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US20020077432A1 - Copolymerization of olefins - Google Patents

Copolymerization of olefins Download PDF

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US20020077432A1
US20020077432A1 US09/824,977 US82497701A US2002077432A1 US 20020077432 A1 US20020077432 A1 US 20020077432A1 US 82497701 A US82497701 A US 82497701A US 2002077432 A1 US2002077432 A1 US 2002077432A1
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transition metal
catalyst
dichloride
bis
zirconium dichloride
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Alison Bennett
Jerald Feldman
Elizabeth McCord
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; 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
    • C08F4/60—Metals; 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
    • C08F4/70—Iron group metals, platinum group metals or compounds thereof
    • C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
    • C08F4/7039—Tridentate ligand
    • C08F4/7052—Monoanionic ligand
    • C08F4/7054—NNN
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Definitions

  • the present invention pertains to a catalyst composition containing a polymerization catalyst on the basis of an early transition metal component and a polymerization catalyst on the basis of a late transition metal component.
  • catalysts of the Ziegler type or the metallocene type for the polymerization of nonpolar olefins such as ethylene and propylene is known.
  • catalysts consist of an early transition metal compound, for example a halide-containing titanium or zirconium compound, in combination with an excess of a co-catalyst, for example an aluminum compound.
  • suitable transition metal compounds with stoichiometric quantities of co-catalyst such as a [Ph 3 C] + or [Me 2 NPh] + salt of a non-coordinated anion has been described.
  • catalyst compositions that contain two or more different olefin polymerization catalysts of the Ziegler type or the metallocene type is known.
  • the combination of two catalysts may be used, one of which creates a polyethylene of different mean molecular weight than the other, for producing reactor blends with broad molecular weight distributions (WO 95/11264).
  • the polymer blends obtained can have improved processing and use properties.
  • the goal of the present invention consisted of supplying a catalyst composition that is suitable for producing polyolefin blends consisting of at least two different polyolefins.
  • the subject of the present invention is thus a catalyst composition containing at least two different polymerization catalysts, of which a) at least one is a polymerization catalyst on the basis of an early transition metal component and b) at least one is a polymerization catalyst on the basis of a late transition metal component.
  • the object of the invention is also a process for polymerization of olefins in the presence of the catalyst composition in accordance with the invention.
  • a preferred object of the invention is a process for homopolymerization of ethylene by the catalyst composition in accordance with the invention, wherein particularly preferably a blend of polyethylenes with branching structure different from one another is obtained.
  • An “early transition metal” is defined as the metals of groups IIIa to VIIa of the Periodic System of the Elements and the metals of the lanthanoid group, whereas a “late transition metal” is defined as the metal of groups VIIIa and IB of the Periodic System of the Elements.
  • oligomerization and oligomers pertain to product or product mixtures which in terms of number average (M n ) are made up of less than 400 monomer units.
  • the words “polymerization” and “polymer” or “polyolefin” pertain to products or product mixtures that in number average (M n ) are made up of more than 400, preferably more than 1000 monomer units.
  • polymerization catalyst designates catalysts that are suitable for producing polymers or polyolefins, i.e., for producing product or product mixtures that consist, in number average, of more than 400 monomer units, preferably more than 1000 monomer units.
  • the catalyst composition in accordance with the invention contains a) at least one polymerization catalyst on the basis of an early transition metal component and b) at least one polymerization catalyst on the basis of a late transition metal component, each of which leads to the formation of another polymer or polyolefin.
  • Each transition metal component contains precisely one transition metal.
  • the catalyst composition in accordance with the invention preferably contains so-called Ziegler catalyst components (as described, for example, in Falbe, J., Regitz, M. (ed.), Römpp's Chemical Dictionary, 9th edition; Thieme, 1992, New York; Vol. 6, page 5128-5129) and/or metallocene catalyst components. Metallocene catalyst components are particularly preferred.
  • the Ziegler catalyst component is preferably a compound of a metal of the group IVa (e.g., titanium, zirconium, or hafnium), Va (e.g., vanadium or niobium), or VIa (e.g., chromium or molybdenum) of the Periodic System of the Elements. Halides, oxides, oxyhalides, hydroxides, or alkoxides are preferred.
  • Ziegler catalyst components are: titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, titanium trichloride, vanadium trichloride, vanadium oxychloride, chromium trichloride, or chromium oxide.
  • Metallocene catalyst components are defined, for example, as cyclopentadienyl complexes.
  • Preferred are cyclopentadienyl complexes of metals of groups IIIa and the lanthanide group (for example, lanthanum or yttrium), as well as metals of group IVa (e.g., titanium, zirconium, or hafnium), Va (e.g., vanadium or niobium) or VIa of the Periodic System of the Elements (e.g., chromium or molybdenum); cyclopentadienyl complexes of titanium, zirconium, or hafnium are particularly preferred.
  • the cyclopentadienyl complexes can be bridges or non-bridged bis-cyclopentadienyl complexes, as described for example in EP 129,368; EP 561,479; EP 545,304; and EP 576,970; monocyclopentadienyl complexes, such as bridges amidocyclopentadienyl complexes that are described, for example, in EP 416,815; polynuclear cyclopentadienyl complexes as described in EP 632,063; pi-ligand-substituted tetrahydropentylenes as described in EP 659,758; or pi-ligand-substituted tetrahydroindenes as described in EP 661,300.
  • Preferred metallocene catalyst components are non-bridges or bridges metallocene
  • M 1 is a metal of the groups IIIa. IVa, Va, or VIa of the Periodic System of the Elements, especially Ti, Zr, or Hf,
  • R 1 are the same or different and are a hydrogen atom or SiR 3 3 , wherein R 3 are the same or different and represent a hydrogen atom or a C 1 -C 40 -carbon-containing group such as C 1 -C 20 -alkyl, C 1 -C 10 -fluoroalkyl, C 1 -C 10 -alkoxy, C 6 -C 20 -aryl, C 6 -C 10 -fluoroaryl, C 6 -C 10 -aryloxy, C 2 -C 10 -alkenyl, C 7 -C 40 -arylalkyl, C 7 -C 40 -alkylaryl, or C 8 -C 40 -arylalkenyl, or R 1 is a C 1 -C 30 -carbon-containing group such as C 1 -C 25 -alkyl, e.g., methyl, ethyl, tert-butyl, cyclohexyl or o
  • R 2 are the same or different and represent a hydrogen atom or SiR 3 3 , wherein R 3 is the same or different, and may be a hydrogen atom or a C 1 -C 40 -carbon-containing group such as C 1 -C 20 -alkyl, C 1 -C 10 -fluoroalkyl, C 1 -C 10 -alkoxy, C 6 -C 14 -aryl, C 6 -C 10 -fluoroaryl, C 6 -C 10 -aryloxy, C 2 -C 10 -alkenyl, C 7 -C 40 -arylalkyl, C 7 -C 40 alkylaryl, or C 8 -C 40 -arylalkenyl, or R 2 are a C 1 -C 30 -carbon-containing group such as C 1 -C 25 -alkyl, e.g., methyl, ethyl, tert-butyl, cyclohexyl, or
  • L 1 may be the same or different and represent a hydrogen atom, a C 1 -C 20 -hydrocarbon group such as C 1 -C 10 -alkyl or C 6 -C 20 -aryl, a halogen atom, or OR 6 , SR 6 , OSiR 3 6 , SiR 3 6 , Pr 2 6 , or NR 2 6 , wherein R 6 is a halogen atom, a C 1 -C 10 -alkyl group, a halogenated C 1 -C 10 -alkyl group, a C 6 -C 20 -aryl group or a halogenated C 6 -C 20 -aryl group, or L 1 are a toluene sulfonyl, trifuoroacetyl, trifluoroacetoxyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl, or 2,2,2-tri-fluoro
  • o is an integer from 1 to 4, preferably 2,
  • Z is a bridging structural element between the two cyclopentadienyl rings, and v is 0 or 1.
