EP0896589A1 - Supported catalyst composition and process for the polymerization of olefin monomers - Google Patents
Supported catalyst composition and process for the polymerization of olefin monomersInfo
- Publication number
- EP0896589A1 EP0896589A1 EP97919758A EP97919758A EP0896589A1 EP 0896589 A1 EP0896589 A1 EP 0896589A1 EP 97919758 A EP97919758 A EP 97919758A EP 97919758 A EP97919758 A EP 97919758A EP 0896589 A1 EP0896589 A1 EP 0896589A1
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- European Patent Office
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- transition metal
- catalyst
- catalyst system
- ligand
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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
- 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
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
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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
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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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—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
- 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
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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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
- 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
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63912—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
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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
- 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
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63916—Component covered by group C08F4/62 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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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
- 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
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component 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
Definitions
- the present invention relates to supported catalyst systems and to the polymerization of ⁇ -olefin monomers using such supported catalyst systems.
- the invention relates to catalyst systems comprising a carrier material, at least one transition metal complex and one or more co-catalysts and to a process for producing polymers by polymerization of ⁇ - olefins using said supported catalyst systems, and to the obtained polymer products and their use.
- EP-A-548,257 describes a supported catalyst system comprising an inert support, a monocyclopentadienyl compound of a "Group 4" transition metal and an aluminoxane.
- Drawbacks of the supported catalyst systems according to EP-A-548,257 are that with these catalysts only products with a low molecular weight can be produced and that these catalyst systems have a low activity. Commercial polymerization of ⁇ - olefin monomers with these catalyst systems is not feasible.
- the present invention provides new supported catalyst systems which are particularly suitable for the production of ⁇ - olefin (co-)polymers having a high molecular weight, and which present high activity.
- the capability of attaining higher than standard molecular weights with the incorporation of a given amount of comonomers under a given set of polymerizing conditions is referred to as the superior "copolymer molecular weight capability" of the present polymerization process.
- this object is attained by providing a catalyst composition and a process for the polymerization of at least one ⁇ -olefin in the presence of the present catalyst composition.
- the catalyst composition includes at least one complex comprising a reduced valency transition metal (M) selected from groups 4-6 of the Periodic Table of Elements, a multidentate monoanionic ligand (X), two monoanionic ligands (L), and, optionally, additional ligands (K). More specifically, the complex of the catalyst composition of the present invention is represented by the following formula (I):
- M a reduced transition metal selected from group 4, 5 or 6 of the Periodic Table of Elements?
- X a multidentate monoanionic ligand represented by the formula: (Ar-R t -),Y(-R t -DR ' n ) q ; Y a cyclopentadienyl, amido (-NR'-), or phosphido group (-PR'-), which is bonded to the reduced transition metal M; R at least one member selected from the group consisting of (i) a connecting group between the Y group and the DR' n group and (ii) a connecting group between the Y group and the Ar group, wherein when the ligand X contains more than one R group, the R groups can be identical to or different from each other; D an electron-donating hetero atom selected from group 15 or 16 of the Periodic Table of Elements; R' a substituent selected from the group consisting of a hydrogen, hydrocarbon radical and hetero atom-containing moiety, except that R' cannot be hydrogen when R' is directly bonded to the electron-donating hetero atom D, wherein when the
- L a monoanionic ligand bonded to the reduced transition metal M, wherein the monoanionic ligand L is not a ligand comprising a cyclopentadienyl, amido (-NR'-), or phosphido (-PR'-) group, and wherein the monoanionic ligands L can be identical or different from each other; K a neutral or anionic ligand bonded to the reduced transition metal M, wherein when the transition metal complex contains more than one ligand K, the ligands K can be identical or different from each other ; m is the number of K ligands, wherein when the K ligand is an anionic ligand m is 0 for M 3+ , m is 1 for M 4+ , and m is 2 for M s+ , and when K is a neutral ligand m increases by one for each neutral K ligand; n the number of the R' groups bonded to the electron-donating hetero atom D, wherein when D is selected
- FIG. 1 is a schematic view of a cationic active site of a trivalent catalyst complex in accordance with an embodiment of the present invention.
- FIG. 2 is a schematic view of a neutral active site of a trivalent catalyst complex of a dianionic ligand of a conventional catalyst complex according to WO-A-93/19104.
- transition metal complex Various components (groups) of the transition metal complex are discussed below in more detail.
- the Transition Metal (M) The transition metal in the complex is selected from groups 4-6 of the Periodic Table of Elements. As referred to herein, all references to the Periodic Table of Elements mean the version set forth in the new IUPAC notation found on the inside of the cover of the Handbook of Chemistry and Physics, 70th edition, 1989/1990, the complete disclosure of which is incorporated herein by reference. More preferably, the transition metal is selected from group 4 of the Periodic Table of Elements, and most preferably is titanium (Ti) .
- the transition metal is present in reduced form in the complex, which means that the transition metal is in a reduced oxidation state.
- reduced oxidation state means an oxidation state which is greater than zero but lower than the highest possible oxidation state of the metal (for example, the reduced oxidation state is at most M 3+ for a transition metal of group 4, at most M 4+ for a transition metal of group 5 and at most M 5+ for a transition metal of group 6).
- the X ligand is a multidentate monoanionic ligand represented by the formula: (Ar-R t -) B Y(-R t -DR ' n ) q .
- a multidentate monoanionic ligand is bonded with a covalent bond to the reduced transition metal (M) at one site (the anionic site, Y) and is bonded either (i) with a coordinate bond to the transition metal at one other site (bidentate) or (ii) with a plurality of coordinate bonds at several other sites (tridentate, tetradentate, etc.). Such coordinate bonding can take place, for example, via the D heteroatom or Ar group(s).
