WO2007005676A2 - Compositions activatrices et leur utilisation dans des catalyseurs et dans la polymerisation d'olefine - Google Patents

Compositions activatrices et leur utilisation dans des catalyseurs et dans la polymerisation d'olefine Download PDF

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WO2007005676A2
WO2007005676A2 PCT/US2006/025709 US2006025709W WO2007005676A2 WO 2007005676 A2 WO2007005676 A2 WO 2007005676A2 US 2006025709 W US2006025709 W US 2006025709W WO 2007005676 A2 WO2007005676 A2 WO 2007005676A2
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silica
group
amide
block
alkyl
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WO2007005676A3 (fr
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Lubin Luo
John Y. Lee
Steven P. Diefenbach
Samuel A. Sangokoya
Christopher G. Bauch
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Albemarle Corp
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Albemarle Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/062—Al linked exclusively to C
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/11—Compounds covalently bound to a solid support
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • metallocene catalysts for olefin polymerization has provided abundant opportunities for designing the active catalytic sites, in an effort to tailor the properties of the resulting polyolefin.
  • Conventional metallocene catalysts typically employ an early transition metal compound, particularly of titanium, zirconium, or hafnium (Group 4), comprising one or two ⁇ 5 - cycloalkanedienyl groups, such as cyclopentadienyl, indenyl, or fluorenyl ligands.
  • methylaluminoxane MAO
  • This resulting catalyst is generally considered homogenous, because at least a portion of the metallocene-organoaluminoxane catalyst system is soluble in the olefin polymerization media. While some advantages are associated with homogeneous systems, several disadvantages also surround their use, such as the small particle size and low bulk density of the resulting polymer, processing problems under slurry polymerization conditions, and the large excess of expensive MAO that is typically required to form the active metallocene catalyst.
  • Supported or heterogeneous catalysts feature several advantages over an analogous homogenous catalyst system and are typically required for most modern commercial polymerization processes. For example, heterogeneous catalysts often promote the formation of substantially uniform polymer particles with a high bulk density, features that are desirable for efficient polymer production. Such catalysts may also be more suited for use in a slurry type polymerization process. Supported metallocene compounds also usually require reaction with an activator compound or composition to convert them into effective olefin polymerization catalysts. [0004] Recent catalyst design efforts toward producing practical heterogeneous metallocene catalysts have centered largely around altering the metallocene precursor.
  • activator compounds, compositions, and methods directed to providing low-cost, supported metallocene-type polymerization catalysts that still exhibit the desired level of activity for polymerizing olefins.
  • activator compounds and compositions would also be suitable for activating a range of transition metal based catalyst precursors other than metallocenes.
  • the present invention meets the above-described needs by providing activator compositions comprising a metal oxide support, an aluminate anion, and a Br ⁇ nsted acidic cation.
  • the aluminum atom of the aluminate anion is covalently bonded to the support through two chelating oxygen atoms on the support, and is also coordinated with at least one bulky functional ligand (as defined herein).
  • the activator aluminate anion is also ionically bonded to an acidic proton.
  • the present invention further provides activator compositions derived from at least: a) metal oxide support having at least one surface hydrogen-bonded hydroxyl group; and b) organoaluminum compound comprising an alkoxide, an aryloxide, an alkyl amide, an aryl amide, an alkyl aryl amide, a dialkyl amide, a diaryl amide, an alkyl thiolate, or an aryl thiolate; wherein the metal oxide support and the organoaluminum compound are combined in amounts sufficient and under contact conditions sufficient to form at least one aluminate anion that is covalently bonded to the metal oxide support through two chelating oxygen atoms and ionically bonded to a H + .
  • the present invention further provides activator compositions comprising [(support)(-0-) 2 Al(ER 3 ) n (R 2 ) 2 . n ]-[H] + or [(support)(-0-) 2 Al(ER 3 ) n (R 2 ) 2 .
  • the support comprises silica, n is 1 or 2, R 2 is hydrogen or a hydrocarbyl ligand having up to about 20 carbon atoms, R 3 is a hydrocarbyl group or a silyl group, each said group having up to about 20 carbon atoms, E is O, S, or NR 4 , wherein (i) R 4 is (a) hydrogen or (b) a hydrocarbyl group or a silyl group, each said group having up to about 10 carbon atoms, or (ii) R 3 and R 4 together form a heterocyclic group having up to about 20 carbon atoms, and Q is a Lewis base.
  • Such activator compositions can also comprise [(support)(-O-)Al(ER 3 ) n (R 2 ) 3 . n ] ' [H] + or [(su P port)(-0-)Al(ER 3 ) n (R 2 ) 3 . n ]-[QH] +
  • FIG. 1 illustrates the infrared (IR) spectra of the OH stretching region of Silica I after (a) calcining at 15O 0 C (spectrum 10), (b) calcining at 600 0 C (spectrum 12), (c) calcining at 800 0 C (spectrum 14), and (d) calcining at 600 0 C followed by treatment of the silica with an excess of PhCH 2 MgCl (spectrum 16).
  • IR infrared
  • FIG. 2 illustrates the infrared (IR) spectra of the OH stretching region of Silica I (a) calcined at 600 0 C (spectrum 20) (b) calcined at 600°C and then reacted withlO mol% DBAB based on the OH concentration on the silica (spectrum 22), (c) calcined at 600 0 C and then reacted with 50 mol% DBAB based on the OH concentration on the silica (spectrum 24), and (d) calcined at 600 0 C and then reacted with 95 mol% DBAB based on the OH concentration on the silica (spectrum 26).
  • FIG. 1 illustrates the infrared
  • IR infrared
  • DBAB infrared spectra of the OH stretching region of Silica I calcined at 600 0 C after the following different treatments: (a) treatment with DBAB based on a molar ratio of A1:OH of 1 :0.95 (spectrum 30); (b) treatment with DBAB followed by treatment with rac-dimethylsilylbis(2-methyl-4-phenyl-indenyl) zirconium dimethyl (Ml) with a ZnOH molar ratio of 220 mol% based on the mmole OH after DBAB treatment (spectrum 32); and (c) treatment with excess BzMgCl (benzyl magnesium chloride) (spectrum 34).
  • IR infrared
  • FIG. 4 compares the infrared (IR) spectra of the OH stretching regions of Silica I calcined at SOO 0 C: (a) before BAM treatment (spectrum 40); (b) after BAM treatment (spectrum 42); and (c) after treatment with excess BzMgCl (benzyl magnesium chloride) (spectrum 44).
  • IR infrared
  • the activators and catalysts of this invention comprise compositions that are supported on a metal oxide support that comprises at least one surface hydrogen-bonded hydroxyl group.
  • This metal oxide support comprises silica, alumina, silica-alumina, or one or more clays.
  • this metal oxide support comprises silica.
  • any type silica containing hydrogen-bonded hydroxyl groups can be used, including, but not limited to, the commercial silicas described in the Examples as Silica I, Silica II, or a combination thereof.
  • the uncalcined silica is observed to contain three basic types of "active" OH groups, referred to herein as free OH (B), hydrogen-bonded (H-bonded) OH (C), and H 2 O-coordinated OH (X), structures of which are illustrated below along with the fingerprint IR resonances for each type of OH group (in cm '1 ). Most of these active OH groups react readily with benzylmagnesium chloride Grignard to produce toluene, and this reaction can be used to quantify the concentration of active OH groups on a particular silica.
  • the H-bonded OH (C) (a surface hydrogen-bonded hydroxyl group) can arise when two silica Si-OH groups are contiguous or neighboring, such that O-( ⁇ -H)-O type H-bonding can form between the two groups.
  • some free and some hydrogen-bonded hydroxyl groups are more inert and do not react with the Grignard reagent C 6 H 5 CH 2 MgCl (also abbreviated PhCH 2 MgCl or BzMgCl), aluminum alkyls, or d-block metal or f-block metal dialkyls. While not intending to be bound by theory, it is believed that these inert OH groups are likely either to be hidden under the surface of the silica or in very narrow pore sites and cannot be accessed using any of these aforementioned reagents. Examples of each of these OH groups, both active and inert, are illustrated by the infrared (IR) resonances shown in FIG.
  • IR infrared
  • FIG. 1 illustrates the IR spectra of the OH stretching region of Silica I: (a) after calcining at 15O 0 C (spectrum 10), (b) after calcining at 600 0 C (spectrum 12), (c) after calcining at 800 0 C (spectrum 14); and (d) after calcining at 600 0 C followed by treatment of the silica with an excess of PhCH 2 MgCl (spectrum 16).
  • an OH group does not react with a Grignard reagent such as B2MgCl, it usually also does not react with a dialkyl catalyst precursor (such as rac-dimethylsilylbis(2-methyl-4-phenyl- indenyl)zirconium dimethyl (Ml)) either.
  • a dialkyl catalyst precursor such as rac-dimethylsilylbis(2-methyl-4-phenyl- indenyl)zirconium dimethyl (Ml)
  • useful metal oxide supports for the activators and catalysts disclosed herein retain significant concentrations or amounts of adjacent or neighboring, hydrogen- bonded hydroxyl groups on the surface, such as illustrated in structure C above, after any calcining treatment.
  • Such structures are possible in a range of support materials.
  • support materials which are useful in the present invention include silica and silica containing metal oxides which are available, for example, as silica particles, silica gels, glass beads, and the like.
  • the silica used in this invention is porous and typically has a surface area in the range of from about 10 to about 700 m 2 /g, a total pore volume in the range of from about 0.1 to about 4.0 cc/g, and an average particle diameter in the range of from about 10 to about 500 ⁇ m.
