WO1998002246A1 - Supported metallocene catalyst for olefin polymerization - Google Patents
Supported metallocene catalyst for olefin polymerization Download PDFInfo
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- WO1998002246A1 WO1998002246A1 PCT/US1997/011092 US9711092W WO9802246A1 WO 1998002246 A1 WO1998002246 A1 WO 1998002246A1 US 9711092 W US9711092 W US 9711092W WO 9802246 A1 WO9802246 A1 WO 9802246A1
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- 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
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- 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
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- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- 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
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- 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
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/61922—Component covered by group C08F4/60 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
- C08F4/61925—Component covered by group C08F4/60 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 non-bridged
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Definitions
- the invention relates to improved catalysts and to modifications and improvements in polymerization and copoly erization of ethylene, undertaken in the presence of catalysts comprising metallocenes of transition metals.
- the catalysts are characterized by extremely high activity.
- the catalysts of the invention operate smoothly in the gas phase, e.g. fluid bed.
- the catalysts produce high molecular weight polymer at temperature and pressure conditions typically found in a commercial fluid bed reactor.
- the catalyst yields high bulk density, granular linear low density polyethylene in slurry polymerizations without reactor fouling.
- the polymer products have narrow molecular weight distribution, are free of gels, and, for linear low density have homogeneous comonomer distribution. Reactor fouling is eliminated in both gas phase fluid bed and slurry polymerizations.
- Polyethylene is produced commercially in a gas phase reaction in the absence of solvents by employing selected chromium and titanium-containing catalysts under specific operating conditions in a fluid bed process. Polyethylene products of those original processes exhibited medium-to- broad molecular weight distribution. To be commercially useful in the gas phase fluid bed process, or slurry reactor process, undertaken at low pressures less than about 1000 psi, the catalyst must exhibit high activity, with concomitant high catalyst productivity, because these process systems do not include catalyst residue removal procedures. Accordingly, catalyst residue in the polymer product must be so small that it can be left in the polymer without causing any undue problems in the fabrication and/or to the ultimate consumer. To this end, the patent literature is replete with developments of new catalysts.
- metallocene compounds of transition metals as catalysts for polymerization and copolymerization of ethylene is one of those developments.
- Metallocenes can be described by the empirical formula Cp MA B .
- These compounds in combination with methylalumoxane (MAO) have been used to produce olefin polymers and copolymers, such as ethylene and propylene homopoly ers, ethylene-butene and ethylene-hexene copolymers.
- Aluminoxanes e.g. methylalumoxane (MAO) have been used as co-catalyst with metallocene catalysts.
- alumoxanes (used interchangeably hereinafter with “aluminoxane”) comprises oligomeric linear and/or cyclic alkylalumoxanes represented by the formula: R- (Al (R) -O) -AIR- for oligomeric, linear alumoxanes and (-
- Al(R)-O-) for oligomeric cyclic alumoxane wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a C.-C- alkyl group and preferably methyl.
- Methylalumoxane is commonly produced by reacting trimethylaluminum with water or with hydrated inorganic salts, such as CuS0.5H 2 0 or
- Methylalumoxane can be also generated in situ in polymerization reactors by adding to them trimethylaluminum and water or water-containing inorganic salts.
- MAO is a mixture of oligomers with a very wide distribution of molecular weights and usually with an average molecular weight of about 900-1200.
- MAO is typically kept in solution in toluene. While the MAO solutions remain liquid at fluid bed reactor temperatures, the MAO itself is a solid at room temperature.
- the slow development of the metallocene catalysts has been in part attributable to the aluminoxane (hereinafter used interchangeably with "alumoxane”) reagent used to activate.
- the invention relates to a metallocene catalyst which does not require an aluminoxane cofeed to the polymerization reactor. Moreover, the catalyst of the invention exhibits high activity and productivity, in the fluid bed gas phase and slurry polymerization and copolymerization of olefins.
- the problems invoked by the use of an alumoxane, methylalumoxane, in catalyst production are addressed by the catalyst of the invention, comprising a carrier material impregnated with alumoxane and derivatives thereof, formed in stages comprising:
- silica which has 0.4 mmoles to 2.5 mmoles, preferably greater than 0.7 mmole, of hydroxyl groups, also referred herein as silanol groups, per gram of silica;
- the silica is porous and has a particle size of 1 to 250 microns, having pores which have an average diameter of 50 to 500 Angstroms and having a pore volume of 0.5 to 5.0 cc/g of carrier; and a surface area of m 2 /g to 600 m 2 /g;
- a volume of a liquid medium comprising an alumoxane and a solvent therefor, wherein the concentration of alumoxane, expressed as Al (elemental) weight percent is 5 to 20; the solution further contains a metallocene which is present in an amount, expressed as elemental metal, which ranges from 0.01 to 2 weight percent; wherein the methylalumoxane provides aluminum in an amount sufficient to provide a ratio of Al to silica, i.e., Al/silica (wt/wt) ranging from 0.05 to 0.40; the volume of liquid medium comprises an aromatic hydrocarbon and an aliphatic or alicydic hydrocarbon and the volume exceeds the total pore volume of the silica support;
- the invention includes the foregoing, activated catalysts, the polymerizations and copolymerizations catalyzed thereby, and the product (s) thereof .
- Catalyst Composition The catalysts of the invention comprise a carrier, an alumoxane and at least one metallocene.
- the process of the invention results in supported catalysts of transition metals and aluminum, with very uniform distribution of metals within catalyst particles and among catalyst particles.
