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WO2009061678A1 - Activation de métallocènes par complexe alumoxanes/ligands contenant des hétéroatomes hétérocycliques à substitution halogène - Google Patents

Activation de métallocènes par complexe alumoxanes/ligands contenant des hétéroatomes hétérocycliques à substitution halogène Download PDF

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Publication number
WO2009061678A1
WO2009061678A1 PCT/US2008/082066 US2008082066W WO2009061678A1 WO 2009061678 A1 WO2009061678 A1 WO 2009061678A1 US 2008082066 W US2008082066 W US 2008082066W WO 2009061678 A1 WO2009061678 A1 WO 2009061678A1
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group
catalyst
heteroatom containing
alumoxane
indenyl
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PCT/US2008/082066
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English (en)
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WO2009061678A8 (fr
Inventor
Matthew W. Holtcamp
Renuka N. Ganesh
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Exxonmobil Chemicals Patents Inc.
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Priority claimed from US11/937,043 external-priority patent/US8022005B2/en
Priority claimed from EP08154608A external-priority patent/EP2112175A1/fr
Application filed by Exxonmobil Chemicals Patents Inc. filed Critical Exxonmobil Chemicals Patents Inc.
Priority to EP08846364A priority Critical patent/EP2217627A1/fr
Priority to CN2008801152165A priority patent/CN101903414A/zh
Publication of WO2009061678A1 publication Critical patent/WO2009061678A1/fr
Publication of WO2009061678A8 publication Critical patent/WO2009061678A8/fr

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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
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—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
    • 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

Definitions

  • the present invention relates to polymerization catalyst activator compounds, to methods of making these activator compounds, to polymerization catalyst systems containing these activator compounds, and to polymerization processes utilizing the same. More specifically, the activators of the invention are the reaction product of a halogen substituted indole and an alkyl alumoxane. BACKGROUND OF THE INVENTION [0003] Polymerization catalyst compounds are typically combined with an activator (or co-catalyst) to yield compositions having a vacant coordination site that will coordinate, insert, and polymerize olefins.
  • Metallocene polymerization catalysts are typically activated with alumoxanes which are generally oligomeric compounds containing — Al(R) — O — subunits, where R is an alkyl group.
  • a common alumoxane activator is methylalumoxane (MAO), typically produced by the hydrolysis of trimethylaluminum (TMA).
  • MAO is expensive to utilize because it generally must be added in great excess relative to the metallocene and because of the high cost of TMA. Additionally, MAO tends to be unstable as it precipitates out of solution over time.
  • Activator complexes having a Group 13 atom have also been suggested as a viable alternative to the expensive alumoxane activators.
  • U.S. Pat. Nos. 6,147,173 and 6,211,105 disclose a polymerization process and polymerization catalyst where the catalyst includes an activator complex having a Group 13 element and at least one halogenated, nitrogen-containing aromatic group ligand.
  • Each of these alternatives including the formation of alumoxane, requires multi- step, complicated syntheses. There is a need, therefore, to provide a simpler method of cocatalyst synthesis and catalyst activation. There is also a need to improve catalyst economics by providing a highly active co-catalyst, particularly in propylene polymerizations.
  • US 6,703,338 discloses heterocyclic compounds (such as indole) combined with alkyl aluminum or alkyl alumoxane and a support material as an activator.
  • Examples 5 and 16 of US 6,703,338 disclose the use of "tetraethylaluminoxane" and 4,5,6,7-tetrafluoroindole with (1,3-Me 5 BuCp) 2 ZrMe 2 to make polyethylene at, among other things, high Mw's and activities below 1500 gpolymer/gcatalyst'hr.
  • US 6,989,341 discloses certain halogenated indoles combined with alkyl aluminum or alumoxane to increase activity.
  • US 6,930,070 discloses compositions having two or more heterocyclic compounds (such as indole/indolyl) combined with an alkyl aluminum or alumoxane as an activator.
  • US 2007/0055028 discloses a process to make higher Mw isotactic polypropylene using a bis-indenyl Group 4 metallocene compound supported on silica where the silica has been treated with an organoaluminum compound (such as triethylaluminum) and a heterocyclic compound (such as 4,5,6,7-tetrafluoroindole).
  • the instant invention provides a method to polymerize propylene with certain bis-indenyl Group 4 metallocene catalysts using an isoalkyl alumoxane at certain ratios that provides, among other things, lower Mw combined with a melting temperature of 14O 0 C or more.
  • Embodiments of the invention include an activator and a catalyst system comprising one or more polymerization catalysts (preferably a bridged bisindenyl Group 4 metallocene) and at least one activator.
  • the activator includes heteroatom containing ligands coordinated to an alkyl alumoxane, wherein the activator is a reaction product of one or more alkyl alumoxanes and one or more heterocyclic heteroatom containing compounds, wherein the heterocyclic heteroatom containing ligands are represented by Formula (I): wherein Y is O, S, PH or, in particular, NH; wherein each substituent X2, X3, X4, X5, X6 and X7 is independently a hydrogen, chlorine, fluorine, iodine or bromine, provided at least one of X2, X3, X4, X5, X6 and X7 is not hydrogen when Y is NH; and wherein the ratio of the heterocyclic heteroatom
  • the catalyst system may be supported or, preferably, non-supported.
  • the alumoxane is isobutylalumoxane.
  • the heterocyclic heteroatom containing ligand is a mono- substituted indole or a di-substituted indole.
  • the substituents are halogens and in particular can be bromine or chlorine.
  • the indole is mono-substituted or di-substituted with bromine and in particular is 5-bromoindole or 5-chloroindole.
  • the halogen is not fluorine.
  • the catalyst system provides a method to prepare isotactic low molecular weight polymers, such as isotactic polypropylene with molecular weights, for example, between about 10,000 and about 200,000 g/mol. Unless otherwise stated all molecular weights are weight average molecular weights in units of g/mol.
  • the catalyst system includes 5-bromoindole in combination with a metallocene, such as rac-Me2Si-(2-methyl-indenyl)2Zr(CH3)2 , rac-Me 2 Si- (2-methyl-4- 3', 5' di tert-butyl phenyl-indenyl) 2 Zr(CH 3 )2 or rac-Me 2 Si-(2-methyl-4-phenyl- indenyl) 2 Zr(CH3)2, and isobutylalumoxane.
  • a metallocene such as rac-Me2Si-(2-methyl-indenyl)2Zr(CH3)2 , rac-Me 2 Si- (2-methyl-4- 3', 5' di tert-butyl phenyl-indenyl) 2 Zr(CH 3 )2 or rac-Me 2 Si-(2-methyl-4-phenyl- indenyl) 2 Zr(CH3)2, and isobutyla
  • this invention relates to a process to polymerize propylene comprising:
  • a catalyst system comprising: a) a metallocene represented by the formula ACp 2 MX 2 where M is Ti, Hf or Zr and M is bound to each Cp group, A is a bridging group connecting the two Cp groups, each Cp is, independently, an indenyl group or a substituted indenyl group, each X is an anionic leaving group, (preferably the metallocene represented by the formula rac- ACp 2 MX 2 where "me” indicates that the metallocene is partially or completely racemized, preferably the metallocene is completely racemized, i.e.
  • an activator comprising one or more heterocyclic heteroatom containing ligands coordinated to an isoalkyl alumoxane, wherein the activator is a reaction product of a solution of one or more isoalkyl alumoxanes and one or more heterocyclic heteroatom containing compounds, wherein the heterocyclic heteroatom containing ligand is represented by:
  • Y is NH or N-R where R is a Ci to Ci 2 alkyl group; each of X2 and X3 is hydrogen, halogen or X2 and X3 may form a six membered aromatic ring; X4, X5, X6 and X7 are hydrogen or a halogen; and wherein the ratio of the heterocyclic heteroatom containing ligand to aluminum is between 0.01 :1 and 10:1 molar equivalents, (and optionally the ratio of water to aluminum in the alumoxane solution is 0.7:1 or less); and 2) obtaining polymer having at least 50 wt% propylene, an Mw of 5,000 to 200,000 g/mol (preferably 10,000 to 120,000) and a melting point of 14O 0 C or more (preferably 145 0 C or more, preferably 15O 0 C or more, preferably 155 0 C or more, preferably 16O 0 C or more, preferably 165 0 C or more, as measured by the DSC procedure described
  • the melting point is 145°C or more, or alternately if the Mw is 50,000 g/mol or more then the melting point is 150 0 C or more.