- tridentate monoanionic ligands include, without limitation, Y-R t -DR ' n _ ⁇ .-R t -DR ' n and Y(-R-DR' n ) 2 .
- R represents a connecting or bridging group between the DR' n and Y, and/or between the electron ⁇ donating aryl (Ar) group and Y. Since R is optional, "t" can be zero.
- the R group is discussed below in paragraph (d) in more detail.
- the Y group of the multidentate monoanionic ligand (X) is preferably a cyclopentadienyl, amido
- the Y group is a cyclopentadienyl ligand (Cp group).
- Cp group cyclopentadienyl ligand
- the term cyclopentadienyl group encompasses substituted cyclopentadienyl groups such as indenyl, fluorenyl, and benzoindenyl groups, and other polycyclic aromatics containing at least one 5-member dienyl ring, so long as at least one of the substituents of the Cp group is an R t -DR' n group or
- R t -Ar group that replaces one of the hydrogens bonded to the five-member ring of the Cp group via an exocyclic substitution.
- Examples of a multidentate monoanionic ligand with a Cp group as the Y group (or ligand) include the following (with the (-R t -DR' n ) or (Ar-R t -) substituent on the ring) : R ' R '
- the Y group can also be a hetero cyclopentadienyl group.
- a hetero cyclopentadienyl group means a hetero ligand derived from a cyclopentadienyl group, but in which at least one of the atoms defining the five-member ring structure of the cyclopentadienyl is replaced with a hetero atom via an endocyclic substitution.
- the hetero Cp group also includes at least one R t -DR' n group or R t -Ar group that replaces one of the hydrogens bonded to the five-member ring of the Cp group via an exocyclic substitution.
- the hetero Cp group encompasses indenyl, fluorenyl, and benzoindenyl groups, and other polycyclic aromatics containing at least one 5-member dienyl ring, so long as at least one of the substituents of the hetero Cp group is an R t -DR' n group or R t -Ar group that replaces one of the hydrogens bonded to the five-member ring of the hetero Cp group via an exocyclic substitution.
- the hetero atom can be selected from group 14, 15 or 16 of the Periodic Table of Elements. If there is more than one hetero atom present in the five- member ring, these hetero atoms can be either the same or different from each other. More preferably, the hetero atom(s) is/are selected from group 15, and still more preferably the hetero atom(s) selected is/are phosphorus.
- hetero ligands of the X group that can be practiced in accordance with the present invention are hetero cyclopentadienyl groups having the following structures, in which the hetero cyclopentadienyl contains one phosphorus atom (i.e., the hetero atom) substituted in the five-member ring:
- the transition metal group M is bonded to the Cp group via an r ⁇ 5 bond.
- the other R' exocyclic substituents (shown in formula (III)) on the ring of the hetero Cp group can be of the same type as those present on the Cp group, as represented in formula (II).
- at least one of the exocyclic substituents on the five- member ring of the hetero cyclopentadienyl group of formula (III) is the R t -DR' n group or the R t -Ar group.
- the numeration of the substitution sites of the indenyl group is in general and in the present description based on the IUPAC Nomenclature of Organic Chemistry 1979, rule A 21.1. The numeration of the substituent sites for indene is shown below. This numeration is analogous for an indenyl group: Indene
- the Y group can also be an amido (-NR'-) group or a phosphido (-PR'-) group.
- the Y group contains nitrogen (N) or phosphorus (P) and is bonded covalently to the transition metal M as well as to the (optional) R group of the (-R t -DR' n ) or (Ar-R t -) substituent.
- the R group is optional, such that it can be absent from the X group. Where the R group is absent, the DR' n or Ar group is bonded directly to the Y group (that is, the DR' n or Ar group is bonded directly to the Cp, amido, or phosphido group). The presence or absence of an R group between each of the DR' n groups and/or Ar groups is independent.
- each of the R group constitutes the connecting bond between, on the one hand the Y group, and on the other hand the DR' n group or the Ar group.
- the presence and size of the R group determines the accessibility of the transition metal M relative to the DR' n or Ar group, which gives the desired intramolecular coordination. If the R group (or bridge) is too short or absent, the donor may not coordinate well due to ring tension.
- the R groups are each selected independently, and can generally be, for example, a hydrocarbon group with 1-20 carbon atoms (e.g., alkylidene, arylidene, aryl alkylidene, etc.). Specific examples of such R groups include, without limitation, methylene, ethylene, propylene, butylene, phenylene, whether or not with a substituted side chain.
- the R group has the following structure:
- R' groups of formula (IV) can each be selected independently, and can be the same as the R' groups defined below in paragraph (g).
- the main chain of the R group can also contain silicon or germanium.
- R groups are: dialkyl silylene (-SiR' 2 -), dialkyl germylene (-GeR' 2 -), tetra-alkyl silylene (-SiR' 2 -SiR' 2 -) , or tetraalkyl silaethylene (-SiR' 2 CR' 2 - ).
- the alkyl groups in such a group preferably have 1-4 carbon atoms and more preferably are a methyl or ethyl group.
- This donor group consists of an electron- donating hetero atom D, selected from group 15 or 16 of the Periodic Table of Elements, and one or more substituents R' bonded to D.
- the number (n) of R' groups is determined by the nature of the hetero atom D, insofar as n being 2 if D is selected from group 15 and n being 1 if D is selected from group 16.
- the R' substituents bonded to D can each be selected independently, and can be the same as the R' groups defined below in paragraph (g) , with the exception that the R' substituent bonded to D cannot be hydrogen.
- the hetero atom D is preferably selected from the group consisting of nitrogen (N) , oxygen (0), phosphorus (P) and sulphur (S); more preferably, the hetero atom is nitrogen (N) .
