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WO1998005422A1 - Catalyseur ziegler-metallocene modifie supporte pour la polymerisation des olefines - Google Patents

Catalyseur ziegler-metallocene modifie supporte pour la polymerisation des olefines Download PDF

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Publication number
WO1998005422A1
WO1998005422A1 PCT/US1997/012027 US9712027W WO9805422A1 WO 1998005422 A1 WO1998005422 A1 WO 1998005422A1 US 9712027 W US9712027 W US 9712027W WO 9805422 A1 WO9805422 A1 WO 9805422A1
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Prior art keywords
catalyst
metallocene
silica
carbon atoms
bis
Prior art date
Application number
PCT/US1997/012027
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English (en)
Inventor
John Tai-Tung Hsieh
Sandra Denise Schregenberger
Ronald Steven Shinomoto
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Mobil Oil Corporation
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Filing date
Publication date
Application filed by Mobil Oil Corporation filed Critical Mobil Oil Corporation
Priority to JP10507915A priority Critical patent/JP2000515425A/ja
Priority to AU37235/97A priority patent/AU3723597A/en
Priority to CA002262948A priority patent/CA2262948A1/fr
Priority to EP97934098A priority patent/EP0946297A4/fr
Publication of WO1998005422A1 publication Critical patent/WO1998005422A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/122—Metal aryl or alkyl compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/49—Hafnium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the invention relates to a mixed or bimetallic catalyst. It also relates to a synthesis for the catalyst which results in improved properties, that are manifested in the bimodal molecular weight distribution products which are produced in the (co)polymerization of ethylene in a single reactor in the presence of this catalyst.
  • Bimodal molecular weight distribution products and broad molecular weight distribution products of ethylene polymers and copolymers contain two components of different molecular weight, one component having a relatively high molecular weight compared to the second component and designated by the acronym HMW (high molecular weight) ; the second component being of relatively lower molecular weight than the HMW component and being designated by the acronym LMW (low molecular weight component.)
  • HMW and the LMW components can have varying molecular weight distribution.
  • the production of two different molecular weight components is related to the hydrogen response, and thus process conditions of polymerization or copolymerization. By comparison, the molecular weight distribution is dependent on the catalyst per se.
  • high molecular weight polyethylene and copolymers of ethylene may be suitable for film or HIC (household and industrial containers) applications.
  • An HIC resin is also characterized by ADS (annular die swell).
  • the catalyst of the invention which will be more fully described below comprises two transition metals. Its method of synthesis directly affects the properties of ethylene polymer and copolymer products produced in catalytic polymerization and copolymerization in the presence of these catalysts.
  • FIG. 1 is a GPC chromatogram of the product of Example 2.
  • FIG. 2 is a GPC chromatogram of the product of Example 5.
  • a novel catalyst component can be activated by an activator which is an alkyl aluminum compound, such as trialkyl aluminum compounds, including trimethylaluminum, triethylaluminum and diisobutylaluminum hydride.
  • an activator which is an alkyl aluminum compound, such as trialkyl aluminum compounds, including trimethylaluminum, triethylaluminum and diisobutylaluminum hydride.
  • the catalyst component comprises at least two transition metals on a support. At least one of the transition metal sources is provided as a non-metallocene.
  • the amount of alkyl aluminum compound activator relative to the non- metallocene transition metal source ranges from 0.1 to 1000 preferably 5 to 200.