  • other polypropylene produced herein may have an Mn of 1) more than 100,000 g/mol when the activity of the catalyst system is 1500 g polymer/g catalyst-hour or more, or 2) between 100,000 and 200,000 g/mol when the activity of the catalyst system is 400 g polymer/g catalyst-hour or more.
  • a catalyst system for olefin polymerization is provided.
  • the catalyst system may be supported or non-supported and includes one or more catalysts and at least one activator.
  • the activator is a reaction product of one or more alkyl alumoxanes (preferably isoalkyl alumoxanes) and one or more heterocyclic heteroatom containing compounds having the general formula (I):
  • Y is O, S, PH or NH; wherein each substituent X2, X3, X4, X5, X6 and X7 is independently a hydrogen, chlorine, fluorine, iodine or bromine, provided at least one of X2, X3, X4, X5, X6 and X7 is not hydrogen when Y is NH.
  • the ring of the heterocyclic compound includes at least one nitrogen, oxygen, and/or sulfur atom, and more preferably includes at least one nitrogen atom.
  • a non- limiting example of a heterocyclic compound includes indole.
  • the activator includes a mono-halogen substituted indole or a bi-halogen substituted indole.
  • the halogen may be chlorine, iodine, bromine, fluorine, or any combination thereof.
  • the halogen is chlorine, bromine, fluorine, or any combination thereof.
  • the alkyl alumoxane is preferably a Ci to Ci 2 alumoxane, such as methyl alumoxane, ethyl alumoxane, tri-isobutyl alumoxane or modified alumoxane.
  • a useful alumoxane is modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under patent number US 5,041,584. It may be preferable to use a visually clear methylalumoxane.
  • MMAO modified methyl alumoxane
  • a cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution.
  • the alumoxane is an isoalkyl alumoxane, preferably the isoalkyl is a C3 to C 12 isoalkyl, preferably isopropyl, isobutyl, isohexyl, isopentyl or isooctyl.
  • activator refers to any compound or component, or combination of compounds or components, capable of enhancing the ability of a catalyst to polymerize olefin monomers to form polyolefins.
  • catalyst is used interchangeably with the terms “catalyst component” and “catalyst compound”, and includes any compound or component, or combination of compounds or components, that is capable of increasing the rate of a chemical reaction, such as the polymerization or oligomerization of one or more olefins.
  • catalyst system as used herein includes at least one "catalyst” and at least one "activator”.
  • the "catalyst system” may also include other components, such as a support for example.
  • the catalyst system may include any number of catalysts in any combination as described herein, as well as any activator in any combination as described herein.
  • reaction product with respect to two or more elements means the result of combining the elements, regardless of whether the elements chemically react.
  • the activator includes one or more heterocyclic nitrogen-containing ligands coordinated to an alumoxane.
  • the heterocyclic nitrogen- containing ligand is an indole represented by Formula (II).
  • the indole includes substituents X2, X3, X4, X5, X6, and X7 located about the heterocyclic ring, as shown in Formula (II).
  • Each substituent X2 to X7 is independently selected from hydrogen, halogens, alkyl groups, aryl groups, alkoxide groups, aryloxide groups, cyano groups, nitrous groups, sulfonyl groups, nitrile groups, phosophyl groups, and alkyl substituted aryl groups wherein each group may be halogenated or partially halogenated.
  • X2 and X3 are hydrogen and X4, X5, X6 and X7 are hydrogen or halogen, provided that at least one of X4, X5, X6 and X7 is halogen.
  • X4 is a halogen and X2, X3, X5, and X7 are each hydrogen.
  • X5 is a halogen and X2, X4, X6, and X7 are each hydrogen.
  • X6 is a halogen and X2, X5 and X7 are each hydrogen.
  • both X5 and X6 are a halogen.
  • the halogen may be chlorine, iodine, bromine, fluorine, or any combination thereof.
  • the halogen is chlorine, bromine, fluorine, or any combination thereof.
  • Useful alumoxanes are oligomeric compounds containing — Al(R) — O — or — Al(R) 2 — O — subunits, where R is an alkyl group, typically a Ci to Ci 2 alkyl group.
  • alumoxanes examples include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, triethylalumoxane, triisobutylalumoxane, tetraethyldialumoxane and di-isobutylalumoxane.
  • MAO methylalumoxane
  • MMAO modified methylalumoxane
  • ethylalumoxane triethylalumoxane
  • triisobutylalumoxane triisobutylalumoxane
  • tetraethyldialumoxane tetraethyldialumoxane
  • di-isobutylalumoxane di-isobutylalumoxane.
  • the alumoxane and the halogen substituted heterocyclic compounds of Formula (I) yield an activator represented by the following Formulas (IV) or (V):
  • M is aluminum
  • JY represents the heterocyclic group of Formula (I) or Formula (II) and is associated with M, and preferably coordinated to M;
  • z is a number from 1 to 1000 preferably 1 to 100, more preferably 5 to 50, and even more preferably 5 to 25;
  • m is a number from 1 to 10, preferably 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10;
  • x is O, 1, 2, 3 or 4;
  • y is 1, 2, 3 or 4;
  • k is O, 1, 2, 3 or 4;
  • Non-limiting examples of substituent R' groups include hydrogen, linear or branched alkyl radicals, linear or branched alkenyl radicals, linear or branched alkynyl radicals, cycloalkyl radicals, aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbamoyl radicals, alkyl radicals, dialkyl radicals, carbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals, straight alkylene radicals, branched alkylene radicals, cyclic alkylene radicals, or any combination thereof.
  • R More specific embodiments of R include a methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl group, including all their isomers, for example tertiary butyl, isopropyl, and the like.
  • R include hydrocarbyl radicals such as fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl; hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)silyl, methyl-bis(difluoromethyl)silyl, bromoethyldimethylgermyl and the like; disubstituted boron radicals including dimethylboron for example; disubstituted Group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine; and Group 16 radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulf ⁇ de and ethyls
  • each R' may include carbon, silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, or germanium atoms and the like. Still further, each R may include olefins such as olefinically unsaturated substituents including vinyl-terminated ligands, such as but-3-enyl, prop-2-enyl, hex-5-enyl and the like, for example. Also, at least two R' groups, preferably two adjacent R' groups, may be joined to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron, or a combination thereof.
  • a substituent group R such as 1-butanyl may form a carbon sigma bond to the metal M.
  • each R is an isoalkyl, preferably the isoalkyl is a C3 to C 12 isoalkyl, preferably isopropyl, isobutyl, isohexyl, isopentyl or isooctyl.
  • the ratio of the heterocyclic heteroatom containing ligand to aluminum is preferably between about 0.01 and about 10: 1 molar equivalents, more particularly between about 0.1 to about 5:1, even more particularly between about 0.2 to about 5:1, e.g. 0.3 to about 4:1 molar equivalents.
  • the ratio of the heterocyclic heteroatom containing ligand to aluminum is preferably between about 0.01 and about 0.4: 1 molar equivalents, more particularly between about 0.1 to about 0.3:1 molar equivalents.
  • Catalyst Compositions [0030]
  • the activators described above may be utilized in conjunction with any suitable polymerization catalyst to form an active polymerization catalyst system.
  • the mole ratio of the metal of the activator to the metal of the catalyst composition is in the range of between 0.3:1 to 10,000:1, preferably 100:1 to 5000:1, and most preferably 500:1 to 2000:1.
  • Exemplary polymerization catalysts include metallocene catalyst compositions, Group 15- containing metal catalyst compositions, and phenoxide transition metal catalyst compositions, which are discussed in more detail below.