  • the silica used in this invention has a surface area in the range of from about 50 to about 500 m 2 /g, a pore volume in the range of from about 0.5 to about 3.5 cc/g, and an average particle diameter in the range of from about 15 to about 150 ⁇ m.
  • the silica used herein has a surface area in the range of from about 200 to about 350 m 2 /g, a pore volume in the range of from about 1.0 to about 2.0 cc/g, and an average particle diameter in the range of from about 10 to about 110 ⁇ m.
  • an average pore diameter of a typical porous silicon dioxide support materials is in the range of from about 10 A to about 1000 A, and in yet another aspect, from about 50 A to about 500 A, or from about 175 to about 350 A.
  • the most useful activators were prepared and calcined such that the support contained significant concentrations or amounts of adjacent, or hydrogen bonded, hydroxyl groups on the surface in order to form the ion-pairs comprising of a siloxyl group chelated aluminate anion and a proton cation.
  • the typical content of adjacent or hydrogen-bonded hydroxyl groups was from about 0.04 to about 3.0 mmol OH/g silica, with or without the presence of free hydroxyl groups, as determined by the Grignard method disclosed herein. In another aspect, the typical content of adjacent or hydrogen-bonded hydroxyl groups was from about 0.10 to about 2.0 mmol OH/g silica, or from about 0.4 to about 1.5 mmol OH/g silica.
  • the support material can also be an inorganic oxide, a covalently bonded metal or metalloid oxide, polymeric support, or any combination thereof.
  • the metal or metalloid oxide supports that can be useful in the present invention typically have surface hydroxyl groups exhibiting a pK a equal to or less than that observed for amorphous silica, namely, a pK a less than or equal to about 11.
  • Any of the conventionally known inorganic oxides, silica, or any other support materials that retain reactive hydroxyl groups, particularly after dehydration treatment, will be suitable as support materials in accordance with this invention.
  • These supporting material should contain adjacent (hydrogen bonded) hydroxyl groups as disclosed herein.
  • the metal oxide compositions can additionally contain oxides of other metals such as Al, K, Mg, Na, Si, Ti or Zr, which can be treated by thermal means, chemical means, or both to remove water and free oxygen.
  • Such treatments can be conducted in various ways, for example, in a vacuum, in a heated oven, in a heated fluidized bed, or with dehydrating agents such as organo silanes, siloxanes, alkyl aluminum compounds, and the like.
  • the extent of treatment should be such that as much retained moisture and oxygen as possible is removed, but that a significant amount of hydroxyl functionality is retained such that hydrogen-bonded hydroxyl groups remain in the support material.
  • calcining these materials up to 800 0 C or even higher, up to a point just below the decomposition temperature of the support material, for several hours should be permissible. If higher loading of a supported anionic activator is desired, lower calcining temperatures for shorter times should be suitable.
  • loadings to achieve from less than about 0.1 mmol to about 3.0 mmol activator/g SiO 2 are typically suitable and can be achieved, for example, by varying the temperature of calcining from abut 200°C to about 1200 0 C.
  • the calcining temperature can also vary from about 400 0 C to 1000°C, or from about 500 0 C to 900 0 C.
  • the support can be calcined at a temperature below about 700 0 C. After calcination, the most useful support materials will retain significant concentrations or amounts of adjacent, hydrogen-bonded hydroxyl groups on the surface in order to form the ion-pairs consisting of a siloxyl group chelated aluminate anion and a proton cation through the two hydrogen-bonded hydroxyl groups.
  • Organoaluminum compounds that are particularly useful in this invention comprise at least one bulky functional ligand (as defined herein).
  • One example process for preparation of an organoaluminum compound comprising at least one bulky functional ligand is by coordinating one or two bulky functional ligands, such as an aryloxide like 2,6-di-t-butyl-4-methylphenoxide, to an organoaluminum compound that also has one or two hydrocarbyl ligands. For example, upon reacting the following components:
  • each R 2 is independently a hydrocarbyl group having up to about 20 carbon atoms or hydrogen;
  • R 3 is a hydrocarbyl group or a silyl group, each said group having up to about 20 carbon atoms;
  • E is O, S, or NR 4 , wherein (i) R 4 is (a) hydrogen or (b) a hydrocarbyl group or a silyl group, each said group having up to about 10 carbon atoms, or (ii) R 3 and R 4 together form a heterocyclic group having up to about 20 carbon atoms; either one or two of the hydrocarbyl groups of A1R 2 3 undergo protonolysis to form the organoaluminum compound R 2 3 . n Al(ER 3 ) n wherein n is 1 or 2.
  • the by-product from this reaction is 1 or 2 molar equivalents of the corresponding hydrocarbon by-product HR 2 , as indicated in Reaction (2).
  • the molar ratio of PIER 3 to aluminum that are useful in Reaction (2) can vary to a considerable extent, but it typically spans the range from about 0.5 to about 2.5.
  • the molar ratio of HER 3 to aluminum can also be from about 1 to about 2. Typically, in the usual reaction, a slight molar excess of HER 3 is used to drive the reaction to completion.
  • each hydrocarbyl group R 2 of A1R 2 3 is typically an alkyl or cycloalkyl group and in another aspect, typically has from 1 to about 20 carbon atoms.
  • Each hydrocarbyl group R 2 can also have from 1 to about 12 carbon atoms, from 1 to about 8 carbon atoms, or from about 2 to about 6 carbon atoms.
  • Useful hydrocarbyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, hexyl, heptyl, and octyl.
  • Each hydrocarbyl group can be cyclic (for example, cycloalkyl, alkyl-substituted cycloalkyl, or cycloalkyl-substituted alkyl groups) or acyclic, and each group can be a linear or a branched alkyl group.
  • each alkyl group of a trialkylaluminum compound is a primary alkyl group, that is, the alpha-carbon atom of each alkyl group is bonded to two hydrogen atoms.
  • Suitable organoaluminum compounds that can be used to form suitable organoaluminum compound reactants of this invention include, but are not limited to, aluminum trialkyls as well as dialkylaluminum hydrides.
  • Examples of trialkylaluminum compounds which can be used in this invention include, but are not limited to, trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tripentylaluminum, trihexylaluminum, triheptylaluminum, trioctylaluminum, and their higher straight chain homologs; triisoburylaluminum, tris(2,4,4-trimethylpentyl)aluminum, tri-2- ethylhexylaluminum, tris(2,4,4,6,6-pentamethylheptyl)aluminum, tris(2-butyloctyl)aluminum, tris(2- hexyldecyl
  • dialkylaluminum hydrides examples include, but are not limited to, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, di(2,4,4-trimethylpentyl)aluminurn hydride, di(2-ethylhexyl)aluminum hydride, di(2-butyloctyl)aluminum hydride, di(2,4,4,6,6-pentamethylheptyl)aluminum hydride, di(2- hexyldecyl)aluminum hydride, dicyclopropylcarbinylaluminum hydride, dicyclohexylaluminum hydride, dicyclopentylcarbinylaluminum hydride, and analogous dialkylaluminum hydrides.
  • triisobutylaluminum, triethylaluminum, and trimethylaluminum are useful organoaluminum compounds.
  • the useful organoaluminum compounds include, but are not limited to, A1R 2 3 , wherein R 2 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-hexyl, n-heptyl, and n-octyl. Most of the examples provided herein utilize A1R 2 3 , wherein R 2 is selected from methyl, ethyl, and isobutyl.
  • the organoaluminum compound is reacted with a compound having the formula HER 3 , wherein R 3 is a hydrocarbyl group having up to about 20 carbon atoms, and E is O, S, or NR 4 , as defined herein.
  • R 3 is a hydrocarbyl group having up to about 20 carbon atoms
  • E is O, S, or NR 4 , as defined herein.
  • a bulky functional ligand ER 3 is derived from 2,6-di-t-butyl-4-methylphenol (BHT), shown schematically in Reaction (2) as forming BHT-modified organoaluminum compounds.
  • the bulky functional ligand is not limited to alkoxide or aryloxide ligands, as this invention also encompasses organoaluminum compounds wherein the aluminum atom is covalently bonded to at least one bulky functional ligand selected from an alkoxide, an aryloxide, an alkyl amide, an aryl amide, an alkyl aryl amide, a dialkyl amide, a diaryl amide, an alkyl thiolate, and an aryl thiolate, and typically having up to about 20 carbon atoms.
  • the bulky functional ligand ER 3 can have up to about 20 carbon atoms, bulky functional ligands up to about 30 carbon atoms, or up to about 60 carbon atoms also work well.
  • R 4 is hydrogen or a hydrocarbyl group having up to about 10 carbon atoms, or R 3 and R 4 together form a heterocyclic group having up to about 20 carbon atoms. Examples of a suitable heterocyclic group include, but
  • the compound having the formula HER 3 used to form the ER 3 ligand of the organoaluminum compound provides a functional atom E such as O, S, or N and the bulky group R 3 such as 2,6- 1 Bu 2 ⁇ -Me-CsH 2 -. Because the usually synthetic method to prepare an ER 3 ligand on R 2 3 . n Al(ER 3 ) n involves the reaction of HER 3 with A1R 2 3, the term ligand can be used interchangeably to refer to either HER 3 or ER 3 .
  • the bulky ER 3 ligand is typically selected from an alkoxide, an aryloxide, an alkyl amide, an aryl amide, an alkyl aryl amide, a dialkyl amide, a diaryl amide, an alkyl thiolate, and an aryl thiolate, having up to about 20 carbon atoms.
  • Examples of ER 3 that are useful in this invention include, but are not limited
  • the bulky HER 3 or ER 3 ligand can be a halogenated or a non-halogenated ligand. Further, the bulky HER 3 or ER 3 ligand can be a fluorinated or a non-fluorinated ligand.
