WO2010026091A1 - Procédé de polymérisation d'oléfines en phase gazeuse - Google Patents

Procédé de polymérisation d'oléfines en phase gazeuse Download PDF

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Publication number
WO2010026091A1
WO2010026091A1 PCT/EP2009/060997 EP2009060997W WO2010026091A1 WO 2010026091 A1 WO2010026091 A1 WO 2010026091A1 EP 2009060997 W EP2009060997 W EP 2009060997W WO 2010026091 A1 WO2010026091 A1 WO 2010026091A1
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Prior art keywords
gas
riser
downcomer
polymerization
process according
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PCT/EP2009/060997
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English (en)
Inventor
Antonio Mazzucco
Silvia Soffritti
Tiziana Caputo
Gianni Collina
Riccardo Rinaldi
Roberta Pica
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Basell Poliolefine Italia S.R.L.
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Publication of WO2010026091A1 publication Critical patent/WO2010026091A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • 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

Definitions

  • TITLE Process for the gas-phase polymerization of olefins
  • the present invention relates to a process for the gas-phase polymerization of olefins using a reactor having interconnected polymerisation zones.
  • the invention relates to the use of a polymerization catalyst with a predefined particle size in a gas-phase polymerization reactor having interconnected polymerisation zones.
  • a widely used technology for gas-phase polymerization processes is the fluidized bed technology.
  • fluidized bed gas-phase processes the polymer is confined in a vertical cylindrical zone (polymer bed).
  • the reaction gases exiting the reactor are taken up by a compressor, cooled and sent back, together with make-up monomers and appropriate quantities of hydrogen, to the bottom of the polymer bed through a distribution plate.
  • Entrainment of solid from the gas exiting the reactor is limited by an appropriate dimensioning of the upper part of the reactor (freeboard, i.e. the space between the upper bed surface and the gas exit point), where the gas velocity is reduced, and, in some designs, by the interposition of cyclones in the gases exit line.
  • the flow rate of the circulating gaseous monomers is set so as to assure a velocity within an adequate range above the minimum fluidization velocity and below the "transport velocity".
  • the heat of reaction is removed exclusively by cooling the circulating gas.
  • the composition of the gas-phase controls the composition of the polymer, while the reaction kinetics is controlled by the addition of inert gases.
  • the reactor is operated at constant pressure, normally in the range 1-4 MPa.
  • a novel gas-phase polymerization process which represents a gas-phase technology alternative to the fluidized bed reactor technology, as to the preparation of olefin polymers, is disclosed in EP-B- 1012195.
  • the polymerization process is carried out in a gas-phase reactor having interconnected polymerization zones, where the growing polymer particles flow through a first polymerization zone (riser) under fast fluidization or transport conditions, leave said riser and enter a second polymerization zone (downcomer) through which they flow in a densif ⁇ ed form under the action of gravity, leave said downcomer and are reintroduced into the riser, thus establishing a circulation of polymer between the two polymerization zones.
  • This polymerization process allows to obtain polymers with a broad molecular weight distribution by establishing different polymerisation conditions in the two interconnected polymerisation zones. This is achieved by introducing into the upper part of the downcomer a gas/liquid mixture, which evaporates and forms a barrier stream preventing or limiting the gases present in the riser from entering the downcomer. Accordingly, different polymerisation conditions can be maintained in the riser and in the downcomer.
  • EP 1012195 is generic as regards the type and size of the catalyst particles to be used in the olefin polymerization: it is disclosed that suitable catalysts are those of controlled morphology, capable of giving polymers in the form of spheroidal particles having a mean dimension between 0.2 and 5 mm, preferably between 0.5 and 3 mm. It is known that when the polymerization of olefins is carried out by means of a gas-phase reactor a high-power compressor must be arranged on the recycle line to provide the continuous recycle of the reaction mixture from the top of the reactor to the bottom part of the reactor.
  • a high-power compressor is arranged on the recycle line in order to provide the gaseous stream with a pressure and velocity suitable to ensure fast fluidization conditions in the polymer bed present in the first polymerization zone (riser): therefore, the establishment of fast fluidisation conditions in the riser causes the recycle compressor to consume a high amount of energy, thus increasing the operating costs of the polymerization plant. Therefore, it would be desirable to decrease the power consumption required by the compressor of the recycle line, without modifying the polymer hold-up inside the first polymerization zone.