- NMR and FTIR characterization indicates that the alumoxane component of the catalyst reacts with silica hydroxyl groups; NMR reveals substantially complete reaction, and consumption of, alumoxane; in accordance with the invention, the alumoxane reacts with a silica support.
- the catalyst is free-flowing and particulate in form comprising dry powder particles having an average particle size of from 1 micron to 250 microns, preferably from 4 microns to 150 microns.
- the catalysts which contain only one transition metal in the form of a metallocene have an activity expressed in kg polymer/g of transition metals.
- the aluminoxane and metallocene loading on the carrier is such that the amount of aluminum, (elemental basis) provided by the aluminoxane, on the carrier ranges from 1 to 40 wt.%, preferably from 5 to 30 wt.%, and most preferably from 5 to 15 wt.%.
- the optimum MAO loading is in the range of 3 to 15 mmoles per gram of silica carrier; if a silica carrier is overloaded with MAO, the catalyst activity is lower and the catalyst particles agglomerate with attendant problems of feeding and resin agglomeration.
- the amount of metallocene on the carrier ranges, on a transition metal elemental basis, from 0.001 to 10 wt.%, preferably from 0.05 to 0.4 wt.%.
- the ratio of AlrZr (on an elemental basis) in the catalyst can range from 25 to 10,000, usually within the range of from 70 to 980 but preferably from 70 to 350 and most preferably from 100 to 350.
- the carrier material is a solid, particulate, porous, preferably inorganic material, such as an oxide of silicon and/or of aluminum.
- the carrier is silica in the form of spherical particles, e.g., as obtained by a spray-drying process.
- the carrier material is used in the form of a dry powder having an average particle size of from 1 micron to 500 microns, preferably from 1 micron to 250 microns, and most preferably 10 microns to 150 microns average particle size. If necessary, the final catalyst containing carrier material may be sieved to insure elimination of large catalyst particles.
- catalyst particles that have a particle size of greater than 500 microns is envisaged; preferably, elimination of particles of greater than 250 micron particle size, and, most preferably, elimination of particles of greater than 150 micron particle size is undertaken.
- Sieving of the material is preferably undertaken after impregnation of the carrier with the metallocene and the aluminoxane.
- the catalyst contains only one transition metal in the form of a metallocene and which is used to form narrow molecular weight LLDPE, to reduce and/or to eliminate gels in the final polyolefin product and to eliminate reactor hot spots, thereby to insure reactor continuity, particularly in the gas phase fluid bed process.
- the surface area of the carrier is at least 3 square meters per gram (m 2/gm) , preferably, 5 to 1200 square meters per gram (m2/gm) and most preferably at least 50 2/gm up to 600 m2/gm.
- the pore volume of the carrier will range from 0.1 to 5 cm 3 /gm, preferably from 0.5 to 3.5 cm 3 /gm.
- the carrier material should be dry, that is, free of physically absorbed water.
- the carrier is silica, which contains [OH] groups or other functional groups that contain active hydrogen.
- 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.
- the silica surface can be modified, well known to people familiar with the art, to provide active functional group to react with alumoxane.
- the active functional group could be from hydroxyl, alcohols, acids, phenols, and silanols.
- silica hydroxyl groups are detectable by IR spectroscopy. Quantitative determinations of the hydroxyl concentration on silica are made by contacting a silica sample with methyl magnesium bromide and measuring methane evolution (by pressure determination) .
- Dehydration of silica material can be effected by heating at 100°C to 600°C, preferably from 150°C to 300°C and most preferably at 250°C.
- silica dehydrated at 600°C (for 16 hours) will have a surface hydroxyl concentration of 0.7 mmoles per gram ( mols/gm) of silica.
- Silica dehydrated at 800°C will be a silica with 0.5 mmole of silica hydroxy per gram silica.
- the effect of increasing silica hydroxyl groups on the catalyst activity and productivity is a positive one.
- 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, described below. It was determined that reaction of the hydroxyl groups of the silica with scavengers, such as trialkylaluminum compounds, e.g., trimethylaluminum (TMA) , reduced the activity of the catalyst produced thereby compared to a catalyst formed with a silica having hydroxyl groups unreacted with such a scavenger. Silicas containing higher hydroxyl numbers produce catalysts of higher activity than silicas of lower hydroxyl numbers.
- scavengers such as trialkylaluminum compounds, e.g., trimethylaluminum (TMA)
- 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 to 0.7 mmole per gram of silica for contact with the solution of aluminoxane and metallocene. By comparison, the dehydration temperatures of 250°C reduce the amount of reactive hydroxyl groups to 2 mmole per gram of silica for contact with the solution of aluminoxane and metallocene.
- the silica used in embodiments of the invention will contain a silanol (OH) concentration of greater than 0.4 mmoles OH per gram silica; preferably it will contain greater than 0.7 mmoles to up to 2.5 mmoles OH per gram of silica. In preferred embodiments, the concentration ranges from 1.6 to 2.5 mmoles/gram silica.
- OH silanol
- all metallocene components can be dissolved with alumoxane and impregnated into the carrier. Catalyst preparation is undertaken under anhydrous conditions and in the absence of oxygen. Metal impregnation temperatures range from 0 to 60°C. Impregnation is effected with agitation.
- the reaction can be detected by NMR analysis.
- the reaction results in depletion of any alumoxane in solution. In preferred embodiments, this results in no free alumoxane in the resulting catalyst.
- the resulting catalyst is characterized by very high transition metal and aluminum efficiencies.