  • this invention also provides for the preparation of suitable organoaluminum compounds A1R 2 2 (ER 3 ) by means other than the protonolysis reaction of A1R 2 3 and HER 3 , for example, from a simple metathesis reaction.
  • A1R 2 2 C1 and M'ER 3 are precursors to the desired compound, and where M' can be a metal ion such as Li + , Na + , K + , 0.5 Mg 2+ , and the like.
  • This invention also encompasses preparation of activator compositions by contacting a suitable organoaluminum compound R 2 3-n Al(ER 3 ) n with a hydroxylated support such as silica.
  • a suitable organoaluminum compound R 2 3-n Al(ER 3 ) n with a hydroxylated support such as silica.
  • these reactions appear to involve coordination of the bulky R 2 3 . n Al(ER 3 ) n with a surface hydroxyl group, to afford a moiety of the type [(support)(- ⁇ -OH- )Al(ER 3 ) n (R 2 ) 3 . n ] or [(support)(-O-)Al(ER 3 ) n (R 2 ) 3 .
  • organoaluminum moiety R 2 3- n Al(ER 3 ) n is bonded to the support through one oxygen group, and can be characterized as an aluminate ion to which an active proton is ionically bonded. Based on the reactivity of the organoaluminum compound R 2 3 .
  • the more stable ⁇ active species [(support)(- ⁇ -OH-)(-O-)Al(ER 3 ) n (R 2 ) 2 - n ], which can be alternatively depicted by the formula [(support)(-O-) 2 Al(ER 3 ) n (R 2 ) 2 - n ] " [H] + , can only form when the neutral aluminum compound has a neighboring OH that can coordinate to the aluminum center thus to form an aluminate covale ⁇ tly bonded to the support through two chelating oxygen atoms on the support and ionically bonded to an active proton.
  • each Al-R in the -AlR 3 moiety (primary aluminum alkyl, an Al center contains three Al-C sigma bonds) > each Al-R in the -AlR 2 moiety (secondary aluminum alkyl, an Al center contains two Al-C sigma bonds) > Al-R in the -AlR moiety (tertiary aluminum alkyl, an Al center contains one Al-C sigma bond), wherein ">" means "more reactive than.”
  • This invention also encompasses preparation of a supported activator composition by contacting the organoaluminum compound R 2 3 . n Al(ER 3 ) n with a hydroxylated support such as silica. This reaction appears to proceed by protonolysis of either an R 2 group or an ER 3 group (such as BHT) on R 2 3 . n Al(ER 3 ) n with a surface hydroxyl, to form a supported aluminum compound wherein the aluminum atom is bonded to the support through oxygen groups.
  • (BHT)Al(i-Bu) 2 (DBAB) with Silica I was examined. The experiments and data discussed here and in the Examples provide a detailed disclosure for how to make and use this invention.
  • Both Schemes 1 and 2 illustrate reactions of DBAB with equimolar amounts of surface OH groups, and both schemes produce inactive bound aluminum sites D, E, D' and E', as shown.
  • an excess of H-bonded OH (C) groups relative to DBAB (A) are employed, to construct active species F illustrated in Scheme 3.
  • Compound F is illustrated in Scheme 3 as comprising a supported aluminate anion wherein the 4-coordinate aluminum atom is bonded to the support through two chelating oxygen atoms on the support, and an acidic proton that originated from a surface hydroxyl is ionically bonded to the aluminate ion.
  • An alternative to the aluminate-ionically bonded proton depiction for compound F is a silica-O-Al(BHT)(i-Bu) moiety that is coordinated by a neighboring surface hydroxyl group, although the difference between these two alternative descriptions is likely more formal than real, especially because there is likely more than one pathway by which compound F can arise.
  • Computational modeling studies suggest that a proton hydrogen bonded to both bridging oxygen atoms of a structure such as F is not favored.
  • active species H' might exist in low concentrations, but it is likely to be a short-lived species (as indicated by *), because of a secondary alkyl in Al- 1 Bu group adjacent to an active proton that would be expected to readily undergo alkane elimination to produce a more stable species H.
  • the tertiary Al-R bond in the -AlR moiety (tertiary) is much less reactive than the corresponding secondary and primary.
  • the reaction stoichiometry indicates that even if compound H was generated in the reaction of DBAB with silica, it eventually reacted with the previously produced free BHT (G) to form F.
  • the Silica I that has been calcined at 600 0 C is commonly employed in this invention and contains a significant amount of H-bonded OH (C) needed for the construction of the active species F, as illustrated in Scheme 3.
  • the Silica I calcined at 15O 0 C is not as useful because it retains a significant amount of coordinated water in the form of H 2 0-coordinated OH (X), which complicated the reaction with DBAB and a metallocene, and reduced the productivity (See Table 4, Entry 1 vs. Entry 2).
  • Silica I calcined at 800 0 C is also not as useful because the content of the surface hydroxyl groups most utilized for forming the active site with DBAB, H-bonded OH (C), was too low, which also reduced the productivities because H-bonded OH was not enough to construct the active sites (See Table 4, Entry 2 vs. Entry 3 and Table 6). Silica I calcined at 800 0 C contains mainly isolated OH ( Figure 1, Spectrum 14). Although a substoichiometric charge of DBAB to OH allowed excess OH groups, these excess OH groups were mainly isolated and could not form an active species since there was no aluminum compound nearby to construct the active species F. These isolated OH groups may form inactive species with metallocene.
  • IR infrared
  • the OH content on the silica is observed to decrease in an amount corresponding to the amount of DBAB used to treat the silica.
  • free BHT was also observed at the beginning of the reactions, it subsequently reacted with the aluminum alkyl (for example, compound H') on silica to release a stoichiometric amount of isobutane.
  • Example 11 and Table 7 also examines the reaction by-products resulting from the treatment of600°C calcined Silica I with different amounts of DBAB and for different reaction times, in order to determine stiochiometries of the by-products and identify kinetic versus thermodynamic products.
  • Scheme 4 considers possible new OH structures formed when H-bonded OH (C) sites are in excess over DBAB reactant. Because the IR spectrum (FIG. 2, spectrum 26) does not exhibit a sharp peak related to free OH (B), the combination of E + B in Scheme 4 can be excluded. In comparing J and F, it is expected that F is much more stable than J because, among other reasons: (a) the additional Al-O bond in F is much stronger than the H-O bond in J; (b) F comprises a more stable four-coordinate aluminate species, whereas J comprises a less stable three-coordinate Al compound; and (c) the possible ionization energy for F can also gain extra stability. Therefore even if J forms as a kinetic product in Scheme 4, it should eventually be converted to more stable F, therefore F is the only favored species formed.
  • F-type sites appear to have different structures that are observed to exhibit a range of activities toward different d-block and f-block metal alkyl compounds.
  • the OH species (activator F) with stretching frequencies at 3690 cm '1 (FIG. 3, spectrum 30) was observed to partially react with a metallocene dialkyl compound 7Yzc-dimethylsilylbis(2-inethyl-4-phenyl-indenyl) zirconium dimethyl (Ml), even though Ml was present in 10 mol% excess based on OH (FIG. 3, spectrum 32).
  • one aspect of this invention involves matching the OH number with a catalyst precursor to optimize the catalyst activity.
  • Example 7 examines the propylene polymerization results obtained from using rac-dimethylsilylbis(2-methyl-4-phenyl-indenyl)zirconium dimethyl (Ml)-derived, DBAB-treated silica supported catalysts, in which parameters are varied such as the DBAB charge used, and the charges of metallocene Ml, and the type silica. The results of these tests are provided in Table 4. [0049] Table 4 (Entries 1, 2 and 3) and Example 7 indicate that, under identical DBAB/OH ratios and metallocene/OH ratios, higher activities were obtained for silica calcined at 600 0 C.
  • This invention encompasses, among other things, the preparation of a supported activator composition by contacting the functionalized bulky organoaluminum compound R 2 3 . n Al(ER 3 ) n with a hydroxylated support such as silica.
  • a hydroxylated support such as silica.
  • the functionalized bulky organoaluminum compounds BAM and DBAB exhibit different reactivities toward a given active proton due to their structural differences between these compounds based on their steric and electronic distinctions.
  • DBAB can react with a free BHT to produce a BAM analog under ambient conditions, as illustrated in reaction 5.
  • BAM is less reactive to an active proton and structurally has more bulky groups than DBAB, somewhat different reactions occur for BAM with active protons on silica.
  • the reaction of BAM with OH on silica is slower when comparing to the reaction of DBAB with OH on silica, although similar aluminum structures result, namely, neutral aluminum compounds along with chelated bulky aluminate-proton ion pair structures.
  • the reaction with OH on silica requires an excess of BAM relative to the moles of OH on silica to obtain desired OH residue to construct the active site.
  • the moles of residual active protons (OH groups) on silica after BAM treatment should roughly match the moles of metallocene to minimize deactivation resulting from excess active protons reacting with the second alkyl group on a metallocene dialkyl.
  • the reaction of a metallocene dialkyl with a first active proton produces a monoalkyl metallocene cation, the active species, and reaction of this species with a second active proton deactivates the catalyst.
  • reaction mechanisms for contacting BAM with the active OH on silica are illustrated in four different schemes, as follows: 1) reaction of BAM with free OH (B) is provided in Scheme 5; and 2) the reaction of BAM with H-bonded OH (C) is illustrated in Schemes 6 and 7.
  • One common theme observed in these reaction schemes is the loss of isobutene from one of the t-butyl groups of the BHT ligand, a reaction catalyzed by active protons.