  • the Applicant has now found that when catalyst components of a decreased particle size are used in the above gas-phase polymerization reactor the power consumption required by the recycle compressor is remarkably reduced, thus decreasing the operating costs of the polymerization plant.
  • said solid catalyst component has an average size P50 ranging from 20 ⁇ m to 65 ⁇ m, preferably from 40 to 60 ⁇ m;
  • the average size P50 indicates a value of diameter, such that 50% of the total particles have a diameter lower than said value.
  • the process of present invention is addressed to improve the operability of a gas-phase reactor having interconnected polymerization zones as described in EP-B- 1012195.
  • the first polymerisation zone which comprises polymer particles flowing upwards under fast fluidisation conditions, is generally referred to as the "riser”.
  • the second polymerisation zone which comprises polymer particles flowing downwards by gravity, is generally referred to as the "downcomer”.
  • Fast fluidization conditions are established in the riser by feeding a gas mixture comprising one or more alpha-olefms at a velocity higher than the transport velocity of the polymer particles.
  • transport velocity and “fast fluidization conditions” are well known in the art; for a definition thereof, see, for example, "D. Geldart, Gas Fluidisation Technology, page 155 et seq., J. Wiley & Sons Ltd., 1986".
  • the riser operates under fast fluidized bed conditions with gas superficial velocities higher than the average particles terminal velocities, so that the polymer particles are entrained upwards by the flow of the reacting monomers.
  • a highly turbulent flow regime is established into the riser: this generates a good heat exchange coefficient between the single particles and the surrounding gas, and also ensures that the reaction temperature is kept reasonably constant along the reaction bed.
  • the polymer particles flow under the action of gravity in a densified form, so that high values of density of the solid (mass of polymer per volume of reactor) are achieved, said density of solid approaching the bulk density of the polymer.
  • a "densified form" of the polymer implies that the ratio between the mass of polymer particles and the reactor volume is higher than 80% of the "poured bulk density" of the obtained polymer.
  • the gas-phase polymerization process herewith described is not restricted to the use of any particular family of polymerization catalysts, with the proviso that the average size P50 of the catalyst particles is within the above indicated values.
  • Any polymerization catalyst in form of a solid powder, either pre-polymerized or not, may be employed: Ziegler-Natta catalyst components, single site catalyst components and chromium-based catalyst components can be mentioned.
  • the polymerization process of the invention is based on the selection of catalyst components with an average size P50 ranging from 20 to 65 ⁇ m, preferably from 40 to 60 ⁇ m, so that the produced polyolef ⁇ n has a particle size P50 in a range from 1000 ⁇ m to 2200 ⁇ m.
  • the use of solid catalyst components of particle size significantly lower than the prior art allows to pursue a save of operating costs when establishing fast fluidization conditions inside the riser.
  • fast fluidization conditions are established by feeding at the bottom of the riser a gas mixture at a velocity higher than the transport velocity of the polymer particles. Due to minor particle size of the polyolefin flowing upwards along the riser, the transport velocity is remarkably decreased with respect to the use of conventional catalyst particles of higher size, so that the riser may be operated at lower gas velocities: according to the invention, the upward velocity of the gas flowing in the riser ranges from 0.8 to 2.0 m/s, preferably from 1.2 to 1.8 m/s.
  • the same density of polymer in the riser (kg of polymer per m 3 of reactor) is achieved at significantly lower fluidization velocities in the riser.
  • the operative conditions of temperature and pressure in the polymerization process of the invention are those usually used in gas-phase catalytic polymerization processes. Therefore, in both riser and downcomer the temperature is generally comprised between 60 0 C and 120 0 C, while the pressure may range from 5 to 50 bar.
  • Preferred catalyst components having P50 from 20 to 65 ⁇ m exploited in the process of the invention are Ziegler-Natta catalyst components based on a titanium halide, preferably TiCU, supported on magnesium halide. Before the feeding to the polymerization said catalyst components have to be necessarily subjected to activation by contacting them with a catalyst activator, and optionally the activated catalyst particles may be successively subjected to a prepolymerization step.