- the class of alumoxanes comprises oligomeric linear and/or cyclic alkylalumoxanes represented by the formula: R-(Al(R)-0) -AIR- for oligomeric, linear alumoxanes and (- Al(R)-O-) for oligomeric cyclic alumoxane wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a C.-C- alkyl group and preferably methyl .
- MAO is a mixture of oligomers with a very wide distribution of molecular weights and usually with an average molecular weight of 800 to 1200. MAO is typically kept in solution in toluene.
- the support preferably a silica support, is impregnated with a solution of alumoxane.
- the solution of alumoxane can contain the metallocene compound(s) , described below.
- the solvent for the alumoxane is preferably toluene.
- hydrocarbon solvents may be used instead of the toluene; illustrative of such hydrocarbons are those which contain 5 to 20 carbon atoms, such as ethylbenzene, xylene, cumene, cyclopentane, cyclohexane, cycloheptane, pentane, isopentane, hexane, isohexane, heptane, octane, and decane or mixture thereof.
- the solvent for the alumoxane can be used to form a solution with a volume which is equal to or less than the pore volume of the silica.
- a critical aspect of the impregnation process is the use of a liquid medium in addition to the alumoxane solution.
- the liquid medium is a hydrocarbon which contains 5 to 20 carbon atoms; illustrative compounds which can be used as the liquid medium include pentane, isopentane, hexane, isohexane, heptane, octane, nonane, decane, dodecane, cyclopentane, cyclohexane, and cycloheptane or mixture thereof. Isomers of these hydrocarbons could also be used.
- the volume of the liquid medium is also critical in that this volume must be sufficient to form a slurry.
- this volume should be 2 to 15 times the pore volume of the support as measured by nitrogen adsorption method (BET method).
- BET method nitrogen adsorption method
- methylalumoxane and metallocene on silica it is critical that during the reaction step between methylalumoxane, metallocene, and silica are complete such that more than 99% of the methylalumoxane and metallocene have reacted with the silica surface or chemically adsorbed on the silica surface and negligible amount of methylalumoxane and metallocene remained in the liquid medium outside of the silica pores.
- the use of the liquid medium results in uniform dispersion of the metals on the surface and pores of the catalyst support.
- Use of the liquid medium improves aluminum distribution, reduces catalyst agglomeration and, indirectly or directly, increases continuity.
- the uniform distribution of aluminum is revealed in electron micrographs of the catalysts.
- Saturated hydrocarbon liquid was found to be a very effective medium to disperse silica, methylalumoxane in toluene, and metallocene to give a supported catalyst with very uniform distribution of metals within catalyst particles and among catalyst particles.
- the final catalyst was characterized by scanning electron microscope FTIR, and solid state NMR.
- methylalumoxane it was found, reacted with the silica hydroxyl group to form methylalumoxane silicate with essentially no free methyl-alumoxane left in the final catalyst as shown by FTIR and solid state NMR.
- FTIR and solid state NMR we also found the aluminum distribution within the particle and among the particles are very uniformly distributed as measured by the
- a common method to detect the distribution of various chemical elements, such as silicon, aluminum, carbon, oxygen, and zirconium, in particles less than 500 microscon in size is the use of electron scanning microscopy.
- the description of the use of a scanning electron microscope is specified in the example section. In effect the catalyst particle are observed under magnification.
- the existence of various elements is detected by the energy dispersive spectrometer equipped on the scanning electron microscope.
- the distribution of each selected element can be displaced on a photograph. Judging from the variation in the intensity of each element among various particles, one can qualitatively determine the distribution of each element on each silica particle. To further quantify these observations, one can randomly select a sample of catalyst particles (for example, 25 particles) in the microscope and measure the aluminum and silicon signal for each silica particle.
- the Al/Si signal ratio can be determined for a cross-section of a catalyst particle.
- the catalyst particles were first sectioned, and 10 cross-sectioned particles were randomly chosen.
- the Al and Si signal were obtained for the center of each particle and the edge (defined as the 2 micron layer just underneath the outmost boundary of a catalyst particle) of each particle.
- Comparison of the average Al/Si signal ratio for (a) the surfaces of the catalyst particles, (b) the centers of the cross-sections of the catalyst particles, and (c) the edges of the cross-sections of the catalyst particles would indicate the uniform distribution of aluminum within the catalyst particles. In general, the difference among the
- Al/Si signal ratios from (a) , (b) and (c) should not be more than 30% more each other and preferably less than 15% from each other.
- the maximum volume of the alumoxane solution is the total pore volume of the carrier material sample. That maximum volume of the alumoxane solution insures that the solvent used in the alumoxane solution does not demonstrate or change the properties of the liquid medium chosen to disperse the silica.
- the pore volume of the carrier material is 1.65 cc/gm
- the volume of alumoxane will be equal to or less than 1.65 cc/gm of carrier material.
- the maximum volume of solution (of metallocene and alumoxane) will equal the total pore volume of the carrier, e.g. silica, which is the pore volume in, e.g., cc/gm, times the total weight of the carrier used.
- the solvent or the hydrocarbon liquid may be removed from the pores of the carrier material by heating and/or under a vacuum or purged with heating in an inert gas, such as nitrogen.
- the hydrocarbon liquid can also be removed by filtering or decanting.
- elevated temperature is employed, the temperature conditions in this step are controlled to reduce, if not to eliminate, agglomeration of impregnated carrier particles and/or crosslinking of the alumoxane.
- solvent can be removed by evaporation effected at relatively low elevated temperatures of above 40° and below 50° to obviate agglomeration of catalyst particles and crosslinking of the alumoxane.