  • the transition metals may be deposited on the support simultaneously. In a preferred embodiment, the two transition metals are deposited on the support stepwise rather than simultaneously.
  • At least one source of the transition metals is a metallocene, preferably a zirconocene; in a most preferred embodiment, the transition metal source provided as the metallocene is deposited on the support before the second transition metal source, a non-metallocene; the embodiments of providing the metallocene results in homogeneous distribution of metallic components.
  • At least one of the non-metallocene transition metals is provided as a contact product of at least three components; additional reactants may be contacted with this source of transition metal.
  • the at least three components include a trihydrocarbylsilanol, an organomagnesium compound and a titanium compound or salt formed by contacting TiCl 4 with an alcohol.
  • the resulting titanium component is highly active; thus, the catalyst requires less titanium loading.
  • the relative amount of the titanium on the support ranges from 0.1 to 1 millimole/g silica, preferably 0.2 to 0.3 millimole/g silica, based on the dehydrated silica.
  • the relative amount of the trihydrocarbylsilanol to the amount of the titanium contacted with it ranges from 0.1 to 10 molar ratio, preferably 0.8 to 1.2 molar ratio.
  • the relative amount of the organomagnesium to the amount of the titanium contacted with it ranges from 0.1 to 10 molar ratio, preferably 0.8 to 1.2 molar ratio.
  • the relative amount of the alcohol contacted with the titanium ranges from 0.001 to 1 molar ratio, preferably 0.2 to 0.6 molar ratio; in preferred embodiments the titanium and alcohol are allowed to contact prior to addition of either the organomagnesium or trialkylsilanol .
  • One of the transition metals is a compound or a salt of Ti(IV) .
  • the titanium source is titanium tetrachloride TiCl.
  • This component is provided as a non- metallocene; metallocene refers to a metal compound which contains a cyclopentadienyl group.
  • this at least one of the transition metals is provided as a contact product of at least three components; additional reactants may be contacted with this source of transition metal and include the support, and derivatives thereof.
  • the support may be alumina, silica, or silica/aluminum or magnesium oxide derivatives.
  • the support is silica.
  • the silica is one in which the average pore diameter ranges from 50 to 500A, preferably 100 to 450A, and most preferably 300 to 400A.
  • the carrier is silica, which contains [OH] groups.
  • the carrier material must have at least some active hydroxyl (OH) groups to produce the catalyst composition of this invention.
  • the hydroxyl group concentration will be at least 0.7 mmole/gram silica.
  • the hydroxyl group concentration of the silica will range from 1.6 to 2.5 mmoles/gram silica. This range is favored by lower drying, dehydration and/or calcination temperatures.
  • silica hydroxyl (herein silanol, silica hydroxyl is used interchangeably) groups are detectable by IR spectroscopy. Quantitative determinations of the hydroxyl concentration on silica are made by contacting a silica sample with methyl magnesium iodide and measuring methane evolution (by pressure determination) . Dehydration of silica material can be effected by heating at 100° to 600°C, preferably from 150° to 350°C and most preferably at 200' to 300"C.
  • Davison 955 silica dehydrated at 600°C will have a surface hydroxyl concentration of 0.7 mmoles per gram (mmols/gm) of silica.
  • Davison 955 silica dehydrated at 800°C will be a silica with 0.5 mmole of silica hydroxy per gram silica.
  • the silicas are not dehydrated and must be dehydrated prior to use.
  • the catalyst synthesis of the catalyst of the invention exhibiting highest activity dictates that the silica contain hydroxyl groups for contact with the solution containing aluminoxane and metallocene.