- the R' group is an alkyl, more preferably an n-alkyl group having 1- 20 carbon atoms, and most preferably an n-alkyl having 1-8 carbon atoms. It is further possible for two R' groups in the DR' n group to be connected with each other to form a ring-shaped structure (so that the DR' n group can be, for example, a pyrrolidinyl group). The DR' n group can form coordinate bonds with the transition metal M. ( f ) The Ar Group
- the electron-donating group (or donor) selected can also be an aryl group (C 6 R' S ), such as phenyl, tolyl, xylyl, mesityl, cumenyl, tetramethyl phenyl, pentamethyl phenyl, a polycyclic group such as triphenylmethane, etc.
- the electron-donating group D of formula (I) cannot, however, be a substituted Cp group, such as an indenyl, benzoindenyl, or fluorenyl group.
- the coordination of this Ar group in relation to the transition metal M can vary from h . 1 to h. 6 .
- the R' groups may each separately be hydrogen or a hydrocarbon radical with 1-20 carbon atoms (e.g. alkyl, aryl, aryl alkyl and the like as shown in Table
- alkyl groups are methyl, ethyl, propyl, butyl, hexyl and decyl.
- aryl groups are phenyl, mesityl, tolyl and cumenyl.
- aryl alkyl groups are benzyl, pentamethylbenzyl, xylyl, styryl and trityl.
- R' groups are halides, such as chloride, bromide, fluoride and iodide, methoxy, ethoxy and phenoxy.
- Y group can be an indenyl, a fluorenyl or a benzoindenyl group.
- the indenyl, fluorenyl, and/or benzoindenyl can contain one or more R' groups as substituents.
- R' can also be a substituent which instead of or in addition to carbon and/or hydrogen can comprise one or more hetero atoms of groups 14-16 of the Periodic Table of Elements.
- a substituent can be, for example, a Si-containing group, such as Si(CH 3 ) 3 .
- the transition metal complex contains two monoanionic ligands L bonded to the transition metal M.
- L group ligands which can be identical or different, include, without limitation, the following: a hydrogen atom; a halogen atom; an alkyl, aryl or aryl alkyl group; an alkoxy or aryloxy group; a group comprising a hetero atom selected from group 15 or 16 of the Periodic Table of Elements, including, by way of example, (i) a sulphur compound, such as sulphite, sulphate, thiol, sulphonate, and thioalkyl, and (ii) a phosphorus compound, such as phosphite, and phosphate.
- the two L groups can also be connected with each other to form a dianionic bidentate ring system.
- L is a halide and/or an alkyl or aryl group; more preferably, L is a Cl group and/or a C x -C t alkyl or a benzyl group.
- the L group cannot be a Cp, amido, or phosphido group. In other words, L cannot be one of the Y groups.
- the K Ligand is a neutral or anionic group bonded to the transition metal M.
- the K group is a neutral or anionic ligand bonded to M.
- neutral K ligands which by definition are not anionic, are not subject to the same rule. Therefore, for each neutral K ligand, the value of m (i.e., the number of total K ligands) is one higher than the value stated above for a complex having all monoanionic K ligands.
- the K ligand can be a ligand as described above for the L group or a Cp group (-C S R' 5 ), an amido group (-NR' 2 ) or a phosphido group (-PR' 2 ).
- the K group can also be a neutral ligand such as an ether, an amine, a phosphine, a thioether, among others.
- the two K groups can be connected with each other via an R group to form a bidentate ring system.
- the X group of the complex contains a Y group to which are linked one or more donor groups (the Ar group(s) and/or
- the number of donor groups linked to the Y group is at least one and at most the number of substitution sites present on a Y group.
- One preferred embodiment of the catalyst composition according to the present invention comprises a transition metal complex in which a bidentate/monoanionic ligand is present and in which the reduced transition metal has been selected from group 4 of the Periodic Table of Elements and has an oxidation state of +3.
- the catalyst composition according to the invention comprises a transition metal complex represented by formula (V) : X
- the Y group in this formula (VI) is a hetero atom, such as phosphorus, oxygen, sulfur, or nitrogen bonded covalently to the transition metal M (see p. 2 of WO-A- 93/19104).
- This means that the Cp a (ZY) b group is of a dianionic nature, and has the anionic charges residing formerly on the Cp and Y groups. Accordingly, the Cp a (ZY) b group of formula (VI) contains two covalent bonds: the first being between the 5-member ring of the Cp group and the transition metal M, and the second being between the Y group and the transition metal.
- the X group in the complex according to the present invention is of a monoanionic nature, such that a covalent bond is present between the Y group (e.g., the Cp group) and transition metal, and a coordinate bond can be present between the transition metal M and one or more of the (Ar-R t -) and (-R t -DR' n ) groups.
- a coordinate bond is a bond (e.g., H 3 N-BH 3 ) which when broken, yields either (i) two species without net charge and without unpaired electrons (e.g., H 3 N: and BH 3 ) or (ii) two species with net charge and with unpaired electrons (e.g., H 3 N- + and BH 3 - ⁇ ).
- a covalent bond is a bond (e.g., CH 3 -CH 3 ) which when broken yields either (i) two species without net charge and with unpaired electrons (e.g., CH 3 - and CH 3 - ) or (ii) two species with net charges and without unpaired electrons (e.g. , CH 3 + and CH 3 : ⁇ ).
- a discussion of coordinate and covalent bonding is set forth in Haaland et al. (Angew. Chem Int. Ed. Eng. Vol. 28, 1989, p. 992), the complete disclosure of which is incorporated herein by reference.
- the transition metal complexes described in WO-A- 93/19104 are ionic after interaction with the co ⁇ catalyst.
- the transition metal complex according to WO-A-93/19104 that is active in the polymerization contains an overall neutral charge (on the basis of the assumption that the polymerizing transition metal complex comprises, a M(III) transition metal, one dianionic ligand and one growing monoanionic polymer chain (POL)).