  • Examples for Z are groups (M 2 R 4 R 5 ) x , wherein M 2 is carbon, silicon, germanium, or tin; x is equal to 1, 2, or 3; and R 4 and R 5 , the same or different, represent a hydrogen atom or a C 1 -C 20 -hydrocarbon-containing group such as C 1 -C 10 -alkyl, C 6 -C 14 -aryl, or trimethylsilyl.
  • Z is equal to CH 2 , CH 2 CH 2 , CH(CH 3 )CH 2 , CH(C 4 H 9 )C(CH 3 ) 2 , C(CH 3 ) 2 , (CH 3 ) 2 Si, (CH 3 ) 2 Ge, (CH 3 ) 2 Sn, (C 6 H 5 ) 2 Si, (C 6 H 5 )(CH 3 )Si, (C 6 H 5 )Ge, (C 6 H 5 ) 2 Sn, (CH 2 ) 4 Si, CH 2 Si(CH 3 ) 2 , o-C 6 H 4 , or 2,2′-(C 6 H 4 ) 2 .
  • Z can also form a monocylic or polycyclic ring system with one or more radicals R 1 and/or R 2 .
  • metallocene catalyst components are:
  • Additional examples are the corresponding metallocene compounds, in which one or both of the chlorine ligands are replaced by bromide, iodide, or methyl.
  • the catalyst composition in accordance with the invention preferably contains a nickel, rhodium, platinum, iron, ruthenium, cobalt or palladium compound, particularly preferably a nickel, iron, or palladium compound.
  • the late transition metal compound preferably contains exclusively or in combination with other ligands, those ligands that coordinate by chelation with the metal over two or more atoms.
  • the two coordinating atoms are nitrogen atoms.
  • Particularly preferred are ligands of the following formulas II and III.
  • R 7 and R 8 independently of one another, are the same or different C 1 -C 40 hydrocarbon radicals, in which preferably the hydrocarbon atom bound to the nitrogen atom is bound to at least two additional carbon atoms.
  • R 7 and R 8 C 6 -C 20 -aryl radicals which are preferably substituted in both ortho- positions, e.g., with C 1 -C 10 -alkyl radicals such as methyl or isopropyl.
  • R 9 and R 10 independently of one another are the same or different, a hydrogen atom or a C 1 -C 40 -hydrocarbon radical, such as C 1 -C 20 -alkyl or C 6 -C 20 -aryl, or R 9 and R 10 together form a ring system preferably derived from acenaphthenequinone.
  • nickel or palladium compounds especially in the oxidation steps of zero or two and with the ligands of Formula III.
  • iron, ruthenium, cobalt, or rhodium catalysts with the ligands of Formula II.
  • the catalyst composition in accordance with the invention contains as the catalyst component on the basis of a late transition metal preferably the nickel or palladium compound described in WO 96/2310 (to which reference is expressly made here), which have a two-toothed ligand coordinated over nitrogen atoms.
  • a late transition metal preferably the nickel or palladium compound described in WO 96/2310 (to which reference is expressly made here), which have a two-toothed ligand coordinated over nitrogen atoms.
  • the late transition metal component can already contain the ligands coordinated with the metal, or they can be obtained by combining a suitable transition metal component with the free ligands or a ligand derivative “in situ” (i.e., in the polymerization reactor).
  • the exemplary late transition metal compounds are:
  • Suitable polymerization catalyst components on the basis of a late transition metal are reaction products of nickel compounds with (Me 3 Si)N ⁇ P ⁇ N(SiMe 3 ) 2 ⁇ N(SiMe 3 ) or (2,4,6-Me 3 C 6 H 2 )P ⁇ C(OSiMe 3 )—PH(2,4,6-Me 3 C 6 H 2 ).
  • the catalyst composition in accordance with the invention contains one or more activators such as Lewis acids.
  • Lewis acid activators preferably comprise boron compounds such as boranes or aluminum compounds such as aluminum alkyls or aluminoxanes.
  • suitable activators are boranes such as trifluoroborane, triphenylborane, tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane, tris(pentafluorophenyl)-borane, tris(tolyl)borane, tris(3,5-dimethylphenyl)borane, tris(3,5-difluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, or dimethylanilinium [(pentafluorophenyl)borane], [H(OEt 2 )][B ⁇ 3,5-(CF 3 ) 2 C 6 F 3 ⁇ 4 ], aluminum
  • the activator can be used in any arbitrary quantities based on the transition metal components of the catalyst composition in accordance with the invention; it is preferably used in excess or in stoichiometric amounts.
  • the same activator or different activators can be used for activating the early and the late transition metal components of the catalyst composition Preferably the same activator is used for all transition metal components.
  • the activation of the different transition metal components can take place at the same location, e.g., in the reactor, or at different locations.
  • an excess of the activator is mixed with the early transition metal component, and this mixture is added to the late transition metal component already contacted with the monomer.
  • An aluminoxane is preferably used as the activator for the catalyst component on the basis of a late transition metal.
  • the activator for the catalyst components on the basis of an early transition metal in the case of a Ziegler catalyst component preferably an aluminum alkyl is used and in the case of a metallocene catalyst component preferably an aluminoxane and/or a borane is used.
  • the catalyst composition in accordance with the invention contains one or several support components.
  • both the early and the late transition metal component can be supported, or only one of the two components may be supported.
  • both components are supported to ensure relatively close spatial proximity of the different catalyst centers and thus to guarantee good mixing of the different polymers formed.
  • the support component is preferably a porous inorganic or organic solid.
  • the support material contains at least one inorganic halide such as MgCl 2 or an inorganic oxide such as SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, ThO 2 ; carbonates such as Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3 , and sulfates such as Na 2 SO 4 , Al 2 (SO 4 ) 3 , BaSO 4 ; nitrates such as KNO 3 , Mg(NO 3 ) 2 , Al(NO 3 ) 3 ; as well as oxides such as Na 2 O, K 2 O, Li 2 O, especially silicon oxide and/or aluminum oxide, or it preferably contains at least one homo- or copolymer, which may be cross linked, e.g., polyethylene, polypropylene, polybutene, polyst
  • the support material may be pretreated, e.g., by heating at temperatures from 50° C. to 1000° C., e.g., in an inert gas stream or under a vacuum at 0.01 bar to 0.001 bar, or by mixing or reacting with a chemical compound.
  • the chemical compound can react with catalyst poisons such as aluminum, magnesium, boron, or lithium alkyls or lead to a functionalization of the surface of the support.
  • catalyst poisons such as aluminum, magnesium, boron, or lithium alkyls
  • the supporting can be performed in that the individual catalyst components are mixed in arbitrary order.
  • the early and the late transition metal compound can be applied to the optimally pretreated support (e.g., consisting of SiO 2 ) and then be treated with the activator, preferably in the presence of monomer.
  • the present invention also pertains to a process for polymerization of olefins in the presence of the catalyst composition in accordance with the invention.
  • polymerization comprises homopolymerization as well as copolymerization.
  • the catalyst system in accordance with the invention can be used for reacting one or more olefinic comonomers such as ethylene or C 3 -C 20 - ⁇ -olefins.