  • Ziegler-Natta catalyst components of the claimed particle size are subjected to activation step, followed by prepolymerization in a loop reactor and successively the prepolymerized catalyst is fed to the riser of a gas-phase polymerization apparatus having two interconnected polymerization zones, as described in EP-B- 1012 195.
  • a Ziegler-Natta catalyst component 1 in form of a powder, an organo-aluminum compound 2 as the catalyst activator, and optionally an electron donor compound, are fed to a pre- contacting vessel 3. These components are contacted in continuous in the vessel 3 at a temperature ranging from 0 0 C to 30 0 C for an average residence time of 5-60 minutes.
  • the catalyst particles are continuously withdrawn from the activation vessel 3 and are fed via line 4 to a prepolymerization reactor 5 to carry out the catalyst prepolymerization.
  • the prepolymerization may be carried out in a liquid medium in whatever type of reactor: continuous stirred tank reactors (CSTR), as well as loop reactors can be used for contacting the olefin monomers with the catalyst particles.
  • CSTR continuous stirred tank reactors
  • loop reactors can be used for contacting the olefin monomers with the catalyst particles.
  • the prepolymerization treatment is preferably carried out in a liquid loop reactor.
  • the liquid medium of the prepolymerization step comprises liquid alpha-olefm monomer(s), optionally with the addition of an inert hydrocarbon solvent.
  • Said hydrocarbon solvent can be either aromatic, such as toluene, or aliphatic, such as propane, hexane, heptane, isobutane, cyclohexane and 2,2,4-trimethylpentane.
  • the amount of hydrocarbon solvent, if any, is lower than 40% by weight with respect to the amount of alpha-olef ⁇ ns, preferably lower than 20% by weight.
  • the catalyst prepolymerization is carried out in the absence of inert hydrocarbon solvents.
  • the prepolymerization step is generally carried out at a low temperature, generally ranging from 20 to 50 0 C, preferably from 25 to 40 0 C.
  • the average residence time in the prepolymerization step generally ranges from 2 to 40 minutes, preferably from 10 to 25 minutes: this parameter may be easily modified by increasing or decreasing the output of the polymeric slurry from the prepolymerizator.
  • the polymerization degree ranges from 60 to 800 g per gram of solid catalyst component, preferably from 150 to 400 g per gram of solid catalyst component.
  • a slurry containing the prepolymerized catalyst particles is discharged from the loop reactor 5 and is fed via line 7 to the riser 8 of a gas-phase reactor having two interconnected polymerization zones.
  • the gas-phase reactor comprises a riser 8 and a downcomer 9, wherein the polymer particles flow, respectively, upward under fast fluidization conditions along the direction of the arrow A and downward under the action of gravity along the direction of the arrow B.
  • the riser 8 and the downcomer 9 are appropriately interconnected by the interconnection bends 10 and 11.
  • one or more olefin monomers are polymerized in the presence of hydrogen as the molecular weight regulator.
  • a gaseous mixture comprising the monomers, hydrogen and propane, as an inert diluent, is fed to the reactor through one or more lines 12, suitably placed at any point of the gas recycling system according to the knowledge of those skilled in art.
  • This solid/gas separation 13 can be effected by using conventional separation means such as, for example, a centrifugal separator (cyclone) of the axial, spiral, helical or tangential type.
  • the recycle gas is divided into two separated gaseous streams, the first one enters the connecting section 11 via line 17 and this stream favors the transfer of the polymer particles from the downcomer 9 to the riser 8.
  • the second stream of recycle gas is fed via line 18 to the bottom of the riser 8 to establish fast fluidization conditions in this polymerization zone.
  • the polymer particles are discharged from the polymerization reactor via a discharge outlet 19, placed at the bottom part of the downcomer 9.
  • the gas mixture coming from the riser can be prevented from entering the downcomer by introducing a gas and/or liquid mixture of different composition through one or more introduction lines placed into the downcomer, preferably at a point close to the upper limit of the volume occupied by the densif ⁇ ed solid flowing downward along the downcomer.
  • the gas and/or liquid mixture of different composition to be fed into the downcomer can optionally be fed in partially or totally liquefied form.
  • the liquefied gas mixture can also be sprinkled over the upper surface of the bed of densif ⁇ ed polymer particles; the evaporation of the liquid in the polymerisation zone will provide the required gas flow.
