra and Rb, together with the carbon atoms connecting them, may also form a ring. Examples of such olefins are ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, norbornene or norbornadiene. In particular, propylene and ethylene are polymerized.
The molecular weight regulator added, if necessary, is hydrogen. The overall pressure in the polymerization system is from 0.5 to 100 bar. The polymerization is preferably carried out in the industrially particularly interesting pressure range of from 5 to 64 bar.
The metallocene is used in a concentration, based on the transition metal, of from 10−3 to 10−8, preferably from 10−4 to 10−7 mol of transition metal per dm3 of solvent or per dm3 of reactor volume. The aluminoxane is used in a concentration of from 10−5 to 10−1 mol, preferably from 10−4 to 10−2 mol, per dm3 of solvent or per dm3 of reactor volume. In principle, however, higher concentrations are also possible.
If the polymerization is carried out as a suspension or solution polymerization, an inert solvent which is customary for the Ziegler low-pressure process is used. For example, the polymerization is carried out in an aliphatic or cycloaliphatic hydrocarbon; examples of these which may be mentioned are butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane.
It is also possible to use a petroleum ether or hydrogenated diesel oil fraction. Toluene can also be used.
The polymerization is preferably carried out in the liquid monomer.
If inert solvents are used, the monomers are metered in in gaseous or liquid form.
The polymerization can have any desired duration since the catalyst system to be used according to the invention exhibits only a low time-dependent drop in polymerization activity.
The process is distinguished by the fact that the metallocenes according to the invention give, in the industrially interesting temperature range of between 30° and 80° C, polymers of high molecular weight, high stereospecificity, narrow molecular weight dispersity and, in particular, high melting point, which is to say high crystallinity and high hardness.
The examples below are intended to illustrate the invention in greater detail.
The following abbreviations are used:
VN = viscosity number is cm3/g
determined
Mw = weight average molecular weight by gel perme-
Mw/Mn = molecular weight dispersity ation chroma-
tography
II = isotactic index (II =mm + 1/2 ms), determined by
13C-NMR spectroscopy
niso = length of the isotactic blocks (in propylene units)
(niso = 1 + 2 mm/mr), determined by 13C-NMR
spectroscopy
The melting points and heats of melting Δ Hmelt were determined using DSC (heating and cooling rate 20° C./min).
Synthesis of the starting substances
I) Synthesis of 2-Me-indene
110.45 g (0.836 mol) of 2-indanone were dissolved in 500 ml of diethyl ether, and 290 cm3 of 3N (0.87 mol) ethereal methylGrignard solution were added dropwise at such a rate that the mixture refluxed gently. After the mixture had boiled for 2 hours under gentle reflux, it was transferred onto an ice/hydrochloric acid mixture, and a pH of 2-3 was established using ammonium chloride. The organic phase was separated off, washed with NaHCO3 and sodium chloride solution and dried, giving 98 g of crude product (2-hydroxy-2-methylindane), which was not purified further.
This product was dissolved in 500 cm3 of toluene, 3 g of p-toluenesulfonic acid were added, and the mixture was heated on a water separator until the elimination of water was complete, and was evaporated, the residue was taken up in dichloromethane, the dichloromethane solution was filtered through silica gel, and the filtrate was distilled in vacuo (80° C./10 mbar).
Yield: 28.49 g (0.22 mol/26%).
The synthesis of this compound is also described in: C. F. Koelsch, P. R. Johnson, J. Am. Chem. Soc., 65 (1943) 567-573.
II) Synthesis of (2-Me-indene)2SiMe2
13 g (100 mmol) of 2-Me-indene were dissolved in 400 cm3 of diethyl ether, and 62.5 cm 3 of 1.6N (100 mmol) n-butyllithium/n-hexane solution were added dropwise over the course of 1 hour with ice cooling, and the mixture was then stirred at −35° C. for a further 1 hour.
6.1 cm3 (50 mmol) of dimehtyldichlorosilane were introduced into 50 cm3 of Et2O, and the lithio salt solution was added dropwise at 0° C. over the course of 5 hours, the mixture was stirred overnight at room temperature and left to stand over the weekend.
The solid which had deposited was filtered off, and the filtrate was evaporated to dryness. The product was extracted using small portions of n-hexane, and the extracts were filtered and evaporated, giving 5.7 g (18.00 mmol) of white crystals. The mother liquor was evaporated, and the residue was then purified by column chromatography (n-hexane/H2CCl2 9:1 by volume), giving a further 2.5 g (7.9 mmol/52%) of product (as an isomer mixture).
Rf(SiO2; n-hexane/H2CCl2 9:1 by volume)=0.37.
The 1H-NMR spectrum exhibits the signals expected for an isomer mixture with respect to shift and integration ratio.
III) Synthesis of (2-Me-Ind)2CH2CH2
3 g (23 mmol) of 2-Me-indene were dissolved in 50 cm3 of THF, 14.4 cm3 of 1.6N (23.04 mmol) n-butyllithium/n-hexane solution were added dropwise, and the mixture was then stirred at 65° C. for 1 hour. 1 cm3 (11.5 mmol) of 1,2-dibromoethane was then added at −78° C., and the mixture was allowed to warm to room temperature and was stirred for 5 hours. The mixture was evaporated, and the residue was purified by column chromatography (SiO2; n-hexane/H2CCl2 9:1 by volume).
The fractions containing the product were combined and evaporated, the residue was taken up in dry ether, the solution was dried over MgSO4 and filtered, and the solvent was stripped off.
Yield: 1.6 g (5.59 mmol/49%) of isomer mixture Rf (SiO2; n-hexane/H2CCl2 9:1 by volume)=0.46.
The 1H-NMR spectrum corresponds to expectations for an isomer mixture in signal shift and integration.