  • the amount of hydroxyl groups, in mmoles/gram silica can be affected by the dehydration temperatures used to condition the silica. Specifically, the dehydration temperatures of 600°C reduce the amount of reactive hydroxyl groups available for contact with the solution of aluminoxane and metallocene.
  • the dehydration temperatures of 250°C increase the amount of reactive hydroxyl groups available for contact with the solution of aluminoxane and metallocene, relative to the silica heat treated, for dehydration purposes to 600°C.
  • preferred dehydration and/or calcination temperatures are below 400°C, more preferably below 300"C, and most preferably at 250°C.
  • the silica used in embodiments of the invention will contain a silanol (OH) concentration of greater than 0.7 mmoles OH per gram silica; preferably it will contain greater than 0.7 mmoles up to 2.5 mmoles OH per gram of silica. In preferred embodiments, the concentration ranges from 1.6 to 1.9 mmoles/gram silica.
  • the trialkylsilanol component has a formula AxByCzSiOH, in which each of A, B, and C is hydrocarbyl of 1 to 10 carbon atoms and each is the same or different, and each of x, y, and z is a number from 1 to three and x+y+z is equal to 3.
  • the hydrocarbyl of A, B and C can be alkyl or aryl. If A, B or C is alkyl, it can contain 1 to 10 carbon atoms, and preferably it contains 1 to 6 carbon atoms, most preferably contains 2 carbon atoms.
  • A, B or C is aryl it can be unsubstituted phenyl or benzyl or substituted phenyl or benzyl; preferably if A, B or C is aryl, it contains 6 to 10 and preferably 6 to 8 carbon atoms.
  • the trialkyl silanol component in the preferred embodiment is triethylsilanol.
  • the organomagnesium compound is preferably a dialkylmagnesium which contains alkyl groups, each being the same or different and each containing 1 to 12 carbon atoms, preferably 4 to 8, and most preferably 4 carbon atoms.
  • alkyl include ethyl butyl, methyl ethyl, dihexyl; most preferably, the alkylmagnesium is dibutylmagnesium.
  • the titanium component comprises a contact product of TiCl* and an aliphatic alcohol of 1 to 12 carbon atoms, preferably 4 to 8 carbon atoms, such as butanol, pentanol, hexanol, heptanol and octanol, and analogs thereof. In Examples below pentanol was employed.
  • the resulting titanium compound has the formula (R*0) a TiCl 4 . a , where a is a number between 0 and 4 and is neither 0 nor 4, and R is alkyl or 1 to 12 carbon atoms. Contact of the reagents is usually undertaken under inert conditions, free of moisture and air.
  • the contact can be undertaken at temperatures in the range of 0° to 100°C. Generally, in the synthesis reported herein the contact temperatures are in the range of 20° to 60 °C. Preferably, the temperature is in the range of from 25° to 45 °C. All stages are undertaken at more or less the same temperature, except the reaction of DBM with Et 3 SiOH which sometimes takes place at 45 ⁇ C to improve component solubility.
  • the first supported transition metal source is contacted with a second source of a transition metal which is a metallocene; as noted below a metallocene is a metal compound and containing at least one cyclopentadienyl group. More preferably, the metallocene is activated. In the most preferred embodiments the metallocene is converted to ionic form. Preferably, this conversion is undertaken with an alumoxane as a cocatalyst. The amount of alumoxane ranges from 50 to 500 molar ratio, preferably 100 to 300 molar ratio. To form catalysts of the invention, all catalyst components can be dissolved with alumoxane and impregnated into the carrier.
  • a metallocene is a metal compound and containing at least one cyclopentadienyl group. More preferably, the metallocene is activated. In the most preferred embodiments the metallocene is converted to ionic form. Preferably, this conversion is undertaken with an
  • the class of alu oxanes comprises oligo eric linear and/or cyclic alkylalu oxanes represented by the formula: R-(Al(R)-0) n -AlR 2 for oligomeric, linear alumoxanes and (-Al(R)-0-) m for oligomeric cyclic alumoxane wherein n is 1-40, preferably 10-20, is 3-40, preferably 3- 20 and R is a C ⁇ -C 8 alkyl group and preferably methyl.