  • olefinic comonomers such as ethylene or C 3 -C 20 - ⁇ -olefins.
  • the early and the late transition metal components can be active for all monomers used, but a transition metal component can also react specifically with only one or more of the monomers used.
  • ethylene and an ⁇ -olefin that preferably has 3 to 20 C atoms may be used. In this process a mixture of two copolymers is obtained, or a mixture of one copolymer with an ethylene homopolymer.
  • the copolymer with the lower ⁇ -olefin fraction is formed from the late transition metal component.
  • ethylene is homopolymerized, wherein a blend of at least two different polyethylenes is obtained, that have a different branching structure.
  • the polymerization process can be carried out in liquid phase or in the gas phase. Preferably the process takes place in liquid phase.
  • inert organic compounds are used as the solvent or suspension medium.
  • aromatic or aliphatic hydrocarbons or mixtures thereof are used. Toluene, xylenes, and saturated aliphatic C 10 -C 30 -hydrocarbons are particularly suitable.
  • the process can also be performed in supercritical media.
  • the polymerization process is performed in the temperature range of ⁇ 100 to 300° C., preferably 0 to 200° C., particularly preferably 25 to 150° C.
  • the process is carried out in the pressure range of 1 to 300 atm, preferably 1 to 100 atm, particularly preferably 3 to 30 atm.
  • the process can take place in one or more steps.
  • reaction conditions e.g., temperature, addition of chain transfer agents such as hydrogen, monomer concentrations, as well as the catalyst concentration, it is possible to control molecular weight distributions, degree of branching, and other properties of the polymer produced.
  • the degree of branching of the polymer can be controlled by way of the monomer concentration.
  • the reaction can also take place in two or more reactors connected in cascade. By introducing the catalyst component into the individual reactors, the ratio of the two catalysts can be modified.
  • the productivity of each individual transition metal component is preferably in excess of 2800 kg polymer/(mol transition metal ⁇ hr), preferably more than 15,000 kg polymer/(mol transition metal ⁇ hr).
  • the catalyst composition in accordance with the invention is suitable for producing reactor blends of two or more polymers that have advantageous application and processing properties.
  • the number-average molecular weights of the individual polymer fractions are preferably in the range of 11 to 10,000 kg/mol, particularly preferably 20 to 1,000 kg/mol.
  • the molar ratio of the fraction of the early transition metal component(s) to the late transition metal component(s) can fall in the range of 0.1:99.9 to 99.9:0.1, preferably 1:30 to 1:1.
  • the ratio of the fractions of the polymers formed by the early and late transition metal complexes can lie in the range of 0.1:99.9 to 99.9:0.1, preferably 10:90 to 90:10, particularly preferably 1:1 to 50:1.
  • the polymerization process in accordance with the invention is particularly suitable for the homopolymerization of ethylene to a blend of two or more polymers, at least one of which has the following branching structure: It contains at least 10 branchings per 1000 carbon atoms and for each 100 methyl branchings, at least two ethyl branchings, at least one butyl branching, and one to fifty amyl or higher branchings are contained.
  • the polymerization process in accordance with the invention is particularly preferably suitable for the polymerization of ethylene to a blend of two or more polymers, at least one of which has the following branching structure: It contains at least 30 branchings per 1000 carbon atoms, and for each 100 methyl branchings at least four ethyl branchings, at least two butyl branchings, and two to thirty amyl or higher branchings are contained.
  • a reactor blend of two polyethylenes can be obtained, of which preferably one has a branching degree of>10 branching/1000 carbon atoms, preferably>20 branchings/1000 carbon atoms, particularly preferably>40 branchings/1000 carbon atoms.
  • Example 1 was repeated with 0.28 mg of the nickel compound and 0.175 mg Cp 2 ZrCl 2 .
  • the polymerization was performed at 40° C. and interrupted after a half hour. 5.8 g polymer were obtained.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Polymerization Catalysts (AREA)

Abstract

The invention relates to a catalyst composition containing at least two different polymerization catalysts of which a) at least one is a polymerization catalyst based on an early transition metal constituent and b) at least one is a polymerization catalyst based on a late transition metal constituent.

Description

  • The present invention pertains to a catalyst composition containing a polymerization catalyst on the basis of an early transition metal component and a polymerization catalyst on the basis of a late transition metal component. [0001]
  • The use of catalysts of the Ziegler type or the metallocene type for the polymerization of nonpolar olefins such as ethylene and propylene is known. Usually, such catalysts consist of an early transition metal compound, for example a halide-containing titanium or zirconium compound, in combination with an excess of a co-catalyst, for example an aluminum compound. More recently the activation of suitable transition metal compounds with stoichiometric quantities of co-catalyst, such as a [Ph[0002] 3C]+or [Me2NPh]+ salt of a non-coordinated anion has been described.
  • The use of catalyst compositions that contain two or more different olefin polymerization catalysts of the Ziegler type or the metallocene type is known. For example, the combination of two catalysts may be used, one of which creates a polyethylene of different mean molecular weight than the other, for producing reactor blends with broad molecular weight distributions (WO 95/11264). The polymer blends obtained can have improved processing and use properties. [0003]
  • The addition of metal components, among then including late transition metals, for olefin polymerization catalysts on the basis of early transition metals to increase the activity or stability of the last-mentioned catalysts has often been described (Herrmann, C., Streck, R. [0004] Angew. Makromol. Chem. 94 (1981): 91-104).
  • The synthesis of branched polymers from ethylene without the use of a comonomer with bimetallic catalysts in which one catalyst oligomerizes part of the ethylene and the other copolymerizes the oligomers thus formed with ethylene has been described (Beach, David L., Kissin, Yury V. [0005] J. Polym. Sci., Polym. Chem. Ed. (1984), 22: 3027-42; Ostoja-Starzewksi K. A., Witte, J., Reichert, K. H., Vasiliou, G., in Transition Metals and Organometallics as Catalysts for Olefin Polymerization. Kaminsky, W., Sinn, H. (eds.); Springer-Verlag, Heidelberg, 1988: p. 349-360). The last-mentioned reference describes, for example, the use of a nickel-containing oligomerization catalyst in combination with a chromium-containing polymerization catalyst.
  • The goal of the present invention consisted of supplying a catalyst composition that is suitable for producing polyolefin blends consisting of at least two different polyolefins. [0006]
  • Surprisingly, it was found that this goal can be accomplished by a special catalyst composition. [0007]
  • The subject of the present invention is thus a catalyst composition containing at least two different polymerization catalysts, of which a) at least one is a polymerization catalyst on the basis of an early transition metal component and b) at least one is a polymerization catalyst on the basis of a late transition metal component. [0008]
  • The object of the invention is also a process for polymerization of olefins in the presence of the catalyst composition in accordance with the invention. A preferred object of the invention is a process for homopolymerization of ethylene by the catalyst composition in accordance with the invention, wherein particularly preferably a blend of polyethylenes with branching structure different from one another is obtained. [0009]
  • An “early transition metal” is defined as the metals of groups IIIa to VIIa of the Periodic System of the Elements and the metals of the lanthanoid group, whereas a “late transition metal” is defined as the metal of groups VIIIa and IB of the Periodic System of the Elements. The terms “oligomerization” and “oligomers” pertain to product or product mixtures which in terms of number average (M[0010] n) are made up of less than 400 monomer units. The words “polymerization” and “polymer” or “polyolefin” pertain to products or product mixtures that in number average (Mn) are made up of more than 400, preferably more than 1000 monomer units. The term “polymerization catalyst” designates catalysts that are suitable for producing polymers or polyolefins, i.e., for producing product or product mixtures that consist, in number average, of more than 400 monomer units, preferably more than 1000 monomer units. The catalyst composition in accordance with the invention contains a) at least one polymerization catalyst on the basis of an early transition metal component and b) at least one polymerization catalyst on the basis of a late transition metal component, each of which leads to the formation of another polymer or polyolefin. Each transition metal component contains precisely one transition metal.