Synthesis of the metallocenes I
IV) rac-Dimethylsilyl(2-Me-4,5,6,7-tetrahydro-1-indenyl)2zirconium dichloride
a. Synthesis of the precursor rac-dimethylsilyl(2-Me-1-indenyl)2zirconium dichloride
1.68 g (5.31 mmol) of the chelate ligand dimethylsilyl(2-methylindene)2 were introduced into 50 cm3 of THF, and 6.63 cm3 of a 1.6N (10.61 mmol) n-BuLi/n-hexane solution were added dropwise at ambient temperature over the course of 0.5 hour. The mixture was stirred for 2 hours at about 35° C., the solvent was stripped off in vacuo, and the residue was stirred with n-pentane, filtered off and dried.
The dilithio salt obtained in this way was added at −78° C. to a suspension of 1.24 g (5.32 mmol) of ZrCl in 50 cm3 of CH2Cl2, and the mixture was stirred at this temperature for 3 hours. The mixture was then warmed to room temperature overnight and evaporated. The 1H-NMR spectrum showed, in addition to the presence of some ZrCl4(thf)2, a rac/meso mixture. After stirring with n-pentane and drying, the solid, yellow residue was suspended in THF, filtered off and examined by NMR spectroscopy. These three working steps were repeated a number of times; finally, 0.35 g (0.73 mmol/14%) of product was obtained in which the rac form, according to 1 H-NMR, was enriched to more than 17:1.
The compound exhibited a correct elemental analysis and the following NMR signals (CDCl3, 100 MHz): δ=1.25 (s, 6H, Si-Me); 2.18 (s, 6H, 2-Me); 6.8 (s, 2H, 3-H-Ind); 6.92-7.75 (m, 8H, 4-7-H-Ind).
b. Synthesis of the end product
0.56 g (1.17 mmol) of the precursor rac-dimethylsilyl(2-Me-1-indenyl)2zirconium dichloride were dissolved in 70 cm3 of CH2Cl2 and the solution was introduced, together with 40 mg of PtO2, into a 200 cm3 NOVA stirred autoclave. The mixture was then stirred at room temperature for 4 hours under an H2 pressure of 40 bar. The filtrate was evaporated, the residue was washed with toluene/n-hexane (1:2 by volume), filtered and evaporated. N-pentane was added, and the suspension obtained was filtered off and dried. The yield was 0.34 g (0.7 mmol/60%). The 1H-NMR spectrum (CD2Cl2, 100 MHz) showed the following signals:
δ=0.90 (s, 6H, Me-Si); 1.43-1.93 (m, 8H, indenyl-H); 2.10 (s, 6H, 2-Me); 2.44-3.37 (m, 8H, indenyl-H); 6.05 (s, 2H, 3-H-Ind).
V) Synthesis of rac-ethylene(2-Me-4,5,6,7-tetrahydrol-indenyl)2zirconium dichloride
a. Synthesis of the precursor rac-ethylene(2-Me-1-indenyl)2zirconium dichloride
14.2 cm3 of 2.5N (35.4 mmol) n-BuLi/n-hexane solution were added dropwise over the course of 1 hour at room temperature to 5.07 g (17.7 mmol) of the ligand ethylene(2-methylindene)2 in 200 cm3 of THF, and the mixture was then stirred at about 50° C. for 3 hours. A precipitate which formed temporarily dissolved again. The mixture was left to stand overnight.
6.68 g (17.7 mmol) of ZrCl4(thf)2 in 250 cm3 of THF were added dropwise, simultaneously with the above dilithio salt solution, to about 50 cm3 of THF at 50° C., and the mixture was then stirred at this temperature for 20 hours. The toluene extract of the evaporation residue was evaporated. The residue was extracted with a little THF, and the product was recrystallized from toluene, giving 0.44 g (0.99 mmol/5.6%) of product in which the rac form was enriched to more than 15:1.
The compound exhibited a correct elemental analysis and the following NMR signals (CDCl3, 100 MHz): δ=2.08 (2s, 6H, 2-Me); 3.45-4.18 (m, 4H, —CH2C-H2—); 6.65 (2H, 3-H-Ind); 7.05-7.85 (m, 8H, 4-7-H-Ind).
b. Synthesis of the end product
56 .g (1.25 mmol) of rac-ethylene(2-Me-1-indenyl)2-zirconium dichloride was dissolved in 50 cm3 of CH2Cl2, and the solution was introduced, together with 40 mg of PtO2, into a 200 cm3 NOVA stirred autoclave. The mixture was then stirred at room temperature for 2 hours under an H2 pressure of 40 bar and evaporated to dryness, and the residue was sublimed in a high vacuum at a bath temperature of about 100° C., giving 0.46 g (1.01 mmol/81%) of product. The elemental analysis was correct, and the 1H-NMR spectrum showed the following signals: δ=1.46-1.92 (m, 8H, indenyl-H), 2.14 (s, 6H, 2-Me); 2.49-2.73 (m, 6H, indenyl-H and —CH2CH2—), 2.89-3.49 (m, 6H, indenyl-H); 6.06 (s, 2H, 3-H-Ind).
VI) Me2Zr[(2-Me-4,5,6,7-H4-Ind)2CH2CH2]
5 cm3 of 1.6N (8 mmol) of ethereal methyllithium solution were added dropwise at −50° C. to 1.27 g (2.79 mmol) of Cl2Zr[(2-Me-4,5,6,7-H4-Ind)2CH2CH2] in 20 cm3 of Et2O, and the mixture was then stirred for 1 hour at −10° C. The solvent was replaced by n-hexane, and the mixture was stirred for a further 2 hours at room temperature, filtered and evaporated.
Yield: 1 g (2.40 mmol/86%); correct elemental analysis.