  • catalysts derived from contacting a molar deficiency of BAM with active OH on silica resulted in lower polymer productivities.
  • this invention provides for the preparation and use of silica-supported aluminate activators comprising bulky functional ligands other than DBAB and BAM coordinated to the aluminum atom.
  • the organoaluminum compound is reacted with a bulky compound having the formula HER 3 , wherein R 3 is a hydrocarbyl group or a silyl group, each said group having up to about 20 carbon atoms, and E is O, S, or NR 4 , as defined herein.
  • the bulky functional ligand is selected from an alkoxide, an aryloxide, an alkyl amide, an aryl amide, an alkyl aryl amide, a dialkyl amide, a diaryl amide, an alkyl thiolate, and an aryl thiolate, and typically having up to about 20 carbon atoms.
  • R 4 is hydrogen or a hydrocarbyl group having up to about 10 carbon atoms, or R 3 and R 4 together form a heterocyclic group having up to about 20 carbon atoms. Examples of a suitable
  • heterocyclic group include, but are not limited to, ' , Y I , and the like.
  • the silica-supported aluminate-proton ion-pair can comprise a carbazole amide ligand.
  • carbazole C J2 H 9 N (9-azafluorene or dibenzopyrrole) was reacted with TIBA to provide an amide compound (Ci 2 H 8 N)Al(I-Bu) 2 , which is an amide analog of DBAB.
  • the amide compound (Ci 2 H 8 N)Al(I-Bu) 2 was supported on Silica I in a manner analogous to that disclosed for the DBAB, which was observed to activate the metallocene Ml toward polymerization of propylene.
  • this invention encompasses metal oxide-supported, Br ⁇ nsted acidic, bulky aluminate activators, in which the aluminate is ionically bonded to a moiety comprising an active proton that imparts the Br ⁇ nsted acidity to the activator composition.
  • the Br ⁇ nsted acidic moiety typically is a proton or a Br ⁇ nsted acidic cation having the formula [QH] + , wherein Q is a Lewis base.
  • [QH] + can be an ammonium-type ion arising from using an amine as the Lewis Base Q.
  • ammonium ion or ammonium-type ion are intended to encompass primary, secondary, or tertiary ammonium ions, as the context allows or requires.
  • the activator of this invention comprises an aluminate ion ionically bonded to an ammonium ion
  • n Al(ER 3 ) n to form an activator, followed by contacting the activator with an amine, termed "post-treatment" of the support or activator with an amine; or 3) by the simultaneous treatment of the hydroxylated support with an amine and a suitable organoaluminum compound R 2 3 .
  • n Al(ER 3 ) n It is expected that different methods can work better with some combinations of hydroxylated support, R 2 3 . n Al(ER 3 ) n and amine. Typically the first method works well and has been employed herein across a wide range of components.
  • the Lewis base Q can be a primary, secondary, or tertiary amine NR ! 3 , or any combination thereof, wherein R 1 in each occurrence is selected independently from a hydrocarbyl group having up to about 20 carbon atoms, or hydrogen.
  • Q can be selected from a variety of amines, including, but not limited to, NMe 2 Ph, NMe 2 (CH 2 Ph), NEt 2 Ph, and NEt 2 (CH 2 Ph), or Q can be selected from a range of long chain amines having a general formulas such as NMe(C n H 2n+ i)(C m H 2m 4-i), NMe 2 (C n H 2n+ i), NEt(C n H 2n+ i)(C m H 2m+ i), and NEt 2 (C n H 2n+ 0, wherein n and m are selected independently from an integer from about 3 to about 20.
  • Examples of long chain amines of the formula NMe(C n H 2n+1 )(C 1n H 21n+1 ) include, but are not limited to, compounds such as NMe(C i 6 H 33 )2, NMe(C 17 H 35 ) 2 , NMe(C 18 H 37 ),, NMe(C 16 H 33 )(C 17 H 35 ), NMe(C 16 H 33 )(C 18 H 37 ), NMe(C 17 H 35 )(C 18 H 37 ), and the like, including any combination thereof.
  • NMe(C 16 H 33 ) 2 is typically the major species in a commercial long chain amine composition which usually comprises a mixture of several amines.
  • the Lewis base typically comprises NMe 2 Ph, NMe 2 (CH 2 Ph), NEt 2 Ph, NEt 2 (CH 2 Ph), or NMe(C 16 H 3 S) 2 .
  • a Lewis base When a Lewis base is employed, it is expected that the base interacts with an active proton situated either on the support itself (pre-treatment) or on the R 2 3 . n Al(ER 3 ) n -treated support (post- treatment), because the active proton is bonded to an oxygen atom.
  • Any Lewis base such as an amine can be used that interacts with at least some of with an active proton, for example, by coordination, hydrogen-bonding, deprotonation, or the like.
  • this invention encompasses an activator composition
  • an activator composition comprising the contact product of: a) a metal oxide support comprising surface hydrogen-bonded hydroxyl groups; b) an organoaluminum compound having at least one bulky functional ligand, which typically comprises an alkoxide, an aryloxide, an alkyl amide, an aryl amide, an alkyl aryl amide, a dialkyl amide, a diaryl amide, an alkyl thiolate, or an aryl thiolate; and c) optionally, a Lewis base Q such as an amine; wherein the metal oxide support, the organoaluminum compound, and the optional Lewis base are contacted in amounts sufficient and under contact conditions sufficient to form at least one aluminate anion covalently bonded to the metal oxide support through two chelating oxygen atoms on the support and ionically bonded to a Br ⁇ nsted acidic cation selected from H + and [QH] + , where [
  • ammonium ion or ammonium-type ion is not intended to limit the bonding or interaction to a particular type, as this terminology is used regardless of whether the amine coordinates, hydrogen-bonds to, deprotonates, deprotonates and ionically-bonds to, deprotonates and ion pairs with, ionically bonds to, or interacts in some other manner with the active proton of the support or the treated support.
  • an amine-treated support or activator when characterized as comprising the contact products of its precursors, these components are contacted in amounts sufficient and under conditions sufficient to form a composition wherein the active proton and Lewis base interact according to any of these interactions listed, which can be formally described as forming a composition comprising at least one aluminate anion and at least one Br ⁇ nsted acidic cation of the formula [QH] + .
  • the Q: Al ratio employed is calculated on the basis of the moles of active OH present in the calcined support or the activator composition, such that an approximately equimolar base (Q):active OH (active proton) ratio is achieved.
  • the molar ratio of Qractive OH can span a range from about 0 to about 1.5.
  • the molar ratio of Q: active OH can also span a range from about 0 to about 1, from about 0.1 to about 1, or from about 0.5 to about 1.
  • Metallocene and non-metallocene single-site catalyst precursors suitable for activation by activator compositions of this invention, can comprise one or more alkylated transition metal component having olefin polymerization potential.
  • the alkyl ligand of the precursor functions as a leaving group upon reaction of the precursor with the proton of the Bronsted acid of the activator composition.
  • hydrocarbyl is a suitable alkylated transition metal ligand.
  • suitable alkylation agent is provided in situ, halogen, alkoxy, aryloxy, and amide transition metal components are all suitable.
  • Catalyst precursors can comprise catalyst precursor ML a X n . a ..
  • M represents any transition metal catalyst compound in which the transition metal thereof is in Group 3 to 10, or in the lanthanide or actinide series, of the Periodic Table of Elements using the new IUPAC format, for example, the Periodic Table appearing on page 27 of the February 4, 1985 issue of Chemical & Engineering News.
  • Suitable catalyst compounds can also be described as d- and f- block metal compounds. See, for example, the Periodic Table appearing on page 225 of Moeller, et al., Chemistry, Second Edition, Academic Press, copyright 1984.
  • Metal constituent of M may comprise Fe, Co, Ni, and Pd, and may comprise metals of Groups 4-6 (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W.
  • catalyst precursors used in this invention can be one or more of any Ziegler-Natta catalyst compound, any metallocene, any single-site non-metallocene, any compound of constrained geometry, any late transition metal complex, and any other transition metal compound or complex reported in the literature or otherwise generally known in the art to be an effective catalyst compound when suitably activated, including mixtures of at least two different types of such transition metal compounds or complexes, such as for example a mixture of a metallocene and a Ziegler-Natta olefin polymerization catalyst compound.
  • L represents group having ligand suitable for either Ziegler-Natta type catalyst precursor, or metallocene type catalyst precursor, or non-metallocene single-site catalyst precursor. At least one L may be group having cyclopentadienyl skeleton, or may be non-cyclopentdienyl; and a plurality of L may be the same or different and may be crosslinked to each other;
  • X represents halogen, alkoxy, aryloxy, amide or hydrocarbyl group having 1 to about 20 carbon atoms; "a" represents a numeral satisfying the expression 0 ⁇ a ⁇ n; and n represents valence of transition metal atom M.
  • group having cyclopentadienyl skeleton can comprise, for example, cyclopentadienyl group, substituted cyclopentadienyl group or polycyclic group having cyclopentadienyl skeleton.
  • Example substituted cyclopentadienyl groups include hydrocarbon group having 1 to about 20 carbon atoms, halogenated hydrocarbon group having 1 to about 20 carbon atoms, silyl group having 1 to about 20 carbon atoms and the like.
  • Silyl group according to this invention can include SiMe 3 and the like.
  • Examples of polycyclic group having cyclopentadienyl skeleton include indenyl group, fluorenyl group and the like.
  • Examples of hetero atoms of the group having at least one hetero atom include nitrogen atom, oxygen atom, phosphorous atom, sulfur atom and the like.