  • As the catalyst component on the basis of an early transition metal, the catalyst composition in accordance with the invention preferably contains so-called Ziegler catalyst components (as described, for example, in Falbe, J., Regitz, M. (ed.), [0011] Römpp's Chemical Dictionary, 9th edition; Thieme, 1992, New York; Vol. 6, page 5128-5129) and/or metallocene catalyst components. Metallocene catalyst components are particularly preferred.
  • The Ziegler catalyst component is preferably a compound of a metal of the group IVa (e.g., titanium, zirconium, or hafnium), Va (e.g., vanadium or niobium), or VIa (e.g., chromium or molybdenum) of the Periodic System of the Elements. Halides, oxides, oxyhalides, hydroxides, or alkoxides are preferred. Exemplary but non-limiting examples of Ziegler catalyst components are: titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, titanium trichloride, vanadium trichloride, vanadium oxychloride, chromium trichloride, or chromium oxide. [0012]
  • Metallocene catalyst components are defined, for example, as cyclopentadienyl complexes. Preferred are cyclopentadienyl complexes of metals of groups IIIa and the lanthanide group (for example, lanthanum or yttrium), as well as metals of group IVa (e.g., titanium, zirconium, or hafnium), Va (e.g., vanadium or niobium) or VIa of the Periodic System of the Elements (e.g., chromium or molybdenum); cyclopentadienyl complexes of titanium, zirconium, or hafnium are particularly preferred. For example, the cyclopentadienyl complexes can be bridges or non-bridged bis-cyclopentadienyl complexes, as described for example in EP 129,368; EP 561,479; EP 545,304; and EP 576,970; monocyclopentadienyl complexes, such as bridges amidocyclopentadienyl complexes that are described, for example, in EP 416,815; polynuclear cyclopentadienyl complexes as described in EP 632,063; pi-ligand-substituted tetrahydropentylenes as described in EP 659,758; or pi-ligand-substituted tetrahydroindenes as described in EP 661,300. [0013]
  • Preferred metallocene catalyst components are non-bridges or bridges metallocene [0014]
    Figure US20020077432A1-20020620-C00001
  • compounds of Formula I [0015]
  • wherein [0016]
  • M[0017] 1 is a metal of the groups IIIa. IVa, Va, or VIa of the Periodic System of the Elements, especially Ti, Zr, or Hf,
  • R[0018] 1 are the same or different and are a hydrogen atom or SiR3 3, wherein R3 are the same or different and represent a hydrogen atom or a C1-C40-carbon-containing group such as C1-C20-alkyl, C1-C10-fluoroalkyl, C1-C10-alkoxy, C6-C20-aryl, C6-C10-fluoroaryl, C6-C10-aryloxy, C2-C10-alkenyl, C7-C40-arylalkyl, C7-C40-alkylaryl, or C8-C40-arylalkenyl, or R1 is a C1 -C 30-carbon-containing group such as C1-C25-alkyl, e.g., methyl, ethyl, tert-butyl, cyclohexyl or octyl, C2-C25-alkenyl, C3-C15-alkylalkenyl, C6-C24-aryl, C5-C24-heteroaryl such as pyridyl, furyl, or quinoyl, C7-C30-arylalkyl, C7-C30-alkylaryl, fluorinated C1-C25-alkyl, fluorinated C6-C24-aryl, fluorinated C7-C30-arylalkyl, fluorinated C7-C30-alkylaryl, or C1-C12-alkoxy, or two or more radicals R1 can be connected together such that the radicals R1 and the atoms of the cyclopentadienyl ring linking them form a C4-C24-ring system which in turn may be substituted,
  • 1 is equal to 5 for v=0, and 1 is equal to 4 for v=1, [0019]
  • Y is either [0020]
  • a) an element of principle group V (e.g., nitrogen or phosphorus) or VI (e.g., oxygen or sulfur) of the Periodic System of the Elements, which bears one or two C[0021] 1-C20-hydrocarbon substituents such as C1-C10-alkyl or C6-C20 aryl, or
    Figure US20020077432A1-20020620-C00002
  • b) [0022]
  • wherein [0023]
  • R[0024] 2 are the same or different and represent a hydrogen atom or SiR3 3, wherein R3 is the same or different, and may be a hydrogen atom or a C1-C40-carbon-containing group such as C1-C20-alkyl, C1-C10-fluoroalkyl, C1-C10-alkoxy, C6-C14-aryl, C6-C10-fluoroaryl, C6-C10-aryloxy, C2-C10-alkenyl, C7-C40-arylalkyl, C7-C40 alkylaryl, or C8-C40-arylalkenyl, or R2 are a C1-C30-carbon-containing group such as C1-C25-alkyl, e.g., methyl, ethyl, tert-butyl, cyclohexyl, or octyl, C2-C25-alkenyl, C3-C15-alkylalkenyl, C6-C24-aryl, C6(?)-C24-heteroaryl, e.g., pyridyl, furyl, or quinolyl, C7-C30-arylalkyl, C7-C30-alkylaryl, fluorinated C1-C25-alkyl, fluorinated C6-C24-aryl, fluorinated C7-C30-arylalkyl, fluorinated C7-C30-alkylaryl, or C1-C12-alkoxy, or two or more radicals R2 can be joined together such that the radicals R2 and the atom of the cyclopentadienyl ring joining them form a C4-C24-ring system which may in turn be substituted, and
  • m is equal to 5 for v=0, and m is equal to 4 for v=1, [0025]
  • L[0026] 1 may be the same or different and represent a hydrogen atom, a C1-C20-hydrocarbon group such as C1-C10-alkyl or C6-C20-aryl, a halogen atom, or OR6, SR6, OSiR3 6, SiR3 6, Pr2 6, or NR2 6, wherein R6 is a halogen atom, a C1-C10-alkyl group, a halogenated C1-C10-alkyl group, a C6-C20-aryl group or a halogenated C6-C20-aryl group, or L1 are a toluene sulfonyl, trifuoroacetyl, trifluoroacetoxyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl, or 2,2,2-tri-fluoroethanesulfonyl group,
  • o is an integer from 1 to 4, preferably 2, [0027]
  • Z is a bridging structural element between the two cyclopentadienyl rings, and v is 0 or 1. [0028]
  • Examples for Z are groups (M[0029] 2R4R5)x, wherein M2 is carbon, silicon, germanium, or tin; x is equal to 1, 2, or 3; and R4 and R5, the same or different, represent a hydrogen atom or a C1-C20-hydrocarbon-containing group such as C1-C10-alkyl, C6-C14-aryl, or trimethylsilyl. Preferably, Z is equal to CH2, CH2CH2, CH(CH3)CH2, CH(C4H9)C(CH3)2, C(CH3)2, (CH3)2Si, (CH3)2Ge, (CH3)2Sn, (C6H5)2Si, (C6H5)(CH3)Si, (C6H5)Ge, (C6H5)2Sn, (CH2)4Si, CH2Si(CH3)2, o-C6H4, or 2,2′-(C6H4)2. Z can also form a monocylic or polycyclic ring system with one or more radicals R1 and/or R2.