VII) Me2Zr[(2-Me-4,5,6,7-H4-Ind)2SiMe2]
4.3 cm3 of 1.6N (6.88 mmol) of ethereal methyllithium solution were added dropwise over the course of 15 minutes at −35° C. to 1.33 g (2.74 mmol) of Cl2Zr[(2-Me-4,5,6,7-H4-Ind)2SiMe2] in 25 cm3 of Et2O. The mixture was stirred for 1 hour, the solvent was replaced by n-hexane, the mixture was stirred for 2 hours at 10° C. and then filtered, the filtrate was evaporated, and the residue was sublimed in a high vacuum.
Yield: 1.02 g (2.49 mmol/89%); correct elemental analysis
VIII) Cl2Zr[(2-Me-4,5,6,7-H4-Ind)2SiMePh]
1.5 g (2.78 mmol) of Cl2Zr[(2-Me-Ind)2SiMePh] and 60 mg of PtO2 in 80 cm3 of H2CCl2 were hydrogenated for 5 hours at 40° C. in a stirred autoclave under an H2 pressure of 30 bar. The mixture was filtered, the solvent was stripped off, and the residue was sublimed in a high vacuum.
Yield: 0.71 g (1.30 mmol/47%); correct elemental analysis.
IX) Cl2Zr[(2-Me-4,5,6,7-H4-Ind)2SiPh2]
0.8 g (1.33 mmol) of Cl2Zr[(2-Me-Ind)2SiPh2], dissolved in 50 cm3 of H2CCl2, were stirred for 3 hours at 40° C. with 30 mg of Pt under an H2 pressure of 50 bar. The mixture was filtered, the filtrate was evaporated, the residue was washed with warm n-hexane, the mixture was filtered, and the filtrate was evaporated.
Yield: 0.36 g (0.59 mmol/44%); correct elemental analysis.
X) Cl2Zr[(2-Et-4,5,6,7-H4-Ind)2CH2CH2]
1.09 g (2.30 mmol) of Cl2Zr[(2-Et-Ind)2CH2CH2] in 80 cm3 of H2CCl2 were hydrogenated for 1 hour at ambient temperature together with 50 mg of PtO2 under an H2 pressure of 80 bar. The mixture was filtered, the filtrate was evaporated, and the residue was sublimed in a high vacuum.
Yield: 0.94 g (1.95 mmol/85%); correct elemental analysis.
XI) Cl2Zr[(2-Et-4,5,6,7-H4-Ind)2SiMe2]
2.00 g (3.96 mmol) of Cl2Zr[(2-Et-Ind)2SiMe2]in 100 cm3 of H2CCl2 were hydrogenated for 3 hours at 35° C. together with 60 mg of PtO2 under an H2 pressure of 50 bar. The mixture was filtered, the filtrate was evaporated, and the residue was recrystallized from n-pentane.
Yield: 1.41 g (2.75 mmol/69%); correct elemental analysis.
XII) Cl2Zr[(2-Me-4,5,6,7-H4-Ind)2CHMeCH2]
0.80 g (1.73 mmol) of Cl2Zr[(2-Me-Ind)2CHMeCH2] in 40 cm3 of H2CCl2 were stirred for 1 hour at ambient temperature together with 30 mg of PtO2 under an H2 pressure of 80 bar, the mixture was then filtered, the filtrate was evaporated, and the residue was sublimed.
Yield: 0.55 g (1.17 mmol/68%); correct elemental analysis.
XIII) Cl2Zr[(2-Me-4,5,6,7-H4-Ind)2CMe2]
0.3 g (0.65 mmol) of Cl2Zr[(2-Me-Ind)2CMe2] in 30 cm3 of H2CCl2 were hydrogenated for 1 hour at ambient temperature together with 30 mg of Pt under an H2 pressure of 70 bar. The solvent was stripped off, and the residue was sublimed in a high vacuum.
Yield: 0.21 g (0.45 mmol/69%); correct elemental analysis
Abbreviations:
Me=methyl, Et=ethyl, Bu=butyl, Ph=phenyl,
Ind=indenyl, THF=tetrahydrofuran, PP=polypropylene,
PE=polyethylene.
Metallocenes I as catalysts for the polymerization of olefins
EXAMPLE 1
12 dm3 of liquid propylene were introduced into a dry 24 dm3 reactor which has been flushed with nitrogen. 35 cm3 of a toluene solution of methylaluminoxane (corresponding to 52 mmol of Al, mean degree of oligomerization n=17) were then added, and the batch was stirred at 30° C. for 15 minutes. In parallel, 5.3 mg (0.011 mmol) of rac-dimethylsilyl(2-Me-4,5,6,7-tetrahydro-1-indenyl)2zirconium dichloride were dissolved in 13.5 cm3 of a toluene solution of methylaluminoxane (20 mmol of Al) and preactivated by standing for 15 minutes. The solution was then introduced into the reactor and the polymerization system was heated to 70° C. (over the course of 5 minutes) and kept at this temperature for 3 hours by cooling.
The activity of the metallocene was 50.3 kg of PP/g of metallocene×h.
VN=37 cm3/g; Mw=24 300 g/mol; Mw/Mn=2.4; II=96.0%; niso=62; M.p.=150° C.; ΔHmelt32 104 J/g.
Example 2
Example 1 was repeated, but 19.5 mg (0.04 mmol) of the metallocene were employed, and the polymerization temperature was 50° C.
The activity of the metallocene was 18.8 kg of PP/g of metallocene×h.
VN=72 cm3/g; Mw=64 750 g/mol; Mw/Mn=2.1; II=96.0%; niso=64; M.p.=154° C.; ΔHmelt=109.5 J/g.
Example 3
Example 1 was repeated, but 58.0 mg (0.12 mmol) of the metallocene were used and the polymerization temperature was 30° C.
The activity of the metallocene was 9.7 kg of PP/g of metallocene×h.
VN=152 cm3/g; Mw=171 000 g/mol; Mw/Mn=2.2; II=99.9%; niso=>500; M.p.=160° C.; ΔHmelt=103 J/g.