  • Example non-metallocene d-block or f-block metal compounds that can be used in this invention include, but are not limited to, transition metal compounds suitable for olefin polymerization such as Ziegler-Natta type catalysts.
  • transition metal of Ziegler-Natta catalysts comprises at least two hydrocarbyl ligands. Examples of Ziegler-Natta catalyst systems are disclosed in U.S. Patent Application Number 2004/0102312, and are described herein as follows.
  • Representative traditional Ziegler-Natta transition metal compounds include, but are not limited to, tetrabenzyl zirconium, tetrakis(trimethylsilylmethyl)zirconium, oxotris(trimethylsilylmethyl)vanadium, tetrabenzyl hafnium, tetrabenzyl titanium, bis(hexamethyl disilazido)dimethyl titanium, tris(trimethylsilylmethyl)niobium dichloride, tris(trimethylsilylmethyl)tantalum dichloride, and combinations thereof.
  • Ziegler-Natta type systems that can be used in this invention include, but are not limited to, transition metal halides, oxyhalides or alkoxyhalides in the presence of an alkylating agent such as a dialkylaluminum alkoxide or trialkyl aluminum compound.
  • Examples of this Ziegler-Natta type system include, but are not limited to, titanium and vanadium halides, oxyhalides or alkoxyhalides, such as titanium tetrachloride (TiCU), vanadium tetrachloride (VCl 4 ) and vanadium oxytrichloride (VOCl 3 ), and titanium and vanadium alkoxides, wherein the alkoxide moiety has a branched or unbranched alkyl group from 1 to 20 carbon atoms, or from 1 to 6 carbon atoms.
  • Any chloride-containing catalyst precursor is suitable once alkylated, including via in-situ alkylation, by methods well-known to those skilled in the art.
  • useful d-block or f-block metal compounds that can be used in this invention include, but are not limited to, the Group 15-containing compounds, such as those disclosed in U.S. Patent Application Number 2004/0102312, and defined above.
  • Examples of Group 15- containing compounds include, but are not limited to, Group 4 imino-phenol complexes, Group 4 bis(amido) complexes, and Group 4 pyridyl-amide complexes that are active towards olefin polymerization to any extent.
  • the Group 15-containing catalyst component can be described by the following formula:
  • ⁇ and ⁇ are groups that each comprise at least one Group 14 to Group 16 atom; and ⁇ (when present) and ⁇ are groups bonded to M through from 1 to 4 Group 14 to Group 16 atoms, wherein at least two atoms are Group 15-containing atoms; more particularly: ⁇ and ⁇ are groups selected from Group 14 and Group 15-containing (and their non-valent equivalents when not linked by a group ⁇ ): alkyls, aryls, alkylaryls, and heterocyclic hydrocarbons, and chemically bonded combinatiqns thereof in one aspect; and selected from Group 14 and Group 15-containing: Ci to Ci O alkyls, C 6 to Cj 2 aryls, C 6 to Ci 8 alkylaryls, and C4to C12 heterocyclic hydrocarbons, and chemically bonded combinations thereof in a further aspect; and selected from C 1 to Ci 0 alkylamines, Ci to C ]0 alkoxys, C 6 to C 20 alkylarylamines, C 6
  • a is typically 0 or 1 ;
  • b is typically an integer from 0 to 2;
  • g is an integer from 1 to 2; wherein in one aspect, a is 1, b is 0, and g is 2;
  • M is selected from Group 3 to Group 12 atoms in one aspect; and selected from Group 3 to Group 10 atoms in a further aspect; and selected from Group 3 to Group 6 atoms in yet another aspect; and selected from Ni, Cr, Ti, Zr and Hf in still a further aspect; and selected from Zr and Hf in yet one other aspect; each X represents halogen, alkoxy, aryloxy, amide or hydrocarbyl group having 1 to about 20 carbon atoms; and n is an integer from 0 to 4 in one aspect; and an integer from 1 to 3 in another aspect; and an integer from 2 to 3 in still another aspect.
  • alkyleneamines As used in this description, “chemically bonded combinations thereof means that adjacent groups, ( ⁇ and ⁇ groups) can form a chemical bond between them; in one aspect, the ⁇ and ⁇ groups are chemically bonded through one or more ⁇ groups therebetween.
  • alkyleneamines As used herein, the terms “alkyleneamines”, “aryleneamines”, describe alkylamines and arylamines (respectively) that are deficient by two hydrogens, thus capable of forming chemical bonds with two adjacent ⁇ groups, or adjacent ⁇ and ⁇ groups.
  • examples of an alkyleneamine include, but are not limited to, -CH 2 CH 2 N(CH 3 )CH 2 CH 2 - and -CH 2 CH 2 N(H)CH 2 CH 2 -.
  • heterocyclic hydrocarbylene or aryleneamine examples include, but are not limited to, -C 5 H 3 N- (divalent pyridine).
  • An "alkylene-arylamine” includes a group such as, for example, - CH 2 CH 2 (C 5 H 3 N)CH 2 CH 2 -.
  • Examples of compounds having the general formula ⁇ b ( ⁇ ) a ⁇ g MX n include, but are not limited to, the following compounds:
  • examples of Ar include 2-MeC 6 H 4 , 2,4,6-Me 3 C 6 H 2 , 2-i-PrC 6 H 4 , and the like; and examples of M include Fe or Ni; and examples of X include Cl, Br, or a Ci to Ci 2 hydrocarbyl;
  • examples of R 2 and R 5 include 2,6-i-Pr 2 C 6 H 3 , 2,6-Me 2 C 6 H 3 , and 2,4,6-Me 3 C 6 H 2 ;
  • examples of R 3 and R 4 include methyl, ethyl, propyl, butyl, and benzyl;
  • examples of M include Pd and Ni;
  • examples of X include Cl, Br, and a Ci to Ci 2 hydrocarbyl such as Me;
  • examples of Ar 1 include 2,6-Me 2 C 6 H 3 and 2,6-J-Pr 2 C 6 H 3 ;
  • examples of Ar 2 include 2,6-Me 2 C 6 H 3 , 2,4,6-Me 3 C 6 H 2 , 2,6-1-Pr 2 C 6 H 3 , and 2,6-Ph 2 C 6 H 3 ;
  • examples of M include V; and
  • examples of X include Cl, Br, and a Ci to C n hydrocarbyl;
  • examples of M include Zr or Hf
  • examples of X include a C] to Ci 2 hydrocarbyl such as CH 2 C 6 H 5
  • examples of R include Me, Ph, or t-Bu
  • examples of D include NMe 2 , OMe, and the like;
  • these metal compounds typically are used in conjunction with an alkylating agent such as a trialkyl aluminum or alkoxyaluminum dialkyl reagent to convert these compounds to the corresponding dialkyl species.
  • an alkylating agent such as a trialkyl aluminum or alkoxyaluminum dialkyl reagent to convert these compounds to the corresponding dialkyl species.
  • Example substituted cyclopentadienyl groups include methylcyclopentadieriyl group, ethylcyclopentadienyl group, n-propylcyclopentadienyl group, n-butylcyclopentadienyl group, isopropylcyclopentadienyl group, isobutylcyclopentadienyl group, sec-butylcyclopentadienyl group, tertbutylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group and the like.
  • Example polycyclic groups having cyclopentadienyl group include indenyl group, 4,5,6,7- tetrahydroindenyl group, fluorenyl group and the like.
  • Example groups having at least one hetero atom include methylamino group, tert-butylamino group, benzylamino group, methoxy group, tert-butoxy group, phenoxy group, pyrrolyl group, thiomethoxy group and the like.
  • One or more groups having cyclopentadienyl skeleton, or one or more group having cyclopentadienyl skeleton and one or more group having at least one hetero atom may be crosslinked with (i) alkylene group such as ethylene, propylene and the like; (ii) substituted alkylene group such as isopropylidene, diphenylmethylene and the like; or (iii) silylene group or substituted silylene group such as dimethylsilylene group, diphenylsilylene group, methylsilylsilylene group and the like.
  • R in transition metal component comprises hydrogen or hydrocarbon group having 1 to about
  • Examples of R include alkyl group having 1 to about 20 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, benzyl group and the like.
  • transition metal component ML a X n -a examples include transition metal component ML a X n -a.
  • M comprises zirconium
  • Additional exemplary transition metal component ML a X n . a include components wherein zirconium is replaced with titanium or hafnium in the above zirconium components.
  • Alkylated catalyst precursors useful in this invention are: 7' ⁇ c-dimethyIsilylbis(2-methyl-4- phenyl-indenyl)zirconium dimethyl; r ⁇ c-dimethylsilylbis(2-methyl-l-indenyl) zirconium dimethyl; rac-dimethylsilylbis(2-methyl-4,5-benzoindenyl) zirconium dimethyl; ethylenebis- (tetrahydroindenyl)zirconium dimethyl, and ethylenebis(indenyl) zirconium dimethyl.
  • Alkylated catalyst precursor can be generated in-situ through reaction of alkylation agent with the halogenated version of the catalyst precursor.
  • alkylation agent for example, bis(cyclopentadienyl)zirconium dichloride can be treated with triisobutylaluminum (TIBA) and then combined with activator composition (A) of this invention.