  • the above technical effect can be achieved by feeding a gas and/or liquid into the downcomer 9 through a line 20 placed at a suitable point of said downcomer 9, preferably in the upper part thereof.
  • the gas and/or liquid mixture has a composition different from that of the gas mixture present in the riser 8.
  • Said gas and/or liquid mixture partially or totally replaces the gas mixture entrained with the polymer particles entering the downcomer.
  • the flow rate of this gas and/or liquid feed can be regulated so that a flow of gas counter-current to the flow of polymer particles is originated in the downcomer 9, particularly at the top thereof, thus acting as a barrier to the gas mixture coming from the riser 8, which is entrained among the polymer particles.
  • feed lines 20 can be placed in the downcomer 9 at different heights, in order to better control the gas-phase composition throughout said downcomer.
  • additional feed lines 20 can be used to introduce gaseous or condensed monomers, optionally together with inert components.
  • their evaporation in downcomer 9 contributes to remove the heat of the polymerisation reaction, thus allowing to control the temperature profile in the downcomer 9 in a reliable way.
  • the section of the bottom of the downcomer 9 can conveniently converge into a restriction 21.
  • adjustable mechanical valves can be employed, such as, for example, a throttle valve, such as a butterfly valve.
  • a stream of a gas also denominated as the "dosing gas" may be fed into the lower part of the downcomer 9 by means of a line 22 placed above a suitable distance from the restriction 21.
  • the dosing gas to be introduced through line 22 is conveniently taken from the recycle line 14, more precisely, downstream the compressor 15 and upstream the heat exchanger 16.
  • the main function of said dosing gas is to control the solid recirculation flow from the downcomer 9 to the riser 8 through the restriction 21.
  • the gas-phase polymerization process of the invention allows the preparation of a large number of olefin powders having an optimal particle size distribution with a low content of fines.
  • polymers that can be obtained are: high-density poly ethylenes (HDPEs having relative densities higher than 0.940) including ethylene homopolymers and ethylene copolymers with ⁇ -olefms having 3 to 12 carbon atoms; linear poly ethylenes of low density (LLDPEs having relative densities lower than 0.940) and of very low density and ultra low density (VLDPEs and ULDPEs having relative densities lower than 0.920 down to 0.880) consisting of ethylene copolymers with one or more ⁇ -olefms having 3 to 12 carbon atoms; elastomeric terpolymers of ethylene and propylene with minor proportions of diene or elastomeric copolymers of ethylene and propylene with a content of units derived from ethylene of between about 30 and 70% by weight; isotactic polypropylene and crystalline copolymers of propylene and ethylene and/or other ⁇ -olefms having a content
  • the above mentioned bimodal polyethylene blends are particularly suitable to be subjected to injection molding for preparing shaped articles.
  • the above mentioned polypropylene blends may be used to prepare films and fibers.
  • the polymerization process of the present invention can be carried out upstream or downstream other conventional polymerization technologies (either in a liquid-phase or a gas-phase) to give rise a sequential multistage polymerization process.
  • a fluidised bed reactor can be used to prepare a first polymer component, which is successively fed to the gas-phase reactor of Fig. 1 to prepare a second and a third polymer component.
  • an ethylene polymer endowed with a tri-modal molecular weight distribution can be obtained, as well as a polypropylene blend comprising three components having a different content in ethylene.
  • the polymerization process of the invention may be performed by means of different types of solid catalyst components, with the proviso that the average size P50 of the catalyst particles fed to the reactor is within the above indicated values.
  • Ziegler- Natta catalyst components, single site catalyst components, and chromium-based catalyst components may be employed in the present invention.
  • Preferred catalyst components of the invention are catalyst components comprising a magnesium halide, a titanium compound having at least a Ti-halogen bond, and optionally electron donor compounds.
  • the magnesium halide is preferably MgCl 2 in active form which is widely known from the patent literature as a support for Ziegler-Natta catalysts.
  • Patents USP 4,298,718 and USP 4,495,338 were the first to describe the use of these compounds in Ziegler- Natta catalysis.
  • the preferred titanium compounds used in the catalyst component of the present invention are TiCU and TiCl 3 ; furthermore, also Ti-haloalcoholates of formula Ti(OR) n _ y X y can be used, where n is the valence of titanium, y is a number between 1 and n-1 X is halogen and R is a hydrocarbon radical having from 1 to 10 carbon atoms.