Comparative Examples A-H
Examples 1 to 3 were repeated, but the metallocenes dimethylsilyl(2-Me-1-indenyl)2zirconium dichloride (metallocene 1), dimethylsilyl(4,5,6,7-tetrahydro-1-indenyl)2zirconium dichloride (metallocene 2) and dimethylsilyl(1-indenyl)2zirconium dichloride (metallocene 3) were used.
Comp. Polym. M.p. ΔHmelt
Ex. Metallocene temp. [° C.] niso [° C.] [J/g]
A 1 70 38 145 86.6
B 1 50 48 148 88.1
C 1 30 48 152 90.2
D 2 70 34 141
E 2 50 38 143
F 3 70 32 140
G 3 50 34 142
H 3 30 37 145
Comparison of Comparative Examples F/G with D/E confirms the positive effect of the 4,5,6,7-tetrahydroindenyl ligand compared with indenyl, and Comparative Examples F/G/H compared with A/B/C show the positive effect of the substitution in the 2-position of the indenyl ligand.
In comparison with Examples 1 to 3, however, only the combination of substitution in the 2-position together with the tetrahydroindenyl system results in very high melting points and heats of melting and thus in high crystallinity and hardness of the polymers.
Example 4
Example 1 was repeated, but 6.8 mg (0.015 mmol) of ethylene(2-Me-4,5,6,7-tetrahydro-1-indenyl)2zirconium dichloride were employed.
The metallocene activity was 72.5 kg of PP/g of metallocene×h.
VN=35 cm3/g; Mw=20 750 g/mol; Mw/Mn=1.9; II=94.5%; niso=34; M.p.=141° C.; ΔHmelt=92.4 J/g.
Example 5
Example 4 was repeated, but 28.1 mg (0.062 mmol) of the metallocene were used and the polymerization temperature was 50° C.
The metallocene activity was 28.5 kg of PP/g of metallocene×h.
VN=51 cm3/g; Mw=28 200 g/mol; Mw/Mn=2.2; II=94.8%; niso=35; M.p.=143° C.; ΔHmelt=97.9 J/g.
Example 6
Example 4 was repeated, but 50 mg (0.110 mmol) of the metallocene were used and the polymerization temperature was 30° C.
The metallocene activity was 10.9 kg of PP/g of metallocene×h.
VN=92 cm3/g; Mw=93 800 g/mol; Mw/Mn=2.2; II=95.5%; niso=48; M.p.=151° C.; ΔHmelt=99.0 J/g.
Comparative Example I-O
Examples 4 to 6 were repeated, but the metallocenes ethylene(1-indenyl)2zirconium dichloride (metallocene 4) and ethylene(2-Me-1-indenyl)2zirconium dichloride (metallocene 5) were used.
Comp. Polym. M.p. ΔHmelt
Ex. Metallocene temp. [° C.] niso [° C.] [J/g]
I 4 70 23 132 64.9
K 4 50 30 138 78.1
L 4 30 29 137 78.6
M 5 70 25 134 77.0
N 5 50 30 138 78.9
O 5 30 32 138 78.6
Comparison of Comparative Examples I to O with Examples 4 to 6 confirms the effect of the substitution in the 2-position together with the use of the tetrahydroindenyl system. niso melting point and heat of melting are significantly higher in each of Examples 4-6, and the crystallinity and hardness of the polymers are thus also significantly improved.

Claims (27)

1. A compound of the formula I for preparing essentially isotactic olefin polymers
Figure USRE039532-20070327-C00012
in which
M1 is a metal from group IVb, Vb or VIb of the Periodic Table
R1 and R2 are identical or different and are a hydrogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group, a C8-C40-arylalkenyl group or a halogen atom,
R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, which is optionally halogenated, a halogen atom, a C6-C10-aryl group, an —NR2 15, —SR15, —OSiR3 15, —SiR3 15 or —PR2 15 radicals in which R15 is a halogen atom, a C1-C10-alkyl group or a C6-C10-aryl group,
R5 and R6 are identical or different and are as defined for R3 and R4, with the proviso that R5 and R6 are not hydrogen,
R7 is
Figure USRE039532-20070327-C00013
where
R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C6-C10-aryl group, a C6-C10-fluoroaryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R11 and R12 or R11 and R13, in each case with the atoms connecting them, form a ring,
M2 is silicon, germanium or tin,
R8 and R9 are identical or different and are as defined for R11
m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2, and
the radicals R10 are identical or different and are as defined for R11, R12 and R13.
2. A compound of the formula I as claimed in claim 1, wherein, in the formula I, M1 is Zr or Hf, R1 and R2 are identical or different and are methyl or chlorine, R3 or R4 are hydrogen, R5 and R6 are identical or different and are methyl, ethyl or trifluoromethyl, R7 is a
Figure USRE039532-20070327-C00014
n plus m is zero or 1, and R10 is hydrogen.
3. A compound of the formula I as claimed in claim 1 wherein the compound is rac-dimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1-indenyl)2zirconium dichloride, rac-ethylene(2-methyl-4,5,6,7-tetrahydro-1-indenyl)2-zirconium dichloride, rac-dimethylsilyl (2-methyl-4,5,6,7-tetrahydro-1-indenyl)2dimethylzirconium or rac-ethylene(2-methyl-4,5,6,7-tetrahydro-1-indenyl)2-dimethylzirconium.
4. A compound as claimed in claim 1, wherein M1 is zirconium, hafnium or titanium.
5. A compound as claimed in claim 1, wherein R1 and R2 are identical or different and are a hydrogen atom, a C1-C3-alkyl group, a C1-C3-alkoxy group, a C6-C8-aryl group, a C6-C8-aryloxy group, a C2-C4-alkenyl group, a C7-C10-arylalkyl group, a C7-C12-alkylaryl group, a C8-C12-arylalkenyl group or chlorine.