  • TIBA triisobutylaluminum
  • Additional non-limiting and representative metallocene compounds that can be used in the present invention include mono-cyclopentadienyl compounds such as pentamethylcyclopentadienyl titanium trimethyl, pentamethylcyclopentadienyl titanium tribenzyl, dimethylsilyltetramethyl- cyclopentadienyl-tert-butylamido titanium dimethyl, dimethylsilyltetramethylcyclopentadienyl-tert- butylamido zirconium dimethyl, dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafnium dihydride, dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafnium dimethyl, unbridged biscyclopentadienyl compounds such as bis(l,3-butylmethylcyclopentadienyl) zirconium dimethyl, bis( 1 ,3-butylmethyl
  • this invention provides a catalyst composition comprising a metal oxide support, an aluminate anion, a cationic d-block or f-block metal compound, and optionally a Lewis base, wherein: a) the aluminum atom of the aluminate anion is covalently bonded to the metal oxide support through two chelating oxygen atoms; b) the aluminum atom of the aluminate anion is covalently bonded to at least one bulky functional ligand, which is typically selected from an alkoxide, an aryloxide, an alkyl amide, an aryl amide, an alkyl aryl amide, a dialkyl amide, a diaryl amide, an alkyl thiolate, and an aryl thiolate; c) the aluminate anion is ionically bonded to the cationic d-block or f-block metal compound; d) the cationic d-block or f
  • the cationic d-block or f-block metal compound has the formula [L n M] + when not coordinated by the Lewis base and [L n M-Q] + when coordinated by the Lewis base, wherein: L n comprises any set of ligands on M selected such that [L n M] + is coordinatively unsaturated; and the at least one ligand of [L n M] + capable of propagating olefin polymerization is hydrogen or a hydrocarbyl ligand having up to about 12 carbon atoms.
  • the aluminate species comprising an aluminate anion bonded to the support through one oxygen atom can be present in the activator composition.
  • R 2 is hydrogen or a hydrocarbyl ligand having up to about 20 carbon atoms
  • R 3 is a hydrocarbyl group or a silyl group, each said group having up to about 20 carbon atoms;
  • E is O, S, or NR 4 , wherein (i) R 4 is (a) hydrogen or (b) a hydrocarbyl group or a silyl group, each said group having up to about 10 carbon atoms, or (ii) R 3 and R 4 together form a heterocyclic group having up to about 20 carbon atoms; [L n M] + is a d-block or f-block metal compound cation capable of polymerizing olefins; and
  • Such a catalyst composition can also comprise [(support)(-O-)Al(ER 3 ) n (R 2 ) 3 . n ] " [L n M] + or [(support)(-0-)Al(ER 3 ) n (R 2 ) 3 . n ] " [L n M-Q] + .
  • This aspect of the invention also encompasses a method for polymerizing olefins, comprising contacting at least one olefin monomer with the catalyst composition of this type.
  • this invention provides a catalyst composition
  • a catalyst composition comprising the contact product of: a) a metal oxide support comprising hydrogen bonded surface hydroxyl groups; b) at least one organoaluminum compound having at least one bulky functional ligand, which is typically selected from an alkoxide, an aryloxide, an alkyl amide, an aryl amide, an alkyl aryl amide, a dialkyl amide, a diaryl amide, an alkyl thiolate, and an aryl thiolate; c) optionally, a Lewis base Q; and d) at least one d-block or f-block metal compound comprising at least one ligand subject to protonolysis to form a catalytically-active cationic species; wherein the metal oxide support, the organoaluminum compound, the optional Lewis base, and the d- block or f-block metal compound are contacted in amounts sufficient and under contact conditions sufficient to form at least one aluminate
  • any d-block or f-block metal compound comprising at least one ligand subject to protonolysis to form a catalytically-active cationic species can be termed a catalyst precursor.
  • This disclosure also encompasses a method of preparing a catalyst composition comprising contacting the components recited above.
  • This aspect further encompasses a method for polymerizing olefins, comprising contacting at least one olefin monomer with the catalyst composition of this type.
  • the present invention also encompasses a method of preparing a composition comprising a metallocene cation and a supported, Br ⁇ nsted acidic, bulky aluminate activator comprising contacting the following constituents: a) at least one organoaluminum compound having the formula A1R 2 3 ; b) a compound of the formula HER 3 , c) optionally a Lewis base Q; and d) at least one metallocene comprising at least one leaving group; in amounts sufficient and under conditions sufficient to form a compound comprising an aluminate anion and a metallocene cation [L n M] + .
  • the metallocene and the supported, Br ⁇ nsted acidic, bulky aluminate activator were brought together in a slurry.
  • the temperature of the reaction mixture is kept in the range of about -78 0 C to about 160 0 C, but typically can be in the range of about 20-90 0 C.
  • the reaction is conducted under an inert atmosphere and in an inert environment such as in an anhydrous solvent slurry. Reaction times vary, but the protonation reactions are typically smooth and often proceed to completion within less than 24 hours.
  • Various aspects of the metal oxide support were considered above.
  • contacting the catalyst precursor with the support can be carried in various ways to synthesize a supported catalyst of this invention.
  • the bulky aluminate activator such as BAM-treated or DBAB-treated silica
  • the bulky aluminate activator can be pre-formed and isolated, then contacted with at least one metallocene to form a catalyst.
  • the bulky aluminate activator can be prepared in situ by contacting a suitable organoaluminum compound such as BAM or DBAB with the appropriate silica sample, the bulky aluminate activator then can be isolated and subsequently contacted with at least one catalyst precursor to form a catalyst.
  • the bulky aluminate activator can be prepared in situ and not isolated, by contacting the organoaluminum compound with silica, and then at least one metallocene can be contacted with this mixture to form a catalyst.
  • an ancillary inert solvent typically a hydrocarbon solvent, for example a liquid paraffinic or aromatic hydrocarbon solvent
  • hydrocarbon solvents that can be employed in these polymerizations include, but are not limited to, heptane, isooctane, decane, toluene, xylene, ethylbenzene, mesitylene, mixtures of liquid paraffinic hydrocarbons, mixtures of liquid aromatic hydrocarbons, or any combination thereof.
  • the solid support or carrier can be any suitable particulate solid, and typically comprises a porous support of some type. Examples include, but are not limited to, talc, zeolites, inorganic oxides, resinous support material such as polyolefins, or any combination thereof.
  • the support material is typically an inorganic oxide in finely divided form.
  • Suitable inorganic oxide support materials which can be employed in this invention include metal oxides. Examples of useful metal oxides include, but are not limited to, silica, alumina, silica-alumina, magnesia, titania, zirconia, and the like, and any combination thereof.
  • Other suitable support materials include finely divided polyolefins such as finely divided polyethylene.
  • Polymers can be produced according to the present invention by homopolymerization of polymerizable olefins, typically 1 -olefins ( ⁇ -olefins) such as ethylene, propylene, 1-butene, styrene, and the like.
  • polymers can be produced according to the present invention by co- polymerization of two or more co-polymerizable monomers, at least one of which is typically a 1- olefin.
  • the other monomer(s) used in forming such co-polymers can be one or more different 1 -olefins, a diolefin, a polymerizable acetylenic monomer, and the like, including any combination thereof.
  • the 1 -olefins that can be polymerized in the presence of the catalysts of this invention typically include ⁇ -olefins having from 2 to about 20 carbon atoms, examples of which include, but are not limited to, ethylene, propylene, 1-butene, 1-hexene, 4-methyl-l-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- hexadecene, and 1-octadecene.
  • the hydrocarbon co-monomers used such as 1 -olefins, diolefins, acetylene monomers, or any combination thereof, typically contain up to about 12 carbon atoms per molecule.
  • the 1 -olefin monomers that are useful in the present invention include ethylene, propylene, 1-butene, 3-methyl-l-butene, 4-methyl-l-pentene, 1-hexene, 1-octene, and the like, including any combination thereof.
  • the supported or unsupported catalysts of this invention are useful in the polymerization of ethylene, propylene, or ethylene and at least one C 3 - C 8 1 -olefin that is co-polymerizable with ethylene.
  • Typical diolefin monomers that can be used to form terpolymers with ethylene and propylene include, but are not limited to, butadiene, hexadiene, norbornadiene, and similar co-polymerizable diene hydrocarbons.
  • 1-Heptyne and 1-octyne are illustrative of suitable co-polymerizable acetylenic monomers which can be used in the present invention.
  • Polymerization of ethylene or co-polymerization with ethylene and an ⁇ -olefin having from 3 to about 10 carbon atoms typically can be performed in either the gas or liquid phase, for example, in a solvent such as toluene or heptane.
  • Such polymerizations can be conducted at conventional temperatures (for example from about 0 0 C to about 12O 0 C) and at conventional pressures (for example, from about ambient pressure to about 50 kg/cm 2 ) using conventional procedures as to molecular weight regulations and the like.
  • the heterogeneous catalysts of this invention can be used in polymerizations conducted as slurry processes, as gas phase processes, or by any other polymerization process that is known in the art.
  • slurry is meant that the particulate catalyst is used as a slurry or dispersion in a suitable liquid reaction medium which can comprise one or more ancillary solvents such as liquid aromatic hydrocarbons and the like, or an excess amount of liquid monomer to be polymerized in bulk.
  • these polymerizations can be conducted at one or more temperatures in the range of about O 0 C to about 160 0 C, and under atmospheric, sub- atmospheric, or super-atmospheric conditions.
  • polymerization adjuvants such as hydrogen
  • polymerizations conducted in a liquid reaction medium containing a slurry or dispersion of a catalyst of this invention can be conducted at temperatures in the range of about 4O 0 C to about 110 0 C
  • usual liquid diluents for such processes include, but are not limited to, hexane, toluene, and similar materials, although the compounds and compositions of this invention are applicable to any polymerization that is conducted outside these ranges and conditions.
  • super-atmospheric pressures are often used and the reactions are often conducted at temperatures in the range of about 50 0 C to about 160°C.