- POL monoanionic polymer chain
- the polymerization active transition metal complex of the catalyst composition according to the present invention is of a cationic nature (on the basis of the assumption that the polymerizing transition metal complex - based on the formula (V) structure - comprises, a M(III) transition metal, one monoanionic bidentate ligand and one growing monoanionic polymer chain (POL ) ) .
- Transition metal complexes in which the transition metal is in a reduced oxidation state have the following structure:
- the transition metal complex of the present invention is precisely the presence, in the transition metal complex of the present invention, of the DR' n or Ar group (the donor), optionally bonded to the Y group by means of the R group, that gives a stable transition metal complex suitable for polymerization.
- the donor optionally bonded to the Y group by means of the R group.
- Such an intramolecular donor is to be preferred over an external (intermolecular) donor on account of the fact that the former shows a stronger and more stable coordination with the transition metal complex.
- the catalyst system may also be formed in situ if the components thereof are added directly to the polymerization reactor system and a solvent or diluent, including liquid monomer, is used in said polymerization reactor.
- the catalyst composition of the present invention also contains a co-catalyst.
- the co-catalyst can be an organometallic compound.
- the metal of the organometallic compound can be selected from group 1, 2, 12 or 13 of the Periodic Table of Elements. Suitable metals include, for example and without limitation, sodium, lithium, zinc, magnesium, and aluminum, with aluminum being preferred. At least one hydrocarbon radical is bonded directly to the metal to provide a carbon-metal bond.
- the hydrocarbon group used in such compounds preferably contains 1-30, more preferably 1-10 carbon atoms. Examples of suitable compounds include, without limitation, amyl sodium, butyl lithium, diethyl zinc, butyl magnesium chloride, and dibutyl magnesium.
- organoaluminium compounds including, for example and without limitation, the following: trialkyl aluminum compounds, such as triethyl aluminum and tri-isobutyl aluminum; alkyl aluminum hydrides, such as di-isobutyl aluminum hydride; alkylalkoxy organoaluminium compounds; and halogen-containing organoaluminium compounds, such as diethyl aluminum chloride, diisobutyl aluminum chloride, and ethyl aluminum sesquichloride.
- trialkyl aluminum compounds such as triethyl aluminum and tri-isobutyl aluminum
- alkyl aluminum hydrides such as di-isobutyl aluminum hydride
- alkylalkoxy organoaluminium compounds alkylalkoxy organoaluminium compounds
- halogen-containing organoaluminium compounds such as diethyl aluminum chloride, diisobutyl aluminum chloride, and ethyl aluminum sesquichloride.
- the catalyst composition of the present invention can include a compound which contains or yields in a reaction with the transition metal complex of the present invention a non-coordinating or poorly coordinating anion.
- a non-coordinating or poorly coordinating anion Such compounds have been described for instance in EP-A-426,637, the complete disclosure of which is incorporated herein by reference.
- Such an anion is bonded sufficiently unstably such that it is replaced by an unsaturated monomer during the co ⁇ polymerization.
- Such compounds are also mentioned in EP-A-277,003 and EP-A-277,004, the complete disclosures of which are incorporated herein by reference.
- Such a compound preferably contains a triaryl borane or a tetraaryl borate or an aluminum equivalent thereof.
- suitable co-catalyst compounds include, without limitation, the following: dimethyl anilinium tetrakis (pentafluorophenyl) borate [C 6 H S N(CH 3 ) 2 H] + [B(C 6 F 5 ) 4 ]-; - dimethyl anilinium bis (7,8-dicarbaundecaborate)- cobaltate (III); - tri (n-butyl)ammonium tetraphenyl borate;
- the transition metal complex is alkylated (that is, the L group is an alkyl group).
- the reaction product of a halogenated transition metal complex and an organometallic compound such as for instance triethyl aluminum (TEA) can also be used.
- the molar ratio of the co-catalyst relative to the transition metal complex in case an organometallic compound is selected as the co-catalyst, usually is in a range of from about 1:1 to about 10,000:1, and preferably is in a range of from about 1:1 to about 2,500:1. If a compound containing or yielding a non-coordinating or poorly coordinating anion is selected as co-catalyst, the molar ratio usually is in a range of from about 1:100 to about 1,000:1, and preferably is in a range of from about 1:2 to about 250:1.
- the transition metal complex as well as the co ⁇ catalyst can be present in the catalyst composition as a single component or as a mixture of several components. For instance, a mixture may be desired where there is a need to influence the molecular properties of the polymer, such as molecular weight and in particular molecular weight distribution.
- the inert support component may be any finely divided solid porous support, including, but not limited to, MgCl 2 , Zeolites, mineral clays, inorganic oxides such as talc, silica, alumina, silica-alumina, inorganic hydroxides, phosphates, sulphates, etc., or resinous support materials such as polyolefins, including polystyrene, or mixtures thereof. These carriers may be used as such or modified, for example by silanes and/or aluminum alkyls and/or aluminoxane compounds, etc.
- the transition metal complex or the co- catalyst is supported on a carrier. It is also possible that both the transition metal complex and the co-catalyst are supported on a carrier.
- the carrier material for the transition metal complex and for the co-catalyst can be the same material or a different material. It is also possible to support the transition metal complex and the co-catalyst on the same carrier.
- the supported catalyst systems of the invention can be prepared as separate compounds, which can be used as such in polymerization reactions or the supported catalyst systems can be formed in situ just before a polymerization reaction starts.
- Supported catalyst systems of the invention may be prepared by several methods.
- the transition metal complex of group 4 - 6 and the aluminoxane component can be mixed together before the addition of the support material, or the mixture can be added to the support material.