6. A compound as claimed in claim 1, wherein R3 and R4 are identical or different and are a hydrogen atom, a fluorine, chlorine or bromine atom, a C1-C4-alkyl group which may be halogenated, a C6-C8-aryl group, a —NR2 15, —SR15, —OSiR3 15, —SiR3 15 or —PR2 15 radical in which R15is a chlorine atom, or a C1-C3-alkyl group or a C6-C8-aryl group.
7. A compound as claimed in claim 1, wherein R3 and R4 are hydrogen.
8. A compound as claimed in claim 1, wherein R5 and R6 are identical.
9. A compound as claimed in claim 1, wherein R5 and R6 are (C1-C4)-alkyl, which may be halogenated.
10. A compound as claimed in claim 1, wherein R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C4-alkyl group, a CF3 group, a C6-C8-aryl group, a pentafluorophenyl group, a C1-C4-alkoxy group, a C2-C4-alkenyl group, a C7-C10-arylalkyl group, a C8-C12-arylalkenyl group or a C7-C12-alkylaryl group, or R11 and R12 or R11 and R13, in each case together with the atoms connecting them, form a ring.
11. A compound as claimed in claim 1, wherein M2 is silicon or germanium.
12. A compound as claimed in claim 1, wherein R7 is ═Cr11R12, ═SiR11R12, ═GeR11R12, —O—, —S—, ═SO, ═PR11 or —P(O)R11.
13. A compound as claimed in claim 1, wherein m and n are identical or different and are zero or 1.
14. A compound as claimed in claim 1, wherein m plus n is zero or 1.
15. A compound as claimed in claim 1, wherein R10is hydrogen or C1-C4-alkyl groups.
16. A compound of the formula II
Figure USRE039532-20070327-C00015
wherein:
M 3 is an alkali metal;
R 3 and R 4 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10-alkyl group, which is optionally halogenated, a C 6 -C 10-aryl group, an —NR 2 15 , SR 15 , OSiR 3 15 or PR 2 15 radical in which R 15 is a halogen atom, a C 1 -C 10-alkyl group or a C 6 -C 10-aryl group,
R 5 and R 6 are identical or different and are as defined for R 3 and R 4 , with the proviso that R 5 and R 6 are not hydrogen,
R 7 is
Figure USRE039532-20070327-C00016
═BR 11 , ═AlR 11 , —Ge—, —Sn—, —O—, —S—, ═SO, ═SO 2 , ═NR 11 , ═CO, ═PR 11 or ═P(O)R 11,
where
R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10-alkyl group, a C 1 -C 10-fluoroalkyl group, a C 6 -C 10-aryl group, a C 6 -C 10-fluoroaryl group, a C 1 -C 10-alkoxy group, a C 2 -C 10-alkenyl group, a C 7 -C 40-arylalkyl group, a C 8 -C 40-arylalkenyl group or a C 7 -C 40-alkylaryl group, or a pair of substituents R 11 and R 12 or R 11 and R 13 in each case with the atoms connecting them, form a ring,
M 2 is silicon, germanium or tin,
R 8 and R 9 are identical or different and are as defined for R 11 m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2, and
the radicals R 10 are identical or different and are as defined for R 11 , R 12 and R 13.
17. A compound of formula II as claimed in claim 16, said compound having the formula:

{( 2 -Me-Ind)2 CH 2 CH 2 }M 2 3,
in which Me is methyl, and Ind is the indenyl group of said formula II.
18. A compound of the formula
Figure USRE039532-20070327-C00017
wherein
R 3 represent hydrogen; halogen, C 1 -C 10-alkyl, which is optionally halogenated; C 6 -C 10-aryl, an —NR 2 15 , —SR 15 , —OSiR 3 15 , —SiR 3 15 or PR 2 15 radical in which R 15 represents halogen, C 1 -C 10-alkyl or C 6 -C 10-aryl;
R 5 is a halogen atom, a C 2 -C 10-alkyl group, a C 1 -C 10-alkyl group which is halogenated, a C 10-aryl group, an NR 2 15 , SR 15 , OSiR 3 15 , SiR 3 15 or PR 2 15 radical in which R 15 is a halogen atom, a C 1 -C 10-alkyl group or a C 6 -C 10-aryl group, and
R 10 are identical or different and are hydrogen, halogen, C 1 -C 10-alkyl, C 1 -C 10-fluoroalkyl, C 6 -C 10-aryl, C 6 -C 10-fluoroaryl, C 1 -C 10-alkoxy, C 2 -C 10-alkenyl, C 7 -C 40-arylalkyl, C 8 -C 40-arylalkenyl, or C 7 -C 40-alkylaryl, or a pair of substituents R 10 , in each case with the atoms connecting them, form a ring, but at least one R 10 is not hydrogen.
19. The compound as claimed in claim 18, wherein R10 is C 1 to C 4-alkyl.
20. The compound as claimed in claim 18, wherein R10 is a hydrogen atom or a C 6 -C 10 aryl group.
21. The compound as claimed in claim 18, wherein the substituents R10 are identical or different and are a hydrogen, C 1 -C 10 alkyl or a C 6 -C 10 aryl.
22. The compound as claimed in claim 18, wherein the substituents R10 are hydrogen and R 5 is ethyl.
23. A compound of the formula
Figure USRE039532-20070327-C00018
wherein
R 3 represents hydrogen; halogen, C 1 -C 10-alkyl, which is optionally halogenated; C 6 -C 10-aryl, an —NR 2 15 , —SR 15 , —OSiR 3 15 , —SiR 3 15 or PR 2 15 radical in which R 15 represents halogen, C 1 -C 10-alkyl or C 6 -C 10-aryl;
R 5 represents any of the radicals defined for R 3 , except that R 5 is not hydrogen; and
R 10 are identical or different and are a hydrogen atom, a halogen atom, a C 2 -C 10-alkyl group, a C 10-aryl group, C 1 -C 10-fluoroalkyl, C 6 -C 10-fluoroaryl, C 1 -C 10-alkoxy, C 2 -C 10-alkenyl, C 7 -C 40-arylalkyl, C 8 -C 40-arylalkenyl, or C 7 -C 40-alkylaryl, or a pair of substituents R 10 , in each case with the atoms connecting them, form a ring, but at least one R 10 is not hydrogen.