  • Metallocene Catalyst Compositions include metallocene catalyst compositions, Group 15- containing metal catalyst compositions, and phenoxide transition metal catalyst compositions, which are discussed in more detail below.
  • Metallocene catalyst compounds are generally described throughout in, for example, 1 & 2 METALLOCENE-BASED POLYOLEFINS (John Scheirs & W. Kaminsky eds., John Wiley & Sons, Ltd. 2000); G. G. Hlatky in 181 COORDINATION CHEM. REV. 243 296 (1999) and in particular, for use in the synthesis of polyethylene in 1 METALLOCENE-BASED POLYOLEFINS 261 377 (2000).
  • the metallocene catalyst compounds as described herein include "half sandwich” and “full sandwich” compounds having one or more Cp ligands (cyclopentadienyl and ligands isolobal to cyclopentadienyl) bound to at least one Group 3 to Group 12 metal atom (preferably a group 4 atom, preferably Hf, Ti or Zr), and one or more leaving group(s) bound to the at least one metal atom.
  • these compounds will be referred to as “metallocenes” or "metallocene catalyst components”.
  • the metallocene catalyst component may be supported on a support material, and may be supported with or without another catalyst component.
  • the Cp ligands are one or more rings or ring system(s), at least a portion of which includes ⁇ -bonded systems, such as cycloalkadienyl ligands and heterocyclic analogues.
  • the ring(s) or ring system(s) typically comprise atoms selected from the group consisting of Groups 13 to 16 atoms, and more particularly, the atoms that make up the Cp ligands are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum and combinations thereof, wherein carbon makes up at least 50% of the ring members.
  • the Cp ligand(s) are selected from the group consisting of substituted and unsubstituted cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl, non-limiting examples of which include cyclopentadienyl, indenyl, fluorenyl and other structures.
  • Such ligands include cyclopentadienyl, cyclopentaphenanthreneyl, indenyl, benzindenyl, fluorenyl, octahydro fluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4- benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7H-dibenzofluorenyl, indeno[l,2-9]anthrene, thiophenoindenyl, thiopheno fluorenyl, hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl, or "F ⁇ Ind”), substituted versions thereof (as described in more detail below), and heterocyclic versions thereof.
  • Preferred Cp ligands include substituted and unsubstituted cyclopentadienyl, indenyl and fluorenyl groups.
  • Bo substituted is meant that at least one hydrogen on the cyclopentadienyl, indenyl or fluorenyl group is replaced with a non-hydrogen atom containing group, preferably a hydrocarbyl group (such as methyl, ethyl, propyl, butyl, isobutyl, hexyl, octyl, and the like) or a heteroatom containing group (preferred heteroatoms include N, P, Br, Cl, and the like).
  • the metal atom "M" of the metallocene catalyst compound may be selected from the group consisting of Groups 3 through 12 atoms and lanthanide Group atoms in one embodiment; and selected from the group consisting of Groups 3 through 10 atoms in a more particular embodiment, and selected from the group consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni in yet a more particular embodiment; and selected from the group consisting of Groups 4, 5 and 6 atoms in yet a more particular embodiment, and a Ti, Zr, Hf atoms in yet a more particular embodiment, and Zr in yet a more particular embodiment.
  • the oxidation state of the metal atom "M” may range from 0 to +7 in one embodiment; and in a more particular embodiment, is +1, +2, +3, +4 or +5; and in yet a more particular embodiment is +2, +3 or +4.
  • the groups bound to the metal atom "M” are such that the compounds described below in the formulas and structures are neutral, unless otherwise indicated.
  • the Cp ligand(s) form at least one chemical bond with the metal atom M to form the "metallocene catalyst compound".
  • the Cp ligands are distinct from the leaving groups bound to the catalyst compound in that they are not highly susceptible to substitution/abstraction reactions.
  • the one or more metallocene catalyst components are represented formula (VI): C p A C p B MX n wherein M is as described above; each X is chemically bonded to M; each Cp group is chemically bonded to M; and n is 0 or an integer from 1 to 4, and either 1 or 2 in a particular embodiment.
  • the ligands represented by Cp A and Cp B in formula (VI) may be the same or different cyclopentadienyl ligands or ligands isolobal to cyclopentadienyl, either or both of which may contain heteroatoms and either or both of which may be substituted by a group R.
  • Cp. A and Cp B are independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and substituted derivatives of each.
  • each Cp A and Cp B of formula (VI) may be unsubstituted or substituted with any one or combination of substituent groups R.
  • Non- limiting examples of substituent groups R as used in structure (VI) include hydrogen radicals, alkyls, alkenyls, alkynyls, cycloalkyls, aryls, acyls, aroyls, alkoxys, aryloxys, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls, carbamoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos, arylaminos, and combinations thereof.
  • alkyl substituents R associated with formula (VI) through (V) include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, and tert-butylphenyl groups and the like, including all their isomers, for example tertiary-butyl, isopropyl, and the like.
  • radicals include substituted alkyls and aryls such as, for example, fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstituted boron radicals including dimethylboron for example; and disubstituted Group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, Group 16 radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and
  • substituents R include olefins such as but not limited to olefinically unsaturated substituents including vinyl-terminated ligands, for example 3-butenyl, 2- propenyl, 5-hexenyl and the like.
  • at least two R groups, two adjacent R groups in one embodiment, are joined to form a ring structure having from 3 to 30 atoms selected from the group consisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron and combinations thereof.
  • a substituent group R group such as 1-butanyl may form a bonding association to the element M.
  • Each X in the formula (VI) above and for the formulas/structures (II) through (V) below is independently selected from the group consisting of: any leaving group in one embodiment; halogen ions, hydrides, Ci to C12 alkyls, C 2 to Ci 2 alkenyls, C 6 to Ci 2 aryls, C 7 to C 20 alkylaryls, Ci to Ci 2 alkoxys, C 6 to Ci 6 aryloxys, C 7 to Ci 8 alkylaryloxys, Ci to Ci 2 fluoroalkyls, C 6 to Ci 2 fluoroaryls, and Ci to Ci 2 heteroatom-containing hydrocarbons and substituted derivatives thereof in a more particular embodiment; hydride, halogen ions, Ci to C 6 alkyls, C 2 to C 6 alkenyls, C 7 to C 18 alkylaryls, Ci to C 6 alkoxys, C 6 to Ci 4 aryloxys, C 7 to Ci 6 alkylaryloxys, Ci to
  • X groups in formula (VI) include amines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicals having from 1 to 20 carbon atoms, fluorinated hydrocarbon radicals (e.g., — C 6 Fs (pentafluorophenyl)), fluorinated alkylcarboxylates (e.g., CF 3 C(O)O " ), hydrides and halogen ions and combinations thereof.
  • X ligands include alkyl groups such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and the like.
  • two or more X's form a part of a fused ring or ring system.
  • the metallocene catalyst component includes those of formula (VI) where Cp A and Cp B are bridged to each other by at least one bridging group, (A), such that the structure is represented by formula (VII):
  • bridged metallocenes These bridged compounds represented by formula (VII) are known as "bridged metallocenes".
  • Cp A , Cp B , M, X and n in structure (VII) are as defined above for formula (VI); and wherein each Cp ligand is chemically bonded to M, and (A) is chemically bonded to each Cp.
  • Non- limiting examples of bridging group (A) include divalent hydrocarbon groups containing at least one Group 13 to 16 atom, such as but not limited to at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom and combinations thereof; wherein the heteroatom may also be Ci to C12 alkyl or aryl substituted to satisfy neutral valency.
  • bridging group (A) include methylene, ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene, 1 ,2-dimethylethylene, 1,2- diphenylethylene, 1,1,2,2-tetramethylethylene, dimethylsilyl, diethylsilyl, methyl-ethylsilyl, trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di(n-butyl)silyl, di(n-propyl)silyl, di(i- propyl)silyl, di(n-hexyl)silyl, dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl, t- butylcyclohexylsilyl, di(t-butylphenyl)silyl, di(p-tolyl)silyl and
  • bridging group (A) may also be cyclic, comprising, for example 4 to 10, 5 to 7 ring members in a more particular embodiment.