- drying is undertaken at 45°C or less for 5 to 7 hours.
- 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 25 to 10,000, preferably 75 to 980, and most preferably 100 to 350.
- 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 24 hours, prior to use in the impregnated step.
- the solvent for the metallocene and alumoxane can be appropriate hydrocarbon solvents, such as toluene, xylene, ethyl benzene, cumean, pentane, isopentane, hexane, isohexane, heptane, and octane, or mixtures thereof, preferably it is toluene.
- the silica impregnant medium comprises an aliphatic or alicyclic diluent.
- the invention further comprises a process for preparing a catalyst for the polymerization and/or copolymerization of ethylene and/or alpha-olefins of 3 to 10 carbon atoms and for producing products exhibiting a bulk density of 15 to 36 lb/ft3.
- the catalyst is in the form of particles, wherein said particles have an average particle size in the range of 1 to 500 microns; wherein said particles comprise silica, a transition metal and aluminum, wherein the ratio of aluminum to transition metal ranges from 70 to 350; wherein the process comprises providing an amorphous porous hydrated silica and dehydrating said silica at a dehydration temperature of less than 300°C to provide a dehydrated silica having a silanol concentration of at least 0.7 illimoles per gram silica, wherein said dehydrated silica is further characterized by a pore volume in the range of 0.1 to 5 cc/gm; providing a volume of a mixture of a metallocene
- the metallocene compound has the formula Cp m MA n B p in which Cp is an unsubstituted or substituted cyclopentadienyl group, 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 cyclopenta-dienyl group.
- the substituents on the cyclopentadienyl group can be preferably straight-or branched chain Cj-Cg 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 2 -, -CH 2 -CH 2 -, -CR'R"- and -CR'R"-CR'R"- where R' and R" are short alkyl groups or hydrogen, -Si(CH 3 ) 2 -, Si (CH 3 ) 2 -CH 2 - CH 2 -Si(CH 3 ) 2 - and similar bridge groups.
- polymethylene or dialkylsilane groups such as -CH 2 -, -CH 2 -CH 2 -, -CR'R"- and -CR'R"-CR'R"- where R' and R" are short alkyl groups or hydrogen, -Si(CH 3 ) 2 -, Si (CH 3 ) 2 -CH 2 - CH 2 -Si(CH 3 ) 2 - 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. If the substituents A and B in the above formula of the metallocene compound are alkyl groups, they are preferably straight-chain or branched C 1.-Co D alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, n-pentyl, n-hexyl or n-octyl or phenyl, benzyl, substituted phenyl, or substituted benzyl groups.
- substituents A and B in the above formula of the metallocene compounds are aryl groups, they are preferably phenyl or benzyl groups or derivatives of these groups.
- Suitable metallocene compounds include: bis (cyclopentadienyl)metal dihalides, bis (cyclopentadienyl)metal hydridohalides, bis (cyclopentadienyl) etal 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 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 hydridochlor
- the metallocene compounds utilized within the embodiment of this art can be used as crystalline solids, as solutions in aromatic hydrocarbons or in a supported form. These catalysts are effective to run at low pressures, up to, specifically no greater than, 1000 psi, at temperatures up to 130 °C. These catalysts exhibit long catalyst life, high activity and productivity, and produce high bulk density products.
- the process of the invention may be undertaken in gas phase, in fluid bed gas phase, or in slurry.
- the catalyst of the invention exhibits long catalyst life.
- the catalyst of the invention allows for the production of linear low density polyethylene in the gas phase or in a slurry polymerization without reactor fouling.
- particulate linear low density polyethylene is produced in the slurry reactor and is not swollen (by the solvent) .
- the products from both the gas phase (e.g. fluid bed) and slurry have a high bulk density, which allows for increased throughput of product per weight of catalyst.
- the polymerization is undertaken at a temperature and/or pressure below the sintering temperature of the polymer particles.
- the process is undertaken in the fluid bed gas phase or in a slurry reactor.
- the high activity of the catalysts herein allow for efficacious low pressure fluid bed gas phase and/or slurry process product production.
- Much lower activity catalysts than those described herein may be employed in high pressure processes at pressures which exceed 400 psi, such as solution and high pressure slurry polymerizations.
- an operating temperature of 30° to 115°C is preferred, and a temperature of 70° to 106°C is most preferred.
- Temperatures of 75° to 90°C are used to prepare products having a density of 0.91 to 0.92, and temperatures of 80° to 100°C are used to prepare products having a density of 0.92 to 0.94, and temperatures of 90° to 115°C are used to prepare products having a density of 0.94 to 0.96.
- linear low density production is conducted at 85°C and high density product is formed at 105°C.
- slurry polymerization linear low density production is conducted at 70 'C and high density production is conducted at 90°C.
- pressures are below 10000 psi, preferably below 1000 psi.
- the fluid bed reactor is operated at pressures of up to 1000 psi, and is preferably operated at a pressure of from 150 to 500 psi, with operation at the higher pressures in such ranges favoring heat transfer since an increase in pressure increases the unit volume heat capacity of the gas.
- the partially or completely activated catalyst is injected into the bed at a point above the distribution plate at a rate equal to its consumption. Since the catalysts used in the practice of this invention are highly active, injection of the fully activated catalyst into the area below the distribution plate may cause polymerization to begin there and eventually cause plugging of the distribution plate.
- Injection into the bed aids in distributing the catalyst throughout the bed and precludes the formation of localized spots of high catalyst concentration.