  • Exemplary but nonlimiting examples of metallocene catalyst components are: [0030]
  • Bis(cyclopentadienyl)titanium dichloride [0031]
  • Bis(indenyl)titanium dichloride [0032]
  • Bis(fluorenyl)titanium dichloride [0033]
  • Bis(tetrahydroindenyl)titanium dichloride [0034]
  • Bis(pentamethylcyclopentadienyl)titanium dichloride [0035]
  • Bis(trimethylsilylcyclopentadienyl)titanium dichloride [0036]
  • Bis(trimethoxysilylcyclopentadienyl)titanium dichloride [0037]
  • Bis(isobutylcyclopentadienyl)titanium dichloride [0038]
  • Bis(3-butenylcyclopentadienyl)titanium dichloride [0039]
  • Bis(methylcyclopentadienyl)titanium dichloride [0040]
  • Bis(1-,3-di-tert.-butylcyclopentadienyl)titanium dichloride [0041]
  • Bis(trifluoromethylcyclopentadienyl)titanium dichloride [0042]
  • Bis(tert.-butylcyclopentadienyl)titaniun dichloride [0043]
  • Bis(n-butylcyclopentadienyl)titanium dichloride [0044]
  • Bis(phenylcyclopentadienyl)titanium dichloride [0045]
  • Bis(N,N-dimethylaminomethyl-cyclopentadienyl)titanium dichloride [0046]
  • Bis(1,3-dimethylcyclopentadienyl)titanium dichloride [0047]
  • Bis(1-methyl-3-n-butylcyclopentadienyl)titanium dichloride [0048]
  • (Cyclopentadienyl) (methylcyclopentadienyl)titanium dichloride [0049]
  • (Cyclopentadienyl) (n-butylcyclopentadienyl)titanium dichloride [0050]
  • (Methylcyclopentadienyl)(n-butylcyclopentadienyl)titanium dichloride [0051]
  • (Cyclopentadienyl)(1-methyl-3-n-butylcyclopentadienyl)titanium dichloride [0052]
  • Methylenebis(cyclopentadienyl)titanium dichloride [0053]
  • Methylenebis(3-methylcyclopentadienyl)titanium dichloride [0054]
  • Methylenebis(3-n-butylcyclopentadienyl)titanium dichloride [0055]
  • Methylenebis(indenyl)titanium dichloride [0056]
  • Methylenebis(tetrahydroindenyl)titanium dichloride [0057]
  • Dimethylsilanediylbis(cyclopentadienyl)titanium dichloride [0058]
  • Dimethylsilanediylbis(tetramethylcyclopentadienyl)titanium dichloride [0059]
  • Dimethylsilanediylbis(3-trimethylsilylcyclopentadienyl)titanium dichloride [0060]
  • Dimethylsilanediylbis(3-methylcyclopentadienyl)titanium dichloride [0061]
  • Dimethylsilanediylbis(3-n-butylcyclopentadienyl)titanium dichloride [0062]
  • Dimethylsilanediylbis(indenyl)titanium dichloride [0063]
  • Dimethylsilanediylbis(tetrahydroindenyl)titanium dichloride [0064]
  • Isopropylidenebis(cyclopentadienyl)titanium dichloride [0065]
  • Isopropylidenebis(3-trimethylsilylcyclopentadienyl)titanium dichloride [0066]
  • Isopropylidenebis(3-methylcyclopentadienyl)titanium dichloride [0067]
  • Isopropyhidenebis(3-n-butylcyclopentadienyl)titanium dichloride [0068]
  • Isopropylidenebis(3-phenylcyclopentadienyl)titanium dichloride [0069]
  • Isopropylidenebis(indenyl)titanium dichloride [0070]
  • Isopropylidenebis(tetrahydroindenyl)titanium dichloride [0071]
  • 1,2-ethanediylbis(cyclopentadienyl)titanium dichloride [0072]
  • 1,2-ethanediylbis(3-methylcyclopentadienyl)titanium dichloride [0073]
  • 1,2-ethanediylbis(3-n-butylcyclopentadienyl)titanium dichloride [0074]
  • 1,2-ethanediylbis(3-phenylcyclopentadienyl)titanium dichloride [0075]
  • 1,2-ethanediylbis(indenyl)titanium dichloride [0076]
  • 1,2-ethanediylbis(tetrahydroindenyl)titanium dichloride [0077]
  • [(Cyclopentadienyldimethylsilyl)(phenyl)amido]titanium dichloride [0078]
  • [(Cyclopentadienyldimethylsilyl)(methyl)amido]titanium dichloride [0079]
  • [(Cyclopentadienyldimethylsilyl)(tert.-butyl)amido]titanium dichloride [0080]
  • [(Cyclopentadienyldimethylsilyl)(cyclohexyl)amido]titanium dichloride [0081]
  • Bis(cyclopentadienyl)zirconium dichloride [0082]
  • Bis(indenyl)zirconium dichloride [0083]
  • Bis(fluorenyl)zirconium dichloride [0084]
  • Bis(tetrahydroindenyl)zirconium dichloride [0085]
  • Bis(1,3-di-tert.-butylcyclopentadienyl)zirconium dichloride [0086]
  • Bis(tetramethylcyclopentadienyl)zirconium dichloride [0087]
  • Bis(trimethylsilylcyclopentadienyl)zirconium dichloride [0088]
  • Bis(trimethoxysilylcyclopentadienyl)zirconium dichloride [0089]
  • Bis(isobutylcyclopentadienyl)zirconium dichloride [0090]
  • Bis(3-butenylcyclopentadienyl)zirconium dichloride [0091]
  • Bis(methylcyclopentadienyl)zirconium dichloride [0092]
  • Bis(trifluoromethylcyclopentadienyl)zirconium dichloride [0093]
  • Bis(tert.-butylcyclopentadienyl)zirconium dichloride [0094]
  • Bis(n-butylcyclopentadienyl)zirconium dichloride [0095]
  • Bis(phenylcyclopentadienyl)zirconium dichloride [0096]
  • Bis(1,3-dimethylcyclopentadienyl)zirconium dichloride [0097]
  • Bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride [0098]
  • (Cyclopentadienyl) (methylcyclopentadienyl)zirconium dichloride [0099]
  • (Cyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride [0100]
  • (Methylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride [0101]
  • (Cyclopentadienyl)(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride [0102]
  • Methylenebis(cyclopentadienyl)zirconium dichloride [0103]
  • Methylenebis(3-methylcyclopentadienyl)zirconium dichloride [0104]
  • Methylenebis(3-n-butylcyclopentadienyl)zirconium dichloride [0105]
  • Methylenebis(indenyl)zirconium dichloride [0106]
  • Methylenebis(tetrahydroindenyl)zirconium dichloride [0107]
  • Dimethylsilanediylbis(cyclopentadienyl)zirconium dichloride [0108]
  • Dimethylsilanediylbis(tetramethylcyclopentadienyl)zirconium dichloride [0109]
  • Dimethylsilanediylbis(3-trimethylsilylcyclopentadienyl)zirconium dichloride [0110]