  • the ring members may be selected from the elements mentioned above, from one or more of B, C, Si, Ge, N and O in a particular embodiment.
  • Non- limiting examples of ring structures which may be present as or part of the bridging moiety are cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene and the corresponding rings where one or two carbon atoms are replaced by at least one of Si, Ge, N and O, in particular, Si and Ge.
  • the bonding arrangement between the ring and the Cp groups may be either cis-, trans-, or a combination.
  • the cyclic bridging groups (A) may be saturated or unsaturated and/or carry one or more substituents and/or be fused to one or more other ring structures. If present, the one or more substituents are selected from the group consisting of hydrocarbyl (e.g., alkyl such as methyl) and halogen (e.g., F, Cl) in one embodiment.
  • the one or more Cp groups which the above cyclic bridging moieties may optionally be fused to may be saturated or unsaturated and are selected from the group consisting of those having 4 to 10, more particularly 5, 6 or 7 ring members (selected from the group consisting of C, N, O and S in a particular embodiment) such as, for example, cyclopentyl, cyclohexyl and phenyl.
  • these ring structures may themselves be fused such as, for example, in the case of a naphthyl group.
  • these (optionally fused) ring structures may carry one or more substituents.
  • these substituents are hydrocarbyl (particularly alkyl) groups and halogen atoms.
  • the metallocene catalyst component is a bridged bisindenyl Group 4 metallocene represented by the formula: ACp 2 MX 2 where M is a Group 4 metal, (preferably Ti, Hf or Zr, preferably Hf or Zr); A is a bridging group connecting the two Cp groups; each Cp is, independently, a substituted indenyl group or an indenyl group bound to M; each X is an anionic leaving group (preferably the metallocene is represented by the formula rac-ACp 2 MX 2 where "me" indicates that the metallocene is partially or completely racemized, preferably the metallocene is completely racemized, i.e.
  • A is as described for Formula (VII).
  • A is represented by the formula -CR**2-(CR**2) n - or -SiR* * 2 - , where n is 0, 1 or 2, and each R** is, independently, H or a Ci to Ci 2 alkyl group, and any two R** may form a cyclic group.
  • R** is H, methyl, or ethyl.
  • A is a dialkylsilyl group (preferably the alky is methyl, ethyl, propyl or butyl, preferably A is dimethylsilyl).
  • each X is independently a Ci to C20 alkyl group or a halogen, preferably methyl, ethyl, propyl, butyl, chlorine or bromine.
  • substituted indenyl group is meant that at least one hydrogen on the indenyl group is replaced with a hydrocarbyl group (such as methyl, ethyl, propyl, butyl, hexyl, octyl, or isomers thereof)) or a heteroatom containing group (preferred heteroatoms include N, P, Br, Cl, and the like).
  • the bridging group A is not counted as a substitution.
  • the substituted indenyl group is not a fluorenyl group.
  • the indenyl group is substituted at the 2 or at the 2 and 4 positions with a hydrocarbyl group (numbering begins at the bridge).
  • Preferred hydrocarbyl groups include Ci to C30 linear, cyclic, or branched, saturated or unsaturated hydrocarbyl groups, such as methyl, ethyl, propyl, butyl, phenyl, benzyl, substituted phenyl, substituted benzyl, and the like.
  • the indenyl group is substituted with from 1, 2, 3, 4, 5, or 6 hydrocarbyl or substituted hydrocarbyl group(s) (preferably Ci to C20 alkyl group(s)).
  • the activity of the catalyst system is 1500 g polymer/g catalyst-hour or more, preferably 1700 g polymer/g catalyst-hour or more, preferably 1900 g polymer/g catalyst-hour or more, preferably 2500 g polymer/g catalyst-hour or more.
  • the metallocene catalyst components include mono-ligand metallocene compounds (e.g., mono cyclopentadienyl catalyst components) such as described in WO 93/08221 for example.
  • the at least one metallocene catalyst component is a bridged "half-sandwich" metallocene represented by the formula (VIII): Cp A (A)QMX n wherein Cp A is defined above and is bound to M; (A) is a bridging group bonded to Q and Cp A ; and wherein an atom from the Q group is bonded to M; and n is 0 or an integer from 1 to 3; 1 or 2 in a particular embodiment.
  • Cp A , (A) and Q may form a fused ring system.
  • the X groups and n of formula (VIII) are as defined above in formula (VI) and (VII).
  • Cp A is selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substituted versions thereof, and combinations thereof.
  • Q is a heteroatom-containing ligand in which the bonding atom (the atom that is bonded with the metal M) is selected from the group consisting of Group 15 atoms and Group 16 atoms in one embodiment, and selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur atom in a more particular embodiment, and nitrogen and oxygen in yet a more particular embodiment.
  • Non-limiting examples of Q groups include alkylamines, arylamines, mercapto compounds, ethoxy compounds, carboxylates (e.g., pivalate), carbamates, azenyl, azulene, pentalene, phosphoyl, phosphinimine, pyrrolyl, pyrozolyl, carbazolyl, borabenzene other compounds comprising Group 15 and Group 16 atoms capable of bonding with M.
  • the at least one metallocene catalyst component is an unbridged "half sandwich" metallocene represented by the formula (IX):
  • Cp A is defined as for the Cp groups in (VI) and is a ligand that is bonded to M; each Q is independently bonded to M; Q is also bound to Cp A in one embodiment; X is a leaving group as described above in (VI); n ranges from 0 to 3, and is 1 or 2 in one embodiment; q ranges from 0 to 3, and is 1 or 2 in one embodiment.
  • Cp A is selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substituted version thereof, and combinations thereof.
  • Q is selected from the group consisting of ROO " , RO-, R(O)-, -NR-, -CR 2 -, -S-, -NR 2 , -CR 3 , -SR, -SiR 3 , -PR 2 , — H, and substituted and unsubstituted aryl groups, wherein R is selected from the group consisting of Ci to C 6 alkyls, C 6 to Ci 2 aryls, Ci to C 6 alkylamines, C 6 to Ci 2 alkylarylamines, Ci to C 6 alkoxys, C 6 to Ci 2 aryloxys, and the like.
  • Non-limiting examples of Q include Ci to Ci 2 carbamates, Ci to Ci 2 carboxylates (e.g., pivalate), C 2 to C 2 o allyls, and C 2 to C 2 o heteroallyl moieties.
  • Ci to Ci 2 carbamates Ci to Ci 2 carboxylates (e.g., pivalate)
  • C 2 to C 2 o allyls C 2 to C 2 o heteroallyl moieties.
  • Q 2 GZ forms a polydentate ligand unit (e.g., pivalate), wherein at least one of the Q groups form a bond with M, and is defined such that each Q is independently selected from the group consisting of — O — , — NR — , — CR 2 — and — S — ; G is either carbon or silicon; and Z is selected from the group consisting of R, — OR, — NR 2 , — CR3, — SR, — SiR 3 , — PR 2 , and hydride, providing that when Q is — NR — , then Z is selected from the group consisting of —
  • each R is independently selected from the group consisting of Ci to C 10 heteroatom containing groups, Ci to C 10 alkyls, C 6 to Ci 2 aryls, C 6 to Ci 2 alkylaryls, Ci to C 10 alkoxys, and C 6 to Ci 2 aryloxys; n is 1 or 2 in a particular embodiment; and
  • T is a bridging group selected from the group consisting of Ci to C 10 alkylenes, C 6 to Ci 2 arylenes and Ci to C 10 heteroatom containing groups, and C 6 to Ci 2 heterocyclic groups; wherein each T group bridges adjacent "Cp A M(Q 2 GZ)X n " groups, and is chemically bonded to the Cp A groups.
  • m is an integer from 1 to 7; m is an integer from 2 to 6 in a more particular embodiment.
