Classifications

• • 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
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/14—Monomers containing five or more carbon atoms
• • 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
• • 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
  • C08F110/14—Monomers containing five or more carbon atoms
• • 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
  • C08F210/14—Monomers containing five or more carbon atoms
• • 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
• • 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 the preparation of polymers of alpha-olefins.
• the invention relates to a process for producing polymers of C 4 -C 30 ⁇ -olefins.
• WO-A-93/24539 discloses catalysts and processes to make low molecular weight, essentially terminally unsaturated, viscous poly( ⁇ -olefin) or copoly( ⁇ -olefin) using Group 4 metallocenes and an aluminoxane cocatalyst.
• the feed contains one or more C 3 to C 20 ⁇ -olefin(s) and at least 1 wt.% isobutene.
• poly( ⁇ -hexene) is obtained by contacting 1-hexene with a (indenyl) 2 ZrCl 2 /MAO system at 40° C for 20 hours.
• the resulting polymer has a Mn of 2653 g/mole.
• This catalyst has a very low polymerization activity.
• EP-A-498 549 discloses the systhesis of ⁇ - olefin polymers, utilizing Ziegler-Natta polymerization. It ' ⁇ s shown that terpolymers of C 10 , C 14 and C 16 monomers can be prepared at 95°C with high molecular weight. All polymerizations result in terpolymers with a broad molecular weight distribution (MWD at least 7).
• WO-A-94/13714 discloses the preparation of amorphous olefinic polymers, preferably poly-n-butenes, using cationic polymerization. The patent shows that at temperatures between -23°C and + 10°C low molecular weight compounds are produced (GPC : MW between 1600 and 3500). Only under specific conditions, higher molecular weight polymers are obtained at low temperature. In the latter case a multimodal distribution was always obtained.
• EP-A-608 707 discloses the copolymerization of C 3 to C 12 ⁇ -olefins with 0.01 to 5 mol% of ethylene, using metallocene catalysts. Polymerizations are carried out at 80 - 100°C using the
• Copolymers containing 2.8 mol% of ethylene have a molecular weight (Mw) of 4 kg/mol .
• Mw molecular weight
• the molecular weight is decreased by a factor of 3 and at the same time the polymerization activity diminished by a factor of 7.
• EP-A-613 873 relates to a process for preparing liquid organic compounds, by contacting one or more ⁇ -olefins containing 8 to 20 carbon atoms per molecule with metallocene catalysts.
• the patent discloses the copolymerization of 1-octene with 1- dodecene at 30° C using a bis(cyclopentadienyl )zirconium dichloride/methyl- aluminoxane system.
• the poly( ⁇ -olefin) obtained had a maximum Mn of 650 g/mol.
• this object is obtained by providing a process for the preparation of polymers of alpha-olefins and inparticular , the preparation of polymers and of copolymers C 4 -C 30 ⁇ - olefins.
• Another object of the present invention is the provision of a polymer and particularly of polymers of C 4 -C 30 ⁇ -olefins by means of a polymerization process with utilization of the catalyst composition according to the invention.
• the purpose of the present invention is to provide such a process, which also solves the problems listed above for the state of the art processes, and which in particular can be used in a broad temperature range to produce polymers of greatly varying molecular weight and a narrow molecular weight distribution, and which can also provide poly( ⁇ -olefin)s which possess at least 30% terminal unsaturation, preferably at least 65% terminal unsaturation, most preferably at least 90% terminal unsaturation.
• terminally unsaturated poly( ⁇ -olefins) can be hydrogenated for improvement of their stability against oxidation, or can be functionalised, to obtain terminally functionalized well-defined poly( ⁇ -olefins) .
• the polymers according to the invention can be used as engine lubricants, hydraulic fluids, gear oils, lubricant additives, adhesives, glue and the like.
• the process of the invention for the preparation of polymers of alpha-olefins comprises contacting, under effective polymerization conditions, at least one ⁇ -olefin having from 4 to 30 carbon atoms 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):
• X a multidentate monoanionic ligand represented by the formula: (Ar-R t -) S 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 multidentate monoanionic ligand X contains more than one substituent R', the substituents R' can be identical or different from each other;
• Ar an electron-donating aryl group;
• 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
• 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. DESCRIPTION OF THE PREFERRED EMBODIMENTS
• transition metal complex Various components (groups) of the transition metal complex are discussed below in more detail.
• 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 -),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 _ 1 -R t -DR'êt 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 (-NR'-), or phosphido (-PR'-) group.
• 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.