  • Methaluminoxane is a mixture of oligomers with a very wide distribution of molecular weights and usually with an average molecular weight of 1200. MAO is typically kept in solution in toluene. The volume of the solution comprising an alumoxane and a solvent therefor can vary, depending on the catalyst sought to be produced.
  • the metallocene compounds can be selected from a large variety of compounds.
  • the amount of this transition metal provided as a metallocene ranges from 0.1 molar ratio to 0.5 molar ratio based on the other transition metal source.
  • the metallocene is added to the solution of the alumoxane prior to impregnating the carrier with the solution.
  • the mole ratio of aluminum provided by aluminoxane, expressed as Al, to metallocene metal expressed as M (e.g. Zr) ranges from 50 to 500, preferably 75 to 400, and most preferably 100 to 300.
  • M e.g. Zr
  • An added advantage of the present invention is that this Al:Zr ratio can be directly controlled.
  • the alumoxane and metallocene compound are mixed together at ambient temperature for 0.1 to 6.0 hours, prior to use in the infusion step.
  • the solvent for the metallocene and alumoxane can be appropriate solvents, such as aromatic hydrocarbons, halogenated aromatic hydrocarbons, ethers, cyclic ethers or esters; preferably it is toluene.
  • the metallocene compound has the formula Cp m MA n B p in which Cp is an unsubstituted or substituted cyclopentadienyl group and unbridged or bridged indenyl, M is zirconium or hafnium and A and B belong to the group including a halogen atom, hydrogen or an alkyl group.
  • the preferred transition metal atom M is zirconium.
  • the Cp group is an unsubstituted, a mono- or a polysubstituted cyclopentadienyl group.
  • the substituents on the cyclopentadienyl group can be preferably straight or branched chain C.-C alkyl groups.
  • the cyclopentadienyl group can be also a part of a bicyclic or a tricyclic moiety such as indenyl, tetrahydroindenyl , fluorenyl or a partially hydrogenated fluorenyl group, as well as a part of a substituted bicyclic or tricyclic moiety.
  • the cyclopentadienyl groups can be also bridged by polymethylene or dialkylsilane groups, such as -CH_-, -CH_- CH 2 -, -CR'R"- and -CR'R H -CR , R H - where R' and R" are short alkyl groups or hydrogen, -SifCH-).,-, Si(CH 3 ) 2 -CH_-CH 2 - Si(CH 3 )_- and similar bridge groups.
  • a and B substituents in the above formula of the metallocene compound are halogen atoms, they belong to the group of fluorine, chlorine, bromine or iodine.
  • substituents A and B in the above formula of the metallocene compound are alkyl groups, they are preferably straight-chain or branched C,-C 8 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, n-pentyl, n-hexyl or n-octyl.
  • Suitable metallocene compounds include bis (cyclopentadienyl)metal dihalides, bis(cyclopentadienyl)metal hydridohalides, bis (cyclopentadienyl)metal monoalkyl monohalides, bis (cyclopentadienyl)metal dialkyls and bis (indenyl)metal dihalides wherein the metal is zirconium or hafnium, halide groups are preferably chlorine and the alkyl groups are C. -C-. alkyls.
  • metallocenes include bis(cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl)hafnium dimethyl , bis (cyclopentadienyl) zirconium hydridochloride, bis (cyclopentadienyl) hafnium hydridochloride, bis(n- butylcyclopentadienyl) zirconium dichloride, bis(n- butylcyclopentadienyl) hafnium dichloride, bis(n- butylcyclopentadienyl) zirconium dimethyl, bis(n- butylcyclopentadienyl) hafnium dimethyl , bis (n- butylcyclopentadienyl) zirconium hydridoch
  • the catalyst in polymerization and copolymerization can be in the solution, slurry, or gas phase.
  • the catalyst is treated with hexene before being introduced into the polymerization.
  • the conditions include a pressure of less than 1000 psi and generally no greater than 350 psi. Temperatures may range from 30° to 120°C. Generally, the polymerization temperature ranges from 50° to 120 C C. The ethylene partial pressures range from 50 to 500 psia. Hydrogen is used as a chain terminator. The partial pressure of hydrogen ranges from 0.1 to 10 psia.