  • the gas phase polymerizations can be performed in a stirred or fluidized bed of catalyst in a pressure vessel adapted to permit the separation of product particles from unreacted gases.
  • hydrogen an inert diluent gas such as nitrogen, or a combination thereof can be introduced or recirculated to maintain the particles at the desired polymerization reaction temperature.
  • An optional aluminum alkyl such as triethylaluminum can be added as a scavenger of water, oxygen, and other impurities.
  • the aluminum alkyl can be employed as a solution in a suitable dry liquid hydrocarbon solvent such as toluene or xylene.
  • concentrations of such aluminum alkyl in hydrocarbon solutions in the range of about 5xlO '5 molar are conveniently used, although solutions of greater or lesser concentrations are useful and can be employed if desired.
  • the resulting polymer product can be withdrawn continuously or semi-continuously, typically at a rate that maintains a constant product inventory in the reactor.
  • the catalyst compositions of this invention can also be used along with small amounts of hydrocarbylborane compounds, examples of which include, but are not limited to, triethylborane, tripropylborane, tributylborane, trisecbutylborane, or any combination thereof.
  • hydrocarbylborane compounds when hydrocarbylborane compounds are used, molar Al/B ratios in the range of about 1/1 to about 1/500 are typical, though higher and lower ratios are also useful.
  • the catalyst levels used in olefin polymerizations can be less than previously used in typical olefin polymerizations conducted on an equivalent scale using more traditional activator compositions.
  • the polymerizations and co-polymerizations conducted according to this invention are carried out using a catalytically-effective amount of the catalyst composition of this invention, which amount can be varied depending upon such factors as the type of polymerization being conducted, the monomers and co-monomers employed, the polymerization conditions being used, and the type of reaction equipment in which the polymerization is being conducted.
  • the amount of the catalyst of this invention used will be such as to provide in the range of from about 0.000001 to about 0.01 percent by weight of the d- or f-block metal, including metallocene, based on the weight of the monomer(s) being polymerized.
  • the amount of the catalyst used in the practice of this invention can be more or less than the amounts encompassed by this range, again depending upon the type of polymerization and the conditions, the monomers and co-monomers employed, the type of reaction equipment employed, and the like, all of which will be readily understood by one of ordinary skill in the art.
  • the product polymer can be recovered from the polymerization reactor by any suitable means.
  • the product typically is recovered by a physical separation technique such as by decantation or the like.
  • the recovered polymer is usually washed with one or more suitably volatile solvents to remove residual polymerization solvent or other impurities, and then dried, typically under reduced pressure, optionally with the addition of heat.
  • the product after removal from the gas phase reactor is typically freed of residual monomer by means of a nitrogen purge, and often can be used without further catalyst deactivation or catalyst removal.
  • Example 10 and Table 6 summarize the propylene polymerization results obtained from using r ⁇ c-dimethylsilylbis(2-methyl-4-phenyl-indenyl)zirconium dimethyl (Ml)-derived catalysts, in which either BAM-treated or DBAB-treated silica were used as activators.
  • Table 6 also shows that a different support Silica II can also be used to make a highly active catalyst, although the calcination conditions can be different (Entry 1 vs. Entry 6).
  • the data from Silica II in Table 6 also seem to indicate that if the hydrogen bonded OH content on Silica II is sufficient (for example, 0.80 mraol/g, Entry 1) and BAM, which is able to form a single siloxyl bonded aluminate-proton ion-pair N with free OH, is used to construct the activator, even the resulting catalyst with a higher Zr loading (0.31%) does not provide a higher polymer productivity (12,300 g/g cat/hr).
  • Example 9 and Table 5 summarize the propylene polymerization results obtained from using four different metallocene-derived catalysts, in which BAM-treated silica was used as the activator.
  • the catalyst analytical results and propylene polymerization results using these catalysts are provided in Table 5.
  • hydrocarbyl is used to specify a hydrocarbon radical group that includes, but is not limited to aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl, and the like, and includes all substituted, unsubstituted, branched, linear, and heteroatom-substituted analogs thereof.
  • ligand abbreviations are used herein to refer either to the parent neutral ligand or to the deprotonated anion, as the context requires.
  • the abbreviation BHT refers either to the substituted phenol, butylated hydroxytoluene, HO-2,6-(/-Bu) 2 -4-Me-C 6 H 2 , or to the deprotonated aryloxide anion, [(0-2,6-(/-Bu) 2 - 4-Me-C 6 H 2 ) " ], as the context requires.
  • ammonium ion or ammonium-type ion are intended to encompass primary, secondary, and tertiary ammonium ions, as the context allows or requires.
  • ⁇ to ER 3 or HER 3 can be defined as follows.
  • a compound HER 3 or a moiety ER 3 is considered to be a "bulky" functional group or ligand when utilized with a particular d-block or f-block metal dialkyl compound if more than about 70% of the metal dialkyl compound has not reacted with HER 3 after 3 hours in solution at room temperature.
  • This criterion for the definition of "bulky” demonstrates that a particular ER 3 functional ligand that is considered bulky when used with one d-block or f-block metal dialkyl compound, may not be considered bulky when used with another d-block or f-block metal dialkyl compound.
  • HER 3 acts as a "functional" group to convert a primary aluminum alkyl A1R 2 3 to a secondary aluminum alkyl R 2 2 A1(ER 3 ) or even to a tertiary aluminum alkyl R 2 A1(ER 3 ) 2 , thereby lowering the reactivity of the organoaluminum compound such that an aluminate ion comprising a tertiary aluminum alkyl bonded to an active proton forms and is stable.
  • This reaction therefore, avoids an active proton in the presence of secondary aluminum alkyl groups in a species such as [support(-O-) 2 AlR 2 2 ] " [H] + , which would be expected to undergo alkane elimination to form
  • H w v Ii denotes a catalyst support or carrier, as is further described herein.
  • the steric bulk of the group R 3 is related to the catalyst structure and stability.
  • a more open catalyst framework is easier to react with a given ER 3 to undergo catalyst deactivation as illustrated above. Therefore the reaction of the catalyst precursor L n MR 2 with HER 3 , as disclosed above, can be used as a gauge to evaluate the R 3 bulkiness.
  • HER 3 does not substantially react with L n MR 2 but does react with A1R 2 3 under desired experimental conditions, then HER 3 is suitable for the construction of the aluminate-proton ion-pair on the support.
  • the bulky functional ligand of this invention generally does not include the -OB(C 6 F 5 ) 2 ligand, and the bulky functional ligand can be fluorinated, non-fluorinated, halogenated, or non-halogenated.
  • any d-block or f-block metal compound comprising at least one ligand subject to protonolysis to form a catalytically-active cationic species can be termed a catalyst precursor.
  • R 2 is selected independently from hydrogen or a hydrocarbyl group having up to about 20 carbon atoms
  • R 2 can be selected independently from at least one of the following: hydrogen or a hydrocarbyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or about 20 carbon atoms.
  • the molar ratio of HER 3 to aluminum typically spans the range from about 0.5 to about 2.5
  • Applicants intend to recite that the molar ratio of HER 3 to aluminum can be at least one of the following, without limitation: about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, about 2.0, about 2.1, about 2.2, about 2.3, about 2.4, or about 2.5.
  • any general structure presented also encompasses all conformational isomers, regioisomers, and stereoisomers that can arise from a particular set of substituents.
  • the general structure also encompasses all enantiomers, diastereomers, and other optical isomers whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as the context requires.
  • Reagents such as benzylmagnesium chloride (PhCH 2 MgCl) in THF, 4-fluorobenzylmagnesium chloride (FC 6 H 4 CH 2 MgCl) in THF, MeLi with LiBr, BHT, carbazol, and the like, were purchased from Aldrich Chemical Company (Milwaukee, WI) and were used as received without further purification.
  • Toluene, ethylene, propylene, and nitrogen used in the polymerization reactions were typically purified by passing through a series of three cylinders: molecular sieves, OXYCLEARoxygen absorbent, and alumina.
  • Ethylene and propylene were polymer grade obtained from Matheson.
  • Isohexane and toluene for activator and catalyst preparation and spectroscopy studies were Albemarle production anhydrous grade and were stored over sodium-potassium alloy. Hexane, C 6 D 6 , and similar hydrocarbon solvents were typically Aldrich anhydrous grade and were dried with and stored over Na/K alloy. Unless otherwise indicated, the DBAB solutions used to treat silica were isohexane solutions. [00123] The FT-infrared spectra were recorded on a NICOLET MAGNA-IR 560 spectrometer with a DRIFTS accessory under inert atmosphere, using a diffuse reflectance method.
  • Samples were prepared by loading, in the drybox under an inert atmosphere, a dry, solid silica compound in an inert cell with KBr windows. NMR studies were undertaken on a BRUKERDPX 400 (400 MHz) instrument, where the NMR instrumental parameters were set up for both quantitative and qualitative measurements. Total Al content on silica was determined using standard Inductively Coupled Plasma (ICP) emission spectroscopy techniques.
  • ICP Inductively Coupled Plasma
  • silica samples were used in the following examples, and the following Table 1 provides some analytical data illustrating the range of properties for these silica samples that were used to develop the present invention.
  • Silica I was a sample of silica sold under the trade name GRACE 952
  • Silica II was a sample obtained from Ineos that is sold under the trade name ES70. Data for average particle sizes include an overall average particle size, and particles size for the weight percent fractions tabulated are provided.
  • any metal oxide or support as disclosed herein works well with this invention. Additional silicas that work well include, but are not limited to those sold under the trade names GRACE 948, ES70X, and ES70W, and similar silicas. Table 1. Properties of Representative Silica Samples Used in Developing the Activators and
  • BHT 2,6-di-t-butyl-4- methylphenol
  • the silica used in this example was the Silica I, calcined at 600 0 C which had an OH content of 0.78 mmol OH/g silica.