• multidentate monoanionic ligand with a Cp group as the Y group include the following (with the (-R t -DR' n ) or (Ar-R t -) substituent on the ring)
• 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 h, 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:
• 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' 5 ), 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 ⁇ 1 to ⁇ 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 L Group The transition metal complex contains two monoanionic ligands L bonded to the transition metal M.
• the 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 4 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 5 R' S ), 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 DR' n group(s)) via, optionally, an R group.
• 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 5 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; triphenylcarbenium tetrakis (pentafluorophenyl) borate; dimethylanilinium tetraphenyl borate; - tris(pentafluorophenyl) borane; and
• 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 polymerization of at least one ⁇ -olefin is carried out using a catalyst composition as described above.
• the ⁇ -olefin(s) is/are suitably chosen from ⁇ -olefins having from 4 to 30 carbon atoms, preferably ⁇ -olefins having from 8 to 20 carbon atoms, and most preferably ⁇ -olefins having from 8 to 18 carbon atoms, ⁇ -olefins with 8 to 20 carbon atoms per molecule are readily available from processes for the oligomerisation of ethylene according to the so called 'conombau"-principle. It may be feasible to select the ethylene-oligomerisation conditions such that mainly products within the desired range of 8 to 20 carbon atoms per molecule are formed.
• olefins having from 4 to 30 carbon atoms per molecule.
• separation techniques such as fractional distillation, olefins within the desired range of 8 to 20 and preferably within the range of 8 to 18 carbon atoms per molecule can easily be recovered.
• a convenient process for the catalytic oligomerisation of ethylene is described in U.S. Patent No. 3,646,915, the complete disclosure of which is incorporated herein by reference.
• alpha- olefins containing 8 to 20, and preferably 8 to 18 carbon atoms per molecule are polymerized to products, typically having a number-average molecular weight in the range of 400 to 3,000, preferably in the range of 400 to 1,000 and most preferably in the range of 400 to 700.
• Products having higher molecular weights e.g. number-average molecular weights of 3,000 or more, generally are less suitable as base materials for lubricants and hence the oligomerisation conditions are preferably selected such that the molecules of the obtained product are predominantly derived from 2 to 8 monomeric units.
• dimers are suitable which are, preferably, derived from monomers having carbon numbers in the higher region of the above mentioned carbon range.
• products having a number-average molecular weight above 3000 g/mol can successivefully be applied.
• further ⁇ -olefin(s) may be used together with the C 4 -C 30 ⁇ -olefins mentioned above, in particular one or more selected from among ethylene, propylene and styrene (substituted or non-substituted), mixtures of which may also be used. More preferably, the ⁇ -olefin is ethylene, propylene or a mixture thereof. Mixtures of the above mentioned monomers can also be used. According to this embodiment of the process of the invention, up to 60 mol% of the further ⁇ -olefin monomer(s) may be incorporated into the polymer and preferably up to 51 mol% (i.e. up to a slight excess of further ⁇ -olefinic monomer(s) with respect to the ⁇ - olefin monomer having 4 to 30 carbon atoms).
• the catalyst composition can be used supported as well as non-supported.
• the transition metal complex or the co- catalyst can be 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 setarate compounds, which can be used as such in polymerization reactions or the supported catalyst systems can be formed by in situ methods just before a polymerization reaction starts.
• the supported catalysts are used mainly in gas phase and slurry processes.
• the carrier used may be any carrier known as carrier material for catalysts, for instance finely divided solid porous support, including, but not limited to MgCl 2 , Zeolites, mineral clays, inorganic oxides such as talc, silica (Si0 2 ), alumina (A1 2 0 3 ), silica-alumina, inorganic hydroxides, phosphates, sulphates, and the like, or resinous support materials such as polyolefins, including polystyrene, or mixtures thereof.
• the type or brand of carrier which is selectable is dependant on the structure of the metallocene.
• These carriers may be used as such or modified, for example by silanes and/or aluminium alkyles and/or aluminoxane compounds, etc.
• Polymerization of the olefins can be effected in the gas phase, in the solid phase as well as in a liquid reaction medium. In the latter case, both solution and suspension polymerization are suitable. Also a very suitable polymerization method according to the present invention is polymerizing in bulk monomer (bulk polymerization) or mixture of monomers.
• the quantity of transition metal to be used in case of solution or suspension or bulk polymerization generally is such that its concentration in the dispersion agent amounts to IO "8 - IO "3 mol/1 , preferably IO "7 - IO "4 mol/1.
• the preparation of polymers containing ⁇ - olefins by means of the catalyst compositions of the present invention is especially appropriate in solution, suspension (slurry) and bulk polymerization.
• a solvent or a combination of solvents may be employed if desired.
• Suitable solvents include toluene, ethylbenzene, one or more 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, kerosine or gas oil.