  • the at least one metallocene catalyst component can be described more particularly in structures (XIa), (XIb), (XIc), (XId) (XIe) and (XIf):
  • M is selected from the group consisting of Group 3 to Group 12 atoms, and selected from the group consisting of Group 3 to Group 10 atoms in a more particular embodiment, and selected from the group consisting of Group 3 to Group 6 atoms in yet a more particular embodiment, and selected from the group consisting of Group 4 atoms in yet a more particular embodiment, and selected from the group consisting of Zr and Hf in yet a more particular embodiment; and is Zr in yet a more particular embodiment; wherein Q in (XIa) to (XIf) is selected from the group consisting of alkylenes, aryls, arylenes, alkoxys, aryloxys, amines, arylamines (e.g., pyridyl) alkylamines, phosphines, alkylphosphines, substituted alkyls, substituted aryls, substituted alkoxys, substituted aryloxys, substitute
  • R 1 through R 13 are independently: selected from the group consisting of hydrogen radical, halogen radicals, Ci to Ci 2 alkyls, C 2 to Ci 2 alkenyls, C 6 to Ci 2 aryls, C 7 to C 20 alkylaryls, Ci to Ci 2 alkoxys, Ci to Ci 2 fluoroalkyls, C 6 to Ci 2 fluoroaryls, and Ci to Ci 2 heteroatom- containing hydrocarbons and substituted derivatives thereof in one embodiment; selected from the group consisting of hydrogen radical, fluorine radical, chlorine radical, bromine radical, Ci to C 6 alkyls, C 2 to C 6 alkenyls, C 7 to C 18 alkylaryls, Ci to C 6 fluoroalkyls, C 2 to C 6 fluoroalkenyls, C 7 to C 18 fluoroalkylaryls in a more particular embodiment; and hydrogen radical, fluorine radical, chlorine radical, methyl, ethyl, propyl, isopropyl, butyl
  • the structure of the metallocene catalyst component represented by (XIa) may take on many forms such as disclosed in, for example, U.S. Pat. Nos. 5,026,798, 5,703,187, and 5,747,406, including a dimer or oligomeric structure, such as disclosed in, for example, U.S. Pat. Nos. 5,026,798 and 6,069,213.
  • R 1 and R 2 form a conjugated 6-membered carbon ring system that may or may not be substituted.
  • Non-limiting examples of metallocene catalyst components consistent with the description herein include: cyclopentadienylzirconium X n , indenylzirconium X n , (l-methylindenyl)zirconium X n , (2- methylindenyl)zirconium X n , (l-propylindenyl)zirconium X n , (2-propylindenyl)zirconium X n , (l-butylindenyl)zirconium X n , (2-butylindenyl)zirconium X n ,
  • a single, bridged, asymmetrically substituted metallocene catalyst component having a racemic and/or meso isomer does not, itself, constitute at least two different bridged, metallocene catalyst components.
  • the "metallocene catalyst component” may comprise any combination of any "embodiment” described herein. Supported Catalyst Systems
  • the activator and/or the polymerization catalyst compound may be combined with one or more support materials or carriers using any one of the support methods known in the art or as described below.
  • the activator is in a supported form, for example deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, a support or carrier.
  • the activator and a catalyst compound may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, a support or carrier.
  • support or “carrier” for purposes of this patent specification are used interchangeably and are any support material, preferably a porous support material, including inorganic or organic support materials.
  • inorganic support materials include inorganic oxides and inorganic chlorides.
  • Other carriers include resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene, divinyl benzene, polyolef ⁇ ns, or polymeric compounds, zeolites, talc, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • the heterocyclic compounds and the alumoxanes described above are combined with one or more support materials or carriers.
  • the heterocyclic compound is combined with a support material, preferably silica, treated with the alumoxane compound, such that the support has aluminum alkyl groups bonded thereto.
  • a support material preferably silica
  • the supported catalyst systems described herein may be prepared, generally, by the reaction of the heterocyclic compound with an alumoxane, the addition of the catalyst precursor, followed by addition of a support material such as silica or alumina.
  • the support materials utilized may be any of the conventional support materials.
  • the supported material is a porous support material, for example, talc, inorganic oxides and inorganic chlorides.
  • support materials include resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefms or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefms or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • the preferred support materials are inorganic oxides that include those Group 2, 3, 4, 5, 13 or 14 metal oxides.
  • the preferred supports include silica, fumed silica, alumina, silica-alumina and mixtures thereof.
  • Other useful supports include magnesia, titania, zirconia, magnesium chloride, montmorillonite, phyllosilicate, zeolites, talc, clays and the like.
  • combinations of these support materials may be used, for example, silica- chromium, silica-alumina, silica-titania and the like.
  • Additional support materials may include those porous acrylic polymers.
  • Other support materials include nanocomposites, aerogels, spherulites, and polymeric beads.
  • Fumed silica available under the trade name CabosilTM. TS-610, available from Cabot Corporation. Fumed silica is typically a silica with particles 7 to 30 nanometers in size that has been treated with dimethylsilyldichloride such that a majority of the surface hydroxyl groups are capped.
  • any of the conventionally known inorganic oxides, such as silica, support materials that retain hydroxyl groups after dehydration treatment methods will be suitable in accordance with the invention. Because of availability, both of silica and silica containing metal oxide based supports, for example, silica-alumina, are preferred. Silica particles, gels and glass beads are most typical.
  • These metal oxide compositions may additionally contain oxides of other metals, such as those of Al, K, Mg, Na, Si, Ti and Zr and should preferably be treated by thermal and/or chemical means to remove water and free oxygen.
  • thermal and/or chemical means to remove water and free oxygen.
  • treatment is in a vacuum in a heated oven, in a heated fluidized bed or with dehydrating agents such as organo silanes, siloxanes, alkyl aluminum compounds, etc.
  • dehydrating agents such as organo silanes, siloxanes, alkyl aluminum compounds, etc.
  • the level of treatment should be such that as much retained moisture and oxygen as is possible is removed, but that a chemically significant amount of hydroxyl functionality is retained.
  • loadings to achieve from less than 0.1 mmol to 3.0 mmol activator/g SiO 2 are typically suitable and can be achieved, for example, by varying the temperature of calcining from 200 0 C to 1,000 0 C, such as from 300 0 C to 900 0 C, 400 0 C to 875 0 C, 500 0 C to 85O 0 C, 600 0 C to 825 0 C, 700 0 C to 800 0 C, and any combination of any limit with any lower limit.
  • the tailoring of hydroxyl groups available as attachment sites in this invention can also be accomplished by the pre-treatment with a less than stoichiometric amount of a chemical dehydrating agent. If calcining temperatures below 400 0 C are employed, difunctional coupling agents (e.g., (CHs) 3 SiCl 2 ) may be employed to cap hydrogen bonded pairs of silanol groups which are present under the less severe calcining conditions. Similarly, use of the Lewis acid in excess of the stoichiometric amount needed for reaction with the transition metal compounds will serve to neutralize excess silanol groups without significant detrimental effect for catalyst preparation or subsequent polymerization.
  • difunctional coupling agents e.g., (CHs) 3 SiCl 2
  • the support is a polymeric support, including hydroxyl- functional-group-containing polymeric substrates, but functional groups may be any of the primary alkyl amines, secondary alkyl amines, and others, where the groups are structurally incorporated in a polymeric chain and capable of a acid-base reaction with the Lewis acid such that a ligand filling one coordination site of the aluminum is protonated and replaced by the polymer incorporated functionality. See, for example, the functional group containing polymers of U.S. Pat. No. 5,288,677.
  • the support material most preferably an inorganic oxide, has a surface area in the range of from about 10 to about 700 m 2 /g, pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 5 to about 500 ⁇ m. More preferably, the surface area of the support material is in the range of from about 50 to about 500 m 2 /g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 ⁇ m.
  • the average pore size of the carrier is typically in the range of from 10 to 1000 angstroms., preferably 50 to about 500 angstroms., and most preferably 75 to about 350 angstroms.
  • the support materials may be treated chemically, for example with a fluoride compound as described in WO 00/12565.
  • a fluoride compound as described in WO 00/12565.
  • Other supported activators are described in for example WO 00/13792 that refers to supported boron containing solid acid complex.
  • the support material having an alumoxane compound bonded thereto may be prepared by combining the aluminum containing compound with the support material in a suitable solvent.