- the production rate of polymer in the bed is controlled by the rate of catalyst injection. Since any change in the rate of catalyst injection changes the rate of generation of the heat of reaction, the temperature of the recycle gas is adjusted to accommodate the change in rate of heat generation. Complete instrumentation of both the fluidized bed and the recycle gas cooling system is, of course, necessary to detect any temperature change in the bed so as to enable the operator to make a suitable adjustment in the temperature of the recycle gas.
- Both low density (0.91 to 0.939 g./cc) and high density (0.94 to 0.965 and above) products with high bulk density, low (hexane) extractables and granular morphology can be prepared in the slurry or gas phase reactor with no fouling.
- the resin produced has a high molecular weight, narrow molecular weight distribution, and homogeneous branching distribution.
- the catalyst ash contains small amounts of Zr and Al, e.g., less than 1 ppm Zr and 50 ppm Al.
- the high activity of the catalysts of the invention which also exhibit long catalyst life and produce high bulk density products are significant factors in the unexpected efficacy of these catalysts in catalytic polymerizations and copolymerizations of olefins.
- Ethylene polymers as well as copolymers of ethylene with one or more C 3 -C 10 alpha-olef ins , can be produced in accordance with the invention.
- copolymers having two monomeric units are possible as well as terpolymers having three monomeric units.
- Particular examples of such polymers include ethylene/1-butene copolymers, ethylene/1-hexene copolymers and ethylene/4-methyl-1-pentene copolymers.
- the catalyst is effective to incorporate comonomer in a regular manner the resin may contain blocks of polymerized product of alpha olefins of 3 to 10 carbon atoms in the resin backbone. These blocks will consist essentially of dimers, oligomers, polymers and admixtures thereof. Because of the excellent comonomer incorporation of the catalyst and the branching homogeneity of the resin, significant amount of hexene saving can be achieved.
- Ethylene/l-butene and ethylene/1-hexene copolymers are the most preferred copolymers polymerized in the process of and with the catalyst of this invention.
- the ethylene copolymers produced in accordance with the present invention preferably contain at least about 80% by weight of ethylene units.
- the cocatalyst of this invention can also be used with the catalyst precursor of this invention to polymerize propylene and other alpha-olefins and to copolymerize them.
- the structure of alpha-olefin polymers prepared with the cocatalyst and the catalyst precursor of this invention depends on the structure of the cyclopentadienyl ligands attached to the metal atom in the catalyst precursor molecule.
- the cocatalyst compositions of this invention can also be used with the catalyst precursors of this invention to polymerize cycloolefins such as cyclopentene.
- Hydrogen may be used as a chain transfer agent in the polymerization reaction of the present invention.
- the ratio of hydrogen/ethylene employed will vary between 0 to 2.0 moles of hydrogen per mole of ethylene in the gas phase. Any gas inert to the catalyst and reactants can also be present in the gas stream.
- the catalyst of the invention exhibits high activity for polymerization of ethylene and higher alpha-olefins and allows the synthesis of ethylene polymers and copolymers with a relatively narrow molecular weight distribution and homogeneous branching distribution.
- the molecular weight distribution is determined as MFR which ranges from 15 to 25, in polymerizations of the invention.
- Branching distribution in ethylene copolymers is evaluated on the basis of the resin's melting point. Relatively homogeneous branching distribution is one which the melting point ranges from 100° to 120°C, depending on comonomer composition.
- the catalyst of the invention contains only one source of transition metal, a metallocene.
- the copolymer products contain 0.1 to 2 ppm of Zr.
- the product has an average particle size of 0.015-0.035 inches, settled bulk density from 20 to 36 lb/ft3.
- the particles of product are spherical.
- the narrow molecular weight distribution low density copolymers have been produced with MI of one (1) and less than 1, down to 0.01.
- the low density products of the invention exhibit a MI which can range from 0.01 to 5, preferably from 0.5 to 4, and most preferably 0.8 to 2.0.
- the low density products of the invention exhibit a melt flow ratio (MFR) of 14 to 25 preferably from 14 to 20; products with MFR ranging from 16 to 18 have been made; MFR is the ratio I 21/12 [wherein 121 is measured at 190 "C in accordance with ASTM D-1238,
- Condition F, and 12 is measured in accordance with ASTM D- 1238, Condition E] .
- the films of the copolymers exhibit balanced tear strength, as measured by ASTM D-1922.
- the LLDPE of the invention exhibits Dart Drop Impact values as measured by ASTM D-1709 of greater than 800.
- the products of the catalysis with the catalyst of the invention can be used as films which are substantially free of gels.
- the films exhibit very low haze values as measured by ASTM D-1003, preferably in the range of 3 to 10, more preferably from 5 to 7.
- Davison 955 silica was dehydrated at 250 °C. 10.0 grams of this dehydrated silica were added to a 300 ml flask; and 50 cc of heptane were added to the silica to form a slurry mixture.
- 0.142 grams of bis(n- butylcyclopentadienyl) zirconium dichloride was dissolved in 13.41 grams of a 30 wt.% methyalumoxane solution in toluene. This solution was added slowly to the silica over a period of 30 minutes. The slurry mixture was then dried at 45°C with nitrogen purge for 16 hours. 13.7 grams of free flowing catalyst were obtained and analyzed to contain 13.2 wt.% Al and 0.23 wt.% Zr.