  • the process conditions include solution, slurry or gas phase polymerization conditions in which the partial pressure of ethylene is within 180 to 400 psia ranges.
  • the products produced in the polymerization or copolymerization are characterized by a density of 0.89 to 0.97, preferably 0.918 to 0.958; by an 121 [ASTM D-1238] of 1 to 100, preferably 5 to 65; and by a molecular weight distribution expressed as MFR (I 2 _/I 2 ) of 30 to 300, preferably 50 to 150 [ASTM D-1238].
  • MFR molecular weight distribution expressed as MFR (I 2 _/I 2 ) of 30 to 300, preferably 50 to 150 [ASTM D-1238].
  • particularly desirable properties obtainable hereby include Annular Die Swell (ADS) by a rheometer of 0.5 to 0.9, preferably 0.65 to 0.75.
  • Annular die swell is measured by weighing 252 centimeters (cm) of a tube extruded at shear rate of 2000 1/sec through an annular die having a tapered entrance angle of 24.4°; die lend length of 3.05 mm; die gap of 0.505 mm and average die diameter of 5.16 mm.
  • Davison 955 silica was dehydrated at 250°C for 16 hours.
  • 0.1 g of Bis(n-butylcyclopentadienyl) Zirconium Dichloride from Boulder Scientific Company
  • 10 ml of methylaluminoxane (MAO) solution (4.76M, from itco/Schering Company)
  • MAO methylaluminoxane
  • 7.4 ml of this reaction product solution was mixed with 5 g of the 250°C dehydrated silica and dried to remove toluene under nitrogen purge at 55° to 60°C at least 4 hours.
  • Example 3 Ethylene Polymerization in Slurry Using Example 1 Catalyst.
  • Example 1 catalyst 0.24 gram of Example 1 catalyst and 300 ml heptane were fed into the reactor, using ethylene pressure slightly above the reactor pressure, to start the polymerization. The polymerization was maintained at 90°C for 1 hour. The polymer slurry was stabilized with an antioxidant package and dried over night at room temperature. The solid product was placed in a vacuum over for 1 hour. The polymer was weighed and a productivity of 1000 g/g cat/hr was calculated. The dry granular product was extruded through a Randcastle mini-extruder. The following melt flow properties were determined: I 2 (melt index) or I 5 and I 2 ⁇ (flow index or FI) [ASTM D-1238].
  • the polymerization conditions are identical to that of Example 3, except 7 ml of Trimethylaluminum alkyl (TMA, the ipreferred cocatalyst ⁇ by-this- system ⁇ " ccf ⁇ atai yli ⁇ sTul:1o ' n * ⁇ j . « - 2 ⁇ "and the comparative Example 1 catalyst were used, j preferred cocatalyst by this system) co-catalyst solution (2.42M) and the comparative Example 1 catalyst were used.
  • TMA Trimethylaluminum alkyl
  • j preferred cocatalyst by this system co-catalyst solution
  • the H 2 /C 2 ratio was adjusted to 0.03 to raise the FI.
  • the stabilized, dry polymer was weighed and a productivity of 1850 g/g cat/hr was calculated.
  • Example 5 The polymerization conditions are identical to that of Comparative Example 2, except the Example 2 catalyst was used and the polymerization time was shortened to hour to avoid hydrogen starvation during the second half hour.
  • the hydrogen/ethylene ratio was 0.02.
  • the stabilized, dry polymers were weighed and a productivity of 2300 g/g cat/hr was calculated.
  • Example 5 The stabilized, dry polymers were weighed and a productivity of 2300 g/g cat/hr was calculated.
  • the granular product was extruded through a Randcastle mini-extruder.
  • Example 2 Catalyst and DIBAH Cocatalyst.
  • the polymerization conditions are identical to that of Example 3, except 1 ml of DIBAH cocatalyst solution (1.258M) and Example 2 catalyst were used, and the polymerization time was shorten to hour to avoid hydrogen starvation during the second half hour.
  • the hydrogen/ethylene ratio of this experiment was adjusted to 0.04 to raise the FI.
  • the stabilized, dry polymer was weighed and a productivity of 2700 g/g cat/hr was calculated.
  • GPC analysis on the extrudate showed that a bimodal MWD suitable for HIC type applications was obtained ( Figure 2) .