  • Four (4) samples of DBAB-treated silica were prepared with A1:OH molar ratios of 0.36:0.78, 0.51 :0.78, 0.73:0.78, and 0.85:0.78, as follows. In each of four, 20 mL vials were charged 1.0 g of the silica calcined as above (OH content 0.78 mmol/g) and 5.0 g of toluene.
  • a 36 wt% DBAB solution (containing 1.0 mmol DBAB/g, from Example 1) was added to the four vials containing silica/toluene slurry in the amounts of 0.36 g, 0.51 g, 0.73 g, and 0.85 g, following by vigorously shaking each vial. These four samples were then transferred to a shaker to shake for a total of about 60 min. The mixture in each vial was filtered to isolate the treated silica, which was washed with 2x3 mL of toluene and 5 mL of isohexane, and then dried under vacuum for 16 hr.
  • FIG. 1 illustrates the infrared (IR) spectra of the OH stretching region of Silica I after (a) calcining at 15O 0 C (spectrum 10), (b) calcining at 600 0 C (spectrum 12), (c) calcining at 800 0 C (spectrum 14), and (d) calcining at 600 0 C followed by treatment of the silica with an excess OfPhCH 2 MgCl (spectrum 16), which is included for comparison.
  • IR infrared
  • the treated silica from each of these reaction mixtures was filtered off, washed with 2x3mL of toluene and 5 mL of isohexane, and then dried under vacuum for 2 hrs. Each sample was subjected to an IR analysis. The IR spectra in the OH region of each sample is provided in FIG. 2, where IR results of silica from vial 1 (spectrum 22), vial 2 (spectrum 24), and vial 3 (spectrum 26) are shown along with the parent silica (spectrum 20) for comparison.
  • H NMR Spectroscopy was used to determine the active proton content in the silica samples and the silica samples that had been treated with a BHT-modified aluminum alkyl compound, for example, DBAB-treated or BAM-treated Silica I.
  • a BHT-modified aluminum alkyl compound for example, DBAB-treated or BAM-treated Silica I.
  • Treated silica samples that were free of toluene were first treated with excess benzyl magnesium chloride, and treated silica samples contained a toluene residue were first treated with 4-fluorobenzylmagnesium chloride.
  • the analysis is based on the reaction of one active proton of the silica reacting with one benzylmagnesium chloride or one 4-fluorobenzylmagnesium chloride to produce one toluene, or one 4-fluorotoluene, respectively. From this reaction, the amounts of the produced toluene or 4-fluorotoluene were quantified by 1 H NMR spectroscopy with normalization to the THF peaks from the Grignard solvent, and the active proton contents was then derived.
  • the NMR instrument employed in the analyses was a BrukerTM DPX 400 (400 MHz) instrument.
  • the benzylmagnesium chloride (C 6 H 5 CH 2 MgCl) and 4- fluorobenzylmagnesium chloride (4-FC 6 H 4 CH 2 MgCl) Grignard solutions used were 2 M THF solutions, that were diluted to 0.1 M with THF that had been dried over Na/K alloy.
  • the following procedures were employed. A 0.200 g- to 0.400 g-sample of silica or treated silica was weighed into a 20 inL vial, to which was quickly added about 3.00 g of the 0.1 M Grignard stock solution, after which the vial was carefully sealed with a Teflon cap. The weights before and after silica sample and Grignard solution addition were recorded for accurate amounts of each component added.
  • the vial was charged and sealed, it was put on a shaker to shake for 30 minutes. The vial was then removed to allow the solids to settle. Because the Grignard reagents usually contain small amount of toluene (for C 6 H 5 CH 2 MgCl) or 4-fluorotoluene (for 4-FCeH 4 CHaMgCl) arising from hydrolysis from adventitious water, these were taken into account in performing the calculations. Therefore, NMR samples of both the Grignard stock solution and a the supernatant of the Grignard-treated silica were prepared and their spectra compared. In both cases, a clean, dry 5 mm NMR tube was charged 0.5 niL of dry C 6 D 6 .
  • toluene for C 6 H 5 CH 2 MgCl
  • 4-fluorotoluene for 4-FCeH 4 CHaMgCl
  • Table 4 summarizes the propylene polymerization results obtained from using 7- ⁇ c-dimethylsilylbis(2-methyl-4-phenyl-indenyl)zirconium dimethyl (Ml)-derived, DBAB- treated silica supported catalysts, comparing silica that was calcined at different temperatures, different DBAB charges, and different charges of metallocene Ml.
  • Any catalyst mentioned in an Entry in Table 4 for which the preparation has not been specifically described herein was prepared according to the procedure given in Example 4 (see entry 7a) and with the stoichiometry shown in Table 4 for that Entry.
  • Entries 1-3 of Table 4 compare calcination temperatures for the treated silica, and show that the highest activity was obtained at a calcination temperature of about 600 0 C, when DBAB/OH and metallocene/OH ratios were identical across all three samples.
  • the very low activity obtained from the catalyst derived from an 800 0 C calcined silica indicates that hydrogen bonded OH groups are useful in formation of the highly active sites since IR spectrum of the 800 0 C calcined silica (FIG. 1, spectrum 14) revealed that free OH groups were dominant.
  • DBAB-treated silica are equally active as indicated by the facts that the 62 and 110 mol% Zr charges based on the same residual OH content on DBAB treated silica show almost the same Zr loadings and the same productivities (Entry 2 vs. 7a), consistent with the IR observation as illustrated in FIG. 3.
  • highly active catalysts can be prepared from different types of silica.
  • Silica II derived from a similar preparation for the Silica I analog also resulted in active supported catalysts (Entry 9, 10, and 11), although the treatment of silica could be slightly different.
  • the resulting supported catalyst was characterized by the following analytical data: Al, 1.40%; Zr, 0.31 wt%.
  • the propylene polymerization productivity of this catalyst was observed to be 12,000 g/g cat/hr. Data from this sample are provided in Table 6, Entry 1.
  • BAM-treated Silica I catalysts according to the procedure used in Example 8B: rac-dimethylsilylbis- (2-methyl-l-indenyl) zirconium dimethyl (M2); rac-dimethylsilylbis(2-methyl-4,5-benzoindenyl) zirconium dimethyl (M3); and ethylenebis(tetrahydroindenyl)zirconium dimethyl (M4), along with r ⁇ c-dimethylsilylbis(2-methyl-4-phenyl-indenyl)zirconium dimethyl (Ml).
  • Table 6 summarizes the propylene polymerization results obtained from using rac-dimethylsilylbis(2-memyl-4-phenyl-indenyl)zirconium dimethyl (Ml)-derived, BAM- or DBAB-treated silica supported catalysts. Table 6. Polymerization Results for Ml -Derived Silica Supported Catalysts 1
  • DBAB-derived and the BAM-derived catalyst systems (Entry 2 versus Entry 3 and Entry 4 versus Entry 5).
  • Entry 2 comparing Entry 2 with Entry 3 clearly shows that active species derived from the H-bonded silica OH moieties, which richly populate the 600 0 C calcined silica, are more vigorous or potent than active species derived from the free OH moieties, which are the major OH species in the 800 0 C calcined silica.
  • free OH can coordinate to a BAM molecule to form the active species N (Scheme 5).
  • DBAB were examined for different DBAB amounts and different reaction times, to determine stiochiometries of the by-products, and examine kinetic versus thermodynamic products produced from this reaction.
  • Silica I which was calcined at 600 0 C, had an OH content of 0.78 mmol OH/g silica, and was used for the experiments reported in Table 7. Given sufficient reaction time, one mole of DBAB reacted with one mole of OH to release one mole of isobutane (abbreviated iC 4 ). With shorter reaction times, where a mixture of kinetic and thermodynamic products are present, both isobutane iC 4 and free BHT phenol were observed.
  • iC 4 isobutane
  • a supported Ml catalyst prepared using DBAB-treated silica was run under the following polymerization conditions: 40 mg catalyst; 2 rnL of 10% TBA; 40 mL of hexene; 80°C; 320 psi ethylene pressure; in a 4 L autoclave reactor.
  • the activity of this catalyst was observed to be 1,700 g/g cat/hr productivity, whereas the productivity of this same catalyst in the polypropylene polymerization test was observed to be 9,500 g/g cat/hr.

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Abstract

Cette invention concerne des composés et des compositions de catalyseurs, utiles dans la polymérisation d'oléfine. Dans un aspect, l'invention se rapporte à des activateurs d'aluminate gonflant, d'acide de Brønsted, supportés par un oxyde métallique et comprenant des composés cationiques de bloc d ou de bloc f liés avec les activateurs supportés. Les catalyseurs de l'invention sont utiles dans des procédés de polymérisation d'oléfine, tels que la polymérisation en phase gaz ou humide d'éthylène et de propylène, qui utilisent des catalyseurs supportés.
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CN111344059A (zh) * 2017-09-13 2020-06-26 卢塞特英国国际有限公司 用于生产烯属不饱和羧酸或者羧酸酯的催化剂和生产方法
JP2020533170A (ja) * 2017-09-13 2020-11-19 ルーサイト インターナショナル ユーケー リミテッド エチレン性不飽和カルボン酸又はエステルを製造するための触媒及びプロセス
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JP7384788B2 (ja) 2017-09-13 2023-11-21 ミツビシ ケミカル ユーケー リミテッド エチレン性不飽和カルボン酸又はエステルを製造するための触媒及びプロセス
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