- Example 3 The same procedures was used as in example 1 except no silica was used. 3.235 grams of solid were collected and analyzed to contain 32.8 wt.% Al and 0.65 wt.% Zr. Example 3
- Davison 955 silica was dehydrated at 250°C. 20.07 grams of this dehydrated silica were added to a 500 ml flask with an addition funnel and equipped with a pedal stirrer. 100 cc isohexane were added through the addition funnel into the silica to form a slurry mixture. In a separate bottle, 0.284 grams of bis(n-butylcyclopentadienyl) zirconium dichloride was dissolved in 32.08 cc of a 30 wt.% methyalumoxane solution in toluene. This solution was added slowly over a period of 30 minutes.
- the slurry was mixed thoroughly, and 20 cc of the clear solvent were decanted from the slurry for analysis of Al and Zr.
- the slurry mixture was then dried at 45 °C with nitrogen purge for 16 hours. 27.8 grams of free flowing catalyst were collected and analyzed to contain 12.0 wt.% Al and 0.22 wt.% Zr.
- Davison 955 silica was dehydrated at 250°C. 20.162 grams of this dehydrated silica were added to a 500 ml flask equipped with an addition funnel and a pedal stirrer. 100 cc isohexane and 0.5 cc of 15 wt.% trimethylaluminum in heptane were added into the addition funnel. This solution was then added to the silica to form a slurry mixture. In a separate bottle, 0.473 grams bis (n-butylcyclopentadienyl) zirconium dichloride was dissolved in 32.2 cc of a 30 wt.% methyalumoxane solution in toluene.
- Davison 955 silica was dehydrated at 600 ° C . 15.63 grams of this dehydrated silica were added to a 500 ml flask equipped with an addition funnel and a pedal stirrer. 75 cc isohexane and 0.4 cc of 15 wt.% trimethylaluminum in heptane were added into the addition funnel. This solution was then added to the silica to form a slurry mixture. In a separate bottle, 0.367 grams bis (n-butylcyclopentadienyl) zirconium dichloride was dissolved in 22.74 cc of a 30 wt.% methyalumoxane solution in toluene.
- Davison 955 silica was dehydrated at 600 'C. 20.06 grams of this dehydrated silica were added to a 500 ml flask with an addition funnel and a pedal stirrer attached. 100 cc isohexane and 0.5cc of 15 wt.% trimethylaluminum in heptane were added to the addition funnel . This solution was then added to the silica to form a slurry mixture.
- Silica was dehydrated at 250°C. 5.00 grams of this silica were added to a 100 ml Schlenk flask equipped with a magnetic stirrer. 25 cc of isohexane were transferred into the flask to form a slurry mixture. This slurry mixture was chilled in an ice bath at 0°C. In a separate bottle, 0.047 grams of bis (n-butylcyclopentadienyl) zirconium dichloride was dissolved in 7.7 cc of 30 wt.% methylalumoxane in toluene. This solution was then transferred slowly into the silica slurry over a period of 5 minutes while stirring vigorously. The slurry mixture was then dried at 45 "C with nitrogen purge for 4 hours. 6.3 grams of free flowing catalyst were obtained and analyzed to contain 11.9 wt.% Al and 0.15 wt.% Zr. Example 9
- Silica was dehydrated at 250 °C. 5.0 gram of this silica were added to a 100 ml Schlenk flask equipped with a magnetic stirrer. 25 cc of isohexane were transferred into the flask to form a slurry mixture. In a separate bottle, 0.047 grams of bis (n-butylcyclopentadienyl) zirconium dichloride was dissolved in 5.5 cc of 30 wt.% methylalumoxane in toluene. This solution was then transferred slowly into the silica slurry over a period of 10 minutes with vigorous stirring. The slurry mixture was then dried at 45 °C with nitrogen purge for 4 hours. 6.4 grams of free flowing dry catalyst were collected and analyzed to contain 10.3 wt.% Al and 0.16 wt.%
- Silica was dehydrated at 600°C. 5.0 grams of this silica were weighed into a 100 ml Schlenk flask equipped with a magnetic stirrer. 25 cc of isohexane were transferred into the flask to form a slurry mixture. In a separate bottle, 0.047 gram of bis (n-butylcyclopentadienyl) zirconium dichloride was dissolved in 5.5 cc of 30 wt.% methylaluminoxane in toluene and additional 1.9 cc of toluene was added. This solution was then transferred slowly into the silica slurry over a period of 10 minutes with vigorous stirring.
- Davison 955 silica was dehydrated at 250°C. 655 grams of this dehydrated silica were added to a two-gallon mix-vessel; and 3280 cc of isopentane were added to the silica to form a slurry mixture. In a separate step, 6.174 grams of bis(n- butylcyclopentadienyl) zirconium dichloride were dissolved in 923 grams of a 30 wt.% methyalumoxane solution in toluene. This solution was then pumped slowly at 12.0 cc/minute to the slurry mixture which was agitated at 120 rpm.
- Example 11 Same as Example 11, except that 664 grams of silica, 3325 cc of isopentane, 934 grams of methylalumoxane, and 6.250 grams of bis(n- butylcyclopentadienyl) were used. 829 grams of free flowing catalyst were obtained and analyzed to contain 12.5 wt.% Al and 0.15 wt.% Zr.
- Example 11 Same as Example 11, except that 658 grams of silica, 3290 cc of isopentane, 923.4 grams of methylalumoxane, and 6.200 grams of bis(n- butylcyclopentadienyl) were used. 912 grams of free flowing catalyst were obtained and analyzed to contain 12.2 wt.% Al and 0.14 wt.% Zr.
- the catalysts were analyzed with a JEOL JSM-840A SEM equipped with a PGT OMEGA EDS detector. EDS scans and maps were collected on a SUN Sparcstation and processed with PGT
- IMIX X-Ray and Imaging Microanalysis Systems
- EDS detection limit is 0.05-1.0 wt.% in a l-8m 3 volume, depending on the matrix.