  • the combining is carried out at any suitable pressure and temperature under an inert atmosphere.
  • the combining is at atmospheric pressure, ambient temperature under nitrogen. More preferably the mixture is heated to less than about 200 0 C, more preferably less than 15O 0 C.
  • the reactants are contacted for a suitable about of time for example, for at least about 1 minute, preferably about 1 minute to about 10 hours, more preferably for about 1 minute to about 3 hours.
  • an antistatic agent or surface modifier that is used in the preparation of the supported catalyst system as described in PCT publication WO 96/11960 may be used with catalyst systems including the activator compounds described herein.
  • the catalyst systems may also be prepared in the presence of an olefin, for example 1-hexene.
  • the activator and/or catalyst system may be combined with a carboxylic acid salt of a metal ester, for example aluminum carboxylates such as aluminum mono, di- and tri- stearates, aluminum octoates, oleates and cyclohexylbutyrates, as described in U.S. Pat. Nos. 6,300,436 and 6,306,984.
  • a method for producing a supported metallocene- type catalyst system which may be used to support the activator described herein.
  • the catalyst compound is slurried in a liquid to form a catalyst solution or emulsion.
  • a separate solution is formed containing the activator.
  • the liquid may be any compatible solvent or other liquid capable of forming a solution or the like with the catalyst compounds and/or activator.
  • the liquid is a cyclic aliphatic or aromatic hydrocarbon, most preferably toluene.
  • the catalyst compound and activator solutions are mixed together heated and added to a heated porous support or a heated porous support is added to the solutions such that the total volume of the metallocene-type catalyst compound solution and the activator solution or the metallocene-type catalyst compound and activator solution is less than four times the pore volume of the porous support, more preferably less than three times, even more preferably less than two times; preferred ranges being from 1.1 times to 3.5 times range and most preferably in the 1.2 to 3 times range.
  • a method of forming a supported catalyst system the amount of liquid, in which the activator described herein and/or a catalyst compound is present, is in an amount that is less than four times the pore volume of the support material, more preferably less than three times, even more preferably less than two times; preferred ranges being from 1.1 times to 3.5 times range and most preferably in the 1.2 to 3 times range.
  • the amount of liquid in which the activator is present is from one to less than one times the pore volume of the support material utilized in forming the supported activator.
  • the amount of heterocyclic heteroatom containing compound ranges from 0.005 grams to 2.0 grams per gram of alumoxane treated silica. In another embodiment, the amount of heterocyclic heteroatom containing compound ranges from 0.05 grams to 1.0 grams per gram of alumoxane treated silica. In yet another embodiment, the amount of heterocyclic containing compound ranges from 0.075 grams to 0.8 grams per gram of alumoxane treated silica.
  • Polymerization Process [0079] The activators and catalysts described above, whether supported or not, are suitable for use in any prepolymerization and/or polymerization process over a wide range of temperatures and pressures.
  • the temperatures may be in the range of from -6O 0 C to about 28O 0 C, preferably from 5O 0 C to about 200 0 C.
  • the polymerization temperature is above O 0 C, above 5O 0 C, above 8O 0 C, above 100 0 C, above 15O 0 C, or above 200 0 C.
  • the pressures employed may be in the range from 1 atmosphere to about 500 atmospheres (approx 101 kPa to 50650 kPa) or higher.
  • Polymerization processes include solution, gas phase, slurry phase, and a high pressure process, or a combination thereof. Particularly preferred is a gas phase or slurry phase polymerization of one or more olefin(s) at least one of which is ethylene or propylene.
  • the process is a solution, high pressure, slurry or gas phase polymerization process of one or more olefin monomers having from 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms.
  • the invention is particularly well suited to the polymerization of two or more olefin monomers of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-octene and 1-decene.
  • Other monomers useful in the process include ethylenically unsaturated monomers, diolefms having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins.
  • Non- limiting monomers useful in the invention may include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene and cyclopentene.
  • a copolymer of ethylene is produced, where with ethylene, a comonomer having at least one alpha-olefm having from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8 carbon atoms, is polymerized in a gas phase process.
  • ethylene or propylene is polymerized with at least two different comonomers, optionally one of which may be a diene, to form a terpolymer.
  • the invention is directed to a polymerization process, particularly a gas phase or slurry phase process, for polymerizing propylene alone or with one or more other monomers including ethylene, and/or other olefins having from 4 to 12 carbon atoms.
  • a continuous cycle is employed where in one part of the cycle of a reactor system, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization. This heat is removed from the recycle composition in another part of the cycle by a cooling system external to the reactor.
  • a gas fluidized bed process for producing polymers a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer.
  • the reactor pressure in a gas phase process may vary from about 100 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the range of from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferably in the range of from about 250 psig (1724 kPa) to about 350 psig (2414 kPa).
  • the reactor temperature in a gas phase process may vary from about 3O 0 C to about 12O 0 C, preferably from about 6O 0 C to about 115 0 C, more preferably in the range of from about 7O 0 C to HO 0 C, and most preferably in the range of from about 7O 0 C to about 95 0 C. In another embodiment, the reactor temperature in a gas phase process is above 6O 0 C.
  • Other gas phase processes include series or multistage polymerization processes. Also gas phase processes contemplated by the invention include those described in U.S. Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, and European publications EP-A-O 794 200 EP- Bl-O 649 992, EP-A-O 802 202 and EP-B-634 421.
  • the process may produce greater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500 Kg/hr).
  • a slurry polymerization process generally uses pressures in the range of from about 1 to about 50 atmospheres (5065 kPa) and even greater and temperatures in the range of O 0 C to about 12O 0 C. In another embodiment, the slurry process temperature is above 100 0 C.
  • a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which ethylene and comonomers and often hydrogen along with catalyst are added.
  • the suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor.
  • the liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane.
  • the medium employed should be liquid under the conditions of polymerization and relatively inert. When a propane medium is used the process must be operated above the reaction diluent critical temperature and pressure. Preferably, a hexane or an isobutane medium is employed.
  • the polymerization technique is referred to as a particle form polymerization, or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution.
  • a particle form polymerization or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution.
  • slurry processes include those employing a loop reactor and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof.
  • Non-limiting examples of slurry processes include continuous loop or stirred tank processes.
  • other examples of slurry processes are described in U.S. Pat. No. 4,613,484, which is herein fully incorporated by reference.
  • the process may produce greater than 2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr (4540 Kg/hr).
  • the slurry reactor may produce greater than 15,000 lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).
  • Examples of solution processes are described in U.S. Pat. Nos. 4,271,060, 5,001,205, 5,236,998 and 5,589,555 and PCT WO 99/32525.
  • the slurry or gas phase process is operated in the presence of the catalyst system described herein and in the absence of or essentially free of any scavengers, such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum and tri-n- hexylaluminum and diethyl aluminum chloride, dibutyl zinc and the like.
  • any scavengers such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum and tri-n- hexylaluminum and diethyl aluminum chloride, dibutyl zinc and the like.
  • the catalyst system may be injected into a reactor, particularly a gas phase reactor.
  • the catalyst system is used in the unsupported form, preferably in a liquid form such as described in U.S. Pat. Nos. 5,317,036 and 5,693,727 and European publication EP-A-O 593 083.
  • the polymerization catalyst in liquid form can be fed with an activator, and/or a support, and/or a supported activator together or separately to a reactor.
  • the injection methods described in PCT publication WO 97/46599 may be utilized.
  • the mole ratio of the metal of the activator component to the metal of the catalyst compound is in the range of between 0.3:1 to 10,000:1, preferably 100:1 to 5000:1, and most preferably 500:1 to 2000:1.
  • the polymers produced can be used in a wide variety of products and end-use applications.
  • the polymers produced include linear low density polyethylene, elastomers, plastomers, high density polyethylenes, medium density polyethylenes, low density polyethylenes, polypropylene and polypropylene copolymers.