24. A compound of the formula
Figure USRE039532-20070327-C00019
wherein
R 3 represents hydrogen; halogen, C 1 -C 10-alkyl, which is optionally halogenated; C 6 -C 10-aryl, an —NR 2 15 , —SR 15 , —OSiR 3 15 , —SiR 3 15 or PR 2 15 radical in which R 15 represents halogen, C 1 -C 10-alkyl or C 6 -C 10-aryl;
R 5 is a halogen atom, a C 2 -C 10-alkyl group, a C 1 -C 10-alkyl group which is halogenated, a C 6 -C 10-aryl group, an NR 2 15 , SR 15 , OSiR 3 15 , SiR 3 15 or PR 2 15 radical in which R 15 is a halogen atom, a C 1 -C 10-alkyl group or a C 6 -C 10-aryl group, and
R 10 are identical or different and are hydrogen, halogen, C 1 -C 10-alkyl, C 1 -C 10-fluoroalkyl, C 10-aryl, C 6 -C 10-fluoroaryl, C 1 -C 10-alkoxy, C 2 -C 10-alkenyl, C 7 -C 40-arylalkyl, C 8 -C 40-arylalkenyl, or C 7 -C 40-alkylaryl, or a pair of substituents R 10 , in each case with the atoms connecting them, form a ring, but at least one R 10 is not hydrogen.
25. A compound of the formula
Figure USRE039532-20070327-C00020
wherein
R 3 represents hydrogen; halogen, C 1 -C 10-alkyl, which is optionally halogenated; C 6 -C 10-aryl, an —NR 2 15 , —SR 15 , —OSiR 3 15 , —SiR 3 15 or PR 2 15 radical in which R 15 represents halogen, C 1 -C 10-alkyl or C 6 -C 10-aryl;
R 5 is a halogen atom, a C 1 -C 10-alkyl group which is optionally halogenated, a C 10-aryl group, an NR 2 15 , SR 15 , OSiR 3 15 , SiR 3 15 or PR 2 15 radical in which R 15 is a halogen atom, a C 1 -C 10-alkyl group or a C 6 -C 10-aryl group, and
R 10 are identical or different and are hydrogen, halogen, C 2 -C 10-alkyl, C 1 -C 10-fluoroalkyl, C 6 -C 10-aryl, C 6 -C 10-fluoroaryl, C 1 -C 10-alkoxy, C 2 -C 10-alkenyl, C 7 -C 40-arylalkyl, C 8 -C 40-arylalkenyl, or C 7 -C 40-alkylaryl, or a pair of substituents R 10 , in each case with the atoms connecting them, form a ring but at least one R 10 is not hydrogen.
26. The compound as claimed in claim 23, wherein R10 is a C 4 -C 10-alkyl.
27. The compound as claimed in claim 25, wherein R10 is a C 4 -C 10-alkyl.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080200708A1 (en) * 2002-10-25 2008-08-21 Basell Polyolefine Gmbh Preparation of Partially Hydrogenated Rac-Ansa-Metallocene Complexes

Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE284708C (en)
US3192276A (en) * 1962-09-10 1965-06-29 Union Carbide Corp Alkylation of indene
EP0129368A1 (en) 1983-06-06 1984-12-27 Exxon Research And Engineering Company Process and catalyst for polyolefin density and molecular weight control
EP0185918A2 (en) 1984-11-27 1986-07-02 Hoechst Aktiengesellschaft Process for preparing polyolefins
DE3726067A1 (en) 1987-08-06 1989-02-16 Hoechst Ag METHOD FOR PRODUCING 1-OLEFIN POLYMERS
EP0316155A2 (en) 1987-11-09 1989-05-17 Chisso Corporation A transition-metal compound having a substituted, bridged bis-cyclopentadienyl ligand
EP0320762A2 (en) 1987-12-18 1989-06-21 Hoechst Aktiengesellschaft Process for the preparation of a chiral, stereorigid metallocen compound
US4871705A (en) * 1988-06-16 1989-10-03 Exxon Chemical Patents Inc. Process for production of a high molecular weight ethylene a-olefin elastomer with a metallocene alumoxane catalyst
EP0336128A2 (en) 1988-03-12 1989-10-11 Hoechst Aktiengesellschaft Process for preparing an alpha-olefin polymer
EP0344887A2 (en) 1988-03-21 1989-12-06 Exxon Chemical Patents Inc. Silicon bridged transition metal compounds
EP0347129A1 (en) 1988-06-16 1989-12-20 Exxon Chemical Patents Inc. Process for production of high molecular weight EPDM elastomers using a metallocene-alumoxane catalyst system
US4892851A (en) 1988-07-15 1990-01-09 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
DE3826075A1 (en) * 1988-07-30 1990-02-01 Hoechst Ag 1-OLEFIN ISO BLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF
EP0355289A1 (en) 1988-07-01 1990-02-28 ATOCHEM NORTH AMERICA, INC. (a Pennsylvania corp.) Accelerometer
EP0366290A2 (en) 1988-10-24 1990-05-02 Chisso Corporation Process for producing olefin polymers
EP0407870A2 (en) 1989-07-08 1991-01-16 Hoechst Aktiengesellschaft Process for preparing cycloolefin polymers
EP0426643A1 (en) 1989-10-30 1991-05-08 Fina Research S.A. Process for the preparation of metallocenes
US5017714A (en) 1988-03-21 1991-05-21 Exxon Chemical Patents Inc. Silicon-bridged transition metal compounds
EP0433990A2 (en) 1989-12-21 1991-06-26 Hoechst Aktiengesellschaft Process for preparing polypropylene molding compositions
EP0442725A2 (en) 1990-02-13 1991-08-21 Mitsui Petrochemical Industries, Ltd. Olefin polymerization solid catalysts and process for the polymerization of olefins