- the gold peaks in the spectra are from the conductive coating applied using a SPI-MODULE sputter coater to prevent charge buildup during the analysis.
- All 12.8K pixel particle maps were collected at a 39mm. working distance (WD) , 20KV accelerating voltage, 6m amp probe current, from secondary electron images (SEI) at 30OX magnification (sections were collected at 500X) with the objective aperture set at the 2 position.
- a filter assigns brightness levels to each pixel which correlate with the relative selected element counts (the highest concentration appears brightest while black indicates the absence of the element) .
- Use of the Al/Si ratio eliminates topographical interference.
- Catalyst sample was mixed well and homogenized by agitation. A representative sample was taken by a small spatula. The catalyst powder was distributed on a 3 cm 2 area of double-sided tape attached to a carbon disk. This sample was then coated with gold using a SPI-MODULE tn " sputter coater. The disk was placed into a JEOL SEM specimen holder and viewed under the conditions specified for the JEOL JSM 840A SEM. An area containing at least 25 particles at 300X magnification was selected and imaged in the secondary electron image (SEI) mode. 25 particles from this image were randomly chosen and were labeled from 1 to 25 on the photograph.
- SEI secondary electron image
- EDS energy dispersive spectrometer
- a spectrum was acquired with the conditions set at 10 seconds, 6nA, 20kV accelerating voltage, 30° take-off angle from the a 4 m 2 small area scan of each numbered particle at 4,000X. From the image menu, integrals at FWHM for the aluminum and silicon peaks were recorded for each of the 25 particles. The total counts for aluminum was divided by the total counts for silicon for each of the 25 particles. Use of the Al/Si ratio eliminates topographical variations for each point analyzed. The 25 Al/Si ratios were then arithmetically averaged to give value for the average Al/Si ratio at surface and the standard deviation of these 25 Al/Si ratios was calculated by standard statistical method. Results are shown in Table 2A.
- the catalyst powder Prior to gold-coating the disk, the catalyst powder was sectioned by running a microtome blade across the tape at a 30° angle. An area containing at least 5 cross-sectioned particles at 500X was selected, imaged, and mapped as in the surface analysis. 5 to 10 particles were randomly chosen from the picture and labelled from 1 to 10. Aluminum and silica signal were collected in similar manner as described in the surface analysis, except that for each particle, the aluminum and silicon signals were collected at the center of each particle and then at the edge of each particle. The edge is typically within 2 microns from the outermost boundary of the silica cross-section. The aluminum and silicon signals were collected from the 5 to 10 particles. The total counts for aluminum was divided by the total counts for silicon for all the signals.
- Al/Si ratio eliminates topographical variations for each point analyzed.
- the 5 to 10 Al/Si ratios at the center of the silica particle were then arithmetically averaged to give value for the average Al/Si ratio at center, and the standard deviation of these 5 to 10 Al/Si ratios at center were calculated by standard statistical method. Results are shown in Table 2B. Similarly, calculation were obtained for the average Al/Si ratio at edge and the standard deviation of these 5 to 10 Al/Si ratios at edge. Results are shown in Table 2C. 2. Results
- the distribution of the Al element is very uniform as shown by the average Al/Si ratios. All the average Al/Si ratios are within the range of 0.33 to 0.37; indicating that the Al distribution is very uniform from one example to another example. It should be noted that as the Al loading on the silica changes this Al/Si ratio would change also. What is important here is that the ratio is very uniform from sample to sample.
- the Al/Si ratio at catalyst outer surfaces has a standard deviation is no more than 25% of the average Al/Si ratio at catalyst surfaces.
- the Al/Si ratio at center of cross-sectioned catalyst particles has standard deviation that is no more than 40% of the average Al/Si ratio at center of cross sectioned catalyst particles.
- the Al/Si ratio at edge of cross-sectioned catalyst particles has standard deviation that is no more than 40% of the average Al/Si ratio at edge of cross-sectioned catalyst particles.
- the Al from MAO reacted with the silica quickly such that less than 1% of the total Al from MAO was still left in the solvent. Most of the Al from MAO was anchored in the silica sites, and therefore no washing step is required.