  • the preparation of the solid catalyst component having the above indicated particle size can be carried out according to several methods.
  • the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR) n _ y X y , where n is the valence of titanium and y is a number between 1 and n, preferably TiCU, with a magnesium chloride deriving from an adduct of suitably small particle size having formula MgCUpROH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms.
  • the adduct can be prepared in suitable spherical form and small particle size by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130 0 C). Then, the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of small spherical particles.
  • a suitably small average particle size is obtained by providing to the system high energy shear stresses by way of maintaining in the mixer conditions such as to have a Reynolds (R EM ) number 10,000 and 80,000, preferably between 30,000 and 80,000.
  • ReM modified Reynolds number
  • the so obtained adduct particles have average particle size determined with the method described in the characterization section below, ranging from 20 to 65 ⁇ m, preferably from
  • P50 according to the same method, wherein P90 is the value of the diameter such that 90% of the total volume of particles have a diameter lower than that value; PlO is the value of the diameter such that 10% of the total volume of particles have a diameter lower than that value and P50 is the value of the diameter such that 50% of the total volume of particles have a diameter lower than that value.
  • the particle size distribution can be inherently narrowed by following the teaching of WO02/051544. However, in alternative to this method or to further narrow the SPAN, largest and/or finest fractions can be eliminated by appropriate means such as mechanical sieving and/or elutriation in a fluid stream.
  • the adduct particles can be directly reacted with Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130 0 C) so as to obtain an adduct in which the number of moles of alcohol is generally lower than 3 preferably between 0.1 and 2.5.
  • the reaction with the Ti compound can be carried out by suspending the adduct particles (dealcoholated or as such) in cold TiCU (generally 0 0 C); the mixture is heated up to 80- 130 0 C and kept at this temperature for 0.5-2 hours.
  • the treatment with TiCU can be carried out one or more times.
  • the electron donor compounds can be added during the treatment with TiCU. They can be added together in the same treatment with TiCU or separately in two or more treatments.
  • internal electron donor compounds can be supported on the MgCl 2 .
  • they can be selected among esters, ethers, amines, and ketones.
  • the use of compounds belonging to 1,3-diethers, cyclic ethers, phthalates, benzoates, acetates and succinates is preferred.
  • the solid catalyst components are activated to form catalysts for the polymerization of olefins by reacting them with catalyst activators which are organo-aluminum compounds, preferably chosen among alkyl-Al compounds and in particular among the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n- hexylaluminum, tri-n-octylaluminum. It is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides, such as AlEt 2 Cl and Al 2 EtSCIs, possibly in mixture with the above cited trialkylaluminums.
  • catalyst activators which are organo-aluminum compounds, preferably chosen among alkyl-Al compounds and in particular among the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-
  • Suitable external electron-donor include silanes, ethers, esters, amines, heterocyclic compounds and ketones.
  • a particular class of preferred external donor compounds is that of silanes of formula
  • Ra 5 Rb 6 Si(OR 7 )c where a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum
  • R 5 , R 6 , and R 7 are alkyl, alkylen, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms.
  • Particularly preferred are the silicon compounds in which a is 1, b is 1, c is 2, at least one of R 5 and R 6 is selected from branched alkyl, cycloalkyl or aryl groups with 3-10 carbon atoms optionally containing heteroatoms and R 7 is a C 1 -C 10 alkyl group, in particular methyl.
  • Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane.
  • a preferred class of the above compound (A) is a metallocene compound belonging to the following formula (I):
  • M is a transition metal belonging to group 4, 5 or to the lanthanide or actinide groups of the
  • M is zirconium, titanium or hafnium
  • the substituents X are monoanionic sigma ligands selected from the group consisting of hydrogen, halogen, R 6 , OR 6 , OCOR 6 , SR 6 , NR 6 2 and
  • R 6 is a hydrocarbon radical containing from 1 to 40 carbon atoms; preferably, the substituents X are selected from the group consisting of -Cl, -Br, -Me, -Et, -n-Bu, -sec-Bu, -
  • p is an integer equal to the oxidation state of the metal M minus 2;
  • q is 0 or 1 ; when q is 0 the bridge L is not present;
  • L is a divalent hydrocarbon moiety containing from 1 to 40 carbon atoms, optionally containing up to 5 silicon atoms, bridging Cp and A; preferably L is selected from Si(CHs) 2 , SiPh 2 , SiPhMe,
  • Cp is a substituted or unsubstituted cyclopentadienyl group, optionally condensed to one or more substituted or unsubstituted, saturated, unsaturated or aromatic rings;
  • A has the same meaning of Cp or it is a NR 7 , -O, S, moiety wherein R 7 is a hydrocarbon radical containing from 1 to 40 carbon atoms.