- the mixture may be prepared in conventional solution in a normally liquid alkane or aromatic solvent.
- solvents include, but are not limited to, linear or branched alkanes such as pentane, hexane, heptane, pentamethyl heptane, isobutane and isopentane, and aromatic solvents such as toluene.
- the solvent is preferably also suitable for use as a polymerization diluent for the liquid phase polymerization of an olefin monomer.
- the aluminoxanes can be placed on the support material followed by the addition of the transition metal complex or conversely, the transition metal complex may be applied to the support material followed by the addition of the aluminoxanes.
- the aluminoxanes can be used as commercially supplied, or may be generated in situ on the solid support, for example, by the addition of a trialkylaluminum compound to a hydrated support, for example by the addition of trimethylaluminum to a wetted or undehydrated silica.
- the supported catalyst may be prepolymerized.
- third components can be added in any stage of the preparation of the supported catalyst.
- Third components can be defined as compounds containing Lewis acidic or basic functionalities exemplified but not limited to compounds such as N.N-dimethylaniline, tetraethoxysilane, phenyltriethoxysilane, bis-tert- butylhydroxy toluene (BHT) and the like.
- Lewis acidic or basic functionalities exemplified but not limited to compounds such as N.N-dimethylaniline, tetraethoxysilane, phenyltriethoxysilane, bis-tert- butylhydroxy toluene (BHT) and the like.
- Transition metal components wherein the metal is titanium have been found to impart beneficial properties to a catalyst system, which is unexpected in view of what is known about the properties of cyclopentadienyl titanium compounds which are cocatalyzed by aluminoxanes.
- titanocenes in their soluble form are generally unstable in the presence of aluminum alkyls
- the metal components of this invention generally exhibit greater stability (i.e. longer catalyst lifetime), resulting in higher catalyst activity rates (expressed as Kg polymer produced per g of Ti per hour).
- a higher ⁇ -olefin comonomer incorporation at a high molecular weight are also surprisingly advantageous features of the catalyst systems according to the invention ("comonomer molecular weight capability").
- the supported catalyst systems of the invention comprise a reduced transition metal complex, a carrier and optionally one or more organo- aluminum compounds and/or a compound which contains or yields in a reaction with the transition metal complex a non-coordinating or poorly coordinating anion.
- the polymerization of ⁇ -olefin monomers is carried out using a supported catalyst system as described above.
- the ⁇ -olefin monomer(s) is/are suitably chosen from the group comprising ethene, propene, butene, pentene, heptene, hexene, octene and styrene (substituted or non-substituted). Mixtures of these compounds may also be used. More preferably, ethene and/or propene is used as ⁇ -olefin.
- olefins results in the formation of (semi)crystalline polyethene homo- and copolymers, of high as well as of low density (HDPE, LDPE, LLDPE, etc.), and polypropene, homo- and copolymers (PP and EMPP (Elastomer modified polypropylene)).
- the monomers needed for such products and the processes to be used are known to those of ordinary skill in the art.
- the process according to the invention is also suitable for the preparation of amorphous or rubber-like copolymers based on ethene and another ⁇ - olefin. Propene is preferably used as the other ⁇ - olefin, so that EPM rubber is formed.
- EPDM ethene propene diene rubber
- Polymerization of the ⁇ -olefin monomer(s) can be effected in a known manner, in the gas phase as well as in a liquid reaction medium. Both solution and suspension polymerization are suitable for use in a liquid reaction medium.
- the supported catalyst systems according to the invention are used mainly in gas phase and slurry processes.
- the quantity of transition metal to be used generally is such that its concentration in the dispersion agent is between about 10 ⁇ and 10 ⁇ 3 mol/1, preferably between about IO -7 and 10"* mol/1.
- the invention will hereafter be described with reference to polymerizations of ⁇ -olefins known per se, which are representative of the polymerization referred to in the present description.
- the process of the present invention can be conducted as a gas phase polymerization (e.g. in a fluidized bed reactor), as suspension/slurry polymerization, as a solid phase powder polymerization or as a so called bulk polymerization process, with excess olefinic monomer used as the reaction medium.
- Dispersion agents may suitably be used for the polymerization, which may be chosen from (but are not limited to) saturated, straight or branched aliphatic hydrocarbons, such as butanes, pentanes, hexanes, heptanes, pentamethyl heptane or mineral oil fractions such as light or regular petrol, naphtha, kerosene or gas oil. Fluorinated hydrocarbons or similar liquids are also suitable for this purpose.
- Aromatic hydrocarbons for instance benzene and toluene, can be used, but because of cost and safety considerations, it is preferable not to use such solvents for production on a tecnnical scale.
- the solvent may yet contain minor quantities of aromatic hydrocarbon, for instance toluene.
- MAO methyl aluminoxane
- toluene can be used as solvent for the MAO in order to supply the MAO in dissolved form to the polymerization reactor. Drying or purification of the solvents is desirable if such solvents are used; this can be accomplished using known procedures by persons of ordinary skill in the art.
- the catalyst and the co-catalyst are used in a catalytically effective amount, i.e. any amount that successivefully results in the formation of polymer. Such amounts may be readily determined by routine experimentation by the skilled artisan.
- the catalyst system may also be formed in situ if the components thereof are added directly to the polymerization reactor system and a solvent or diluent, including liquid monomer, is used in the polymerization reactor. If a solution or bulk polymerization is to be used it is preferably carried out at temperatures well above the melting point of the polymer to be produced, typically, but not limited to, temperatures between 120°C and 260°C.
- the process is carried out under suspension or gasphase polymerization conditions which typically take place at temperatures well below the melting temperature of the polymer to be produced, typically, but not limited to, temperatures below 105°C.
- the polymer resulting from the polymerization can be worked up by methods known to the skilled artisan.