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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DE69731293T DE69731293T2 (en) | 1996-07-11 | 1997-06-25 | METHOD FOR PRODUCING A SUPPORTED METAL CELL CALCULATOR FOR OLEFIN POLYMERIZATION |
JP10506039A JP2000516644A (en) | 1996-07-11 | 1997-06-25 | Supported metallocene catalysts for olefin polymerization |
EP97932296A EP0910471B1 (en) | 1996-07-11 | 1997-06-25 | Process for preparing a supported metallocene catalyst for olefin polymerization |
AU35792/97A AU731623B2 (en) | 1996-07-11 | 1997-06-25 | Supported metallocene catalyst for olefin polymerization |
CA002260182A CA2260182C (en) | 1996-07-11 | 1997-06-25 | Supported metallocene catalyst for olefin polymerization |
Applications Claiming Priority (2)
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US68281896A | 1996-07-11 | 1996-07-11 | |
US08/682,818 | 1996-07-11 |
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PCT/US1997/011092 WO1998002246A1 (en) | 1996-07-11 | 1997-06-25 | Supported metallocene catalyst for olefin polymerization |
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EP (1) | EP0910471B1 (en) |
JP (1) | JP2000516644A (en) |
KR (1) | KR100490714B1 (en) |
AU (1) | AU731623B2 (en) |
DE (1) | DE69731293T2 (en) |
ES (1) | ES2229373T3 (en) |
TW (1) | TW448192B (en) |
WO (1) | WO1998002246A1 (en) |
Cited By (9)
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WO2006049699A1 (en) | 2004-10-29 | 2006-05-11 | Exxonmobil Chemical Patents Inc | Catalyst compound containing divalent tridentate ligand |
US7220804B1 (en) | 2000-10-13 | 2007-05-22 | Univation Technologies, Llc | Method for preparing a catalyst system and its use in a polymerization process |
WO2010084049A1 (en) | 2009-01-23 | 2010-07-29 | Evonik Oxeno Gmbh | Film |
WO2010084047A1 (en) | 2009-01-23 | 2010-07-29 | Evonik Oxeno Gmbh | Pe mib slurry polymerization |
WO2010084054A1 (en) | 2009-01-23 | 2010-07-29 | Evonik Oxeno Gmbh | Polyolefin gas phase polymerization with 3-substituted c4-10-alkene |
WO2011078923A1 (en) | 2009-12-23 | 2011-06-30 | Univation Technologies, Llc | Methods for producing catalyst systems |
WO2013113797A1 (en) | 2012-01-31 | 2013-08-08 | Norner As | Multimodal polyethylene polymers and process preparing said polymer |
US20170114199A1 (en) * | 2011-11-24 | 2017-04-27 | Hanwha Total Petrochemical Co., Ltd. | Catalyst for olefin polymerization and co-polymerization and method for olefin polymerization and co-polymerization with using the same |
US10604603B2 (en) | 2014-12-22 | 2020-03-31 | Norner Verdandi As | Polyethylene for pipes |
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BR112012014854B1 (en) * | 2009-12-18 | 2019-09-24 | Total Petrochemicals Research Feluy | PROCESS FOR PREPARING A PARTICULAR POLYETHYLENE PRODUCT |
KR101721194B1 (en) | 2013-11-28 | 2017-03-29 | 주식회사 엘지화학 | Method for preparing supported metallocene catalyst |
EP4032917A4 (en) * | 2020-10-16 | 2023-01-04 | LG Chem, Ltd. | Metallocene-supported catalyst, and method for preparing olefine polymer using same |
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- 1997-06-25 DE DE69731293T patent/DE69731293T2/en not_active Expired - Fee Related
- 1997-06-25 KR KR10-1999-7000059A patent/KR100490714B1/en not_active IP Right Cessation
- 1997-06-25 EP EP97932296A patent/EP0910471B1/en not_active Expired - Lifetime
- 1997-06-25 ES ES97932296T patent/ES2229373T3/en not_active Expired - Lifetime
- 1997-06-25 JP JP10506039A patent/JP2000516644A/en not_active Ceased
- 1997-06-25 AU AU35792/97A patent/AU731623B2/en not_active Ceased
- 1997-07-08 TW TW086109627A patent/TW448192B/en active
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Cited By (12)
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US7220804B1 (en) | 2000-10-13 | 2007-05-22 | Univation Technologies, Llc | Method for preparing a catalyst system and its use in a polymerization process |
US7776977B2 (en) | 2000-10-13 | 2010-08-17 | Univation Technologies, Llc | Method for preparing a catalyst system and its use in a polymerization process |
WO2006049699A1 (en) | 2004-10-29 | 2006-05-11 | Exxonmobil Chemical Patents Inc | Catalyst compound containing divalent tridentate ligand |
WO2010084049A1 (en) | 2009-01-23 | 2010-07-29 | Evonik Oxeno Gmbh | Film |
WO2010084047A1 (en) | 2009-01-23 | 2010-07-29 | Evonik Oxeno Gmbh | Pe mib slurry polymerization |
WO2010084054A1 (en) | 2009-01-23 | 2010-07-29 | Evonik Oxeno Gmbh | Polyolefin gas phase polymerization with 3-substituted c4-10-alkene |
US20120142882A1 (en) * | 2009-01-23 | 2012-06-07 | Evonik Oxeno Gmbh | Pe mib slurry polymerisation |
WO2011078923A1 (en) | 2009-12-23 | 2011-06-30 | Univation Technologies, Llc | Methods for producing catalyst systems |
US20170114199A1 (en) * | 2011-11-24 | 2017-04-27 | Hanwha Total Petrochemical Co., Ltd. | Catalyst for olefin polymerization and co-polymerization and method for olefin polymerization and co-polymerization with using the same |
WO2013113797A1 (en) | 2012-01-31 | 2013-08-08 | Norner As | Multimodal polyethylene polymers and process preparing said polymer |
US10604603B2 (en) | 2014-12-22 | 2020-03-31 | Norner Verdandi As | Polyethylene for pipes |
US10995169B2 (en) | 2014-12-22 | 2021-05-04 | Norner Verdandi As | Polyethylene for pipes |
Also Published As
Publication number | Publication date |
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TW448192B (en) | 2001-08-01 |
ES2229373T3 (en) | 2005-04-16 |
EP0910471A4 (en) | 1999-09-22 |
EP0910471B1 (en) | 2004-10-20 |
KR20000023611A (en) | 2000-04-25 |
JP2000516644A (en) | 2000-12-12 |
EP0910471A1 (en) | 1999-04-28 |
DE69731293D1 (en) | 2004-11-25 |
DE69731293T2 (en) | 2005-03-24 |
AU3579297A (en) | 1998-02-09 |
AU731623B2 (en) | 2001-04-05 |
KR100490714B1 (en) | 2005-05-24 |
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