• a suspension utilizing a perfluorinated hydrocarbon or similar liquid may in particular be used.
• excess olefinic monomer may be used as the reaction medium (so-called bulk polymerization processes) .
• Aromatic hydrocarbons for instance benzene and toluene, as well as perfluorinated hydrocarbons can also be used, but because of their cost as well as on account of safety considerations, it will be preferred not to use such solvents for production on a commercial scale. In polymerization processes on a commercial scale it is preferred, therefore, to use low-priced solvent, such as aliphatic hydrocarbons or mixtures thereof, as marketed by the petrochemical industry. If an aliphatic hydrocarbon is used as solvent, the solvent may yet contain minor quantities of aromatic hydrocarbon, for instance toluene.
• methyl aluminoxane (MAO)
• 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 is desirable if such solvents are used; this can be done without problems by the average person skilled in the art.
• Gas-phase and slurry/suspension polymerizations are preferably carried out at temperatures well below the melting temperature of the polymer produced, typically below 115°C.
• a solution or bulk polymerization is usually carried out at temperatures above the melting temperature of the polymers produced, typically above -100°C, preferably above 0°C, more preferably above 25°C and most preferably above 80°C.
• the polymer solution or suspension resulting from the polymerization can be worked up by a method known per se.
• 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 mostly be omitted because the quantity of catalyst in the polymer, in particular the content of halogen and transition metal is very low in the system according to the invention.
• Polymerization can be effected at atmospheric pressure, at sub-atmospheric pressure, or at elevated pressure of up to 500 MPa, continuously or discontinuously.
• the polymerization is performed at pressures between 1 kPa and 35 MPa. Higher pressures can be applied if the polymerization is carried out in so-called high-pressure reactors. In such a high-pressure process, the process according to the present invention can also be used with good results.
• 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 the poly( ⁇ - olefin)s which can be obtained by means of the L97/
• 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 with reflux. (THF stands for tetrahydrofurane) .
• Example I This example concerns polymerization of octene using (dibutylaminoethyl)- tetramethylcyclopentadienyltitanium(III) dichloride (C 5 Me 4 (CH 2 ) 2 NBu 2 TiCl 2 ) as a catalyst.
• 2-Lithium-2-butene was prepared from 2-bromo- 2-butene (16.5 g; 0.122 mol) and lithium (2.8 g; 0.4 mol) as in Example I.
• the ester of a) (7.0 g? 0.031 mol) was added with reflux in approx. 5 minutes, followed by stirring for about 30 minutes.
• water 200 ml was carefully added dropwise.
• the water layer was separated off and extracted twice with 50 ml of CH 2 C1 2 .
• the combined organic layer was washed once with 50 ml of water, dried with K 2 C0 3 , filtered and evaporated. The yield was 9.0 g (100%).
• the polymer was dried in a rotating evaporator (at 80°C and 10 mbar pressure).
• the polymer was found to have a number average molecular weight Mn of 896 and was found, with X H-NMR, to be mainly terminally unsaturated.
• This example relates to the preparation of an octene / 1-octadecene copolymer using Et (Cp( iPr ) 3 )NMe 2 TiCl 2 as a catalyst.
• 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.
• the resulting mixture was stirred for 1 minute.
• the polymerization reaction was started by introduction of the mixture from the catalyst metering vessel into the reactor. After one hour of polymerization, 25.2 grams of product were removed from the reactor.
• This example concerns polymerization of 1- octene in the presence of ethylene using EtCp*NMe 2 TiCl 2 as catalyst.
• the polymerization was started by the addition of this mixture from the catalyst premixing vessel into the reactor. After 30 minutes, the polymerization reaction was stopped, the polymer was drained from the reactor and was dried. The polymer yield was 19.9 grams.
• the polymer was analysed by SEC-DV using universal calibration. The Mw of the polymer was 270 kg/mol. The octene content in the polymer was 70 wt.%. This example shows that the polymerization of higher olefins is also possible in the presence of a lower olefin, such as ethylene, under effective polymerization conditions using the catalyst system of this invention.
• a polymerization was performed under the conditions described in Example I e) but with the addition of 0.011 mol triethylaluminium and 2.5xl0" 5 mol of the transition metal complex dimethyl-bis- (pentamethyl-cyclopentadienyl)zirconium.
• the polymer formed was found to have a Mn of 224 g/mol. GC-MS measurements on the product showed that a large portion of the polymer formed, contained saturated chain ends which is uneconomical for functionalisation reactions.

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• 1997
  • 1997-05-01 CA CA002253576A patent/CA2253576A1/en not_active Abandoned
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