- the catalyst is de-activated at some point during the processing of the polymer.
- the de-activation is also effected in a manner known per se, e.g. by means of water or an alcohol. Removal of the catalyst residues can usually be omitted because the quantity of catalyst in the polymer, in particular the content of halogen and transition metal, is very low when the catalyst system according to the invention is used.
- Polymerization can be effected at atmospheric pressure, at sub-atmospheric pressure, or at elevated pressure of up to 500 MPa, continuously or discontinuously.
- Slurry and solution polymerization normally take place at lower pressures, preferably below 20 MPa.
- the polymerization can also be performed in several steps, in series as well as in parallel. If required, the catalyst composition, temperature, hydrogen concentration, pressure, residence time, etc. may be varied from step to step. In this way it is also possible to obtain products with a wide molecular weight distribution.
- the invention also relates to a polyolefin polymer which can be obtained by means of the polymerization process according to the invention.
- TiCl 3 the esters used and the lithium reagents, 2-bromo-2-butene and 1-chlorocyclohexene were obtained from Aldrich Chemical Company.
- TiCl 3 .3THF was obtained by heating TiCl 3 for 24 hours in THF (tetrahydrofurane) with reflux.
- Mz * , Mw * and Mn * are molecular weights determined by conventional calibration of SEC-DV.
- Example I Preparation of a supported catalyst system comprising (dimethylaminoethyl) tetramethyleyelopentadienyl-titanium(III)dichloride (C 5 Me 4 ((CH 2 ) 2 NMe 2 )TiCl 2 ).
- Example II Preparation of an ethene/octene copolymer with bimodal MWD, using a supported catalyst system comprising (dimethylaminoethyl) tetramethylcyclopentadienyl-titanium(III)dichloride (C 5 Me 4 ( (CH 2 ) 2 NMe 2 )TiCl 2 ).
- Octene was distilled and dried over a moleculare sieve of type 13X.
- a catalyst dosing vessel having a content of 100 ml 25 ml of an alkane mixture was dosed as dispersion medium. The desired amount of catalyst was then introduced. The catalyst slurry thus obtained was subsequently dosed to the reactor. The polymerisation reaction was thus started and carried out under isotherm conditions. The ethene pressure was maintained constant at 8 bar absolute. The ethene addition was interrupted after t minutes and the reaction mixture was collected and quenched with methanol. Irganox 1076 (TM) was then added to the product as anti-oxidant to stabilise the polymer. The polymer was dried under vacuum at 70°C for 24 hours. Using this general procedure 18 g octene were introduced into the reactor.
- Example III Preparation of an ethene/octene copolymer with unimodal MWD, using a supported catalyst system comprising (dimethylaminoethyl) tetramethylcyclopentadienyl-titanium(III)dichloride
- dimethylaminoethyl chloride (11.3g, 105 mmol, freed from HCl by the method of Rees W.S. Jr. & Dippel K.A. in OPPI BRIEFS vol 24, No 5, 1992) was added via a dropping funnel in 5 minutes. The solution was allowed to warm to room temperature after which it was stirred over night. The progress of the reaction was monitored by GC. After addition of water (and pet-ether), the organic layer was separated, dried and evaporated under reduced pressure. Next to starting material iPr 3 -Cp (30%), 5 isomers of the product
- Solid TiCl 3 3THF (18.53g, 50.0 mmol) was added to a solution of the potassium salt of iPr 3 -Cp in 160 ml of THF at-60°C at once, after which the solution was allowed to warm to room temperature. The color changed from blue to green. After all the TiCl 3 .3THF had disappeared the reaction mixture was cooled again to - 60°C. After warming to room temperature again, the solution was stirred for an additional 30 minutes after which the THF was removed at reduced pressure.
- a supported catalyst was prepared according to the method described in example VI.
- the Ti-component was, however, the metal complex of example Vila.
- the Al/Ti ratio in the supported catalyst was determined using neutron activation analysis and atomic absorption spectromety to be 285.
- octene and ethene were copolymerised at 80 C.
- the copolymer formed was stabilized and dried, and characterised using SEC- DV.
- the molecular weight distribution (MWD) of the product was determined using universal calibration and appeared to be 6.8.
- the Mw of the polymer was determined using the same method to have the high value of 1.2*10 6 g/mol.
- the Mz appeared to be 5.6*10 6 g/mol.
- Example VIII Preparation of an ethene/octene copolymer using a supported catalyst system comprising Cp( iPr ) 3 (EtNMe 2 )TiCl 2 at a relatively high temperature.
- Mw was determined as described in example VII and was shown to amount 180 kg/mol.
- ethene/octene copolymerisation was carried out as described in example VIII except for the fact that triethylaluminium (TEA) was introduced into the reactor before the supported catalyst was.
- TEA triethylaluminium
- the amount of the scavenger TEA used was such that the Al/Tl-ratio was 40.
- the copolymer yield was 8.4 kg/gTi*5min, the MWD was 8.4 kg/gTi*5min, the MWD was 8.4 kg/gTi*5min, the MWD was 8.4 kg/gTi*5min, the MWD was 8.4 kg/gTi*5min, the MWD was 8.4 kg/gTi*5min, the MWD was 8.4 kg/gTi*5min, the MWD was 8.4 kg/gTi*5min, the MWD was 8.4 kg/gTi*5min, the MWD was 8.4 kg/gTi*5min, the MWD was 8.4 kg/gTi*5min, the MWD was 8.4 kg/gTi*5min, the MWD was 8.4 kg/gTi*5min, the MWD was 8.4 kg/gTi*5min
- a supported Ti catalyst was synthesized as described in example IV. 1.6 g MAO/Si0 2 (Witco, see example IV) was slurried in 12 ml dry toluene. 4.6*10 "5 moles of the transition metal complex of example Xa was added under stirring at 300 K. The resulting slurry was dried under vacuum for 2 hours at 300 K. A fine, free- flowing powder was obtained.