  • Dimethylsilanediylbis(3-methylcyclopentadienyl)zirconium dichloride [0111]
  • Dimethylsilanediylbis(3-n-butylcyclopentadienyl)zirconium dichloride [0112]
  • Dimethylsilanediylbis(indenyl)zirconium dichloride [0113]
  • Dimethylsilanediylbis(tetrahydroindenyl)zirconium dichloride [0114]
  • Isopropylidenebis(cyclopentadienyl)zirconium dichloride [0115]
  • Isopropylidenebis(3-trimethylsilylcyclopentadienyl)zirconium dichloride [0116]
  • Isopropylidenebis(3-methylcyclopentadienyl)zirconium dichloride [0117]
  • Isopropylidenebis(3-n-butylcyclopentadienyl)zirconium dichloride [0118]
  • Isopropylidenebis(3-phenylcyclopentadienyl)zirconium dichloride [0119]
  • Isopropylidenebis(indenyl)zirconium dichloride [0120]
  • Isopropylidenebis(tetrahydroindenyl)zirconium dichloride [0121]
  • 1,2-ethanediylbis(cyclopentadienyl)zirconium dichloride [0122]
  • 1,2-ethanediylbis(3-methylcyclopentadienyl)zirconium dichloride [0123]
  • 1,2-ethanediylbis(3-n-butylcyclopentadienyl)zirconium dichloride [0124]
  • 1,2-ethanediylbis(3-phenylcyclopentadienyl)zirconium dichloride [0125]
  • 1,2-ethanediylbis(indenyl)zirconium dichloride [0126]
  • 1,2-ethanediylbis(tetrahydroindenyl)zirconium dichloride [0127]
  • Bis(cyclopentadienyl)hafnium dichloride [0128]
  • Bis(trimethylsilylcyclopentadienyl)hafnium dichloride [0129]
  • Bis(methylcyclopentadienyl)hafnium dichloride [0130]
  • Bis(n-butylcyclopentadienyl)hafnium dichloride [0131]
  • Bis(1-,3-dimethylcyclopentadienyl)hafnium dichloride [0132]
  • Methylenebis(cyclopentadienyl)hafnium dichloride [0133]
  • Methylenebis(3-n-butylcyclopentadienyl)hafnium dichloride [0134]
  • Dimethylsilanediylbis(cyclopentadienyl)hafnium dichloride [0135]
  • Dimethylsilanediylbis(3-methylcyclopentadienyl)hafnium dichloride [0136]
  • Dimethylsilanediylbis(3-n-butylcyclopentadienyl)hafnium dichloride [0137]
  • Isopropylidenebis(cyclopentadienyl)hafnium dichloride [0138]
  • 1,2-Ethanediylbis(cyclopentadienyl)hafnium dichloride [0139]
  • 1,2-Ethanediylbis(3-methylcyclopentadienyl)hafnium chloride [0140]
  • 1,2-Ethanediylbis(3-n-butylcyclopentadienyl)hafnium dichloride [0141]
  • [(Cyclopentadienyldimethylsilyl)(phenyl)amido]zirconium dichloride [0142]
  • [(Cyclopentadienyldimethylsilyl)(methyl)amido]zirconium dichloride [0143]
  • [(Cyclopentadienyldimethylsilyl)(tert.-butyl)amido]zirconium dichloride [0144]
  • [(Cyclopentadienyldimethylsilyl)(cyclohexyl)amido]zirconium dichloride [0145]
  • 1-Silacyclopentan-1,1-bis(indenyl)zirconium dichloride [0146]
  • 1,6-bis[methylsilylbis(indenyl)zirconium dichloride]hexane [0147]
  • 1,4-disila-1,4-bis[cyclopentadienylzirconium dichloride]cyclohexane [0148]
  • 1,4-disila-1,4-bis[cyclopentadienyltitanium dichloride]cyclohexane [0149]
  • Additional examples are the corresponding metallocene compounds, in which one or both of the chlorine ligands are replaced by bromide, iodide, or methyl. [0150]
  • As catalyst components on the basis of a late transition metal, the catalyst composition in accordance with the invention preferably contains a nickel, rhodium, platinum, iron, ruthenium, cobalt or palladium compound, particularly preferably a nickel, iron, or palladium compound. The late transition metal compound preferably contains exclusively or in combination with other ligands, those ligands that coordinate by chelation with the metal over two or more atoms. Preferably, the two coordinating atoms are nitrogen atoms. Particularly preferred are ligands of the following formulas II and III. [0151]
    Figure US20020077432A1-20020620-C00003
  • Here, R[0152] 7 and R8, independently of one another, are the same or different C1-C40 hydrocarbon radicals, in which preferably the hydrocarbon atom bound to the nitrogen atom is bound to at least two additional carbon atoms. Preferred are R7 and R8 C6-C20-aryl radicals, which are preferably substituted in both ortho- positions, e.g., with C1-C10-alkyl radicals such as methyl or isopropyl. R9 and R10 independently of one another are the same or different, a hydrogen atom or a C1-C40-hydrocarbon radical, such as C1-C20-alkyl or C6-C20-aryl, or R9 and R10 together form a ring system preferably derived from acenaphthenequinone.
  • Particularly preferred are nickel or palladium compounds, especially in the oxidation steps of zero or two and with the ligands of Formula III. [0153]
  • Also preferred are iron, ruthenium, cobalt, or rhodium catalysts with the ligands of Formula II. [0154]
  • The catalyst composition in accordance with the invention contains as the catalyst component on the basis of a late transition metal preferably the nickel or palladium compound described in WO 96/2310 (to which reference is expressly made here), which have a two-toothed ligand coordinated over nitrogen atoms. [0155]
  • The late transition metal component can already contain the ligands coordinated with the metal, or they can be obtained by combining a suitable transition metal component with the free ligands or a ligand derivative “in situ” (i.e., in the polymerization reactor). [0156]
  • Examples of particularly suitable late transition metal components are listed in the following. Here, the designation An pertains ligands of Formula III, in which the radicals R[0157] 9 and R10 form a ring system derived from acenaphthenequinone, which are shown in the following
    Figure US20020077432A1-20020620-C00004
  • Formula: [0158]
  • The designation Me=methyl, Et=ethyl, and [0159] iPr=isopropyl.