EP0485823A1 (en) 1990-11-12 1992-05-20 Hoechst Aktiengesellschaft 2-Substituted bisindenyl-metallocenes, process for their preparation and their use as catalysts for the polymerization of olefins
EP0485821A1 (en) 1990-11-12 1992-05-20 Hoechst Aktiengesellschaft Metallocenes with 2-substituted indenyl-derivates as ligands, process for their preparation and their use as catalysts
EP0500005A1 (en) 1991-02-18 1992-08-26 Hoechst Aktiengesellschaft Process for the preparation of substituted indenes
EP0529908A1 (en) 1991-08-20 1993-03-03 Mitsubishi Chemical Corporation Catalyst useful for the polymerization of olefin
US5243001A (en) 1990-11-12 1993-09-07 Hoechst Aktiengesellschaft Process for the preparation of a high molecular weight olefin polymer
US5278264A (en) 1991-08-26 1994-01-11 Hoechst Ag Process for the preparation of an olefin polymer
US5296434A (en) 1991-06-18 1994-03-22 Basf Aktiengesellschaft Soluble catalyst systems for the preparation of polyalk-1-enes having high molecular weights
US5324800A (en) 1983-06-06 1994-06-28 Exxon Chemical Patents Inc. Process and catalyst for polyolefin density and molecular weight control

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0753766B2 (en) * 1985-11-22 1995-06-07 三井石油化学工業株式会社 Method for producing alpha-olefin random copolymer
ES2114978T3 (en) 1992-08-03 1998-06-16 Targor Gmbh PROCEDURE FOR OBTAINING AN OLEPHINE POLYMER UNDER THE USE OF METALLOCES WITH SPECIAL SUBSTITUTION INDENYL LIGANDS.

Patent Citations (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE284708C (en)
US3192276A (en) * 1962-09-10 1965-06-29 Union Carbide Corp Alkylation of indene
EP0129368A1 (en) 1983-06-06 1984-12-27 Exxon Research And Engineering Company Process and catalyst for polyolefin density and molecular weight control
US5324800A (en) 1983-06-06 1994-06-28 Exxon Chemical Patents Inc. Process and catalyst for polyolefin density and molecular weight control
EP0185918A2 (en) 1984-11-27 1986-07-02 Hoechst Aktiengesellschaft Process for preparing polyolefins
US4769510A (en) * 1984-11-27 1988-09-06 Hoechst Aktiengesellschaft Process for the preparation of polyolefins
DE3726067A1 (en) 1987-08-06 1989-02-16 Hoechst Ag METHOD FOR PRODUCING 1-OLEFIN POLYMERS
US4931417A (en) 1987-11-09 1990-06-05 Chisso Corporation Transition-metal compound having a bis-substituted-cyclopentadienyl ligand of bridged structure
EP0316155A2 (en) 1987-11-09 1989-05-17 Chisso Corporation A transition-metal compound having a substituted, bridged bis-cyclopentadienyl ligand
EP0320762A2 (en) 1987-12-18 1989-06-21 Hoechst Aktiengesellschaft Process for the preparation of a chiral, stereorigid metallocen compound
US5103030A (en) 1987-12-18 1992-04-07 Hoechst Aktiengesellschaft Process for the preparation of a chiral stereorigid metallocene
EP0336128A2 (en) 1988-03-12 1989-10-11 Hoechst Aktiengesellschaft Process for preparing an alpha-olefin polymer
EP0344887A2 (en) 1988-03-21 1989-12-06 Exxon Chemical Patents Inc. Silicon bridged transition metal compounds
US5017714A (en) 1988-03-21 1991-05-21 Exxon Chemical Patents Inc. Silicon-bridged transition metal compounds
EP0347129A1 (en) 1988-06-16 1989-12-20 Exxon Chemical Patents Inc. Process for production of high molecular weight EPDM elastomers using a metallocene-alumoxane catalyst system
US4871705A (en) * 1988-06-16 1989-10-03 Exxon Chemical Patents Inc. Process for production of a high molecular weight ethylene a-olefin elastomer with a metallocene alumoxane catalyst
EP0355289A1 (en) 1988-07-01 1990-02-28 ATOCHEM NORTH AMERICA, INC. (a Pennsylvania corp.) Accelerometer
EP0351392A2 (en) 1988-07-15 1990-01-17 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
US4892851A (en) 1988-07-15 1990-01-09 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
DE3826075A1 (en) * 1988-07-30 1990-02-01 Hoechst Ag 1-OLEFIN ISO BLOCK POLYMER AND METHOD FOR THE PRODUCTION THEREOF
EP0366290A2 (en) 1988-10-24 1990-05-02 Chisso Corporation Process for producing olefin polymers
EP0407870A2 (en) 1989-07-08 1991-01-16 Hoechst Aktiengesellschaft Process for preparing cycloolefin polymers
US5087677A (en) 1989-07-08 1992-02-11 Hoechst Aktiengesellschaft Process for the preparation of cycloolefin polymers
EP0426643A1 (en) 1989-10-30 1991-05-08 Fina Research S.A. Process for the preparation of metallocenes
EP0433990A2 (en) 1989-12-21 1991-06-26 Hoechst Aktiengesellschaft Process for preparing polypropylene molding compositions
EP0442725A2 (en) 1990-02-13 1991-08-21 Mitsui Petrochemical Industries, Ltd. Olefin polymerization solid catalysts and process for the polymerization of olefins
US5145819A (en) 1990-11-12 1992-09-08 Hoechst Aktiengesellschaft 2-substituted disindenylmetallocenes, process for their preparation, and their use as catalysts in the polymerization of olefins