- Mw * was 430 kg/mol
- Mz * was found to be 1.2*10 6 g/mol
- the MWD of the copolymer was found to be 4.6.
- Example XII Preparation of a polyethene with high molecular weight using a supported catalyst system comprising two metal complexes.
- a polymerisation was performed with the catalyst that was synthesized.
- the polymerisation conditions were as in example X.
- the polymer formed had a broadened MWD of
- Example XIII Preparation of an ethene/octene copolymer of high octene content using a supported catalyst system comprising two metal complexes.
- a polymerisation was performed under the conditions described in example X but with the catalyst that was synthesized in example XII.
- the difference with the reaction conditions described in example X was that 25 ml octene were introduced in the reactor before the start of the polymerisation reaction.
- the polymer that was formed during the polymerisation reaction was treated as described in example X and appeared to be a copolymer with an octene content in the polymer chains of 19 wt.% as determined by using X H-NMR.
- the Mz * appeared to be as high as 1.3*10 6 g/mol
- Mw * was 560 kg/mol
- the MWD appeared to be 4.8.
- Example XIV Preparation of an ethene homopolymer using a catalyst system comprising (dimethylaminoethyl) tetramethylcyclopentadienyl-titanium(III)dichloride (C s Me 4 ( (CH 2 ) 2 NMe 2 )TiCl 2 ) supported on Si0 2 .
- a catalyst system comprising (dimethylaminoethyl) tetramethylcyclopentadienyl-titanium(III)dichloride (C s Me 4 ( (CH 2 ) 2 NMe 2 )TiCl 2 ) supported on Si0 2 .
- a supported catalyst was prepared in the following way.
- a slurry was obtained from the resulting dry supported catalyst.
- a supported catalyst was prepared in the following way. 20 ml dry toluene were added to 3.05 g dried MgCl 2
- a supported catalyst was prepared in the following way. 10 ml dry toluene were added to 1.45 g MA0/Si0 2 (Witco) and subsequently 4.1 ml of a 0.01 M solution of the reduced transition metal complex of example VII were added at room temperature. The mixture was then evacuated under continuous stirring at room temperature. 50 ml of dry toluene were added and the suspension was mixed. The suspension was washed with a surplus of dry toluene and evacuated under constant mixing.
- a slurry in an alkane medium (C 6 -fraction) was obtained from the resulting free flowing powder and a polymerisation experiment was performed following the procedure described in example X.
- the resulting polymer particles which showed an excellent morphology and no rector fouling whatsoever, were studied by SEC-DV using universal calibration in order to determine molecular weight characteristics.
- the Mn of the polymer was found to be 210 kg/mol, Mw was 800 kg/mol and Mz was found to be 1800 kg/mol.
- MA0/Si02 184 mg MA0/Si02 were weighed in a 100 mL Schlenk vessel (MAO on PQ MS3040 silica, obtained from Witco GmbH, 21.7 wt% Al). 10 mL of a 1*10-2 M solution of C 5 Me 4 (CH 2 ) 2 NMe 2 )TiMe2 in toluene were added to the solid MA0/Si0 2 while stirring at room temperature.
- the catalyst was prepared according to example I(A-C). The catalyst was methylated with MeLi in diethylether .
- the slurry was introduced into a IL reactor, that had been filled with 0,75 L PMH at 95 C and kept at a constant ethylene pressure of 6 bar. The activity was immediate and remained constant in time.
- Catalyst activity amounted 1535 gPE/g catalyst.hr.
- Example XVIII al Preparation of bis(trimethylsilyl)cvclopentadiene A roundbottom flask with a content of 5 L, supplied with a peddle stirrer, thermometer, dripping funnel, and N 2 inlet was filled with 550 mL dry THF. 66 g. (1.0 mol) freshly cracked cyclopentadiene was added thereto, whereafter the reaction mixture was cooled to
- the reaction mixture was distilled at 4.4 mbar and 61 °C. After distillation 138 g. bistrimethylsilyl-Cp was obtained.
- the product was characterised with GC, GC-MS, 13 C- en X H-NMR.
- a roundbottom flask with a content of 250 mL supplied with a thermometer, a dripping funnel and N 2 - inlet was filled with 80 mL dry THF. 15 g. (71.43 mmol) bistrimethylsilyl-Cp was added thereto, whereafter was cooled to -30 °C. Thereafter 1 equivalent (44.6 mL/1.6 M) butyllithium was added in 10 min. The reaction mixture was allowed to warm up to room temperature.
- a roundbottom flask with a content of 500 mL supplied with a thermometer, a dripping funnel and N 2 -inlet was filled with 100 mL dry THF and 6.4 g. (71.9 mmol) tosylchloride.
- the slurry was introduced into a IL reactor, that had been filled with 0,75 L PMH and 4*10 "3 mol trioctylaluminium (TOA) at 40 C and kept at a constant ethylene pressure of 6 bar.
- TOA trioctylaluminium
- Catalyst activity amounted 183 gPE/g catalyst.hr. A nice, finely evided, free flowing polyethylene powder was obtained. No reactor fouling occurred.
- the slurry was introduced into a IL reactor, that had been filled with 0,75 L PMH and 4*10 "4 mol trioctylaluminium (TOA) at 40 C and kept at a constant ethylene pressure of 6 bar. The activity was immediate. The reactor contents were heated from 40 to
- Catalyst activity amounted 405 gPE/g catalyst.hr. A nice, finely devided, free flowing polyethylene powder was obtained. No reactor fouling occurred.