  • the polymers typically ethylene or propylene based polymers, have a density in the range of from 0.86 g/cc to 0.97 g/cc, preferably in the range of from 0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900 g/cc to 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to 0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to 0.940 g/cc, and most preferably greater than 0.915 g/cc, preferably greater than 0.920 g/cc, and most preferably greater than 0.925 g/cc. Density is measured in accordance with ASTM-D-1238.
  • the polymers produced typically have a molecular weight distribution, a weight average molecular weight to number average molecular weight (M w /M n ) of greater than 1.5 to about 15, particularly greater than 2 to about 10, more preferably greater than about 2.2 to less than about 8, and most preferably from 2.5 to 8.
  • the polymers may have a narrow molecular weight distribution and a broad composition distribution or vice-versa, and may be those polymers described in U.S. Pat. No. 5,798,427.
  • the polymers typically have a narrow composition distribution as measured by Composition Distribution Breadth Index (CDBI). Further details of determining the CDBI of a copolymer are known to those skilled in the art.
  • CDBI Composition Distribution Breadth Index
  • the polymers in one embodiment have CDBFs generally in the range of greater than 50% to 100%, preferably 99%, preferably in the range of 55% to 85%, and more preferably 60% to 80%, even more preferably greater than 60%, still even more preferably greater than 65%.
  • polymers produced using a catalyst system described herein have a CDBI less than 50%, more preferably less than 40%, and most preferably less than 30%.
  • the polymers in one embodiment have a melt index (MI) or (I 2 ) as measured by ASTM-D-1238-E (190/2.16) in the range from no measurable flow to 1000 dg/min, more preferably from about 0.01 dg/min to about 100 dg/min, even more preferably from about 0.1 dg/min to about 50 dg/min, and most preferably from about 0.1 dg/min to about 10 dg/min.
  • the polymers have a melt index ratio (I2I/I2) (I 21 is measured by ASTM-D-1238-F) (190/21.6) of from 10 to less than 25, more preferably from about 15 to less than 25.
  • the polymers in a preferred embodiment, have a melt index ratio (I21/I2) of from greater than 25, more preferably greater than 30, even more preferably greater that 40, still even more preferably greater than 50 and most preferably greater than 65.
  • melt index ratio (I 21 ZI 2 ) may be of from 5 to 300, 10 to 200, 20 to 180, 30 to 160, 40 to 120, 50 to 100, 60 to 90, and a combination of any upper limit with any lower limit.
  • propylene based polymers are produced. These polymers include atactic polypropylene, isotactic polypropylene, hemi-isotactic and syndiotactic polypropylene.
  • propylene polymers include propylene block or impact copolymers. Propylene polymers of these types are well known in the art see for example U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851, 5,036,034 and 5,459,117.
  • the propylene polymers have an MwZMn of more than 1 to 4, preferably less than 2, preferably from 1.2 to 2.
  • Useful propylene polymers prepared herein may have an Mn of more than 100,000 g/mol, preferably more than 200,000 g/mol, preferably more than 350,000 g/mol, preferably more than 500,000 g/mol.
  • the polypropylene may have an Mn of 100,000 to 200,000 g/mol.
  • the polypropylene (preferably having at least 50 wt% propylene, preferably at least 80 wt% propylene, preferably at least 90 wt% propylene) may have an Mn of 10,000 to 50,000 g/mol (alternately from 15,000 to 45,000g/mol, alternately from 20,000 to 40,000 gZmol and a melting point of 14O 0 C or more (preferably 145 0 C or more, preferably 15O 0 C or more, preferably 155 0 C or more, preferably 16O 0 C or more, preferably 165 0 C or more).
  • the polypropylene produced herein has an Mw from 5,000 to 120,000 (preferably from 10,000 to 100,000 preferably from 12,000 to 75,000 preferably from 15,000 to 50,000 gZmol) and a melting point above 14O 0 C (preferably 145 0 C or more, preferably 15O 0 C or more, preferably 155 0 C or more, preferably 16O 0 C or more, preferably 165 0 C or more), provided that the melting point is also greater than or equal to 0.000143x(Mw in gZmol)+133, (preferably +134, preferably +135) and optionally, an Mw/Mn of 4 or less, preferably 2.5 or less, preferably from greater than 1 to 2.
  • the melting point is 145 0 C or more (preferably 15O 0 C or more, preferably 155 0 C or more, preferably 16O 0 C or more, preferably 165 0 C or more) or alternately if the Mw is 50,000 g/mol or more then the melting point is 15O 0 C or more (preferably 155 0 C or more, preferably 16O 0 C or more, preferably 165 0 C or more).
  • the polypropylene may be isotactic, highly isotactic, syndiotactic, or highly syndiotactic.
  • Comonomer is preferably present in the polymers (such as the propylene polymers) at 0 to 50 wt%, alternately from 1 to 20 wt%, alternately from 2 to 10 wt%.
  • the polymers may be blended and/or coextruded with any other polymer.
  • Non- limiting examples of other polymers include linear low density polyethylenes, elastomers, plastomers, high pressure low density polyethylene, high density polyethylenes, polypropylenes and the like.
  • the polymers produced and blends thereof are useful in such forming operations as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotary molding.
  • Films include blown or cast films formed by coextrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, membranes, etc. in food-contact and non-food contact applications.
  • Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, geotextiles, etc.
  • Extruded articles include medical tubing, wire and cable coatings, pipe, geomembranes, and pond liners. Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc.
  • a catalyst system comprising: a metallocene; an activator comprising one or more heterocyclic heteroatom containing ligands coordinated to an alkyl alumoxane, wherein the activator is a reaction product of one or more alkyl alumoxane and one or more heterocyclic heteroatom containing compounds, wherein the heterocyclic heteroatom containing ligand is represented by:
  • Y is O, S, PH or NH; wherein each substituent X2, X3, X4, X5, X6 and X7 is independently a hydrogen, chlorine, fluorine, iodine or bromine, provided at least one of X2, X3, X4, X5, X6 and X7 is not hydrogen when Y is NH; and wherein the ratio of the heterocyclic heteroatom containing ligand to aluminum is between about 0.01 and about 10 molar equivalents. 2.
  • a process to polymerize one or more olefins comprising the step of contacting one or more olefins with a catalyst system of any of paragraphs 1 through 8. 10. The process of paragraph 9, wherein the one olefin is propylene.
  • this invention relates to : IA.
  • a process to polymerize propylene comprising:
  • a metallocene represented by the formula ACp 2 MX 2 where M is Ti, Hf or Zr (preferably Hf or Zr) and is bound to each Cp group; A is a bridging group connecting the two Cp groups; each Cp is, independently, an indenyl group or a substituted indenyl group (preferably substituted with from 1, 2, 3, 4, 5, or 6 hydrocarbyl or substituted hydrocarbyl group(s) (preferably Ci to C 2 o alkyl group(s)), preferably the indenyl group is substituted at the 2 position or at the 2 and 4 positions; each X is an anionic leaving group; (preferably the metallocene represented by the formula rac- ACp 2 MX
  • an activator comprising one or more heterocyclic heteroatom containing ligands coordinated to an isoalkyl alumoxane (preferably where the alkyl is a C3 to Ci 2 isoalkyl, preferably isopropyl, isobutyl, isohexyl, isopentyl, or isooctyl), wherein the activator is a reaction product of a solution of one or more isoalkyl alumoxanes (preferably where the isoalkyl is a C3 to C 12 isoalkyl, preferably isopropyl, isobutyl, isopentyl, isohexyl, or isooctyl), and one or more heterocyclic heteroatom containing compounds, wherein the heterocyclic heteroatom containing ligand is represented by:
  • Y is NH or N-R where R is a Ci to Ci 2 alkyl group; wherein each of X2 and X3 is hydrogen, halogen or X2 and X3 may form a six membered aromatic ring (preferably X2 and X3 are H); X4, X5, X6 and X7 are, independently, hydrogen or a halogen, provided at least one of X2, X3, X4, X5, X6 and X7 is not hydrogen, (preferably X4, X5, X6 and X7 are all halogen, alternately one, two, or three of X4, X5, X6 and X7 is/are halogen (and optionally those of X4, X5, X6 and X7 that are not halogen are H), in a preferred embodiment, X5 is bromine and X4, X6 and X7 are H); and preferably wherein the ratio of the heterocyclic heteroatom containing ligand to aluminum is between 0.01 :
  • a catalyst system (optionally supported) comprising: a) a metallocene represented by the formula ACp 2 MX 2 where M is Ti, Hf or Zr and is bound to each Cp group, A is a bridging group connecting the two Cp groups, each Cp is, independently, an indenyl group or a substituted indenyl group (preferably substituted with from 1 to 6 Ci to C20 alkyl groups, preferably the indenyl group is substituted at the 2 position or at the 2 and 4 positions), each X is an anionic leaving group, (preferably the metallocene represented by the formula rac- ACp 2 MX 2 where "me" indicates that the metallocene is partially or completely racemized, preferably the metallocene is completely racemized, i.e.