  • [[(2,6-[0160] iPr2C6H3)—N═C(H)—C(H)═N-(2,6-iPr2C6H3)]NiBr2]
  • [[(2,6-[0161] iPr2C6H3)—N═C(Me)—C(Me)═N-(2,6-iPr2C6H3)]NiBr2]
  • [[(2,6-[0162] iPr2C6H3)—N═C(An)—C(An)═N-(2,6-iPr2C6H3)]NiBr2]
  • [[(2,6-Me[0163] 2C6H3)—N═C(H)—C(H)═N-(2,6-Me2C6H3)]NiBr2]
  • [[(2,6-Me[0164] 2C6H3)—N═C(Me)—C(Me)═N-(2,6-Me2C6H3)]NiBr2]
  • [[(2,6-Me[0165] 2C6H3)—N═C(An)—C(An)═N-(2,6-Me2C6H3)]NiBr2]
  • The exemplary late transition metal compounds are: [0166]
  • [[(2,6-[0167] iPr2C6H3)—N═C(H)—C(H)═N-(2,6-iPr2C6H3)]PdMe(NC—Me)]+SbF6 −
  • [[(2,6-[0168] iPr2C6H3)—N═C(Me)—C(Me)═N-(2,6-iPr2C6H3)]PdMe(NC—Me)]+SbF6 −
  • [[(2,6-[0169] iPr2C6H3)—N═C(An)—C(An)═N-(2,6-iPr2C6H3)]PdMe(NC—Me)]+SbF6 −
  • [[(2,6-[0170] iPr2C6H3)—N═C(H)—C(H)═N-(2,6-iPr2C6H3)]PdMe(NC—Me)]+BF4 −
  • [[(2,6-[0171] iPr2C6H3)—N═C(Me)—C(Me)═N-(2,6-iPr2C6H3)]PdMe(NC—Me)]+BF4 −
  • [[(2,6-[0172] iPr2C6H3)—N═C(An)—C(An)═N-(2,6-iPr2C6H3)]PdMe(NC—Me)]+BF4 −
  • [[(2,6-[0173] iPr2C6H3)—N═C(H)—C(H)═N-(2,6-iPr2C6H3)]Pd(NC—Me)2]2+(SbF6 −)
  • [[(2,6-[0174] iPr2C6H3)—N═C(Me)—C(Me)═N-(2,6-iPr2C6H3)]Pd(NC—Me)2]2+(SbF6 −)
  • [[(2,6-[0175] iPr2C6H3)—N═C(An)—C(An)═N-(2,6-iPr2C6H3)]Pd(NC—Me)2]2+(SbF6 −)
  • [[(2,6-[0176] iPr2C6H3)—N═C(H)—C(H)═N-(2,6-iPr2C6H3)]Pd(NC—Me)2]2+(BF4 −)2
  • [[(2,6-[0177] iPr2C6H3)—N═C(Me)—C(Me)═N-(2,6-iPr2C6H3)]Pd(NC—Me)2]2+(BF4 −)
  • [[(2,6-[0178] iPr2C6H3)—N═C(An)—C(An)═N-(2,6-iPr2C6H3)]Pd(NC—Me)2]2+(BF4 31 )2
  • [[(2,6-[0179] iPr2C6H3)—N=50 C(H)—C(H)═N-(2,6-iPr2C6H3)]NiMe(OEt2)]+[B(3,5-(F3C)2C6H3)4]−
  • [[(2,6-[0180] iPr2C6H3)—N═C(Me)—C(Me)═N-2,6-iPr2C6H3)]NiMe(OEt2)]+[B(3,5-(F3C)2C6H3)4]−
  • [[(2,6-[0181] iPr2C6H3)—N═C(An)—C(An)═N-(2,6-iPr2C6H3)]NiMe(OEt2)]+[B(3,5-(F3C)2C6H3)4]−
  • [[(2,6-[0182] iPr2C6H3)—N═C(H)—C(H)═N-(2,6-iPr2C6H3)]NiMe(NC—Me)]+SbF6 −
  • [[(2,6-[0183] iPr2C6H3)—N═C(AN)—C(An)═N-(2,6-iPr2C6H3)]NiMe(NC—Me)]+SbF6 −
  • [[(2,6-[0184] iPr2C6H3)—N═C(Me)—C(Me)═N-(2,6-iPr2C6H3)]NiMe(NC—Me)]+SbF6 −
  • [2,6-[(2,6-[0185] iPr2C6H3)—N═C(Me)]pyridyl]FeBr2
  • [2,6-[(2,6-Me[0186] 2C6H3)—N═C(Me)]pyridyl]FeBr2
  • [2,6-[(2,6-[0187] iPr2C6H3)—N═C(Me)]pyridyl]CoBr2
  • [2,6-[(2,6-Me[0188] 2C6H3)—N═C(Me)]pyridyl]CoBr2
  • [2,6-[(2,6-[0189] iPr2C6H3)—N═C(Me)]pyridyl]FeBr3
  • [2,6-[(2,6-Me[0190] 2C6H3)—N═(Me)]pyridyl]FeBr3
  • [2,6-[(2,6-[0191] iPr2C6H3)—N═C(Me)]pyridyl]CoBr3
  • [2,6-[(2,6-Me[0192] 2C6H3)—N═C(Me)]pyridyl]CoBr3
  • In place of the dibromides listed, the corresponding compounds in which one or both of the bromide ligands has been replaced by chloride, iodide, or methyl may be used. [0193]
  • Additional examples of suitable polymerization catalyst components on the basis of a late transition metal are reaction products of nickel compounds with (Me[0194] 3Si)N═P{N(SiMe3)2}═N(SiMe3) or (2,4,6-Me3C6H2)P═C(OSiMe3)—PH(2,4,6-Me3C6H2).
  • Preferably the catalyst composition in accordance with the invention contains one or more activators such as Lewis acids. [0195]
  • Lewis acid activators preferably comprise boron compounds such as boranes or aluminum compounds such as aluminum alkyls or aluminoxanes. Examples of suitable activators are boranes such as trifluoroborane, triphenylborane, tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane, tris(pentafluorophenyl)-borane, tris(tolyl)borane, tris(3,5-dimethylphenyl)borane, tris(3,5-difluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, or dimethylanilinium [(pentafluorophenyl)borane], [H(OEt[0196] 2)][B{3,5-(CF3)2C6F3}4], aluminum alkyls such as Al(C2H5)3, Al(CH2CH(CH3)2)3, Al(C3H7)3, Al[(CH2)3CH3]3, Al[(CH2)5CH3)3, Al(C6F5)3, Al(C2H5)2Cl, Al2(C2H5)3Cl2, or AlCl3, or aluminoxanes such as methylaluminoxane, isobutylaluminoxane, butylaluminoxane, heptylaluminoxane, and methylbutylaluminoxane. Particularly preferably, aluminoxanes are used.
  • The activator can be used in any arbitrary quantities based on the transition metal components of the catalyst composition in accordance with the invention; it is preferably used in excess or in stoichiometric amounts. The same activator or different activators can be used for activating the early and the late transition metal components of the catalyst composition Preferably the same activator is used for all transition metal components. The activation of the different transition metal components can take place at the same location, e.g., in the reactor, or at different locations. In a preferred embodiment variant, an excess of the activator is mixed with the early transition metal component, and this mixture is added to the late transition metal component already contacted with the monomer. [0197]
  • An aluminoxane is preferably used as the activator for the catalyst component on the basis of a late transition metal. [0198]
  • As the activator for the catalyst components on the basis of an early transition metal, in the case of a Ziegler catalyst component preferably an aluminum alkyl is used and in the case of a metallocene catalyst component preferably an aluminoxane and/or a borane is used. [0199]
  • Optionally the catalyst composition in accordance with the invention contains one or several support components. In this case both the early and the late transition metal component can be supported, or only one of the two components may be supported. In a preferred exemplified variant, both components are supported to ensure relatively close spatial proximity of the different catalyst centers and thus to guarantee good mixing of the different polymers formed. [0200]
  • The support component is preferably a porous inorganic or organic solid. Preferably the support material contains at least one inorganic halide such as MgCl[0201] 2 or an inorganic oxide such as SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, ThO2; carbonates such as Na2CO3, K2CO3, CaCO3, MgCO3, and sulfates such as Na2SO4, Al2(SO4)3, BaSO4; nitrates such as KNO3, Mg(NO3)2, Al(NO3)3; as well as oxides such as Na2O, K2O, Li2O, especially silicon oxide and/or aluminum oxide, or it preferably contains at least one homo- or copolymer, which may be cross linked, e.g., polyethylene, polypropylene, polybutene, polystyrene, polystyrene cross linked with divinylbenzene, polyvinyl chloride, acrylate-butadiene-styrene copolymer, polyamide, polymethacrylate, polycarbonate, polyester, polyacetal, or polyvinyl alcohol. Polymer blends can also be used.