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Abstract

Nouveau catalyseur bimétallique préparé à partir de silanol de trialkyle, de dibutylmagnésium, d'un complexe de chlorure alcoxy-titane et d'un produit de réaction métallocène-alumoxane supporté sur de la silice. Ce catalyseur peut polymériser l'éthylène et des oléfines supérieures à l'aide de triéthylaluminiun (TEA), d'hydrure de diisobutylaluminium (DIBAH), de triméthylaluminium (TMA) et d'autres alkyles d'aluminium en tant que cocatalyseurs afin de produire des résines à répartition des poids moléculaires bimodale convenant pour des applications de conteneurs ménagers et industriels réutilisables et/ou de films à poids moléculaire élevé.
PCT/US1997/012027 1996-08-02 1997-07-11 Catalyseur ziegler-metallocene modifie supporte pour la polymerisation des olefines WO1998005422A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP10507915A JP2000515425A (ja) 1996-08-02 1997-07-11 オレフィン重合用の支持された改質チーグラ―メタロセン触媒
AU37235/97A AU3723597A (en) 1996-08-02 1997-07-11 Supported modified ziegler-metallocene catalyst for olefin polymerization
CA002262948A CA2262948A1 (fr) 1996-08-02 1997-07-11 Catalyseur ziegler-metallocene modifie supporte pour la polymerisation des olefines
EP97934098A EP0946297A4 (fr) 1996-08-02 1997-07-11 Catalyseur ziegler-metallocene modifie supporte pour la polymerisation des olefines

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US69173496A 1996-08-02 1996-08-02
US08/691,734 1996-08-02

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WO1998005422A1 true WO1998005422A1 (fr) 1998-02-12

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EP (1) EP0946297A4 (fr)
JP (1) JP2000515425A (fr)
KR (1) KR20000029770A (fr)
AU (1) AU3723597A (fr)
CA (1) CA2262948A1 (fr)
WO (1) WO1998005422A1 (fr)

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WO1999048934A1 (fr) * 1998-03-25 1999-09-30 Bp Chemicals Limited Compositions polymeres
EP0996648A1 (fr) * 1997-07-14 2000-05-03 ExxonMobil Oil Corporation Catalyseur pour la fabrication du polyethylene par distribution large ou bimodale de la masse moleculaire
US6573343B1 (en) 1998-12-16 2003-06-03 Borealis Technology Oy Multistep process for preparing polyolefins having high melt strength

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US5032562A (en) * 1989-12-27 1991-07-16 Mobil Oil Corporation Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution
US5525678A (en) * 1994-09-22 1996-06-11 Mobil Oil Corporation Process for controlling the MWD of a broad/bimodal resin produced in a single reactor

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JP2000514493A (ja) * 1996-07-15 2000-10-31 モービル・オイル・コーポレーション 吹込成形およびフィルム用途用コモノマー前処理２金属系触媒

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US4525557A (en) * 1984-02-27 1985-06-25 Gulf Oil Corporation Catalyst and process for the polymerization of ethylene
US5032562A (en) * 1989-12-27 1991-07-16 Mobil Oil Corporation Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution
US5525678A (en) * 1994-09-22 1996-06-11 Mobil Oil Corporation Process for controlling the MWD of a broad/bimodal resin produced in a single reactor

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0996648A1 (fr) * 1997-07-14 2000-05-03 ExxonMobil Oil Corporation Catalyseur pour la fabrication du polyethylene par distribution large ou bimodale de la masse moleculaire
EP0996648A4 (fr) * 1997-07-14 2004-05-26 Exxonmobil Oil Corp Catalyseur pour la fabrication du polyethylene par distribution large ou bimodale de la masse moleculaire
WO1999048934A1 (fr) * 1998-03-25 1999-09-30 Bp Chemicals Limited Compositions polymeres
JP2002507637A (ja) * 1998-03-25 2002-03-12 ビーピー ケミカルズ リミテッド ポリマー組成物
US6489427B1 (en) * 1998-03-25 2002-12-03 Bp Chemicals Limited Polymer compositions
US6573343B1 (en) 1998-12-16 2003-06-03 Borealis Technology Oy Multistep process for preparing polyolefins having high melt strength

Also Published As

Publication number Publication date
CA2262948A1 (fr) 1998-02-12
KR20000029770A (ko) 2000-05-25
JP2000515425A (ja) 2000-11-21
EP0946297A4 (fr) 2000-08-09
EP0946297A1 (fr) 1999-10-06
AU3723597A (en) 1998-02-25

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