  • an activator comprising one or more heterocyclic heteroatom containing ligands coordinated to an isoalkyl alumoxane (preferably where the isoalkyl is a C 3 to Ci 2 isoalkyl, preferably isopropyl, isobutyl, isopentyl, isohexyl, or isooctyl), wherein the activator is a reaction product of a solution of one or more isoalkyl alumoxanes (preferably where the alkyl is a C 3 to C 12 isoalkyl, preferably isopropyl, isobutyl, isopentyl, isohexyl, or isooctyl), and one or more heterocyclic heteroatom containing compounds, wherein the heterocyclic heteroatom containing ligand is represented by:
  • Y is NH or N-R where R is a Ci to Ci 2 alkyl group; wherein each of X2 and X3 is hydrogen, halogen or X2 and X3 may form a six membered aromatic ring (preferably X2 and X3 are H);
  • X4, X5, X6 and X7 are hydrogen or a halogen, provided that at least one of X$%,X5,X6, or
  • X7 is a halogen (preferably X5 is bromine and X4, X6 and X7 are H); and wherein the ratio of the heterocyclic heteroatom containing ligand to aluminum is between
  • the ratio of water to aluminum in the alumoxane solution is 0.7:1 or less.
  • alumoxane comprises isobutyl alumoxane or isohexyl alumoxane.
  • the catalyst system described above is supported, typically on silica.
  • Isobutylalumoxane was obtained commercially from Akzo Nobel Chemicals Inc. in two formulations: isobutylalumoxane (0.65 H2O/A1), 3.5 wt% Al in hexanes and isobutylalumoxane (0.80 H 2 O/ Al), 3.5 wt% Al in heptane.
  • the solvents used in both these formulations proved unsuitable for downstream reactions so, the solvents were replaced with the more polar solvent, toluene.
  • the slurry was weighed and re-dissolved in an appropriate amount of toluene to give a 10 wt% solution.
  • IBAO isobutylalumoxane solutions
  • IBAO 0.6 wt% in toluene
  • IBAO 0.65, 10 wt% in toluene
  • isobutylalumoxane (0.80 H 2 O/ Al), 3.5 wt% Al in heptane was dried under vacuum to remove the heptane to yield a viscous slurry. The slurry was weighed and then re-dissolved in an appropriate amount of toluene to give a 10 wt% solution.
  • This isobutylalumoxane solution, IBAO (0.80, 10 wt% in toluene), was used to prepare a series of liquid catalysts by reaction with selected organic ligands as shown below.
  • Triisobutyl aluminum (TIBAL) was obtained from Akzo Chemicals, Inc. and used without further purification.
  • Tri n-octyl aluminum (TNOAL) was obtained from Akzo
  • the reactors were heated to 4O 0 C and propylene was first charged to the reactor.
  • Polymerizations were halted by addition of approximately 400 psig O 2 / Ar (5 mole% O 2 ) gas mixture to the autoclaves for approximately 30 seconds. The polymerizations were quenched after 45 minutes polymerization time. The reactors were cooled and vented. The polymer was isolated after the remaining reaction components were removed in- vacuo.
  • polymer sample solutions were prepared by dissolving polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity from Sigma- Aldrich) containing 2,6-di-te/t-butyl-
  • BHT 4-methylphenol (BHT, 99% from Aldrich) at 145°C in a shaker oven for approximately 3 hours.
  • the typical final concentration of polymer in solution is between 0.4 to 0.9 mg/mL with a BHT concentration of 1.25 mg BHT/mL of TCB. Samples are cooled to 135 0 C for testing
  • Samples for DSC were performed on a TA Instruments QlOO DSC. Sample preparation.
  • approximately 0.07 g of each polymer were weighed into tared glass vials. Each glass vial was then weighed by the Bohdan weigh station, and 2.8 ml of trichlorobenzene with BHT was added to each vial using the Rapid GPC prep station to obtain 25 mg/ml solutions. The polymers were then dissolved at 165 0 C with mixing bars and agitation. The Rapid GPC station then automatically dispensed approximately 0.4 ml of each polymer solution into DSC pans. The trichlorobenzene was evaporated at 165 0 C over approximately 15 minutes.
  • the DSC pans were then annealed in an oven purged with nitrogen to give them the same thermal history.
  • the samples were annealed at 22O 0 C for 15 minutes, and allowed to cool overnight to room temperature. DSC measurements.
  • the following heating and cooling sequence were used to test samples in a high throughput mode.
  • the first melt occurs when the pans are annealed in parallel in the purged oven.

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Abstract

L'invention porte sur un activateur, un système de catalyse et leurs utilisations. Selon un aspect, le système de catalyse comprend un ou plusieurs catalyseurs de polymérisation et au moins un activateur. L'activateur consiste en ligands contenant des hétéroatomes hétérocycliques et coordonnés à un alumoxane. L'activateur est le produit de réaction d'un ou plusieurs alumoxanes et de composés contenant des hétéroatomes hétérocycliques. Lesdits ligands sont représentés par la formule ci-après dans laquelle: Y est O, S, PH ou NH; chaque substituant X2, X3, X4, X5, X6, et X7 est sélectionné indépendamment parmi: hydrogène, chlore, fluor, iode, et brome, sous réserve qu'au moins l'un des X2, X3, X4, X5, X6 et X7 ne soit pas hydrogène lorsque Y est NH; le rapport ligand/aluminium est compris entre environ 0,01 et environ 10 équivalents molaires. Le système de catalyseurs peut être sur support ou sans support.
PCT/US2008/082066 2007-11-08 2008-10-31 Activation de métallocènes par complexe alumoxanes/ligands contenant des hétéroatomes hétérocycliques à substitution halogène WO2009061678A1 (fr)

Priority Applications (2)

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EP08846364A EP2217627A1 (fr) 2007-11-08 2008-10-31 Activation de métallocènes par complexe alumoxanes/ligands contenant des hétéroatomes hétérocycliques à substitution halogène
CN2008801152165A CN101903414A (zh) 2007-11-08 2008-10-31 金属茂的卤素取代的杂环型含杂原子的配体-铝氧烷活化

Applications Claiming Priority (4)

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US11/937,043 2007-11-08
US11/937,043 US8022005B2 (en) 2007-11-08 2007-11-08 Halogen substituted heterocyclic heteroatom containing ligands-alumoxane activation of metallocenes
EP08154608.7 2008-04-16
EP08154608A EP2112175A1 (fr) 2008-04-16 2008-04-16 Activateur de métallocènes comprenant au moins un ligand hétérocyclique substitué par halogène, coordonné à un alumoxane

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6703338B2 (en) * 2002-06-28 2004-03-09 Univation Technologies, Llc Polymerization catalyst activators, method of preparing, and their use in polymerization processes
US20070055028A1 (en) * 2004-01-07 2007-03-08 Casty Gary L Preparation of polymerization catalyst activators utilizing indole-modified silica supports

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6703338B2 (en) * 2002-06-28 2004-03-09 Univation Technologies, Llc Polymerization catalyst activators, method of preparing, and their use in polymerization processes
US20070055028A1 (en) * 2004-01-07 2007-03-08 Casty Gary L Preparation of polymerization catalyst activators utilizing indole-modified silica supports

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