  • The support material may be pretreated, e.g., by heating at temperatures from 50° C. to 1000° C., e.g., in an inert gas stream or under a vacuum at 0.01 bar to 0.001 bar, or by mixing or reacting with a chemical compound. The chemical compound can react with catalyst poisons such as aluminum, magnesium, boron, or lithium alkyls or lead to a functionalization of the surface of the support. Here it makes no difference whether the support material already bears functional groups or whether these are only introduced after the pretreatment by corresponding reactions on the surface. [0202]
  • The supporting can be performed in that the individual catalyst components are mixed in arbitrary order. For example, the early and the late transition metal compound can be applied to the optimally pretreated support (e.g., consisting of SiO[0203] 2) and then be treated with the activator, preferably in the presence of monomer.
  • The present invention also pertains to a process for polymerization of olefins in the presence of the catalyst composition in accordance with the invention. The term “polymerization” comprises homopolymerization as well as copolymerization. [0204]
  • The catalyst system in accordance with the invention can be used for reacting one or more olefinic comonomers such as ethylene or C[0205] 3-C20-α-olefins. For the case that two or more comonomers are used, the early and the late transition metal components can be active for all monomers used, but a transition metal component can also react specifically with only one or more of the monomers used. For example, ethylene and an α-olefin that preferably has 3 to 20 C atoms may be used. In this process a mixture of two copolymers is obtained, or a mixture of one copolymer with an ethylene homopolymer. Preferably the copolymer with the lower α-olefin fraction is formed from the late transition metal component. Particularly preferably in the process in accordance with the invention, ethylene is homopolymerized, wherein a blend of at least two different polyethylenes is obtained, that have a different branching structure.
  • The polymerization process can be carried out in liquid phase or in the gas phase. Preferably the process takes place in liquid phase. Preferably inert organic compounds are used as the solvent or suspension medium. Particularly preferably, aromatic or aliphatic hydrocarbons or mixtures thereof are used. Toluene, xylenes, and saturated aliphatic C[0206] 10-C30-hydrocarbons are particularly suitable. The process can also be performed in supercritical media.
  • The polymerization process is performed in the temperature range of −100 to 300° C., preferably 0 to 200° C., particularly preferably 25 to 150° C. The process is carried out in the pressure range of 1 to 300 atm, preferably 1 to 100 atm, particularly preferably 3 to 30 atm. The process can take place in one or more steps. [0207]
  • Through the selection of appropriate reaction conditions, e.g., temperature, addition of chain transfer agents such as hydrogen, monomer concentrations, as well as the catalyst concentration, it is possible to control molecular weight distributions, degree of branching, and other properties of the polymer produced. The degree of branching of the polymer can be controlled by way of the monomer concentration. The reaction can also take place in two or more reactors connected in cascade. By introducing the catalyst component into the individual reactors, the ratio of the two catalysts can be modified. [0208]
  • The productivity of each individual transition metal component is preferably in excess of 2800 kg polymer/(mol transition metal×hr), preferably more than 15,000 kg polymer/(mol transition metal×hr). [0209]
  • The catalyst composition in accordance with the invention is suitable for producing reactor blends of two or more polymers that have advantageous application and processing properties. The number-average molecular weights of the individual polymer fractions are preferably in the range of 11 to 10,000 kg/mol, particularly preferably 20 to 1,000 kg/mol. The molar ratio of the fraction of the early transition metal component(s) to the late transition metal component(s) can fall in the range of 0.1:99.9 to 99.9:0.1, preferably 1:30 to 1:1. The ratio of the fractions of the polymers formed by the early and late transition metal complexes can lie in the range of 0.1:99.9 to 99.9:0.1, preferably 10:90 to 90:10, particularly preferably 1:1 to 50:1. [0210]
  • The polymerization process in accordance with the invention is particularly suitable for the homopolymerization of ethylene to a blend of two or more polymers, at least one of which has the following branching structure: It contains at least 10 branchings per 1000 carbon atoms and for each 100 methyl branchings, at least two ethyl branchings, at least one butyl branching, and one to fifty amyl or higher branchings are contained. [0211]
  • The polymerization process in accordance with the invention is particularly preferably suitable for the polymerization of ethylene to a blend of two or more polymers, at least one of which has the following branching structure: It contains at least 30 branchings per 1000 carbon atoms, and for each 100 methyl branchings at least four ethyl branchings, at least two butyl branchings, and two to thirty amyl or higher branchings are contained. [0212]
  • In particular, a reactor blend of two polyethylenes can be obtained, of which preferably one has a branching degree of>10 branching/1000 carbon atoms, preferably>20 branchings/1000 carbon atoms, particularly preferably>40 branchings/1000 carbon atoms. [0213]
  • The preparation of the polymer blend already in the reactor reduces the energy consumption, requires no subsequent blending processes, and permits simple control of the molecular weight distributions and the molecular weight fractions of the various polymers. In addition, good mixing of the polymers can be achieved. The production of a blend of two or more polymers of different degrees of branching from ethylene without addition of a comonomer reduces the cost of the olefins used as well as the plant costs and other costs for preparing the comonomer. [0214]
  • The examples that follow will serve to explain the invention.[0215]
    • EXAMPLE 1
  • In a 1 liter steel autoclave with heating/cooling jacket and mechanical agitator, a solution of 2.2 mg [{(2,6-[0216] iPr2C6H3)—N═C(An)—C(An)═N-(2,6-iPr2C6H3)}NiBr2] in 600 ml toluene are placed. The solution was saturated by briefly agitating under 10 atm with ethylene. Then the reactor was depressurized, and a solution of 0.05 mg bis(cyclopenta-dienyl)zirconium dichloride in 10 ml of a 10% solution of methylaluminoxane in toluene was added. The autoclave was closed, and a constant pressure of 10 atm ethylene was applied. The autoclave was controlled at 50° C. After 15 min the reaction was interrupted by releasing the ethylene and destroying the catalyst with isopropanol.
  • The reaction mixture obtained was poured into 1 L of HCl-acidified methanol. The polymer product was dried under vacuum. 33.4 g of polymer were obtained. [0217]
  • 1H-NMR (1,2-C[0218] 6D4Cl2: 120° C.): 21 branchings/1000 carbon atoms.
    • EXAMPLE 2
  • Example 1 was repeated with 0.28 mg of the nickel compound and 0.175 mg Cp[0219] 2ZrCl2. The polymerization was performed at 40° C. and interrupted after a half hour. 5.8 g polymer were obtained. 1H-NMR (1,2-C6D4Cl2: 120° C.): 12 branchings/1000 carbon atoms.

Claims (9)

1. Catalyst composition containing at least two different polymerization catalysts, of which a) at least one is a polymerization catalyst on the basis of an early transition metal component and b) at least one is a polymerization catalyst on the basis of a late transition metal component.
2. Catalyst composition in accordance with claim 1, wherein the early transition metal component is a Ziegler catalyst component and/or a metallocene catalyst component.
3. Catalyst component in accordance with claim 1 or 2, wherein each of the transition metal components has a productivity that is greater than 2800 kg polymer/(mol transition metal×hr).
4. Catalyst composition in accordance with one or more of the claims 1 to 3, additionally containing one or several activators.
5. Catalyst composition in accordance with one or more of the claims 1 to 4, simultaneously containing one or more supports.
6. Process for polymerization of olefins in the presence of a catalyst composition in accordance with one or more of the claims 1 to 5.
7. Process in accordance with claim 6, wherein ethylene is polymerized.
8. Polyolefin that can be produced in accordance with the process of claim 6 or 7.
9. Use of a catalyst composition in accordance with one or more of the claims 1 to 5 for olefin polymerization.
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