  • the above catalyst system may be supported on an inert carrier having average size P50 in the range 20-65 ⁇ m, by depositing the compound (A), or the reaction product of the compound
  • the preferred carriers are particles of silica, alumina, magnesium halides, olefin polymers or prepolymers (i.e. polyethylenes, polypropylenes or styrene-divinylbenzene copolymers).

Abstract

Procédé de polymérisation d'oléfines en présence d'un composant de type catalyseur solide et d'un activateur de catalyseur, le procédé étant mis en œuvre dans un réacteur en phase gazeuse doté de zones de polymérisation interconnectées, les particules de polymères en croissance s'écoulant vers le haut à travers une première zone de polymérisation (zone ascendante) dans des conditions de fluidisation rapide, quittant ladite zone ascendante et entrant une seconde zone de polymérisation (zone descendante) à travers laquelle elles s'écoulent vers le bas sous l'action de la gravité, quittant ladite zone descendante et étant réintroduites dans la zone ascendante, ce qui établit une circulation de polymères entre lesdites zones ascendante et descendante, le procédé étant caractérisé en ce que ledit composant de type catalyseur solide présente une granulométrie moyenne P50 comprise entre 20 µm et 65 µm et en ce que le gaz s'écoule vers le haut dans ladite première zone de polymérisation à une vitesse comprise entre 0,8 et 2,0 m/s.
PCT/EP2009/060997 2008-09-04 2009-08-26 Procédé de polymérisation d'oléfines en phase gazeuse WO2010026091A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP08163659 2008-09-04
EP08163659.9 2008-09-04
US19110508P 2008-09-05 2008-09-05
US61/191,105 2008-09-05

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4298718A (en) * 1968-11-25 1981-11-03 Montecatini Edison S.P.A. Catalysts for the polymerization of olefins
US4495338A (en) * 1968-11-21 1985-01-22 Montecatini Edison S.P.A. Components of catalysts for the polymerization of olefins
WO1997004015A1 (fr) * 1995-07-20 1997-02-06 Montell Technology Company B.V. Procede et appareil de polymerisation en phase gazeuse d'alpha-olefines
WO2002051544A1 (fr) * 2000-12-22 2002-07-04 Basell Poliolefine Italia S.P.A. Procede de preparation d'un support spherique comprenant un dihalogenure de mg
EP1012195B1 (fr) * 1998-07-08 2003-02-05 Basell Poliolefine Italia S.p.A. Procede et dispositif de polymerisation en phase gazeuse
WO2006120187A1 (fr) * 2005-05-13 2006-11-16 Basell Poliolefine Italia S.R.L. Procédé pour la polymérisation d'oléfines en phase gazeuse

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4495338A (en) * 1968-11-21 1985-01-22 Montecatini Edison S.P.A. Components of catalysts for the polymerization of olefins
US4298718A (en) * 1968-11-25 1981-11-03 Montecatini Edison S.P.A. Catalysts for the polymerization of olefins
WO1997004015A1 (fr) * 1995-07-20 1997-02-06 Montell Technology Company B.V. Procede et appareil de polymerisation en phase gazeuse d'alpha-olefines
EP1012195B1 (fr) * 1998-07-08 2003-02-05 Basell Poliolefine Italia S.p.A. Procede et dispositif de polymerisation en phase gazeuse
WO2002051544A1 (fr) * 2000-12-22 2002-07-04 Basell Poliolefine Italia S.P.A. Procede de preparation d'un support spherique comprenant un dihalogenure de mg
WO2006120187A1 (fr) * 2005-05-13 2006-11-16 Basell Poliolefine Italia S.R.L. Procédé pour la polymérisation d'oléfines en phase gazeuse

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