- Example XX a Synthesis of (C,Me 4 (SiMe ? CH 7 PPH ? )TiCl 7 To 1.57 g (4.15 mmol) of ⁇ (2- diphenylphosphino-l-sila-1, 1- dimethyl)ethyl ⁇ tetramethylcyclopentadiene, dissolved in 10 mL of diethyl ether, 8.3 mL of lithium- diisopropylamide (0.5M in diethyl ether; 4.15 mmol) were added at -78°C. After 18 hours' stirring at room temperature, a turbid yellow/orange solution had formed. The diethyl ether was evaporated, and the residue was washed twice with petroleum ether.
- the organolithium compound was dissolved in 20 mL of tetrahydrofuran. Then the yellow/orange solution was added, at -78°C, to 1.36 g (3.76 mmol) of Ti (III)C1 3 .3THF. The reaction mixture was then stirred for 3 hours in the cold bath and afterwards for 18 hours at room temperature. A dark-green solution had now formed, which was boiled down and washed twice with lOmL of petroleum ether.
- the slurry was introduced into a IL reactor, that had been filled with 0,75 L PMH and 4*10 -4 mol trioctylaluminium (TOA) at 90 C and kept at a constant ethylene pressure of 6 bar. The activity was immediate. The reactor temperature was set at 100 C. A free-flowing powder was obtained. No reactor fouling occurred.
- X grammes MAO/PQ MS3040 (Witco) were evacuated during 1.5 hrs (typical weight loss 5%, mainly organic solvents). Then a metallocene solution was added, typically about 30% of the total pore volume of the MAO/silica. After catalyst addition the solids were stirred during 1.5 hrs. Then a catalyst slurry was prepared. All syntheses were performed in the glove box.
- a catalyst slurry with a Zr ,Ti-concentration of about 1 *10 ⁇ 5 mol/ml was prepared. Polymerisation was performed in a glass B ⁇ chi reactor. In the 1.5 L reactor 750 mL pentamethylheptane was added, followed by 4*10 ⁇ 3 mol trioctylaluminium (TOA) as scavenger. The required amount of catalyst, usually between 5*10" 6 mol and 2*10" 5 mol on transition metal basis, was introduced into the reactor at 40°C via a catalyst dosing vessel. The reactor was heated to 80°C. This took about 10 min. Then the polymerisation was performed for another 10 min., making the total polymerisation time 20 min.
- TOA trioctylaluminium
- the ethylene pressure in the reactor was kept constant at 5 ato and the ethylene flow required to keep the pressure at 5 ato was determined.
- the polymerisation was stopped and the polymer slurry drained from the reactor.
- the polymer slurry was killed using methanol, stabilized by addition of Irganox 1076 and dried under reduced pressure at 50°C.
- the polymer yield was determined and the molecular weight studied by GPC, if reguired.
- the TMS-cat was obtained according to the preparation method described in Example XVIIIa and the PPH-cat was obtained according to the method described in Example XXa.
- a catalyst slurry in toluene was prepared (2*10 ⁇ 6 mol/ml). Under the standard conditions described under the general polymerisation procedure, but now from 40 to 100°C and with 4*10" 4 mol TOA, a polymerisation was performed with 20 micromoles of catalyst, based on Ti. No. reactor fouling was observed. 43.4 g PE were formed in 20 min.
- Example XXIb The same catalyst was also introduced at
- the molecular weights of the particles formed were:
- Mw 950 kg/mol
- Mn 56 kg/mol
- Mz 2400 kg/mol.
- the catalyst was synthesized by adding simultaneously solutions of both metallocenes to the MAO/silica slurry. A slurry of light green/yellowish powder in colourless solvent was obtained with a transition metal concentration of 5*10 " ⁇ mol/ml . The catalyst was first tested with 4*10 ⁇ 4 mol/1 TOA, from 40-80°C, 20 min. polymerisation time.
- the product had an IV (decaline, 135°C) of 11.5 dl/g.
- the catalyst was synthesized and tested as described under e. Testing lasted 20 min. No reactor fouling occurred.
- the catalyst was synthesized according to synthesis route II). A yellowish powder was obtained. A polymerisation was performed with 1.5 micromoles transition metal, following the polymerization procedure described under e). The constant polymerisation prophile resulted in a catalyst yield of 1080 gPE/g cat.hr.
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US6100414A (en) * | 1998-04-02 | 2000-08-08 | Eastman Chemical Company | Cyclopentadienyl transition metal compounds useful as polymerization catalysts |
KR100586118B1 (ko) | 1998-05-01 | 2006-06-02 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | 올레핀 중합반응을 위한 삼좌 리간드-함유 금속 촉매 착체 |
US6403773B1 (en) | 1998-09-30 | 2002-06-11 | Exxon Mobil Chemical Patents Inc. | Cationic group 3 catalyst system |
ES2219842T3 (es) * | 1998-12-21 | 2004-12-01 | Sabic Polyethylenes B.V. | Procedimiento para la polimerizacion de olefinas. |
US7390861B2 (en) | 2000-10-19 | 2008-06-24 | Exxonmobil Chemical Patents Inc. | Cationic group-3 catalyst system |
CA2424887A1 (en) | 2000-10-25 | 2002-08-01 | Exxonmobil Chemical Patents Inc. | Cationic catalyst system |
US7196148B2 (en) | 2001-10-25 | 2007-03-27 | Exxon Mobil Chemical Patents Inc. | Cationic catalyst system |
EP2923756B1 (en) | 2012-11-26 | 2018-05-30 | Braskem S.A. | Metallocene catalyst supported by hybrid supporting means, process for producing same, polymerization process for producing an ethylene homopolymer or copolymer with broad or bimodal molar mass distribution, use of the supported metallocene catalyst and ethylene polymer with broad or bimodal molar mass distribution |
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