EP0485821A1 (en) 1990-11-12 1992-05-20 Hoechst Aktiengesellschaft Metallocenes with 2-substituted indenyl-derivates as ligands, process for their preparation and their use as catalysts
US5243001A (en) 1990-11-12 1993-09-07 Hoechst Aktiengesellschaft Process for the preparation of a high molecular weight olefin polymer
US5276208A (en) 1990-11-12 1994-01-04 Hoechst Aktiengesellschaft Metallocenes containing ligands of 2-substituted idenyl derivatives, process for their preparation, and their use as catalysts
EP0485823A1 (en) 1990-11-12 1992-05-20 Hoechst Aktiengesellschaft 2-Substituted bisindenyl-metallocenes, process for their preparation and their use as catalysts for the polymerization of olefins
EP0500005A1 (en) 1991-02-18 1992-08-26 Hoechst Aktiengesellschaft Process for the preparation of substituted indenes
US5296434A (en) 1991-06-18 1994-03-22 Basf Aktiengesellschaft Soluble catalyst systems for the preparation of polyalk-1-enes having high molecular weights
EP0529908A1 (en) 1991-08-20 1993-03-03 Mitsubishi Chemical Corporation Catalyst useful for the polymerization of olefin
US5561093A (en) 1991-08-20 1996-10-01 Mitsubishi Chemical Corporation Catalyst useful for the polymerization of olefins
US5278264A (en) 1991-08-26 1994-01-11 Hoechst Ag Process for the preparation of an olefin polymer
US5329033A (en) 1991-08-26 1994-07-12 Hoechst Aktiengesellschaft Process for the preparation of an olefin polymer

Non-Patent Citations (20)

* Cited by examiner, † Cited by third party
Title
Adock et al., Austr. J. Chem., vol. 29, "Substituent Effects by <SUP>19 </SUP>F Nuclear Magnetic Resonance: Polar and pi-Electron Effects", pp. 2571-2581.
Bulletin de la Societe Chimique de France, "Etude de monomeres halogenes et de leur polymerisation cationique", No. 11, pp. 3092-3095, (1973).
Chemical Abstracts 90:567 103691p; (1978).
Criegee et al., Chem. Ber., vol. 94, "Uber den Nickelkomplex C<SUB>18 </SUB>H<SUB>22</SUB>Ni und den daraus gewonnenen Kohlenwasserstoff C<SUB>13</SUB>H<SUB>18</SUB>", pp. 3461-3468 (1964).
Esperas, S., Acta Chemica Scandinavica, "The Crystal and Molecular Structure of Cyano(nethylisocyanide)gold(I)", A 30, No. 7, pp. 527-530 (1976).
Ewen, J.A., et al, J. Am. Chem. Soc., Crystal Structures and Sterospecific Propylene Polymerizations with Chiral Hafnium Metallocene Catalysts, vol. 109, 1987, pp. 6544-6545.
Hart et al., Notes, J. Am. Chem. Soc., vol. 72, "Acylation-Alkylation Studies", pp. 3286-3287 (1950).
J. Org. Chem., "Friedel-Crafts Chemistry. A Mechanistic Study of the Reaction of 3-Chloro-4'-fluoro-2-methylpropiophenone with AlCl<SUB>3 </SUB>and AlCl<SUB>3 </SUB>-CH<SUB>3</SUB>NO<SUB>2</SUB>", vol. 43, No. 16, pp. 3126-3131 (1978).
J. Org. Chem., "Friedel-Crafts Reactions of Ethyl Cyclopropanecarboxylate", vol. 46, pp. 3758-3760 (1981).
JACS (Nov. 1967) 89(23) 5868-5876. *
Katz, Thomas J., J. Am. Chem. Soc., "Asymmetric Synthesis of Helical Metallocenes", vol. 108, 1986, pp. 179-181.
Marechal et al., Bull. Soc. Chim. Fr. 6, "Homopolymerisation cationlique des dimethyl-4,7,dimethyl-4,6 et dimethyl-5,6 indenes", No. 348, pp. 1981-2039, (1969).
Miyamota, T.K., et al., Chemistry Letters, The Chemical Society of Japan, "A Bulky Ligand and its Organometallic Compound: Synthesis of Heptamethyliden and a Ferrocene-Type Complex, Fe(n<SUP>5</SUP>-C<SUB>9</SUB>Me<SUB>7</SUB>)<SUB>2</SUB>", pp. 729-730 (1981).
Piccoliovazzi, N. et al., Organometallics, "Electronic Effects in Homogeneous Indenylzirconium Ziegler-Natta Catalysts", vol. 9, pp. 3098-3105 (1990).
Röll, V.W., et al., Angew. Chem., "Stereo- und Regioselektivitat von chiralen, alkylsubstituierten ansa-Zirconocen-Katalysatoren bei der Methylalumoxan-alaivierten Propen-Polymerization", vol. 102, No. 3, pp. 339-341 (1990).
Soga, K. et al., Macromolecules, "Perfect Conversion of Aspecific Sites into Isopecific Sites in Ziegler-Natta Catalysts", vol. 22, pp. 3824-3826 (1989).
Spaleci et al., New J. Chem., "Stereorigid Metallocenes: Correlations Between Structure and Behavior in Homopolymerizations of Propylene", vol. 14, pp. 499-503, 1990. *
Spaleck et al., New J. Chem., "Stereorigid Metallocenes: Correlations Between Structure and Behaviour in Homopolymerizations of Propylene", vol. 14, pp. 499-503 (1990).
Winter v. Fujita, 53 U.S.P.Q.2d 1234 (Bd of Appeals 1999).
Winter v. Fujita, 53 U.S.P.Q.2d 1478 (Bd of Appeals 2000).

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US7619106B2 (en) * 2002-10-25 2009-11-17 Basell Polyolefine Gmbh Preparation of partially hydrogenated rac-ansa-metallocene complexes

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